KR20200079231A - Siloxane resin composition, cured film and display device - Google Patents

Abstract

Provided is a siloxane resin composition having excellent storage stability and a cured film excellent in adhesion and chemical resistance of a glass substrate or a metal substrate even at a low temperature curing condition of 100°C or lower. It is a siloxane resin composition containing (A) polysiloxane, (B) photosensitizer, (C) polymerizable compound having phosphorus atom and (D) silane compound having ureido group.

Description

Siloxane resin composition, cured film and display device

The present invention relates to a siloxane resin composition, a cured film and a display device.

Currently, capacitive touch panels are used in most smartphones or tablet terminals. The touch sensor used in the capacitive touch panel has a wiring patterned with ITO (Indium Tin Oxide) or metal (silver molybdenum, aluminum, etc.) on the glass, and has an insulating film and a protective film protecting the wiring at the crossing of the wiring. The structure is general. In addition to transparency, the insulating film formed at the intersections of the wirings has a fine pattern processability, adhesion to a metal substrate such as a glass substrate or a conductive film serving as a base substrate, and an etchant solution or an alkali release solution used to form a conductive film pattern. Chemical resistance is required.

On the other hand, even when a low temperature treatment of 200°C or less is employed, a polyfunctional (meth)acrylic having a specific functional group as a photosensitive resin composition for an organic EL device having excellent adhesion between a cured product and a substrate and excellent elastic recovery properties A photosensitive resin composition for an organic electroluminescent device having an alkali developable composition comprising a rate monomer, a siloxane compound having two or more hydrolyzable alkoxy groups, and a photoradical polymerization initiator as essential components has been proposed (for example, a patent) Reference 1). Further, as a resin composition capable of forming a transparent film having excellent heat resistance and chemical resistance, polymerization having a developable group and substantially free of radically polymerizable groups, and a polymerizable radical having a radically polymerizable group and substantially free of developable groups A resin composition having two types of polysiloxanes of a sex polysiloxane, and having a polyfunctional monomer and a polyfunctional cyclic ether compound having two or more cyclic ether structures has been proposed (for example, see Patent Document 2).

However, in recent years, development of an on-cell type touch panel that directly forms a touch sensor on a liquid crystal panel or an organic EL panel has been actively conducted. In this method, it is necessary to form a touch sensor at a low temperature below the heat resistance temperature of the liquid crystal material or the organic EL material. In particular, it is said that the heat-resistant temperature of the organic EL material is 100°C or less. Therefore, even at a curing temperature of 100°C or less, a photosensitive transparent material that can be used as an insulating film and a protective film is required.

Japanese Patent Publication 2015-67733 Japanese Patent Publication 2012-14930

Even when the resin composition described in Patent Documents 1 to 2 is cured at a low temperature of 100°C or lower, curing is insufficient, the adhesion between the glass substrate and the metal substrate is still insufficient, and the cured film is dissolved in an etchant solution or a resist stripping solution. , There was also a problem in chemical resistance. In addition, when these resin compositions contain a phosphoric acid compound, condensation of the polysiloxane tends to proceed due to acidity, which has a problem in storage stability.

Therefore, it is an object of the present invention to provide a siloxane resin composition capable of obtaining a cured film excellent in storage stability and excellent in adhesion and chemical resistance of a glass substrate or a metal substrate even under low temperature curing conditions of 100°C or lower.

The present invention is a siloxane resin composition containing (A) a polysiloxane, (B) a photosensitizer, (C) a polymerizable compound having a phosphorus atom, and (D) a silane compound having a ureido group.

The siloxane resin composition of the present invention is excellent in storage stability. According to the siloxane resin composition of the present invention, a cured film excellent in adhesiveness and chemical resistance of a glass substrate or a metal substrate can be obtained even under low temperature curing conditions of 100°C or lower.

The siloxane resin composition of the present invention contains (A) a polysiloxane, (B) a photosensitizer, (C) a polymerizable compound having a phosphorus atom, and (D) a silane compound having a ureido group. When the siloxane resin composition of the present invention is a negative photosensitive resin composition, (A) polysiloxane has solubility in an alkali developer and has a function as a binder resin capable of pattern processing by photolithography. When the siloxane resin composition of the present invention is a positive photosensitive resin composition, (A) polysiloxane provides high heat resistance and light resistance by condensation during thermal curing. (B) The photosensitive agent has a function of imparting a negative or positive photosensitive property and enabling formation of a fine pattern by photolithography. (C) The polymerizable compound having a phosphorus atom can improve adhesion to a metal substrate and chemical resistance. On the other hand, in the prior art, when (C) contains a polymerizable compound having a phosphorus atom, (C) condensation of the polysiloxane proceeds due to acidity of the polymerizable compound having a phosphorus atom, so storage stability decreases. In the present invention, the effect of improving storage stability is exhibited by combining the polymerizable compound having the phosphorus atom (C) and the silane compound having the (D) ureido group as the weakly basic substance. In addition, (D) the silane compound having a ureido group exerts an effect of improving adhesion and chemical resistance to a metal substrate and a glass substrate.

(A) Polysiloxane

In the siloxane resin composition of the present invention, (A) polysiloxane refers to a polymer having a weight average molecular weight (Mw) of 1,000 or more having a siloxane bond in the main chain skeleton. Here, (A) Mw of polysiloxane represents polystyrene conversion value measured by gel permeation chromatography (GPC). From the viewpoint of coating properties, (A) Mw of the polysiloxane is more preferably 2,000 or more. On the other hand, from the viewpoint of coating properties and solubility in a developer, the Mw of the polysiloxane (A) is preferably 100,000 or less, and more preferably 50,000 or less.

When the siloxane resin composition of the present invention is a negative photosensitive resin composition, it is preferable that the polysiloxane (A) has a cationic polymerizable group (a1), a radical polymerizable group (a2), and an alkali-soluble group (a3). (a1) By having a cationically polymerizable group, it can be cured at a lower temperature, and hardness can be improved under low temperature curing conditions of 100°C or lower. Moreover, since the penetration of the chemical solution is suppressed by improving the crosslinking density of the cured film, the chemical resistance can be further improved. (a2) Since having a radically polymerizable group makes it easy to impart contrast between the curing degree of the exposed portion and the unexposed portion, it is possible to suppress the occurrence of developing residues and obtain a more precise pattern. Moreover, by having a radically polymerizable group (a2), photocurability can be improved and hardness can be improved under low temperature curing conditions of 100°C or lower. Moreover, since the penetration of the chemical solution is suppressed by improving the crosslinking density of the cured film, the chemical resistance can be further improved. (a3) By having an alkali-soluble group, developability can be improved and generation of development residues can be suppressed. Moreover, by having (a3) alkali-soluble group, (a3) alkali-soluble group acts as an acidic catalyst, and (A) condensation of polysiloxane proceeds, so that hardness can be improved under low temperature curing conditions of 100°C or lower. In addition, chemical resistance can be further improved by improving the crosslinking density of the cured film.

(a1) The content of the cationic polymerizable group is preferably 1 to 30 mol% based on 100 mol% of the total content of the (a1) cationic polymerizable group, (a2) radical polymerizable group and (a3) alkali-soluble group. (a1) By setting the content of the cationic polymerizable group to 1 mol% or more, the crosslinking reaction by cationic polymerization can proceed more effectively, and the hardness and chemical resistance of the cured film can be further improved. (a1) The content of the cationic polymerizable group is more preferably 5 mol% or more. On the other hand, by setting the content of the cationic polymerizable group (a1) to 30 mol% or less, the hydrophilicity of the cured film can be appropriately suppressed to further improve hardness and chemical resistance. (a1) The content of the cationic polymerizable group is more preferably 20 mol% or less. Further, the content of the radically polymerizable group (a2) is preferably 50 to 90 mol% relative to the total content of 100 mol% of the (a1) cationic polymerizable group, (a2) radically polymerizable group and (a3) alkali-soluble group. (a2) When the content of the radically polymerizable group is 50 mol% or more, the crosslinking reaction by radical polymerization can be sufficiently advanced, and hardness and chemical resistance can be further improved. In addition, by setting the content of the radically polymerizable group (a2) to 50 mol% or more, a more accurate pattern can be obtained because contrast between the exposed portion and the unexposed portion is easily provided. On the other hand, by setting the content of the radically polymerizable group (a2) to 90 mol% or less, a more precise pattern can be obtained. (a2) The content of the radically polymerizable group is more preferably 85 mol% or less.

Epoxy group, styryl group, (meth)acryloyl group, alkali soluble group with respect to the total content of (a1) cationic polymerizable group, (a2) radical polymerizable group and (a3) alkali soluble group of polysiloxane in this invention The content of can be calculated by ²⁹ Si-NMR. For a solution in which polysiloxane was mixed with hexamethylcyclotrisiloxane as a reference substance, a ²⁹ Si-NMR measuring device (for example, AVANCE400 (manufactured by Bruker)) was used, and the room temperature (approx. ²⁹ Si-NMR is measured at 22°C), and the content of each group is calculated from the peak integral ratio. However, the measured nuclear frequency is 79.4948544 MHz ( ²⁹ Si nucleus), the spectrum width is 40 kHz, and the pulse width is 4.2 μsec (90° pulse).

(a1) a cationic polymerizable group, (a2) a radical polymerizable group and (a3) a polysiloxane having an alkali-soluble group, an organosilane compound having a cationic polymerizable group, an organosilane compound containing a radically polymerizable group, an organo having an alkali-soluble group It can be obtained by hydrolysis and polycondensation of a silane compound and other organosilane compounds as necessary.

(a1) Examples of the cationic polymerizable group include an epoxy group, an oxetanyl group, and a vinyl ether group. Among these, an epoxy group and an oxetanyl group are preferable, and the chemical resistance and hardness of the cured film under low temperature curing conditions can be further improved.

(a1) Examples of the organosilane compound having a cationic polymerizable group include glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycine Doxyethyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane , γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltriisopropoxysilane, γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyltri(methoxyethoxy)silane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltrimethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutylbutyl Trimethoxysilane, γ-glycidoxybutyltriethoxysilane, σ-glycidoxybutyltrimethoxysilane, σ-glycidoxybutyltriethoxysilane, (3,4-epoxycyclohexyl)methyltrimethoxy Methoxysilane, (3,4-epoxycyclohexyl)methyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltripropoxysilane, 2-(3,4-epoxycyclohexyl)ethyltributoxy Silane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriphenoxy Cysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltriethoxysilane, 4-(3,4-epoxycyclohexyl)butyltri Methoxysilane, 4-(3,4-epoxycyclohexyl)butyltriethoxysilane, glycidoxymethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, α-glycidoxyethylmethyldimethoxysilane, α -Glycidoxyethylmethyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylmethyldiethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyl Diethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ- Glycidoxypropylmethyldipropoxysilane, β-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldi(methoxyethoxy) Organosilane compounds having an epoxy group such as silane, γ-glycidoxypropylethyl dimethoxysilane, and γ-glycidoxypropylethyl diethoxysilane; 3-[(3-ethyloxetan-3-yl)methoxy]propyltrimethoxysilane, 3-[(3-ethyloxetan-3-yl)methoxy]propyltriethoxysilane, 3-[( 3-ethyloxetan-3-yl)methoxy]propyltriacetoxysilane, 3-[(3-ethyloxetan-3-yl)methoxy]propylmethyldimethoxysilane, 3-[(3-ethyloxy Cetane-3-yl)methoxy]propylmethyldiethoxysilane, 3-[(3-ethyloxetan-3-yl)methoxy]propylmethyldiacetoxysilane, 3-[(3-ethyloxetane-3 -Yl)methoxy]propyldimethylmethoxysilane, 3-[(3-ethyloxetan-3-yl)methoxy]propyldimethylethoxysilane, 3-[(3-ethyloxetan-3-yl)methoxy Methoxy]propyldimethylacetoxysilane, (3-ethyloxetan-3-yl)methoxytrimethoxysilane, (3-ethyloxetan-3-yl)methoxytriethoxysilane, bis[(3-ethyl Oxetan-3-yl)methoxy]dimethoxysilane, bis[(3-ethyloxetan-3-yl)methoxy]diethoxysilane, tris[(3-ethyloxetan-3-yl)methoxy] And organosilane compounds having an oxetanyl group such as methoxysilane and tris[(3-ethyloxetan-3-yl)methoxy]ethoxysilane. You may use 2 or more types of these. Among these, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, 3-[(3-ethyloxetane-3) from the viewpoint of crosslinkability and curability. -Yl)methoxy]propyltrimethoxysilane is preferred.

(a2) As a radically polymerizable group, vinyl group, (alpha)-methylvinyl group, allyl group, styryl group, (meth)acryloyl group etc. are mentioned, for example. Among these, a styryl group having high hydrophobicity or thermal reactivity and a (meth)acryloyl group having high photoreactivity are preferable, and the chemical resistance and hardness of the cured film can be further improved. It is more preferable to use both a styryl group and a (meth)acryloyl group.

(a2) Examples of the organosilane compound having a radically polymerizable group include organosilane compounds having vinyl groups such as vinyl trimethoxysilane, vinyl triethoxysilane and vinyl tri(methoxyethoxy)silanesilane; Organosilane compounds having α-methylvinyl groups such as vinyl methyl dimethoxysilane, vinyl methyl diethoxysilane, and vinyl methyl di(methoxyethoxy) silane; Allyl trimethoxysilane, allyltriethoxysilane, allyltri(methoxyethoxy)silane, allylmethyldimethoxysilane, allylmethyldiethoxysilane, allylmethyldi(methoxyethoxy)silane, etc. Ganosilane compounds; Styryl trimethoxysilane, styryl triethoxysilane, styryl tri(methoxyethoxy)silane, styrylmethyldimethoxysilane, styrylmethyldiethoxysilane, styrylmethyldi(methoxyethoxy)silane Organosilane compounds having styryl groups; γ-(meth)acryloylpropyltrimethoxysilane, γ-(meth)acryloylpropyltriethoxysilane, γ-(meth)acryloylpropyltri(methoxyethoxy)silane, γ-(meta ) Having a (meth)acryloyl group such as acryloylpropylmethyldimethoxysilane, γ-(meth)acryloylpropylmethyldiethoxysilane, and γ-(meth)acryloylpropyl(methoxyethoxy)silane Organosilane compounds and the like.

(a3) As an alkali-soluble group, a carboxylic acid group, a carboxylic acid anhydride group, etc. are mentioned, for example. Among these, carboxylic acid anhydride groups are more preferable.

(a3) organosilane compounds having alkali-soluble groups, such as 3-trimethoxysilylpropylsuccinic anhydride, 3-triethoxysilylpropylsuccinic anhydride, 3-triphenoxysilylpropylsuccinic anhydride, 3-trime Organosilane compounds having carboxylic acid anhydride groups such as methoxysilylpropylcyclohexyldicarboxylic acid anhydride and 3-trimethoxysilylpropylphthalic anhydride; You may use 2 or more types of these. Among these, from the viewpoint of developability, 3-trimethoxysilylpropylsuccinic anhydride and 3-triethoxysilylpropylsuccinic anhydride are preferred.

Examples of other organosilane compounds include methyl trimethoxysilane, methyl triethoxysilane, methyl tri(methoxyethoxy)silane, methyl tripropoxysilane, methyl triisopropoxysilane, and methyl tributoxy. Silane, ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxy Silane, N-(2aminoethyl)-3-aminopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β- (Aminoethyl)-γ-aminopropyltrimethoxysilane, β-cyanoethyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldimethoxy Silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropylmethyldiethoxysilane, cyclohexylmethyldimethoxysilane, octadecylmethyldimethoxy Silane, tetramethoxysilane, tetraethoxysilane, and the like. You may use 2 or more types of these.

(A) Polysiloxane can be obtained by hydrolyzing an organosilane compound, and then condensing the obtained hydrolyzate in the presence of a solvent or without a solvent.

In the hydrolysis, the reaction scale, the size and shape of the reaction vessel, etc. are considered, and various conditions such as, for example, acid (base) concentration, reaction temperature, and reaction time can be appropriately set.

In the hydrolysis reaction, a catalyst such as an acid catalyst or a base catalyst may be used. In the present invention, a base catalyst is preferred, and a basic aqueous solution using diisobutylamine, diazabicycloundecene, dicyclohexylamine, or the like is more preferable. The content of the catalyst is preferably 0.1 parts by weight or more, and more preferably 5 parts by weight or less, based on 100 parts by weight of the total alkoxysilane compound used in the hydrolysis reaction. Here, the total amount of the alkoxysilane compound refers to the total amount of the alkoxysilane compound, its hydrolyzate and its condensate, and is said to be as follows.

Examples of the solvent used in the hydrolysis reaction include diacetone alcohol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and propylene glycol mono-t-butyl Ether, γ-butyrolactone, and the like are preferred. You may use 2 or more types of these. The content of the solvent is preferably 80 parts by weight or more, and more preferably 200 parts by weight or less with respect to 100 parts by weight of the total alkoxysilane compound.

When a solvent is produced by a hydrolysis reaction, it is also possible to hydrolyze with a solventless solvent. It is also preferable to adjust to an appropriate concentration as a resin composition by further adding a solvent after completion of the hydrolysis reaction. Further, after hydrolysis, all or part of the product alcohol or the like may be distilled off by heating and/or under reduced pressure, after which a preferable solvent may be added.

Ion-exchanged water is preferable as water used for the hydrolysis reaction. The amount of water is preferably 1.0 to 4.0 mol with respect to 1 mol of the alkoxysilane compound.

The heating temperature in the condensation reaction is preferably 100 to 110°C. The condensation reaction is preferably carried out while distilling and removing water and alcohol produced by the hydrolysis and condensation reaction out of the reaction system.

Further, from the viewpoint of storage stability of the composition, it is preferable that the catalyst is not included in the polysiloxane solution after the hydrolysis and condensation reaction, and the catalyst can be removed as necessary. As the removal method, treatment with water washing and/or ion exchange resin is preferred. Water washing is a method of diluting a polysiloxane solution with a suitable hydrophobic solvent, and then washing the water several times with water to concentrate the organic layer obtained with an evaporator or the like. Treatment in the ion exchange resin is a method of contacting a polysiloxane solution with a suitable ion exchange resin.

The content of the polysiloxane (A) in the siloxane resin composition of the present invention is preferably 10 to 80% by weight. In addition, the content of the polysiloxane (A) in the siloxane resin composition is preferably 10% by weight or more, more preferably 20% by weight or more in the solid content. On the other hand, the content of (A) polysiloxane is preferably 50% by weight or less in the solid content.

(B) photosensitizer

In the siloxane resin composition of the present invention, the photosensitive agent (B) has a function of providing a negative or positive photosensitive property and enabling formation of a fine pattern by a photolithography method. When providing a negative photosensitive property, it is preferable to contain (b1) a radical polymerization initiator, and a high-precision pattern-shaped partition wall can be formed. Moreover, it is preferable to contain a polyfunctional monomer. On the other hand, when providing a positive photosensitive property, it is preferable to contain a photo-acid generator. As the photo-acid generator, a (b2) quinone diazide compound is preferable.

(b1) A radical polymerization initiator represents a compound that decomposes and/or reacts with light (including ultraviolet rays or electron beams) or heat, and generates radicals. As the radical polymerization initiator, a photoradical generator that decomposes and/or reacts with light (including ultraviolet rays and electron beams) to generate radicals is preferable. It is more preferable to contain a photoradical generator and a thermal radical generator that decomposes and/or reacts with heat to generate radicals.

Examples of the photoradical generator include α-aminoalkylphenone compounds, acylphosphine oxide compounds, oxime ester compounds, ketone compounds, benzoin compounds, acyloxime compounds, metalocene compounds, thioxanthone compounds, and amino groups. Benzophenone compounds, benzoic acid ester compounds having amino groups, ketone compounds, coumarin compounds, anthracene compounds, azo compounds, carbon tetrabromide, tribromophenylsulfone, and the like. You may contain 2 or more types of these. Of these, α-aminoalkylphenone compounds, acylphosphine oxide compounds, oxime ester compounds, benzophenone compounds having amino groups, and benzoic acid ester compounds having amino groups are preferred. Since these compounds are also involved in crosslinking of the siloxane as a base or acid during light irradiation and thermal curing, the hardness can be further improved.

Examples of the α-aminoalkylphenone compound include 2-methyl-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-dimethylamino-2-(4-methylbenzyl)- 1-(4-morpholin-4-yl-phenyl)-butan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, and the like. As the acylphosphine oxide compound, for example, 2,4,6-trimethylbenzoylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzoyl) -(2,4,4-trimethylpentyl)-phosphine oxide and the like. Examples of the oxime ester compound include 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, 1,2-octanedione, and 1-[4-(phenylthio)-2- (o-benzoyloxime)], 1-phenyl-1,2-butadione-2-(o-methoxycarbonyl)oxime, 1,3-diphenylpropanetrione-2-(o-ethoxycarbonyl ) Oxime, ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(o-acetyloxime) and the like. Examples of the benzophenone compound having an amino group include 4,4-bis(dimethylamino)benzophenone, 4,4-bis(diethylamino)benzophenone, and the like. Examples of the benzoic acid ester compound having an amino group include ethyl p-dimethylaminobenzoate, 2-ethylhexyl-p-dimethylamino benzoate, ethyl p-diethylaminobenzoate, and the like.

As the thermal radical generator, for example, 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamine], 2,2'-azobis[2-methyl-N-(2 -Propenyl)-2-methylpropionamine], 2,2'-azobis(N-butyl-2-methylpropionamine), dimethyl2,2'-azobis(isobutyrate), 4,4'-azo Bis(4-cyanovaleric acid), 2,2'-azobis[2-(2-imidazolin-2-yl)propane]2 hydrochloride, 2,2'-azobis[2-(2-imi Dazolin-2-yl)propane], 2,2'-azobis(2-methylpropionamidine)2 hydrochloride, 2,2'-azobis[N-(2-carboxyethyl)2-methylpropionamidine ]n hydrates and the like are listed. You may contain 2 or more types of these. Among these, from the viewpoint of the hardness of the cured film, dimethyl 2,2'-azobis (isobutyrate) is preferred.

The content of the radical polymerization initiator (b1) in the siloxane resin composition is preferably 1% by weight or more in solids, and more preferably 10% by weight or less.

The polyfunctional monomer represents a compound having two or more (meth)acryloyl groups. By containing a polyfunctional monomer, the crosslinking reaction can be more effectively performed to further improve the hardness and chemical resistance of the cured film. From the viewpoint of further improving the sensitivity and hardness, the double bond equivalent of the polyfunctional monomer is preferably 80 to 400 g/mol.

As a polyfunctional monomer, for example, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tripenta Erythritol heptaacrylate, tripentaerythritol octaacrylate, tetrapentaerythritol nonaacrylate, tetrapentaerythritol decaacrylate, pentapentaerythritol undecaacrylate, and the like are listed. Among these, dipentaerythritol hexaacrylate is preferable from the viewpoint of improving hardness and chemical resistance.

The photoacid generator refers to a compound that generates acid by causing cleavage at the time of exposure, and more specifically, by exposure wavelength 365nm (i-ray), 405nm (h-ray), 436nm (g-ray) or a mixture of these. Represents a compound that generates an acid.

(b2) The quinone diazide compound generates a carboxylic acid group by exposure, and the exposed portion can be dissolved by development. (b2) As the quinone diazide compound, a compound in which the sulfonic acid of naphthoquinone diazide is bonded to the compound having a phenolic hydroxyl group as an ester is preferable. As a compound having a phenolic hydroxyl group used herein, for example, Bls-Z, TekP-4HBPA (tetrakis P-DO-BPA), TrlsP-HAP, TrlsP-PA, BlsRS-2P, BlsRS-3P (above, trade name , Honshu Chemical Industry Co., Ltd.), BIR-PC, BIR-PTBP, BIR-BIPC-F (above, trade name, ASAHI YUKIZAI CORPORATION product), 4,4'-sulfonyl diphenol, BPFL (trade name, JFE Chemical Corporation products) and the like. As the quinonediazide compound, it is preferable to introduce 4-naphthoquinonediazidesulfonic acid or 5-naphthoquinonediazidesulfonic acid into the compound having these phenolic hydroxyl groups as an ester bond, for example, THP-17, TDF- 517 (trade name, manufactured by Toyo Gosei Co., Ltd), SBF-525 (trade name, manufactured by AZ Electronic Materials), and the like.

In addition, the siloxane resin composition of the present invention may contain a photoacid generator other than the (b2) quinone diazide compound. The acid functions as a catalyst that promotes the dehydration condensation of silanol. When an acid is present during thermal curing, condensation of unreacted silanol groups is promoted, and the degree of crosslinking of the cured film is increased. Further, when the siloxane resin composition contains a compound having a cyclic ether group, the acid functions as a polymerization catalyst for the cyclic ether group. The polymerization of the cyclic ether group is promoted by the presence of an acid during thermal curing, thereby increasing the crosslinking degree of the cured film. By these, the hardness and chemical resistance of the cured film can be further improved. As the acid to be generated, strong acids such as perfluoroalkylsulfonic acid and p-toluenesulfonic acid are preferred.

(b2) As a photoacid generator other than a quinone diazide compound, for example, SI-100, SI-101, SI-105, SI-106, SI-109, PI-105, PI-106, PI-109, NAI -100, NAI-1002, NAI-1003, NAI-1004, NAI-101, NAI-105, NAI-106, NAI-109, NDI-101, NDI-105, NDI-106, NDI-109, PAI-01 , PAI-101, PAI-106, PAI-1001 (all brand names, products of Midori Kagaku co., ltd.), SP-077, SP-082 (all brand names, ADEKA CORPORATION products), TPS-PFBS (brand names, Toyo Gosei Co., Ltd.), CGI-MDT, CGI-NIT (all trade names, manufactured by BASF Japan Ltd.), WPAG-281, WPAG-336, WPAG-339, WPAG-342, WPAG-344, WPAG-350, WPAG -370, WPAG-372, WPAG-449, WPAG-469, WPAG-505, WPAG-506 (all trade names, manufactured by Wako Pure Chemical Industries, Ltd.) are listed. You may contain 2 or more types of these. Among these, CGI-MDT is preferred.

The content of the photo-acid generator in the siloxane resin composition is preferably 0.5% by weight or more, preferably 25% by weight or less, from the viewpoint of improving hardness, chemical resistance, and developability.

(C) a polymerizable compound having a phosphorus atom

In the siloxane resin composition of the present invention, (C) a polymerizable compound having a phosphorus atom refers to a compound containing a phosphorus atom and a radically polymerizable functional group (radical polymerizable group). Examples of the radical polymerizable group include vinyl group, α-methylvinyl group, allyl group, styryl group, (meth)acryloyl group, γ-(meth)acryloylethyl group, and γ-(meth)acryloylpropyl group. Etc. are listed. Among these, a (meth)acryloyl group, a γ-(meth)acryloylethyl group, and a γ-(meth)acryloylpropyl group having high light and thermal reactivity are preferable, and the chemical resistance of the cured film can be further improved. (C) As a polymerizable compound having a phosphorus atom, a compound having a structure represented by the following general formula (1) is preferable.

In the formula (1), R ¹ represents a monovalent organic group having a radical polymerizable group. R ² represents a monovalent organic group having hydrogen, an alkyl group having 1 to 20 carbon atoms, or a radically polymerizable group. It is preferable that the monovalent organic group having a radically polymerizable group has a hydroxyl group as well as a radically polymerizable group. By having a radically polymerizable group and a hydroxyl group, when curing the siloxane resin composition by heat or light, a polymerizable compound having a phosphorus atom (C) is efficiently introduced into the polysiloxane (A) to bleed out upon curing. Can be suppressed. As the monovalent organic group having a radically polymerizable group, a γ-(meth)acryloylethyl group and a γ-(meth)acryloylpropyl group are preferable.

As a compound having a structure represented by the general formula (1), for example, 2-methacryloyloxyethyl acid phosphate (trade name P-1M, manufactured by Kyoeisha Chemical co., ltd.), 2-acryloyloxy Ethyl acid phosphate (trade name P-1A, manufactured by Kyoeisha Chemical co., ltd.), ethylene oxide-modified phosphoric acid dimethacrylate (trade name PM-21, manufactured by Nippon Kayaku Co., Ltd.), phosphoric acid-containing epoxy methacrylate ( Phosphoric acid (meth)acrylates, such as the trade name "New Frontier" (registered trademark) S-23A, manufactured by DKS Co. Ltd.); Vinyl phosphate compounds such as vinylphosphonic acid (trade names VPA-90, VPA-100, manufactured by BASF Corp.) and the like. You may contain 2 or more types of these.

The content of the polymerizable compound having a phosphorus atom (C) in the siloxane resin composition is preferably 1% by weight or more in solids, and more preferably 30% by weight or less.

(D) Silane compound having ureido group

(D) Examples of the silane compound having a ureido group include 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-phenylureidopropyltrimethoxysilane, and 3-phenylureido Propyl triethoxysilane, 4-ureidobutyltrimethoxysilane, 4-ureidobutyltriethoxysilane, 4-phenylureidobutyltrimethoxysilane, 4-phenylureidobutyltriethoxysilane, etc. do. You may contain 2 or more types of these. Among these, 3-ureidopropyltriethoxysilane and 3-ureidopropyltrimethoxysilane are preferable from the viewpoint of further improving the adhesion to the metal substrate and the glass substrate.

The content of the silane compound having a (D) ureido group in the siloxane resin composition is preferably 0.1% by weight or more in solids, and more preferably 1% by weight or less.

In the siloxane resin composition of the present invention, the equivalent ratio ((C)/(D)) of the polymerizable compound having a phosphorus atom (C) to the silane compound having a (D) ureido group is the adhesion to the metal substrate and the glass substrate. From the viewpoint of further improving the, 8/2 or more is preferred, and 9/1 or more is more preferable. On the other hand, from the viewpoint of storage stability, the equivalent ratio ((C)/(D)) is preferably 9.9/0.1 or less, and more preferably 9.5/0.5 or less. In addition, the equivalent ratio ((C)/(D)) can be calculated from Formula (2).

Equivalent ratio ((C)/(D)) = ((C) Weight of polymerizable compound having phosphorus atom (g)/(C) Number of phosphorus atoms in polymerizable compound having phosphorus atom (pieces))/((D ) Weight of silane compound having ureido group (g)/(D) Number of ureido groups in silane compound having ureido group (pieces)

(Compound having a cyclic ether group)

It is preferable that the siloxane resin composition of this invention contains the compound which has a cyclic ether group. As a cyclic ether group, an epoxy group and an oxetanyl group are preferable. By containing a compound having a cyclic ether group, the cationic polymerizability improves, so that chemical resistance and hardness can be further improved. (A) When the polysiloxane (a1) contains an epoxy group as a cationic polymerizable group, it is more preferable that the compound having a cyclic ether group has an oxetanyl group, and (A) polysiloxane is (a1) oxetanyl as a cationic polymerizable group. When containing a group, it is more preferable that the compound having a cyclic ether group has an epoxy group. By coexisting an epoxy group and an oxetanyl group in the siloxane resin composition, the efficiency of cationic polymerization of the epoxy group and the oxetanyl group can be improved, thereby further improving chemical resistance and hardness.

The content of the compound having a cyclic ether group in the siloxane resin composition is preferably 1% by weight or more in solids, and more preferably 20% by weight or less.

The siloxane resin composition of the present invention may contain other silane compounds in addition to the silane compound having a (D) ureido group. As another silane compound, the organosilane compound etc. which were illustrated as a raw material of (A) polysiloxane are mentioned, for example. From the viewpoint of further improving sensitivity, hardness, and adhesion, γ-(meth)acryloylpropyltrimethoxysilane, γ-(meth)acryloylpropyltriethoxysilane, and styryl trimethoxysilane are preferred. From the viewpoint of improving adhesion, the content of the other silane compound in the siloxane resin composition is preferably 1% by weight or more, and more preferably 10% by weight or less.

The siloxane resin composition of the present invention may contain a curing agent. Examples of the curing agent include nitrogen-containing organic substances, silicone resin curing agents, various metal alkoxylates, various metal chelate compounds, isocyanate compounds and polymers thereof, methylolated melamine derivatives, methylolated urea derivatives, and the like. You may contain 2 or more types of these. Among these, metal chelate compounds, methylolated melamine derivatives, and methylolated urea derivatives are preferred from the viewpoint of stability of the curing agent and processability of the siloxane resin composition.

The siloxane resin composition of the present invention may contain a sensitizer within a range that does not impair the effects of the present invention. Sensitivity can be improved by containing a sensitizer. The sensitizer is preferably an anthracene-based compound from the viewpoint of high sensitivity and suppression of fading by light irradiation. The 9,10-2 substituted anthracene-based compound is more preferable, and from the viewpoint of improving the solubility of the sensitizer and reactivity of the photodimerization reaction, the 9,10-dialkoxyanthracene-based compound is more preferable.

The content of the sensitizer in the siloxane resin composition of the present invention is preferably 0.005 to 5 parts by mass based on 100 parts by mass of the polysiloxane (A).

The siloxane resin composition of the present invention may contain an ultraviolet absorber. By containing the ultraviolet absorber, a more precise pattern can be formed, and light resistance of the cured film can be improved. As a UV absorber, a benzotriazole type compound, a benzophenone type compound, and a triazine type compound are preferable from the viewpoint of transparency and non-coloring properties.

The siloxane resin composition of the present invention may contain a polymerization inhibitor. By containing a suitable amount of the polymerization inhibitor, a more precise pattern can be formed. Examples of the polymerization inhibitors include di-t-butylhydroxytoluene, butylhydroxyanisole, hydroquinone, 4-methoxyphenol, 1,4-benzoquinone and t-butylcatechol. In addition, as commercially available polymerization inhibitors, "IRGANOX" (registered trademark) 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425, 1520, 245, 259, 3114, 565, 295 (above trade names, BASF Japan Co. , Ltd. products) and the like.

The siloxane resin composition of the present invention may contain a solvent. Solvents having a boiling point of 250° C. or lower under atmospheric pressure are preferred. Moreover, from the viewpoint of suppressing the residual of the solvent in the cured film, it is preferable to contain 50% by weight or more of the total amount of the solvent having a boiling point of 150°C or lower under atmospheric pressure.

Examples of the solvent having a boiling point of 150° C. or lower under atmospheric pressure include, for example, ethanol, isopropanol, 1-propyl alcohol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether. Among these, propylene glycol monomethyl ether is preferred from the viewpoint of coatability. You may contain 2 or more types of solvents.

The content of the solvent in the siloxane resin composition of the present invention is generally 50 to 95% by weight, for example, when film formation is performed by spin coating.

The siloxane resin composition of the present invention may contain various surfactants such as fluorine-based surfactants and silicone-based surfactants. Leveling property at the time of coating can be improved by containing a surfactant. As a surfactant, for example, "Megafac" (registered trademark) F142D, F172, F173, F183, F445, F470, F475, F477, F554, F556, F563 (above trade names, manufactured by DIC Corporation), NBX-15, 218 ( Fluorine-based surfactants such as the above trade names and NEOS Corporation products); Fluorine-based surfactants such as "BYK" (registered trademark) 333, 301, 331, 345, and 307 (above trade names, manufactured by BYK Japan KK); Silicone surfactants such as "BYK" 333, 301, 331, 345, and 307 (above trade names, manufactured by BYK Japan KK); Polyalkylene oxide-based surfactants; And poly(meth)acrylate-based surfactants. You may contain 2 or more types of these.

The content of the surfactant in the siloxane resin composition is preferably 0.01% by weight or more, and more preferably 1.0% by weight or less, from the viewpoint of improving leveling properties during application.

The siloxane resin composition of the present invention may contain additives such as a dissolution inhibiting agent, a stabilizer, and an antifoaming agent, if necessary.

A typical production method of the siloxane resin composition of the present invention will be described below. The siloxane resin composition of the present invention can be obtained, for example, by mixing the above-mentioned components (A) to (D) and other components as necessary. More specifically, for example, (B) a photosensitizer, (C) a polymerizable compound having a phosphorus atom, (D) a silane compound having a ureido group, and other additives are added to an optional solvent, stirred and dissolved, (A) The method of filtering the solution obtained by adding polysiloxane and stirring for 20 minutes to 3 hours is listed.

Next, the cured film of the present invention will be described. The cured film of the present invention is obtained by curing the siloxane resin composition described above. The film thickness of the cured film is preferably 0.1 to 15 μm. The transmittance at a wavelength of 400 nm of the cured film is preferably 85% or more. Moreover, the transmittance|permeability of a cured film can be adjusted to a desired range by an exposure amount or a thermosetting temperature.

Next, the manufacturing method of the cured film of this invention is demonstrated, for example. It is preferable that the siloxane resin composition of the present invention is coated on a base substrate, prebaked, and then a negative pattern is formed by exposure and development, followed by heat curing.

Examples of the method for applying the siloxane resin composition include microgravure coating, spin coating, dip coating, curtain flow coating, roll coating, spray coating, and slit coating.

Examples of the prebaking heating device include a hot plate, an oven, and the like. The pre-baking temperature is preferably 50 to 130°C, and the pre-baking time is preferably 30 seconds to 30 minutes. The film thickness after pre-baking is preferably 0.1 to 15 µm.

Examples of the exposure light source include ultraviolet rays such as i-ray, g-ray, and h-ray, KrF (wavelength 248 nm) laser, ArF (wavelength 193 nm) laser, and the like. Examples of the exposure machine include a stepper, a mirror projection mask aligner (MPA), a parallel light mask aligner (PLA), and the like. The exposure amount is preferably about 10 to 4000 J/m ² (equivalent to a wavelength of 365 nm). It may be exposed through a desired mask, or may be exposed without passing through the mask.

As the development method, it is preferable to immerse the exposed pre-baked film in a developer for 5 seconds to 10 minutes by a method such as shower, dipping, paddle, or the like. Examples of the developer include inorganic alkalis such as hydroxides, carbonates, phosphates, silicates, and borates of alkali metals; Amines such as 2-diethylaminoethanol, monoethanolamine, and diethanolamine; And aqueous solutions of alkali compounds such as quaternary ammonium salts such as tetramethylammonium hydroxide and choline. After development, it is preferable to rinse with water, and then dry baking may be performed at a temperature of 50 to 130°C.

As a heat hardening processing apparatus, a hot plate, an oven, etc. are mentioned. The heating and curing temperature is preferably 60 to 180°C, and the heating and curing time is preferably 15 minutes to 1 hour.

The cured film of the present invention is a protective film for a touch panel, various hard coat materials, a flattening film for a TFT, an overcoat for a color filter, an antireflection film, a passivation film, and various protective films, such as an optical filter, an insulating film for a touch panel, an insulating film for a TFT, and a color. It can be used for photo spacers for filters. Among these, since it has high board|substrate adhesiveness, chemical-resistance, and hardness, it can use suitably as a protective film for touch panels, an insulating film for touch panels, and a metal wiring protection film.

Next, the touch sensor of the present invention will be described. The touch sensor of the present invention has a transparent electrode, a metal wiring, a metal wiring protection film for a touch panel made of the above-mentioned cured film, an insulating film for a touch panel, and the like.

Next, the display device of the present invention will be described. The display device of the present invention has at least one selected from the group consisting of a liquid crystal cell, an organic EL cell, a mini LED cell, and a micro LED cell, a substrate, and the cured film described above. The mini LED cell refers to a cell in which a number of LEDs having a length and width of about 100 μm to 10 mm are arranged. The micro LED cell refers to a cell in which a plurality of LEDs having a length and width of less than 100 μm are arranged.

Examples of the display device of the present invention include a liquid crystal display device, an organic EL display device, a mini LED display device, a micro LED display device, and the like.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. Among the compounds used in the synthesis examples and examples, abbreviations are shown below.

PGMEA: Propylene glycol monomethyl ether acetate

PGME: Propylene glycol monomethyl ether

TBC: 4-tert-butylpyrocatechol

The solid content concentration of the polysiloxane solution in the following synthesis examples was determined by the following method. The polysiloxane solution was weighed in 1.0 g in an aluminum cup, and heated at 250°C for 30 minutes using a hot plate to evaporate the liquid. The solid content remaining in the aluminum cup after heating was weighed, and the solid content concentration of the polysiloxane solution was determined from the weight ratio before and after heating.

Epoxy group, styryl group, (meth)acryloyl group, alkali with respect to the total content of (a1) cationic polymerizable group, (a2) radical polymerizable group and (a3) alkali-soluble group of polysiloxane in the following synthesis example The content of the soluble group was measured by ²⁹ Si-NMR by the following method. Polysiloxane was mixed with hexamethylcyclotrisiloxane as a reference material, AVANCE 400 (Bruker Co.) was used, and ²⁹ Si-NMR was measured at room temperature (about 22° C.) by DD/MAS method, and the peak Content of each group was calculated from secretion. However, the measurement nuclear frequency was 79.4948544MHz ( ²⁹ Si nucleus), the spectrum width was 40kHz, the pulse width was measured under the conditions of 4.2μsec (90° pulse).

The weight average molecular weight (Mw) in the following synthesis examples was measured by the following method. As a measuring device, HLC-8220 (manufactured by TOSO CO., LTD.) was used, tetrahydrofuran was used as the developing solvent, and polystyrene conversion was measured by gel permeation chromatography (GPC) under the conditions of a developing rate of 0.4 ml/min. I got it.

Synthesis Example 1 Synthesis of cationic polymerizable group, radical polymerizable group, and alkali-soluble group-containing polysiloxane (A-1)

In a 500 ml three-necked flask, 22.21 g (0.090 mol) of γ-glycidoxypropyl trimethoxysilane, 67.40 g (0.300 mol) of p-styryl trimethoxysilane, and γ-acryloylpropyl trimethoxy 28.16 g (0.12 mol) of silane, 27.43 g (0.090 mol) of 3-triethoxysilylpropylsuccinic acid, 0.287 g of TBC, and 158.04 g of PGME were added and dicyclohexyl was added to 34.07 g of water while stirring at 40°C. A dicyclohexylamine aqueous solution in which 0.726 g of amine (0.50% by weight relative to the input monomer) was dissolved was added over 30 minutes. After stirring for 2 hours, the flask was immersed in an oil bath at 70°C and stirred for 90 minutes. Thereafter, the oil bath was heated to 115°C over 30 minutes. After 1 hour from the start of the heating, the inner temperature of the solution reached 100°C, and heated and stirred there for 2 hours (the inner temperature was 100 to 110°C) to obtain a solution of polysiloxane (A-1). Further, during the heating and heating and stirring, the pressure holes were classified at 0.05 l/class. During the reaction, 97.42 g of by-products methanol and water were distilled in total. PGME was added to the obtained solution so that the solid content concentration was 40% by weight. Epoxy group, styryl group, (meth)acryloyl group, alkali solubility to 100 mol% of the total content of (a1) cationic polymerizable group, (a2) radical polymerizable group and (a3) alkali soluble group of the obtained polysiloxane (A-1) The content of the groups was 15 mol%, 50 mol%, 20 mol% and 15 mol%, respectively. Moreover, the weight average molecular weight of the obtained polysiloxane (A-1) was 2,500.

Synthesis Example 2 Synthesis of cationic polymerizable group, radical polymerizable group and alkali-soluble group-containing polysiloxane (A-2)

25.10 g (0.090 mol) of 3-[(3-ethyloxetan-3-yl)methoxy]propyltrimethoxysilane instead of 22.21 g (0.090 mol) of γ-glycidoxypropyltrimethoxysilane In the same manner as in Synthesis Example 1, a solution of polysiloxane (A-2) having a solid content concentration of 40% by weight was obtained. Oxetanyl group, styryl group, (meth)acryloyl group with respect to 100 mol% of the total content of (a1) cationic polymerizable group, (a2) radical polymerizable group and (a3) alkali-soluble group of the obtained polysiloxane (A-2), The content of the alkali-soluble group was 15 mol%, 50 mol%, 20 mol% and 15 mol%, respectively. Moreover, the weight average molecular weight (Mw) of the obtained polysiloxane (A-2) was 2,400.

Synthesis Example 3 Synthesis of polysiloxane (A-3) containing radically polymerizable groups and alkali-soluble groups

In a 500 ml three-necked flask, 87.62 g (0.390 mol) of p-styryl trimethoxysilane, 28.16 g (0.12 mol) of γ-acryloylpropyl trimethoxysilane, and 3-triethoxysilylpropyl succinic acid were added. Dicyclohexylamine aqueous solution of 27.43 g (0.090 mol), 0.347 g of TBC, 155.05 g of PGME added and stirred at 40° C., while dissolving 0.716 g of dicyclohexylamine (0.50% by weight relative to the input monomer) while stirring at 40° C. Was added over 30 minutes. By the same procedure as in Synthesis Example 1, a solution of polysiloxane (A-3) having a solid content concentration of 40% by weight was obtained. The styryl group, (meth)acryloyl group, alkali-soluble group of 100 mol% of the total content of the (a1) cationic polymerizable group, (a2) radical polymerizable group and (a3) alkali-soluble group of the obtained polysiloxane (A-3) Contents were 60 mol%, 20 mol%, and 15 mol%, respectively. Moreover, the weight average molecular weight (Mw) of the obtained polysiloxane (A-3) was 2,500.

Synthesis Example 4 Synthesis of cationic polymerizable group, radical polymerizable group, and alkali-soluble group-containing polysiloxane (A-4)

1.48 g (0.006 mol) of γ-glycidoxypropyl trimethoxysilane, 86.27 g (0.384 mol) of p-styryl trimethoxysilane, and γ-acryloylpropyl trimethoxysilane in a 500 ml 3-neck flask 28.16 g (0.120 mol), 3-triethoxysilylpropyl succinic acid 27.43 g (0.090 mol), TBC 0.343 g, PGME 155.25 g, and stirred at 40° C., dicyclohexylamine in 34.07 g water A dicyclohexylamine aqueous solution in which 0.717 g (0.50% by weight relative to the charged monomer) was dissolved was added over 30 minutes. A polysiloxane (A-4) solution having a solid content concentration of 40% by weight was obtained by the same procedure as in Synthesis Example 1. Epoxy group, styryl group, (meth)acryloyl group, alkali solubility for 100 mol% of the total content of (a1) cationic polymerizable group, (a2) radical polymerizable group and (a3) alkali soluble group of the obtained polysiloxane (A-4) The content of the groups was 1 mol%, 64 mol%, 20 mol%, and 15 mol%, respectively. Moreover, the weight average molecular weight (Mw) of the obtained polysiloxane (A-4) was 2,500.

Synthesis Example 5 Synthesis of cationic polymerizable group, radical polymerizable group and alkali-soluble group-containing polysiloxane (A-5)

In a 500 ml three-necked flask, 44.42 g (0.18 mol) of γ-glycidoxypropyl trimethoxysilane, 47.18 g (0.21 mol) of p-styryl trimethoxysilane, and γ-acryloylpropyl trimethoxysilane 28.16 g (0.12 mol) of silane, 27.43 g (0.090 mol) of 3-triethoxysilylpropylsuccinic acid, 0.226 g of TBC, 161.02 g of PGME, and dicyclohexyl in 34.07 g of water while stirring at 40°C A dicyclohexylamine aqueous solution in which 0.736 g of amine (0.50% by weight relative to the input monomer) was dissolved was added over 30 minutes. By the same procedure as in Synthesis Example 1, a solution of polysiloxane (A-5) having a solid content concentration of 40% by weight was obtained. Epoxy group, styryl group, (meth)acryloyl group, alkali solubility for 100 mol% of the total content of (a1) cationic polymerizable group, (a2) radical polymerizable group and (a3) alkali soluble group of the obtained polysiloxane (A-5) The content of the groups was 30 mol%, 35 mol%, 20 mol% and 15 mol%, respectively. Moreover, the weight average molecular weight (Mw) of the obtained polysiloxane (A-5) was 2,700.

Synthesis Example 6 Synthesis of cationic polymerizable group, radical polymerizable group and alkali-soluble group-containing polysiloxane (A-6)

In a 500 ml three-necked flask, 22.21 g (0.090 mol) of γ-glycidoxypropyl trimethoxysilane, 98.55 g (0.42 mol) of γ-acryloylpropyl trimethoxysilane, 3-triethoxysilylpropyl succinic acid Dicyclohexyl in which 27.43 g (0.090 mol), 0.296 g of TBC, and 162.53 g of PGME were added, and while stirring at 40°C, 0.741 g of dicyclohexylamine (0.50% by weight relative to the input monomer) was dissolved in 34.07 g of water. The aqueous amine solution was added over 30 minutes. A solution of polysiloxane (A-6) having a solid content concentration of 40% by weight was obtained in the same manner as in Synthesis Example 1. Epoxy group, (meth)acryloyl group, alkali soluble group of 100 mol% of the total content of the (a1) cationic polymerizable group, (a2) radical polymerizable group and (a3) alkali soluble group of the obtained polysiloxane (A-6) Content was 15 mol%, 70 mol%, and 15 mol%, respectively. Moreover, the weight average molecular weight (Mw) of the obtained polysiloxane (A-6) was 2,700.

Synthesis Example 7 Synthesis of cationic polymerizable group and alkali-soluble group-containing polysiloxane (A-7)

3-trimethoxysilylpropylsuccinic acid 15.76g (0.060mol), methyl trimethoxysilane 40.93g (0.300mol), phenyltrimethoxysilane 35.74g (0.180mol), γ- 14.81 g (0.060 mol) of glycidoxypropyl trimethoxysilane and 100.28 g of PGME were added, and while stirring at 40° C., 33.53 g of water and 0.54 g of dicyclohexylamine (0.50% by weight based on the input monomer) were added. It was added over a period of minutes. By the same procedure as in Synthesis Example 1, a solution of polysiloxane (A-7) having a solid content concentration of 40% by weight was obtained. The content of the glycidyl group and alkali-soluble group relative to the total content of 100 mol% of the (a1) cationic polymerizable group, (a2) radical polymerizable group and (a3) alkali-soluble group of the obtained polysiloxane (A-7) is 50 mol%, respectively. , 50 mol%. Moreover, the weight average molecular weight (Mw) of the obtained polysiloxane (A-7) was 2,600.

Synthesis Example 8 Synthesis of polysiloxane (A-8) containing radically polymerizable groups

In a 500 ml three-necked flask, 33.65 g (0.150 mol) of p-styryl trimethoxysilane, 35.15 g (0.150 mol) of γ-acryloylpropyl trimethoxysilane, 0.206 g of TBC, and 72.14 g of PGME were added. Then, while stirring at room temperature, 16.20 g of water and 0.34 g of dicyclohexylamine (0.50% by weight relative to the charged monomer) were added over 30 minutes. By the same procedure as in Synthesis Example 1, a solution of polysiloxane (A-8) having a solid content concentration of 40% by weight was obtained. The content of the styryl group and (meth)acryloyl group to 100 mol% of the total content of the (a1) cationic polymerizable group, (a2) radical polymerizable group and (a3) alkali-soluble group of the obtained polysiloxane (A-8) is 50, respectively. Mol% and 50 mol%. Moreover, the weight average molecular weight (Mw) of the obtained polysiloxane (A-8) was 2,600.

Synthesis Example 9 Synthesis of cationic polymerizable group-containing polysiloxane (A-9)

In a 500 ml three-necked flask, 34.05 g (0.250 mol) of methyltrimethoxysilane, 99.15 g (0.500 mol) of phenyltrimethoxycysilane, 31.25 g (0.150 mol) of 3-ethoxysilane, 3-(3, 24.64 g (0.100 mol) of 4-epoxycyclohexyl)propyl trimethoxysilane, 174.95 g of PGMEA, and a phosphoric acid aqueous solution in which 0.945 g of phosphoric acid (0.50% by weight relative to the input monomer) was dissolved in 56.70 g of water while stirring at room temperature Was added over 30 minutes. By the same procedure as in Synthesis Example 1, a solution of polysiloxane (A-9) having a solid content concentration of 40% by weight was obtained. The molar ratio of repeat units derived from methyltrimethoxysilane, phenyltrimethoxysilane, tetraethoxysilane, and 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane in polysiloxane (A-9) is 25 mol%, 50 mol%, 15 mol%, and 10 mol%, respectively. Moreover, the weight average molecular weight of the obtained polysiloxane (A-9) was 4,200.

The compositions of Synthesis Examples 1 to 9 are collectively shown in Table 1.

Evaluation in each Example and the comparative example was performed by the following method.

(1) Pattern processability

The siloxane resin composition obtained by each example and comparative example was spin-coated on an ITO substrate using a spin coater ("1H-360S (trade name)" manufactured by MIKASA CO., LTD), and hot plated (Dainippon Screen Mfg. The product was prebaked at 100°C for 2 minutes using "SCW-636 (trade name)" manufactured by Co., Ltd., to prepare a prebaked film having a thickness of 2.0 µm.

For Examples 1 to 16, 18 to 19 and Comparative Examples 1 to 2, a parallel light mask aligner ("PLA-501F (trade name)" manufactured by Canon Inc.) was used thereafter, and the width of the ultrahigh pressure mercury lamp was used as a light source. through the gray scale mask 10 to for a line and space pattern having a mask pattern or the measurement sensitivity of 200㎛ prebake film to the exposure dose 50mJ / cm 2 ~ 300mJ / cm 2 was exposed while changing the exposure dose by 50mJ / cm ^2. Thereafter, using an automatic developing device ("AD-2000 (trade name)" manufactured by TAKIZAWA CO., LTD.), shower development was performed with an aqueous potassium hydroxide solution having a concentration of 0.045% by weight for 60 seconds, followed by rinsing with water for 30 seconds. did.

For Example 17, the exposure amount of the pre-baked film was then measured using a parallel light mask aligner, a pattern mask having a line-and-space pattern with a width of 10 to 200 µm, or a gray scale mask for sensitivity measurement, using an ultra-high pressure mercury lamp as a light source. up to ^{50mJ / cm 2 ~ 300mJ / cm} 2 was exposed while changing the exposure dose by 50mJ / cm ^2. Thereafter, an automatic developing device ("AD-2000 (trade name)" manufactured by TAKIZAWA CO., LTD.) was used, shower developed for 90 seconds with a 2.38% by weight aqueous tetramethylammonium hydroxide solution, and then rinsed with water for 30 seconds. Then, using a parallel light mask aligner and using an ultra-high pressure mercury lamp as a light source, bleaching was performed by exposing at an exposure dose of 500 mJ/cm ² (i-line) without passing through a photomask.

The line and space pattern after development is magnified and observed at a magnification of 100 times using an optical microscope, and the exposure amount to form a 50 µm line and space pattern with a width of 1 to 1 (hereinafter referred to as an optimal exposure amount) is used as sensitivity. The minimum pattern dimension after development at the optimum exposure dose was taken as the resolution. In addition, the developing residue of the unexposed portion was evaluated according to the following criteria.

A: There is no development residue in the unexposed area

B: Developing residue in the unexposed area

(2) Substrate adhesion

The glass substrate obtained by sputtering ITO or MAM on a glass substrate and surface using a spin coater (MIKASA CO., LTD product "1H-360S (trade name)") obtained by each example and comparative example. Hereinafter, spin coating on the "ITO substrate" or "MAM substrate"), respectively, and using a hot plate (Dainippon Screen Mfg. Co., Ltd. product "SCW-636 (trade name)") for 2 minutes at 100 DEG C. After baking, a prebaked film having a thickness of 2.0 µm was produced.

For Examples 1 to 16, 18 to 19 and Comparative Examples 1 to 2, thereafter, using a parallel light mask aligner (Canon Inc. product "PLA-501F (trade name)"), the ultra-high pressure mercury lamp was used as a light source. The baked film was fully exposed to an exposure amount of 150 mJ/cm ² , and used in an oven (ESPEC Corp. product “IHPS-222 (trade name)”) and cured at 100° C. for 30 minutes in air to produce a cured film having a thickness of 1.8 μm.

For Example 17, thereafter, an automatic developing apparatus (TAKIZAWA CO., LTD. product "AD-2000 (trade name)") was used, shower development was performed with a 2.38% by weight aqueous tetramethylammonium hydroxide solution for 90 seconds, followed by 30 with water. After rinsing for a second, use a parallel light mask aligner (``PLA-501F (trade name)'' manufactured by Canon Inc.), and use a super high-pressure mercury lamp as a light source to expose the pre-baked film at an exposure dose of 150 mJ/cm ² , and expose the oven (ESPEC Corp. product "IHPS-222 (trade name)") was used and cured at 100°C for 30 minutes in air to produce a cured film having a film thickness of 1.8 mu m.

The obtained cured film was evaluated in accordance with JIS "K5600-5-6 (established date = 1999/04/20)", and substrate adhesion was evaluated by the following method. On the surface of the cured film on the glass substrate, the ITO substrate, and the MAM substrate, 100 parallel grids of 1 mm×1 mm were fabricated by drawing parallel straight lines of 11 vertically and horizontally orthogonal to each other to reach the base of the glass plate using a cutter knife. . Cellophane adhesive tape (width = 18 mm, adhesive force = 3.7 N/10 mm) was adhered to the cured film surface, rubbed with an eraser (JIS S6050 pass product), held at one end of the tape, and held at right angles to the plate to peel off instantly. The remaining number of grids at the time was counted visually. The adhesiveness was evaluated based on the following criteria from the peeling area of the grid, and 4 or more was set as a pass.

5: peeling area is 0%

4: Peeling area is more than 1% and less than 5%

3: Peeling area 5% or more and less than 15%

2: Peeling area of 15% or more and less than 35%

1: Peeling area is more than 35% and less than 65%

0: The peeling area was 65% or more.

(3) Chemical resistance (N300 resistance)

The cured film on the glass substrate, ITO substrate, and MAM substrate obtained by the method described in (2) above was immersed in a 3.5% by weight aqueous oxalic acid aqueous solution of ITO etchant at 42°C for 2 minutes, and 40°C in resist stripping solution N300 ( Conditions 1), 50°C (condition 2), 60°C (condition 3), and 70°C (condition 4) were each immersed for 1 minute. About the cured film after immersion, board|substrate adhesiveness was evaluated by the procedure similar to (2) above according to JIS "K5600-5-6 (established date = 1999/04/20)". When the peeling area of the grid was less than 5%, it was judged that there was chemical resistance under the conditions.

From the conditions judged to have chemical resistance, the chemical resistance was evaluated according to the following criteria, and one or more were set as pass.

4: Conditions 1, 2, 3, 4 all have chemical resistance

3: Chemical resistance under conditions 1, 2, and 3

2: Chemical resistance only in conditions 1 and 2

1: Chemical resistance in condition 1 only

0: No chemical resistance under all conditions

(4) Hardness

About the cured film of the film thickness of 1.8 micrometers obtained by the method of said (2), pencil hardness was measured according to JISK5600-5-4 (1999).

(5) Storage stability

About the siloxane resin composition obtained by each Example and the comparative example, using the E-type viscometer, measuring the viscosity after maintaining for 1 minute on conditions of temperature 25 degreeC and rotation speed 100rpm, put it into the sealed container, and put it in 23 degreeC, In 7 days. The viscosity after storage was measured in the same manner, the rate of change of viscosity was calculated by the following formula, and storage stability was evaluated by the following criteria.

Viscosity change rate (%) = (viscosity after storage (mPa·s)-viscosity before storage (mPa·s))×100/(viscosity before storage (mPa·s))

A: Viscosity change rate is less than 5%

B: Viscosity change rate is 5% or more but less than 10%

C: The rate of change in viscosity exceeds 10%.

Example 1

Under a yellow lamp, (B) as a photosensitizer, ethane, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(o-acetyloxime) ( "IRGACURE" (registered trademark) OXE-02 (trade name)" manufactured by BASF Japan Ltd.) (hereinafter "OXE02") 0.080 g, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (""IRGACURE "819 (trade name)" manufactured by BASF Japan Ltd.) (hereinafter referred to as "IC-819") 0.160 g, dimethyl 2,2'-azobis (isobutyrate) 0.080 g, 1,3-dioxohexahydro-2H- 0.060 g of 4,7-methanoisoindole-2-yltrifluoromethanesulfonic acid (manufactured by "CGI-MDT" (trade name) BASF Japan Ltd.), ethylenebis(oxyethylene)bis[3- (5-tert-butyl-4-hydroxy-m-tolyl)propionate] 1.199 g of a 1% by weight PGME solution of (""IRGANOX" (trademark) BASF Japan Ltd. product), ( C) As a polymerizable compound having a phosphorus atom, 2-methacryloyloxyethyl acid phosphate ("Light ester P-1M (trade name)" manufactured by Kyoeisha Chemical co., ltd.) (hereinafter "P-1M") PGMEA 50% by weight solution 0.90g, (D) silane compound having a ureido group, PGMEA 50% by weight solution of 3-ureidopropyl trimethoxysilane 0.040g (equivalent ratio (C) / (D) = 9.6/0.4 ), as a cyclic ether compound, OXT-191 (trade name) (Toagosei Co., Ltd. product) (hereinafter, ``OXT-191'') PGMEA 10% by weight solution 0.800 g, polyfunctional monomer, dipenta 1.999 g of a 50% by weight PGME solution of erythritol hexaacrylate ("KAYARAD" (registered trademark) DPHA (trade name) Nippon Kayaku Co., Ltd.), 50% by weight of PGME of γ-acryloylpropyl trimethoxysilane % Solution 0.240g, as a sensitizer, 9.10-dipropoxytracene ("DPA (trade name)" manufactured by KAWASAKI KASEI CHEMICALS.) 0.02 0 g was dissolved in a mixed solvent of 4.953 g of PGME and 0.075 g of PGMEA, and 0.200 g (corresponding to a concentration of 100 ppm) of a PGME 1% by weight solution of fluorine-based surfactant "F-554 (trade name)" (manufactured by DIC Corporation) was added. , Stirred. Thereafter, as a polysiloxane (A), 4.718 g of a solution of the polysiloxane (A-1) synthesized in Synthesis Example 1 was added and stirred. Then, it filtered with a 0.45 micrometer filter, and obtained the siloxane resin composition (P-1). About the obtained siloxane resin composition (P-1), pattern processability, board|substrate adhesiveness, chemical resistance, hardness, and storage stability were evaluated. Table 4 shows the results.

Example 2

4.718 g of a solution of polysiloxane (A-2) in place of the solution of polysiloxane (A-1), epoxy compound 2,2'-(((((1-(4-(2-( 4-(oxiran-2-ylmethoxy)phenyl)propan-2-yl)phenyl)ethane-1,1-diyl)bis(4,1-phenylene))bis(oxy))bis(methylene))bis (Oxylan) The siloxane resin was carried out in the same manner as in Example 1, except that 0.800 g of a 10% by weight PGMEA solution of ("VG-3101L (trade name)" PRINTEC, INC.) (hereinafter "VG-3101L") was used. A composition (P-2) was obtained. The obtained siloxane resin composition (P-2) was used for evaluation in the same manner as in Example 1.

Example 3

A siloxane resin composition (P-3) was obtained in the same manner as in Example 1, except that 4.718 g of a solution of polysiloxane (A-3) was used instead of the solution of polysiloxane (A-1). The obtained siloxane resin composition (P-3) was used for evaluation in the same manner as in Example 1.

Example 4

A siloxane resin composition (P-4) was obtained in the same manner as in Example 1 except that 4.718 g of a solution of polysiloxane (A-4) was used instead of the solution of polysiloxane (A-1). The obtained siloxane resin composition (P-4) was used for evaluation in the same manner as in Example 1.

Example 5

A siloxane resin composition (P-5) was obtained in the same manner as in Example 1, except that 4.718 g of a solution of polysiloxane (A-5) was used instead of the solution of polysiloxane (A-1). The obtained siloxane resin composition (P-5) was used for evaluation in the same manner as in Example 1.

Example 6

A siloxane resin composition (P-6) was obtained in the same manner as in Example 1, except that 4.718 g of a solution of polysiloxane (A-6) was used instead of the solution of polysiloxane (A-1). The obtained siloxane resin composition (P-6) was used for evaluation in the same manner as in Example 1.

Example 7

A siloxane resin composition (P-7) was obtained in the same manner as in Example 1 except that 4.718 g of a solution of polysiloxane (A-7) was used instead of the solution of polysiloxane (A-1). The obtained siloxane resin composition (P-7) was used for evaluation in the same manner as in Example 1.

Example 8

A siloxane resin composition (P-8) was obtained in the same manner as in Example 1 except that 4.718 g of a solution of polysiloxane (A-8) was used instead of the solution of polysiloxane (A-1). The obtained siloxane resin composition (P-8) was used for evaluation in the same manner as in Example 1.

Example 9

0.90 g of a 50% by weight solution of PGMEA of 2-acrylic oil oxyethyl acid phosphate ("P-1A (trade name)" manufactured by Kyoeisha Chemical Co., Ltd.) instead of a polymerizable compound having a phosphorus atom (P1-M) A siloxane resin composition (P-9) was obtained in the same manner as in Example 1 except that the equivalent ratio (C)/(D)=9.6/0.4) was used. The obtained siloxane resin composition (P-9) was used for evaluation in the same manner as in Example 1.

Example 10

Instead of the polymerizable compound having a phosphorus atom (P1-M), phosphoric acid-containing epoxy methacrylate "S-23A (trade name)" DKS Co. Ltd. A siloxane resin composition (P-10) was obtained in the same manner as in Example 1 except that 0.90 g (equivalent ratio (C)/(D) = 9.6/0.4) of a 50% by weight PGMEA solution of the product) was used. The obtained siloxane resin composition (P-10) was used for evaluation in the same manner as in Example 1.

Example 11

Instead of a silane compound having a ureido group (3-ureidopropyltrimethoxysilane), 0.040 g of a 50% by weight solution of PGMEA of 3-ureidopropyltriethoxysilane (equivalent ratio (C)/(D)=9.6/0.4 ) Was carried out in the same manner as in Example 1, to obtain a siloxane resin composition (P-11). The obtained siloxane resin composition (P-11) was used for evaluation in the same manner as in Example 1.

Example 12

Instead of a silane compound having a ureido group (3-ureidopropyltrimethoxysilane), 0.040 g of a 50 wt% solution of PGMEA of 3-phenylureidopropyltrimethoxysilane (equivalent ratio (C)/(D)=9.6/0.4 ) Was carried out in the same manner as in Example 1, to obtain a siloxane resin composition (P-12). The obtained siloxane resin composition (P-12) was used for evaluation in the same manner as in Example 1.

Example 13

Instead of the cyclic ether compound (OXT-191), 3,3'-(oxybis(methylene))bis(3-ethyloxetane) (``OXT-221 (trade name)'' manufactured by Toagosei Co., Ltd.) A siloxane resin composition (P-13) was obtained in the same manner as in Example 1 except that 0.800 g of a 10 wt% PGMEA solution was used. The obtained siloxane resin composition (P-13) was used for evaluation in the same manner as in Example 1.

Example 14

Instead of the cyclic ether compound (VG-3101LOXT-191), 2, 2'-((((9H-fluorene-9,9-diyl)bis(4,1-phenylene))bis(oxy))bis (Methylene)) siloxane resin composition (P-) in the same manner as in Example 2, except that 0.800 g of a 10 wt% PGMEA solution of bis(oxirane ("PG-100 (trade name)" manufactured by Toagosei Co., Ltd.)) was used. 14) was obtained Using the obtained siloxane resin composition (P-14), evaluation was conducted in the same manner as in Example 1.

Example 15

A siloxane resin composition (P-15) was obtained in the same manner as in Example 1 except that 4.918 g of a solution of polysiloxane (A-1) was used and no cyclic ether compound was added. The obtained siloxane resin composition (P-15) was used for evaluation in the same manner as in Example 1.

Example 16

A siloxane resin composition (P-16) was obtained in the same manner as in Example 2 except that 4.918 g of a solution of polysiloxane (A-2) was used and no cyclic ether compound was added. The obtained siloxane resin composition (P-16) was used for evaluation in the same manner as in Example 1.

Example 17

Under yellow light (B) as a photosensitizer, THP-17 (trade name, manufactured by Toyo Gosei Co., Ltd.) 0.640 g, (C) a polymerizable compound having a phosphorus atom, 0.950 g of a 50% by weight PGMEA solution of P-1M, (D) As a silane compound having a ureido group, 0.050 g (equivalent ratio (C)/(D) = 9.6/0.4) of a 50% by weight PGMEA solution of 3-ureidopropyltrimethoxysilane), PGME 4.600 g and PGMEA 5.900 It was dissolved in a mixed solvent of g, 0.200 g (corresponding to a concentration of 100 ppm) of a PGME 1% by weight solution of "F-554 (trade name)" (manufactured by DIC Corporation), a fluorine-based surfactant, was added and stirred. Thereafter, as the polysiloxane (A), 7.146 g of a solution of the polysiloxane (A-9) synthesized in Synthesis Example 9 was added and stirred. Subsequently, it filtered with a 0.45 micrometer filter, and obtained the siloxane resin composition (P-17). Using the obtained siloxane resin composition (P-16), pattern workability, substrate adhesion, chemical resistance, hardness, and storage stability were evaluated.

Example 18

(C) As a polymerizable compound having a phosphorus atom, 50% by weight of a solution of PGMEA 50% by weight of P-1M, (D) as a silane compound having a ureido group, 50% by weight of PGMEA of 3-ureidopropyltrimethoxysilane A siloxane resin composition (P-18) was obtained in the same manner as in Example 1 except that the solution was 0.200 g (equivalent ratio (C)/(D)=8.0/2.0). The obtained siloxane resin composition (P-18) was used for evaluation in the same manner as in Example 1.

Example 19

(C) As a polymerizable compound having a phosphorus atom, a 50% by weight solution of PGMEA of P-1M is 0.990g, (D) As a silane compound having a ureido group, 50% by weight of PGMEA of 3-ureidopropyltrimethoxysilane The siloxane resin composition (P-19) was obtained by carrying out similarly to Example 1 except having made the solution into 0.010 g (equivalent ratio (C)/(D)=9.9/0.1). The obtained siloxane resin composition (P-19) was used for evaluation in the same manner as in Example 1.

Comparative Example 1

The same as in Example 1 except that the solution of polysiloxane (A-1) was 5.947 g, and a polymerizable compound having a phosphorus atom (C) was not added (equivalent ratio (C)/(D)=0.0/10.0). This was carried out to obtain a siloxane resin composition (P-20). The obtained siloxane resin composition (P-20) was used for evaluation in the same manner as in Example 1.

Comparative Example 2

The same as in Example 1 except that the solution of polysiloxane (A-1) was 4.738 g, and (D) a silane compound having a ureido group was not added (equivalent ratio (C)/(D)=10.0/0.0). It was carried out to obtain a siloxane resin composition (P-21). The obtained siloxane resin composition (P-21) was used for evaluation in the same manner as in Example 1.

The compositions of Examples 1 to 19 and Comparative Examples 1 to 2 are shown in Tables 2 to 4, and the evaluation results are shown in Table 5.

Industrial availability

The cured film obtained by curing the siloxane resin composition of the present invention includes various hard coat films such as a protective film or an insulating film for a touch panel, an insulating film for a touch sensor, a flattening film for a TFT of a liquid crystal or an organic EL display, a metal wiring protective film, an insulating film, and an antireflection film , Anti-reflection film, optical filter, color filter overcoat, pillar material, etc.

Claims (10)

(A) A siloxane resin composition containing a polysiloxane, (B) a photosensitizer, (C) a polymerizable compound having a phosphorus atom, and (D) a silane compound having a ureido group. According to claim 1,
The siloxane resin composition in which the photosensitive agent (B) is a radical polymerization initiator (b1). According to claim 1,
The siloxane resin composition in which the photosensitive agent (B) is a quinone diazide compound (b2). The method according to any one of claims 1 to 3,
The (C) siloxane resin composition in which the equivalent ratio ((C)/(D)) of the (C) polymerizable compound having a phosphorus atom to a silane compound having a ureido group is 8/2 or more and 9.9/0.1 or less. The method according to any one of claims 1 to 4,
The siloxane resin composition in which the polysiloxane (A) has (a1) a cationic polymerizable group, (a2) a radical polymerizable group and (a3) an alkali-soluble group. The method of claim 5,
In the polysiloxane (A), the content of the cationic polymerizable group (a1) relative to the total content of 100 mol% of the (a1) cationic polymerizable group, (a2) radical polymerizable group, and (a3) alkali-soluble group is 1 to 30 mol%, (a2) A siloxane resin composition having a radical polymerizable group content of 50 to 90 mol%. The method according to any one of claims 1 to 6,
A siloxane resin composition further containing a compound having a cyclic ether group. A cured film of the siloxane resin composition according to any one of claims 1 to 7. A touch sensor having the cured film according to claim 8. A display device having at least one selected from the group consisting of a liquid crystal cell, an organic EL cell, a mini LED and a micro LED cell, a substrate and the cured film according to claim 8.