TW202020024A - Resin composition and cured film obtained therefrom - Google Patents

Abstract

Provided is a resin composition which has a low refractive index, is excellent in terms of heat resistance, chemical resistance, and applicability, and has excellent patternability. The resin composition comprises (A) a polysiloxane and (B) a solvent, and is characterized in that the polysiloxane (A) includes a structure represented by any of specific general formulae (1) to (3) and a structure represented by either of specific general formulae (4) and (5).

Description

Resin composition and its cured film

The present invention relates to a resin composition, a cured film thereof, a solid-state imaging element including the cured film, an organic electroluminescence (EL) element, and a display device.

In recent years, in light-emitting diode (Light Emitting Diode, LED) light sources, etc. have been used to introduce light from the side in liquid crystal displays, organic EL TVs, etc., to achieve narrower frames and thinner thicknesses. In particular, recently, with regard to liquid crystal displays, companies are investing in research and development of transparent liquid crystal displays as new display devices. At this time, in order to efficiently guide light incident from the side in a certain direction, a low refractive index, high transparency, excellent chemical resistance to chemicals used in the processing process, and a heating step are required A novel material with good heat resistance that does not cause deterioration such as yellowing. As shown in Patent Document 1, Patent Document 2, and Patent Document 3, materials with high transparency and low refractive index are known as polysiloxane materials, and are widely used in liquid crystal displays, touch panels, solid-state imaging devices, etc. . However, for these materials, in order to set a low refractive index, the operation of adding a large amount of fluorine-containing siloxane compounds or adding particles such as silicon dioxide nanoparticles or hollow silicon dioxide, but adding a large amount of fluorine-containing In the case of a siloxane compound, reduction in chemical resistance and heat resistance cannot be avoided. When particles are added, when processing into a pattern, fine irregularities on the surface or edge cannot be avoided. There is a strong demand for low-refractive-index materials with no added particles and excellent heat resistance and chemical resistance. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2007-119744 [Patent Document 2] Japanese Patent Laid-Open No. 2013-014680 [Patent Document 3] Japanese Patent Laid-Open No. 2015-129908

[Problems to be solved by the invention] In order to solve the above-mentioned problems, an object of the present invention is to provide a resin composition as a low-refractive-index material that does not contain particles, is excellent in heat resistance and chemical resistance, and is excellent in pattern processability. [Means to solve the problem]

That is, the present invention is a resin composition containing (A) polysiloxane and (B) a solvent. The resin composition is characterized in that the (A) polysiloxane contains at least one of the following The structures represented by formula (1) to general formula (3), and at least one or more structures represented by the following general formula (4) to general formula (5).

[Chem 1]

(Y is an alicyclic or aromatic linking group having 5 to 10 carbon atoms; R ¹ represents a single bond or an alkylene group having 1 to 4 carbon atoms, and R ² independently represents hydrogen or an alkyl group having 1 to 4 carbon atoms. Group, R ³ independently represents an organic group having 1 to 8 carbon atoms, X represents a hydrogen atom or an acid dissociable group, a represents an integer of 1 to 3, and n represents an integer of 1 to 10) [Effect of the Invention]

According to the present invention, it is possible to provide a resin composition having a low refractive index, excellent heat resistance, chemical resistance, and coatability, and excellent pattern processability.

Hereinafter, the present invention will be described in detail.

<(A) Polysiloxane> The resin composition of the present invention contains polysiloxane containing at least one or more structures represented by the following general formula (1) to general formula (3), and at least one or more of the following general formula (4) to the structure represented by the general formula (5). By containing at least one or more structures represented by (1) to (3) and at least one or more structures represented by (4) to (5) in the polysiloxane, the alkali of the polysiloxane can be increased Solubility and the effect of suppressing alkali dissolution due to the interaction between the photosensitizer and silanol can be exhibited. Therefore, the contrast between the exposed and unexposed areas before and after development can be improved, and a film with excellent resolution can be obtained.

[Chem 2]

(Y is an alicyclic or aromatic linking group having 5 to 10 carbon atoms; R ¹ represents a single bond or an alkylene group having 1 to 4 carbon atoms, and R ² independently represents hydrogen or an alkyl group having 1 to 4 carbon atoms. Group, R ³ independently represents an organic group having 1 to 8 carbon atoms, X represents a hydrogen atom or an acid dissociable group, a represents an integer of 1 to 3, and n represents an integer of 1 to 10) General formula (1) to general In the structure represented by formula (3), Y is a C5-10 alicyclic or aromatic linking group. R ¹ represents a single bond or an alkylene group having 1 to 4 carbon atoms, R ² independently represents hydrogen or an alkyl group having 1 to 4 carbon atoms, R ³ independently represents an organic group having 1 to 8 carbon atoms, and X represents A hydrogen atom or an acid dissociable group, a represents an integer of 1 to 3, and n represents an integer of 1 to 10.

Specific examples of the alkylene group for R ¹ include methylene group, ethyl group, n-propyl group, isopropyl group, n-butyl group, and tert-butyl group.

Specific examples of the alkyl group of R ² include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutoxy, and tert-butyl groups.

Examples of the organic group of R ³ include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, cyclohexyl, phenyl, and naphthyl.

X is a hydrogen atom or an acid dissociable group. When there are a plurality of X, X may be the same or different. Here, the acid dissociable group refers to a group that dissociates in the presence of an acid to generate a polar group. The acid dissociable group has an acetal structure or a ketal structure which is relatively stable to a base, and these are dissociated by the action of an acid. Specific examples include alkoxycarbonyl groups, acetal groups, silane groups, and acetyl groups, but are not limited thereto. Examples of the alkoxycarbonyl group include a third butoxycarbonyl group, a third pentyloxycarbonyl group, a methoxycarbonyl group, an ethoxycarbonyl group, and an isopropoxycarbonyl group. Examples of the acetal group include methoxymethyl, ethoxyethyl, butoxyethyl, cyclohexyloxyethyl, benzyloxyethyl, phenethyloxyethyl, and ethoxy Propyl, benzyloxypropyl, phenethyloxypropyl, ethoxybutyl, ethoxyisobutyl, etc. Examples of the silane group include trimethylsilyl, ethyldimethylsilyl, methyldiethylsilyl, triethylsilyl, isopropyldimethylsilyl, and methyldi-iso Propylsilyl, tri-isopropylsilyl, tert-butyldimethylsilyl, methyldi-tert-butylsilyl, tri-tert-butylsilyl, phenyldimethylsilyl , Methyldiphenylsilyl, triphenylsilyl, etc. Examples of the acetyl group include acetyl group, propyl group, butyl group, heptyl group, hexyl group, pentyl group, trimethyl acetyl group (pivaloyl group), isopentyl group, and lauryl group ( lauryloyl group), nutmeg acetyl group, palm amide group, stearyl amide group, ethylene diamide group, propylene diamide group, butyl diamide group, glutaryl group, hexamethylene amide group, piperoyl group (piperoyl group) , Octanediyl, nonadienyl, decanediyl, propenyl, propynyl, methacryl, crotonyl, oleoyl, maleic diacyl, fumaryl Acyl, mesyl, camphoroyl group, benzoyl, phthaloyl, o-xylylene, m-xylylene, p-xylylene, naphthalene, tolyl , Hydratropoyl group (hydratropoyl group), attoyl group, cinnamyl acetyl group, furan methanyl group, thiophene methanyl group, nicotinic amide group, isonicotinyl amide group, etc. A part or all of the hydrogen atoms of these acid dissociable groups may be substituted with fluorine atoms. In addition, regarding these acid dissociable groups, a single type may be introduced into the (A) polysiloxane compound, or a plurality of types may be introduced.

The structure represented by general formula (1) to general formula (3) can also be expressed as the following (1') to (3'), and the structure represented by general formula (1) to general formula (3) and the following ( 1') to (3') are the same.

[化2-1]

In addition, the structure represented by the general formula (4) and the general formula (5) can also be expressed as the following (4'), (5'), the structure represented by the general formula (4) and the general formula (5) and the following The descriptions (4') and (5') are the same.

[Chem 2-2]

The structure represented by the general formula (1) to general formula (3) is preferably a structure represented by the following general formula (6) to general formula (8). By improving the compatibility of the photosensitizer and the siloxane with the following structure, it is possible to prevent white turbidity of the film due to phase separation during thermal curing, and a cured film can be formed without impairing transparency.

[Chemical 3]

As a specific example of the portion represented by the general formula, a is an integer of 1 to 3. From the viewpoint of solubility and drug resistance, a is preferably 1 to 2, and more preferably a is 1. If these specific examples are represented by the general formula, the following structures can be cited.

[Chem 4]

Here, * represents a bond directly bonded to R ¹ . When R ¹ is a single bond, it represents a bond directly bonded to a silicon atom. By including these structures, a composition having a low refractive index, excellent coatability, and excellent pattern processability can be obtained. These structures preferably contain 5 mol% to 50 mol% in (A) polysiloxane, and more preferably contain 5 mol% to 30 mol%. The content ratio of the organosilane units represented by the general formula (1) to the general formula (3) can measure ²⁹ Si-Nuclear Magnetic Resonance (NMR) of polysiloxane, and an aromatic group is bonded according to The ratio of the peak area of Si to the peak area of Si derived from the organic silane unit to which the aromatic group is not bonded is determined.

In addition, ¹ H-NMR, ¹⁹ F-NMR, ¹³ C-NMR, infrared (Infrared, IR), and time-of-flight mass spectrometry (Time of Flight) Flight-Mass Spectrometry (TOF-MS), etc. for identification.

Next, in the structure represented by the general formula (4) or the general formula (5), in the formula, R ² independently represents hydrogen or an alkyl group having 1 to 4 carbon atoms. Specific examples of the siloxane having the structure represented by the general formula (4) or the general formula (5) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetraisopropoxy Silane, tetrabutoxysilane, tetrabutoxysilane, methyl silicate 51 (manufactured by Fusang Chemical Industry Co., Ltd.), M silicate 51, silicate 40, silicate 45 (Tama Chemical Industry Co., Ltd.), methyl silicate 51, methyl silicate 53A, ethyl silicate 48 (made by Colcoat Co., Ltd.), etc. By containing these organosilanes, chemical resistance can be improved. The ideal content is 5 mol% to 50 mol% in the polysiloxane as a hydrolysis condensate, and more preferably 5 mol% to 30 mol%. The content ratio of the organosilane unit represented by the general formula (4) or the general formula (5) can be ¹ H-NMR, ¹³ C-NMR, ²⁹ Si-NMR, IR, TOF-MS, elemental analysis, ash determination, etc. Find it out in combination.

Furthermore, (A) polysiloxane can also contain the structure represented by following General formula (9)-General formula (11).

[Chemical 5]

(R ² independently represents hydrogen or a C 1-4 alkyl group, R ³ independently represents a C 1-8 organic group, and R ⁴ represents a C 1-10 organic group having a fluorine group) as Specific examples of the fluorine-containing silane compound having the structure of general formula (9) to general formula (11) include trifluoroethyltrimethoxysilane, trifluoroethyltriethoxysilane, and trifluoroethane Triisopropoxysilane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, trifluoropropyltriisopropoxysilane, heptafluorodecyltrimethoxysilane, seventeen Fluorodecyltriethoxysilane, heptafluorodecyltriisopropoxysilane, tridecylfluorooctyltriethoxysilane, tridecylfluorooctyltrimethoxysilane, tridecylfluorooctyltrimethoxysilane Oxysilane, trifluoroethylmethyldimethoxysilane, trifluoroethylmethyldiethoxysilane, trifluoroethylmethyldiisopropoxysilane, trifluoropropylmethyldimethoxy Silane, trifluoropropylmethyl diethoxysilane, trifluoropropylmethyldiisopropoxysilane, heptafluorodecylmethyldimethoxysilane, heptafluorodecylmethyldiethyl Oxysilane, heptafluorodecylmethyldiisopropoxysilane, tridecafluorooctylmethyldimethoxysilane, tridecafluorooctylmethyldiethoxysilane, tridecafluorooctylmethyl Diisopropoxysilane, trifluoroethylethyldimethoxysilane, trifluoroethylethyldiethoxysilane, trifluoroethylethyldiisopropoxysilane, trifluoropropylethane Dimethoxysilane, trifluoropropylethyldiethoxysilane, trifluoropropylethyldiisopropoxysilane, heptafluorodecylethyldimethoxysilane, heptafluorodecyl Ethyldiethoxysilane, heptafluorodecylethyldiisopropoxysilane, tridecylfluorooctylethyldiethoxysilane, tridecylfluorooctylethyldimethoxysilane, thirteen Fluorooctylethyl diisopropoxysilane, etc. Two or more of these can also be used.

Among these, from the viewpoint of chemical resistance, it is preferable to use: trifluoroethyltrimethoxysilane, trifluoroethyltriethoxysilane, trifluoroethyltriisopropoxysilane, trifluoroethylene Fluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, trifluoropropyltriisopropoxysilane, heptafluorodecyltrimethoxysilane, heptafluorodecyltriethoxysilane, Heptafluorodecyl triisopropoxysilane, tridecylfluorooctyl triethoxysilane, tridecylfluorooctyl trimethoxysilane, tridecylfluorooctyl triisopropoxysilane. In addition, from the viewpoint of forming a uniform coating film, it is particularly preferable to use: trifluoroethyltrimethoxysilane, trifluoropropyltrimethoxysilane, heptafluorodecyltrimethoxysilane, tridecanefluoro Octyl trimethoxysilane. The content in the polysiloxane (A) is preferably 5 mol% to 50 mol%, and more preferably 10 mol% to 40 mol% from the viewpoint of drug resistance. In the (A) polysiloxane used in the resin composition of the present invention, in addition to the organosilane compound, other organosilane compounds may be copolymerized. Specific examples of the copolymerizable organosilane compound include methyltrimethoxysilane, methyltriethoxysilane, methyltris(methoxyethoxy)silane, methyltripropoxysilane, Methyltriisopropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane, octadecyltrimethoxysilane, octadecyltrimethoxysilane Ethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-(N,N-glycidyl)aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, γ-aminopropyltrimethyl Oxysilane, γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, β-cyanoethyltriethoxysilane, Glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethyl Oxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltriisopropoxysilane, γ-glycidoxypropyltributoxysilane, γ-shrink Glyceryloxypropyltris(methoxyethoxy) silane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxybutyl Trimethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, σ-shrinkage Glyceryloxybutyltrimethoxysilane, σ-glycidoxybutyltriethoxysilane, (3,4-epoxycyclohexyl)methyltrimethoxysilane, (3,4-epoxycyclohexyl ) Methyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltripropoxysilane, 2-(3,4-epoxycyclohexyl)ethyltributoxysilane, 2 -(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 2-(3,4-epoxycyclohexyl) Ethyltriphenoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltriethoxysilane, 4-( 3,4-epoxycyclohexyl)butyltrimethoxysilane, 4-(3,4-epoxycyclohexyl)butyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethyl Oxysilane, γ-glycidoxypropylmethyl dimethyl dimethoxy silane, γ-aminopropyl methyl dimethoxy silane, γ-aminopropyl methyl dimethoxy silane , N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, glycidoxymethyldimethoxysilane, glycidoxymethylmethyldiethyl Oxysilane, α-glycidoxyethylmethyldimethoxysilane, α-glycidoxyethylmethyldiethoxysilane, β-glycidoxyethylmethyldimethoxy Silane, β-glycidoxyethylmethyldiethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ- Glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, β-glycidoxypropylmethyldibutoxysilane, γ-glycidyl Oxypropylmethyl bis (methoxyethoxy) silane, γ-glycidoxypropyl ethyl dimethoxy silane, γ-glycidoxy propyl ethyl diethoxy silane, 3 -Chloropropylmethyldimethoxysilane, 3-chloropropylmethyldiethoxysilane, cyclohexylmethyldimethoxysilane, octadecylmethyldimethoxysilane, tetramethoxy Silane, tetraethoxysilane, γ-propenyl propyltrimethoxysilane, γ-propenyl propyltriethoxysilane, γ-propenyl propyltris(methoxyethoxy) silane , Γ-methacryl propyltrimethoxysilane, γ-methacryl propyltriethoxysilane, γ-methacryl propyltris(methoxyethoxy) silane, γ-methacryl propylmethyl dimethoxy silane, γ-methacryl propyl methyl diethoxy silane, γ-acryl propyl methyl dimethoxy silane, γ -Acryloylpropylmethyldiethoxysilane, γ-methacryloylpropylpropyl (methoxyethoxy)silane, etc.

Two or more of these can also be used. Furthermore, if necessary, an organic silane compound having a hydrophilic group may be copolymerized as a raw material of polysiloxane. The organic silane compound having a hydrophilic group is preferably an organic silane compound having a carboxylic acid structure or an organic silane compound having a carboxylic acid anhydride structure, and more preferably an organic silane compound having a carboxylic acid anhydride structure.

As a specific example of the organosilane compound having a carboxylic anhydride structure, an organosilane compound represented by any of the following general formula (12) to general formula (14) may be mentioned. Two or more of these can also be used.

[化6]

In general formula (12) to general formula (14), R ⁵ to R ⁷ , R ⁹ to R ¹¹ and R ¹³ to R ¹⁵ represent an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, Phenyl, phenoxy, or alkylcarbonyloxy having 2 to 6 carbon atoms. R ⁸ , R ¹² and R ¹⁶ represent a single bond, or a linear aliphatic hydrocarbon group having 1 to 10 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 16 carbon atoms, an alkylcarbonyloxy group having 2 to 6 carbon atoms, or a carbonyl group , An ether group, an ester group, an amide group, an aromatic group, or a divalent group having any of these. These groups may also be substituted. h and k represent the integer of 0-3.

Specific examples of R ⁸ , R ¹² and R ¹⁶ include: -C ₂ H ₄ -, -C ₃ H ₆ -, -C ₄ H ₈ -, -O-, -C ₃ H ₆ OCH ₂ CH( OH)CH ₂ O ₂ C-, -CO-, -CO ₂ -, -CONH-, organic groups listed below and the like.

[化7]

Specific examples of the organosilane compound represented by the general formula (12) include 3-trimethoxysilylpropyl succinic anhydride, 3-triethoxysilylpropyl succinic anhydride, 3-triphenoxy Silylpropyl succinic anhydride, etc.

Specific examples of the organosilane compound represented by the general formula (13) include 3-trimethoxysilylpropylcyclohexyldicarboxylic anhydride and the like.

Specific examples of the organosilane compound represented by the general formula (14) include 3-trimethoxysilylpropylphthalic anhydride and the like.

The content of the component derived from the hydrolysis/condensation reaction product (siloxane compound) of the alkoxysilane compound in the resin composition is preferably 10% by mass or more relative to the total solid content excluding the solvent, and more It is preferably 20% by mass or more. In addition, it is more preferably 80% by mass or less. By containing the silicone compound in this range, the transmittance and crack resistance of the coating film can be further improved.

The hydrolysis reaction is preferably carried out in a solvent for 1 minute to 180 minutes after adding an acid catalyst and water to the alkoxysilane compound, and then reacting at room temperature to 110°C for 1 minute to 180 minutes. By carrying out the hydrolysis reaction under such conditions, abrupt reactions can be suppressed. The reaction temperature is more preferably 40°C to 105°C.

In addition, it is preferable to obtain the silanol compound by a hydrolysis reaction, and thereafter, the reaction solution is heated at 50° C. or higher and the boiling point of the solvent or lower for 1 hour to 100 hours to perform a condensation reaction. In addition, in order to increase the polymerization degree of the siloxane compound obtained by the condensation reaction, reheating or addition of an alkali catalyst may be performed.

Regarding various conditions in the hydrolysis, the reaction scale, the size and shape of the reaction vessel, etc. may be considered, and for example, the acid concentration, reaction temperature, reaction time, etc. may be set to obtain physical properties suitable for the intended use.

Examples of the acid catalyst used in the hydrolysis reaction include hydrochloric acid, acetic acid, formic acid, nitric acid, oxalic acid, hydrochloric acid, sulfuric acid, phosphoric acid, polyphosphoric acid, polycarboxylic acid or its anhydride, and ion exchange resin. Particularly preferred is an acidic aqueous solution using formic acid, acetic acid or phosphoric acid.

The preferable content of the acid catalyst is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, and preferably 10 parts by mass with respect to 100 parts by mass of all alkoxysilane compounds used in the hydrolysis reaction. 5 parts by mass or less. Here, the amount of all alkoxysilane compounds refers to the total amount including the alkoxysilane compound, its hydrolysate and its condensate, and is the same below. By setting the amount of the acid catalyst to 0.05 parts by mass or more, the hydrolysis proceeds smoothly, and by setting it to 10 parts by mass or less, the control of the hydrolysis reaction becomes easy.

The weight average molecular weight (Mw) of (A) polysiloxane used in the resin composition of the present invention is not particularly limited, and is converted to polystyrene measured by gel permeation chromatography (Gel Permeation Chromatography, GPC) It is preferably 1,000 or more, and more preferably 2,000 or more. In addition, it is preferably 100,000 or less, and more preferably 50,000 or less. By setting Mw to the above range, good coating characteristics can be obtained, and the solubility in the developing solution when forming a pattern also becomes good.

In the resin composition of the present invention, the content of (A) polysiloxane is not particularly limited, and can be arbitrarily selected according to the required film thickness or use. In the resin composition, it is usually 5 to 80% by mass. The solid content is preferably 5% by mass or more and 50% by mass, and more preferably 20% by mass or more and 40% by mass or less.

The water used in the hydrolysis reaction is preferably ion exchanged water. The amount of water can be arbitrarily selected, and it is preferably used in the range of 1.0 mol to 4.0 mol relative to 1 mol of the alkoxysilane compound.

In addition, from the viewpoint of storage stability of the composition, it is preferable that the hydrolyzed and partially condensed polysiloxane solution does not contain the catalyst, and the catalyst can be removed if necessary. The removal method is not particularly limited, and in terms of ease of operation and removal, water washing and/or ion exchange resin treatment are preferred. The so-called water washing refers to the following method: after diluting the polysiloxane solution with an appropriate hydrophobic solvent, washing with water several times to obtain an organic layer, and concentrating the obtained organic layer with an evaporator or the like. The treatment with an ion exchange resin refers to a method of bringing a polysiloxane solution into contact with an appropriate ion exchange resin.

If the (A) polysiloxane used in the resin composition of the present invention is an organosilane compound derived from any structure derived from the general formula (1) to the general formula (3), it is derived from the general formula (4) or an organosilane compound of any structure of the general formula (5), and preferably an organosilane compound of any structure derived from the general formula (9) to the general formula (11), a metal compound described later If the hydrolysis is carried out in the presence of particles and the hydrolysate is condensed, the refractive index and hardness of the cured film are further improved. It is considered that the reason is that by conducting polymerization of polysiloxane in the presence of metal compound particles, a chemical bond (covalent bond) with the metal compound particles is formed in at least a part of the polysiloxane, and the metal compound particles are uniformly dispersed On the other hand, the storage stability of the coating liquid and the homogeneity of the cured film are improved. In addition, the refractive index of the obtained cured film can be adjusted by the type of metal compound particles. In addition, as the metal compound particles, those exemplified as metal compound particles described later can be used.

<(B) Solvent> The resin composition of the present invention contains (B) a solvent.

The solvent used in the resin composition of the present invention is not particularly limited, and among them, it is preferably an aromatic hydrocarbon-based solvent containing one or more kinds of hetero atoms. Although aromatic hydrocarbon solvents with heteroatoms have high polarity, organic compounds with rigid skeletons, such as naphthoquinone diazide, have high solubility. Therefore, they produce intermolecular molecules with both silicone and naphthoquinone diazide. The interaction makes it possible to suppress the thinning of the developed film and improve the contrast between the unexposed part and the exposed part in the evaluation of the sensitivity of the coating film. In addition, in order to improve the handling of the solvent, it is preferably in the form of a liquid at 23° C. and 1 atmosphere. If the melting point becomes higher than this, it needs to be heated during use, and it is difficult to dispose as a solvent. Furthermore, the boiling point of the solvent is preferably 100°C or higher and 300°C or lower, and more preferably 120°C or higher and 250°C or lower. By having a boiling point of 100° C. or higher, the volatility of the solvent can be moderately suppressed, the leveling property during coating can be improved, and a uniform coating film can be easily formed. In addition, by having a boiling point of 300° C. or less, it is difficult to leave a solvent after thermal curing of the film, which can reduce outgassing of the cured film. Specific examples of the aromatic hydrocarbon-based solvent having a hetero atom include benzyl alcohol, 2-methylbenzyl alcohol, 3-methylbenzyl alcohol, 4-methylbenzyl alcohol, 4-isopropylbenzyl alcohol, and 1 -Phenylethyl alcohol, 2-phenyl-2-propanol, 2-ethylbenzyl alcohol, 3-ethylbenzyl alcohol, 4-ethylbenzyl alcohol, anisole, 1,2-dimethoxy Benzene, 1,3-dimethoxybenzene, 1,4-dimethoxybenzene, phenyl ether, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, dibenzyl Ether, methyl benzoate, ethyl benzoate, 1,4-bis(methoxymethyl)benzene.

The content of these solvents is preferably 10% by mass to 50% by mass relative to all solvents in the resin composition, and more preferably 20% by mass to 40% by mass. With a content of 50% by mass or less, when the resin composition is applied and dried, the drying property becomes good. In addition, with a content of 10% by mass or more, the compatibility of the siloxane and the photosensitizer is improved, and the coatability is improved.

In addition, as a preferred (B) solvent used in the resin composition of the present invention, specifically, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, Ethers such as propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol mono-third butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether; ethylene glycol monoethyl ether acetate, Propylene glycol monomethyl ether acetate, propyl acetate, butyl acetate, isobutyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl lactate, ethyl lactate Acetate esters such as esters, butyl lactate, ethyl acetoacetate, methyl acetoacetate, propyl acetate, butyl acetoacetate, and benzyl acetoacetate; acetone acetone, methyl propyl ketone , Methyl butyl ketone, methyl isobutyl ketone, cyclopentanone, 2-heptanone and other ketones; methanol, ethanol, propanol, butanol, isobutyl alcohol, amyl alcohol, 4-methyl-2 -Alcohols such as amyl alcohol, 3-methyl-2-butanol, 3-methyl-3-methoxy-1-butanol, diacetone alcohol; aromatic hydrocarbons such as toluene and xylene; and γ- Butyrolactone, N-methylpyrrolidone, etc. These can be used alone or in combination.

Among these, examples of particularly preferred solvents are propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol mono-third butyl ether, diacetone alcohol, γ-butyrolactone, ethyl lactate, etc. These can be used alone or in combination of two or more.

The content of all solvents in the resin composition of the present invention is preferably in the range of 100 parts by mass to 9900 parts by mass, more preferably 100 parts by mass to 5000 parts by mass relative to 100 parts by mass of all alkoxysilane compounds. range.

＜(C) naphthoquinonediazide compound＞ The resin composition of the present invention preferably contains (C) naphthoquinonediazide compound. The resin composition containing the naphthoquinonediazide compound is formed into a positive type in which the exposed portion is removed with a developer. The naphthoquinonediazide compound used is not particularly limited, but it is preferably a compound obtained by ester-bonding naphthoquinonediazidesulfonic acid to a compound having a phenolic hydroxyl group. The compound in which the position and the para position are each independently hydrogen or a substituent represented by the general formula (15).

[Chem 8]

In the formula, R ¹⁷ , R ¹⁸ , and R ¹⁹ each independently represent any one of a C 1-10 alkyl group, a carboxyl group, a phenyl group, and a substituted phenyl group. In addition, R ¹⁷ , R ¹⁸ , and R ^{19 may} form a ring. The alkyl group may be either unsubstituted or substituted, and can be selected according to the characteristics of the composition. Specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-hexyl, cyclohexyl, n-heptyl, and n-octyl , Trifluoromethyl, 2-carboxyethyl. In addition, examples of the substituent on the phenyl group include a hydroxyl group and a methoxy group. In addition, specific examples when R ¹⁷ , R ¹⁸ , and R ¹⁹ form a ring include cyclopentane ring, cyclohexane ring, adamantane ring, and fluorene ring.

In the case where the ortho position and para position of the phenolic hydroxyl group are other than those mentioned above, such as a methyl group, oxidative decomposition is caused by thermal curing to form a conjugated compound represented by a quinoid structure, and the cured film is colored without color Transparency is reduced. Furthermore, these naphthoquinonediazide compounds can be synthesized by a known esterification reaction between a compound having a phenolic hydroxyl group and naphthoquinonediazide sulfonyl chloride.

Specific examples of the compound having a phenolic hydroxyl group include the following compounds (all manufactured by Honshu Chemical Industry Co., Ltd.).

[化9]

[化10]

As the naphthoquinone diazide sulfonyl chloride used as a raw material, 4-naphthoquinone diazide sulfonyl chloride or 5-naphthoquinone diazide sulfonyl chloride can be used. The 4-naphthoquinone diazide sulfonate compound has absorption in the i-ray (wavelength 365 nm) region, so it is suitable for i-ray exposure. In addition, the 5-naphthoquinonediazide sulfonate compound absorbs in a wide range of wavelengths, so it is suitable for exposure at a wide range of wavelengths. Preferably, 4-naphthoquinonediazidesulfonate compound and 5-naphthoquinonediazidesulfonate compound are selected according to the wavelength of exposure. The 4-naphthoquinone diazide sulfonate compound and the 5-naphthoquinone diazide sulfonate compound can also be used in combination. Examples of the naphthoquinonediazide compound preferably used in the present invention include compounds represented by the following general formula (16).

[Chem 11]

In the formula, R ²⁰ represents hydrogen or an alkyl group selected from C 1-8. R ²¹ , R ²² , and R ²³ represent any one of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group, a carboxyl group, and an ester group. Each R ²¹ , R ²² , and R ²³ may be the same or different. Q represents any one of 5-naphthoquinonediazidesulfonyl and a hydrogen atom, and not all of Q are hydrogen atoms. b, c, d, α, and β represent integers from 0 to 4. Among them, α+β≧3. By using the naphthoquinonediazide compound represented by the general formula (16), the sensitivity or resolution in pattern processing is improved.

The addition amount of the naphthoquinonediazide compound is not particularly limited, but it is preferably 1 part by mass to 30 parts by mass relative to 100 parts by mass of the resin (polysiloxane), and more preferably 1 part by mass to 15 parts by mass. When the addition amount of the naphthoquinonediazide compound is less than 1 part by mass, the dissolution contrast between the exposed portion and the unexposed portion is too low, and sufficient photosensitivity for practical use does not appear. In addition, in order to further obtain a good dissolution contrast, it is preferably 5 parts by mass or more. On the other hand, when the addition amount of the naphthoquinone diazide compound is more than 30 parts by mass, the whitening of the coating film caused by the deterioration of the compatibility between the polysiloxane and the naphthoquinone diazide compound, Or the coloration caused by the decomposition of the quinonediazide compound caused by heat curing becomes remarkable, and therefore, the colorless transparency of the cured film decreases. In addition, in order to further obtain a highly transparent film, it is preferably 15 parts by mass or less.

<(D) Metal compound particles> The present invention preferably contains metal compound particles. The metal compound particles are not particularly limited, and from the viewpoint of adjusting the refractive index, it is preferable to contain (D) silicon dioxide particles. From the viewpoint of compatibility, it is preferable to set the resin as follows: in the presence of (D) silica particles and (B) solvent, the resin derived from the general formula (1) to the general formula (3) A silane compound of any structure, and a silane compound derived from the structure of the general formula (4) or the general formula (5), hydrolyzed and then subjected to a condensation reaction, and a composite siloxane with (D) silicon dioxide particles Department of resin. (D) The silicon dioxide particles preferably have a number average particle size of 1 nm to 200 nm. In order to obtain a cured film with a high visible light transmittance, it is more preferable that the number average particle diameter is 1 nm to 120 nm. Among them, in the case of having hollow silica particles, the number average particle diameter is more preferably 30 nm to 100 nm. If it is 1 nm or more, the low refractive index is sufficient, and if it is 200 nm or less, the reflection is sufficiently suppressed, and the hardness of the film becomes sufficiently high. (D) The number-average particle size of the silica particles can be directly measured by the gas adsorption method or dynamic light scattering method, X-ray small-angle scattering method, using a transmission electron microscope or a scanning electron microscope, etc. Perform the measurement. The number average particle diameter of the particles of the present invention refers to a value measured by dynamic light scattering method.

Examples of the (D) silicon dioxide particles used in the present invention include silicon dioxide particles having a porous interior and/or hollow, or silicon dioxide particles having a non-porous interior and having no hollow interior. Among these (D) silicon dioxide particles, in terms of reducing the refractive index of the coating film, it is preferable that the inside is porous and/or has hollow silicon dioxide particles. The silica particles that are not porous and do not have a hollow interior have a refractive index of 1.45 to 1.5, and therefore the expected effect of reducing the refractive index is small. On the other hand, the silica particles having a porous interior and/or having a hollow portion have a refractive index of 1.2 to 1.4, so the effect of reducing the refractive index is large. That is, the silica particles having a porous interior and/or having a hollow can be preferably used in terms of providing excellent hardness and low refractive index.

The silicon dioxide particles having a hollow inside suitably used in the present invention refer to silicon dioxide particles having a hollow portion surrounded by a shell. In addition, the porous silica particles used in the present invention refer to silica particles having a large number of voids on the surface or inside of the particles. Among these, in consideration of the hardness of the transparent film, it is preferable to have hollow silica particles having high strength of the particles themselves. (D) The refractive index of the silicon dioxide particles themselves is preferably 1.2 to 1.4, more preferably 1.2 to 1.35. Furthermore, these (D) silicon dioxide particles can be produced by the method disclosed in Japanese Patent No. 3272111 and Japanese Patent Laid-Open No. 2001-233611. In addition, as such (D) silicon dioxide particles, for example, the particles disclosed in Japanese Patent Laid-Open No. 2001-233611, or the commercially available particles shown in Japanese Patent No. 3272111 and the like can also be cited. .

(D) The refractive index of silicon dioxide particles can be measured by the following method. Matrix resin with (D) dioxide content adjusted to (D) silicon dioxide particle content of 0% by mass, 20% by mass, 30% by mass, 40% by mass, 50% by mass solids concentration of 10% A sample of the mixed solution of silicon particles was applied on a silicon wafer with a spin coater with a thickness of 0.3 μm to 1.0 μm, and then heated and dried using a hot plate at 200° C. for 5 minutes to obtain a coating film. . Next, the refractive index at a wavelength of 633 nm is obtained using, for example, an ellipsometer (manufactured by Otsuka Electronics Co., Ltd.), and the value of (D) 100% by mass of the silica particles is extrapolated to obtain.

Introducing silica particles that are porous and/or hollow into the coating material not only optimizes the refractive index of the film obtained from the coating material, but also increases the hardness of the film, which is preferable.

Examples of silica particles that are not porous and do not have a hollow interior include IPA-ST with a particle diameter of 12 nm and isopropyl alcohol as a dispersant, and those with a particle diameter of 12 nm and methyl isobutyl ketone as a dispersant. MIBK-ST, IPA-ST-L with a particle size of 45 nm using isopropyl alcohol as a dispersant, and IPA-ST-ZL with a particle size of 100 nm using isopropyl alcohol as a dispersant (above, trade name, Nissan Chemical Industries (Manufactured by Co., Ltd.), OSCAL 101 with a particle size of 12 nm using γ-butyrolactone as a dispersant, OSCAL 105 with a particle size of 60 nm using OSG with a γ-butyrolactone as a dispersant, Oscalu (OSCAL) 106 (above, trade name, manufactured by Nichiwa Chemical Industry Co., Ltd.) using diacetone alcohol as a dispersant at a particle size of 120 nm. In addition, the presence or absence of hollowness can be confirmed with a particle cross-sectional image using a TEM (Transmission Electron Microscope) photograph.

Examples of commercially available (D) silica particles include: organic silica sol "OSCAL" (manufactured by Nikon Catalyst Chemical Industry Co., Ltd.), colloidal silica "Snotex" (Snowtex), organic silica sol (manufactured by Nissan Chemical Industry Co., Ltd.), high-purity colloidal silica, high-purity organic sol "Quartron" (Fuso Chemical Industry Co., Ltd.), etc.

In addition, in order to obtain a cured film with a low refractive index, it is preferable to contain hollow silica particles. The presence or absence of hollowness can be confirmed with a particle cross-sectional image using a TEM (scanning electron microscope) photo. (D) The content of the silica particles is not particularly limited, and can be set to an appropriate amount according to the application, and is generally set to about 1% by mass to 80% by mass of all solid components of the silicone resin composition.

The resin composition of the present invention can be obtained by mixing at least the (A) polysiloxane, (B) solvent, and preferably (C) naphthoquinonediazide compound. At this time, it can be diluted with an arbitrary solvent. The mixing temperature is not particularly limited, and it is preferably in the range of 5°C to 50°C for ease of operation.

The siloxane resin composition of the present invention may contain various hardeners that accelerate or facilitate curing of the resin composition. Specific examples of the hardener include nitrogen-containing organic compounds, silicone resin hardeners, various metal alcoholates, various metal chelate compounds, isocyanate compounds and their polymers, methylolated melamine derivatives, and methylolated urea derivatives It may contain one kind, or two or more kinds of these substances. Among them, metal chelate compounds can be preferably used in terms of transparency of the coating film and stability of the hardener.

Examples of metal chelate compounds include titanium chelate compounds, zirconium chelate compounds, aluminum chelate compounds, and magnesium chelate compounds. These metal chelate compounds can be easily obtained by reacting a chelating agent with a metal alkoxide. Examples of chelating agents include β-diketones such as acetone acetone, benzylacetone, and dibenzoylmethane; β-ketones such as ethyl acetoacetate and ethyl acetoacetate Ester and so on. Preferred specific examples of the metal chelate compound include: ethyl acetate ethyl diisopropoxide, aluminum tris(ethyl acetate) aluminum, aluminum acetyl acetate diisopropoxide aluminum, monoethyl acetate Aluminum chelate compounds such as acetylacetate bis(ethylacetate) aluminum, tris(acetylpyruvate)aluminum, etc., ethyl acetoacetate magnesium monoisopropoxide, bis(ethyl acetoacetate) magnesium , Magnesium chelate compounds such as magnesium acetoacetate monoisopropoxide, magnesium bis(acetylpyruvate), etc. The content of the hardener in the solid content of the silicone resin composition is preferably 0.1% by mass to 10% by mass, and more preferably 0.5% by mass to 6% by mass.

Polysiloxane promotes hardening by acid. Therefore, the resin composition of the present invention may contain a hardening catalyst such as a thermal acid generator. Examples of the thermal acid generator include various onium salt-based compounds, such as aromatic diazonium salts, osmium salts, diarylphosphonium salts, triarylammonium salts, and triarylselenium salts, sulfonate esters, and halogen compounds.

As specific examples, the osmium salt may include: 4-hydroxyphenyl dimethyl alkane trifluoromethanesulfonate (prototype "W" manufactured by Sanshin Chemical Industry Co., Ltd.), benzyl-4-hydroxyphenylmethyl鋶Trifluoromethanesulfonate (prototype "O" manufactured by Sanshin Chemical Industry Co., Ltd.), 2-methylbenzyl-4-hydroxyphenylmethyl benzotrifluoromethanesulfonate (prototype "N" Sanshin Chemical Industry Co., Ltd.), 4-methylbenzyl-4-hydroxyphenylmethyl alkane trifluoromethanesulfonate, 4-hydroxyphenylmethyl-1-naphthylmethyl alkane trifluoromethane Sulfonate, 4-Methoxycarbonyloxyphenyl dimethyl alkane trifluoromethanesulfonate (prototype "J" manufactured by Sanshin Chemical Industry Co., Ltd.), benzyl-4-methoxycarbonyloxy Triphenylmethanesulfonate trifluoromethanesulfonate (prototype "T" manufactured by Sanshin Chemical Industry Co., Ltd.), 4-acetoxyphenylbenzylmethylsulfonium trifluoromethanesulfonate (prototype "U" Sanshin Chemical Industry Co., Ltd.), 4-acetoxyphenylmethyl-4-methylbenzyl alkane trifluoromethanesulfonate, 4-acetoxyphenyl dimethyl dimethyl alkane Trifluoromethanesulfonate (prototype "V" manufactured by Sanshin Chemical Industry Co., Ltd.), 4-hydroxyphenyl dimethyl hexafluorophosphate, benzyl-4-hydroxyphenylmethyl hexafluorophosphate Salt, 2-methylbenzyl-4-hydroxyphenylmethyl hexafluorophosphate, 4-methylbenzyl-4-hydroxyphenylmethyl hexafluorophosphate, 4-hydroxyphenylmethyl- 1-naphthylmethyl hexafluorophosphate, 4-methoxycarbonyloxyphenyl dimethyl hexafluorophosphate, benzyl-4-methoxycarbonyloxyphenyl methyl hexafluorophosphate Salt, 4-acetoxyphenylbenzylmethyl alkane hexafluorophosphate (prototype "A" manufactured by Sanshin Chemical Industry Co., Ltd.), 4-acetyloxyphenylmethyl-4-methyl Benzyl alkene hexafluorophosphate, 4-acetoxyphenyl dimethyl alkane hexafluorophosphate (trade name "SI-150" manufactured by Sanshin Chemical Industry Co., Ltd.), "SI-180L" (Sanshin Chemical industry (manufactured by the company), 4-hydroxyphenyl dimethyl hexafluoroantimonate, benzyl-4-hydroxyphenylmethyl hexafluoroantimonate, 2-methylbenzyl-4-hydroxy Phenylmethylaluminium hexafluoroantimonate, 4-methylbenzyl-4-hydroxyphenylmethylaluminium hexafluoroantimonate, 4-hydroxyphenylmethyl-1-naphthylmethylaluminium hexafluoroantimonate Acid salt, 4-methoxycarbonyloxyphenyldimethylammonium hexafluoroantimonate, benzyl-4-methoxycarbonyloxyphenylmethylammonium hexafluoroantimonate, 4-acetoxy Phenylphenylbenzylmethylammonium hexafluoroantimonate, 4-acetoxyphenylmethyl-4-methylbenzylammonium hexafluoroantimonate, 4-acetoyloxyphenyldimethylammonium Hexafluoroantimonate, 4-acetoxyphenyl dimethyl hexamethylene hexafluoroantimonate, benzyl-4-hydroxyphenylmethyl aram hexafluoroantimonate, etc.

The aromatic diazonium salt may be exemplified by chlorobenzene diazonium hexafluorophosphate, dimethylaminobenzene diazonium hexafluoroantimonate, naphthyl diazonium hexafluorophosphate, dimethylaminonaphthalene Base diazonium tetrafluoroborate and so on.

Examples of diaryliodonium salts include: diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, 4,4 '-Di-tertiary butyl-diphenylphosphonium trifluoromethanesulfonate, 4,4'-di-tertiary butyl-diphenylphosphonium tetrafluoroborate, 4,4'-di-third Butyl-diphenylphosphonium hexafluorophosphate, etc.

Examples of triaryl alkane salts include triphenyl alkane tetrafluoroborate, triphenyl alkane hexafluorophosphate, triphenyl alkane hexafluoroantimonate, tri(p-chlorophenyl) alkane tetrafluoroborate, tri( P-chlorophenyl) alkane hexafluorophosphate, tri (p-chlorophenyl) alkane hexafluoroantimonate, 4-third butyl triphenyl alkane hexafluorophosphate, etc.

Examples of triaryl selenium salts include triphenyl selenium tetrafluoroborate, triphenyl selenium hexafluorophosphate, triphenyl selenium hexafluoroantimonate, bis(chlorophenyl) phenyl selenium tetrafluoroborate, di (Chlorophenyl) phenyl selenium hexafluorophosphate, bis (chlorophenyl) phenyl selenium hexafluoroantimonate, etc.

Sulfonates can be exemplified by benzoin tosylate, p-nitrobenzyl-9,10-ethoxyanthracene 2-sulfonate, 2-nitrobenzyl tosylate, 2,6-dinitro Benzyl tosylate, 2,4-dinitrobenzyl tosylate, etc.

Examples of halogen compounds include 2-chloro-2-phenylacetophenone, 2,2',4'-trichloroacetophenone, 2,4,6-tris(trichloromethyl)-s-triazine, 2 -(P-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2- (P-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-methoxy-1'-naphthyl)-4,6-bis(trichloro Methyl)-s-triazine, bis-2-(4-chlorophenyl)-1,1,1-trichloroethane, bis-1-(4-chlorophenyl)-2,2,2-tri Chloroethanol, bis-2-(4-methoxyphenyl)-1,1,1-trichloroethane, etc.

In addition, 5-norbornene-2,3-dicarboxyamideimide trifluoromethanesulfonate (trade name "NDI-105" manufactured by Green Chemical Co., Ltd.), 5-norbornene-2 ,3-Dicarboxy acetylimidyl tosylate (trade name "NDI-101" manufactured by Green Chemical Co., Ltd.), 4-methylphenyl sulfonyloxyimino-α-(4-methyl Oxyphenyl) acetonitrile (trade name "PAI-101" manufactured by Green Chemical Co., Ltd.), trifluoromethylsulfonyloxyimino-α-(4-methoxyphenyl) acetonitrile (trade name "PAI-105" manufactured by Green Chemical Co., Ltd.), 9-camphor sulfonyloxyimino-α-4-methoxyphenylacetonitrile (trade name "PAI-106" manufactured by Green Chemical Co., Ltd.) 、1,8-Naphthalimide butane sulfonate (trade name "NAI-1004" manufactured by Green Chemical Co., Ltd.), 1,8-Naphthalene imidate tosylate (trade name) "NAI-101" manufactured by Green Chemical Co., Ltd.), 1,8-naphthalene dimethylimidimide trifluoromethanesulfonate (trade name "NAI-105" manufactured by Green Chemical Co., Ltd.), 1,8- Examples of thermal acid generators such as naphthalimide nonafluorobutane sulfonate (trade name "NAI-109" manufactured by Green Chemical Co., Ltd.) are examples.

In order to improve the fluidity during coating, the resin composition of the present invention may contain various surfactants such as various fluorine-based surfactants and silicone-based surfactants. The type of surfactant is not particularly limited, for example, "Megafac (registered trademark)" F142D, Megafac F172, Megafac F173, Megafac F183, Mega ( Megafac) F430, Megafac F444, Megafac F445, Megafac F470, Megafac F475, Megafac F477, Megafac F553, Megafac ) F554, Megafac F555, Megafac F556, Megafac F559, Megafac F560, Megafac F563 (above, manufactured by Dainippon Ink Chemical Industry Co., Ltd.) , NBX-15, FTX-218, DFX-18 (manufactured by NEOS), LE-604, LE-605, LE-606, LE-607 (manufactured by Kyoeisha Chemical Co., Ltd.) Fluorine-based surfactants; BYK-333, BYK-301, BYK-331, BYK-345, BYK-307 (manufactured by BYK-Chemie Japan), KL-402, KL-403 , KL-404, KL-700, LE-302, LE-303, LE-304, LE-604, LE-605, LE-606, LE-607 (made by Kyoeisha Chemical Co., Ltd.) and other silicone systems Surfactants; polyalkylene oxide-based surfactants; poly(meth)acrylate-based surfactants, etc. Two or more of these can also be used.

Furthermore, the resin composition of the present invention may contain a silane coupling agent, a cross-linking agent, a cross-linking accelerator, a sensitizer, a thermal radical generator, a dissolution accelerator, a dissolution inhibitor, a stabilizer, an antifoaming agent, if necessary And other additives.

<Method of forming cured film> The cured film of the present invention is obtained by curing the resin composition of the present invention or the photosensitive resin composition as the resin composition of the present invention. Here, the photosensitive resin composition will be described in detail. As one embodiment of the method for manufacturing the cured film of the photosensitive resin composition, it is preferable to include the following steps. (I) A step of applying a photosensitive resin composition on a substrate to form a coating film; (II) The steps of exposure and development of the coating film; and (III) The step of heating the developed coating film. The following is an example.

The photosensitive resin composition is coated on the substrate by a known method such as spin coating or slit coating, and heated (pre-baking) using a heating device such as a hot plate or an oven. The pre-baking is preferably performed within a temperature range of 50°C to 150°C for 30 seconds to 30 minutes. The film thickness after pre-baking is preferably 0.1 μm to 15 μm.

After pre-baking, use a stepper, a Mirror Projection Mask Aligner (MPA), a parallel light mask aligner (Parallel Light Mask Aligner, PLA), etc. The mask required for interposing is subjected to pattern exposure at about 10 J/m ² to 4000 J/m ² (conversion of exposure at a wavelength of 365 nm).

After exposure, the (un)exposed part is dissolved and removed by development to obtain a negative pattern or a positive pattern. The resolution of the pattern is preferably 15 μm or less. The developing method is preferably dipping in the developing solution for 5 seconds to 10 minutes by spraying, dip, coating, or the like. As the developer, a known alkaline developer can be used, and examples thereof include inorganic bases such as hydroxides, carbonates, phosphates, silicates, and borates of alkali metals, 2-diethylaminoethanol, monoethanolamine, Aqueous solutions such as amines such as diethanolamine, tetramethylammonium hydroxide (Tetramethylammonium hydroxide, TMAH), and choline. Two or more of these can also be used. In addition, after development, it is preferably rinsed with water. If necessary, a heating device such as a hot plate or an oven may be used to perform dehydration drying and baking in a temperature range of 50°C to 150°C. After heating the film for 30 seconds to 30 minutes in a temperature range of 50°C to 300°C using a heating device such as a hot plate or an oven (soft baking), use a heating device such as a hot plate or oven at 150°C to 450°C Heating (curing) within a temperature range of about 30 seconds to 2 hours, thereby obtaining a cured film.

From the viewpoint of productivity in pattern formation, the sensitivity of the photosensitive resin composition at the time of exposure is preferably 1500 J/m ² or less, and more preferably 1000 J/m ² or less. The sensitivity during exposure is obtained by the following method. Using a spin coater to spin-coat the photosensitive resin composition on a silicon wafer at an arbitrary number of revolutions, pre-bake at 120°C for 3 minutes using a hot plate to produce a pre-baked film with a film thickness of 1 μm . A gray scale mask with a line and space pattern of 1 μm to 10 μm for the measurement of sensitivity using ultra-high pressure mercury lamps using PLA (PLA-501F manufactured by Canon Co., Ltd.) gray-scale mask) After exposure of the pre-baked film, using an automatic developing device (AD-2000 manufactured by Takizawa Industries Co., Ltd.) and using 2.38% by mass TMAH aqueous solution for 90 seconds shower development, followed by water rinse 30 second. From the formed pattern, the exposure amount of the line and the space pattern analyzed with a width of 1 to 1 at a width of 10 μm was determined as the sensitivity.

Thereafter, as a thermosetting step, a hot plate was cured at 220° C. for 5 minutes to produce a cured film, and the minimum pattern size of sensitivity was obtained as the resolution after curing.

FIG. 1 shows a specific example of the method for manufacturing the cured film of this embodiment. First, the resin composition of the present invention is applied on the substrate 1 to form a coating film 2. This is cured by overheating, thereby obtaining a cured film 3.

FIG. 2 shows a specific example of the method of manufacturing the cured film of this embodiment. The operation is performed as described above until the initial formation of the coating film 2. Next, the coating film 2 is irradiated with actinic rays 4 and exposed. This is hardened by heating, thereby obtaining a cured film 3.

FIG. 3 shows a specific example of the method for manufacturing the cured film of this embodiment. The operation is performed as described above until the initial formation of the coating film 2. Next, the coating film 2 irradiates the coating film 2 with actinic rays 4 to expose it. The exposed coating film is developed, thereby obtaining a pattern 6. The pattern is irradiated with actinic rays 5 and heat-cured to obtain a cured film 3.

The cured film obtained by curing the fat composition of the present invention preferably has a light transmittance of 90% or more per 1 μm film thickness at a wavelength of 400 nm, and more preferably 92% or more. Such a high transmittance can be easily obtained, for example, by using a photosensitive resin composition using a highly transparent polysiloxane as a resin component.

The transmittance per 1 μm film thickness at a wavelength of 400 nm of the cured film was obtained by the following method. The photosensitive resin composition was spin-coated on a TEMPAX glass plate at an arbitrary number of revolutions using a spin coater, and pre-baked at 100°C for 3 minutes using a hot plate. Using a hot plate, the film was thermally cured at 220° C. for 5 minutes to produce a cured film with a thickness of 1 μm. The ultraviolet-visible absorption spectrum of the obtained cured film was measured using MultiSpec-1500 manufactured by Shimadzu Corporation, and the transmittance at a wavelength of 400 nm was obtained. As another method, the spectroscopic ellipsometer FE5000 manufactured by Otsuka Electronics Co., Ltd. can be used to measure the extinction coefficient and the film thickness at each wavelength of the target cured film, and can be obtained by the following formula.

Transmittance = exp (-4πkt/λ) Among them, k represents the extinction coefficient, t represents the film thickness, and λ represents the measurement wavelength.

The resin composition of the present invention and a cured film obtained by curing it can be suitably used for solid-state imaging elements, optical filters, organic EL elements, and liquid crystal displays as display devices, organic EL TVs, and particularly transparent liquid crystal TVs Waiting. More specifically, examples include anti-reflection films, anti-color mixing walls, transparent pixels, and displays for solid-state imaging optical filters such as back-illuminated complementary metal oxide semiconductor (Complementary Metal Oxide Semiconductor, CMOS) image sensors Thin film transistor (Thin Film Transistor, TFT) substrate flattening material, liquid crystal display, transparent display (see-through display) and other color filters and its protective film, phase shifter, anti-reflection film, etc. In addition, it can also be used as a buffer coat (interlayer insulating film) or various protective films for semiconductor devices. [Example]

Hereinafter, the present invention will be described more specifically with examples, but the present invention is not limited to these examples. The compounds using abbreviations among the compounds used in Synthesis Examples and Examples are shown below. PGMEA: propylene glycol monomethyl ether acetate CPN: cyclopentanone gBL: γ-butyrolactone BzOH: benzyl alcohol BzME: benzyl methyl ether MBz: methyl benzoate MTMS: methyltrimethoxysilane PhTMS: Phenyltrimethoxysilane TES: Tetraethoxysilane HfTMS: 4-(2-hydroxy-1,1,1,3,3,3-hexafluoroisopropyl)-1-triethoxysilylbenzene CFTMS: trifluoropropyltrimethoxysilane.

<Measurement of Ratio of Substituents> ²⁹ Si-NMR measurement was performed, and the ratio to the integral value of each organosilane was calculated from the overall integral value to calculate the ratio. A sample (liquid) was injected into an NMR sample tube made of "Teflon" (registered trademark) with a diameter of 10 mm for measurement. The measurement conditions of ²⁹ Si-NMR are shown below.

Device: JNM GX-270 manufactured by Nippon Electronics Co., Ltd. Measurement method: gated decoupling method Nuclear frequency: 53.6693 MHz ( ²⁹ Si core), spectral width: 20000 Hz Pulse width: 12 μsec (45° pulse) ), pulse repetition time: 30.0 sec Solvent: acetone-d6, reference substance: tetramethylsilane Measurement temperature: room temperature, sample rotation speed: 0.0 Hz.

<Measurement of solid content concentration> The solid content concentration of the polysiloxane solution is obtained by the following method. Weigh 1.5 g of polysiloxane solution into an aluminum cup and use a hot plate to heat at 250°C for 30 minutes to evaporate the liquid components. The solid content remaining in the aluminum cup after heating was weighed to determine the solid content concentration of the polysiloxane solution.

Synthesis Example 1 Synthesis of HfTMS (Hf-1) In order to synthesize the Hf compound (H1), the following reaction is performed.

[化12]

In a 300 mL three-necked flask equipped with a reflux tube, take pre-dried Hf compound (H-1) 6.46 g (20.0 mmol), tetrabutylammonium iodide 7.38 g (40.0 mmol), and bis( Acetonitrile) (1,5-cyclooctadiene) rhodium (I) tetrafluoroborate 0.2280 g (0.60 mmol). Then, under argon atmosphere, 120 mL of dehydrated N,N-dimethylformamide, 11.1 mL (80.0 mmol) of triethylamine after dehydration, and 7.40 mL of triethoxysilane were added ( 40.0 mmol), warm to 80°C and stir for 4 hours. After the reaction system was naturally cooled to room temperature, N,N-dimethylformamide as a solvent was distilled off, and then 200 mL of diisopropyl ether was added. The diatomaceous earth was brought into contact with the generated precipitate and filtered, and then the filtrate was washed three times with 100 mL of water, and Na2SO4 was added for dehydration and drying, followed by filtration, and then the solvent was distilled off. The residue as a reactant was distilled using a Kugelrohr apparatus at 140°C to 190°C and 200 Pa to obtain HfTMS (Hf-1) as a colorless liquid. The ¹ H-NMR measurement results of the obtained HfTMS (Hf-1) are shown below.

¹ H-NMR (solvent CDCl3 (deuterated chloroform), TMS (tetramethylsilane)): δ8.03 (1H, s), 7.79 (2H, d, J=7.6Hz), 7.47 (1H, t, J =7.6Hz), 4.16 (1H, s), 3.88 (6H, q, J=5.0Hz), 1.24 (9H, t, J=7.4Hz).

Synthesis Example 2 Synthesis of HfTMS (Hf-2) In order to synthesize the Hf compound (H1), the following reaction is performed.

[Chem 13]

Instead of the Hf compound (H-1), the Hf compound (H-2) was used, except that the HfTMS (Hf-2) was obtained by the same procedure as in Synthesis Example 1. The ¹ H-NMR measurement results of the obtained HfTMS (Hf-1) are shown below. ¹ H-NMR (solvent CDCl3 (deuterated chloroform), TMS (tetramethylsilane)): δ7.74 (4H, dd, J=18.6, 18.3Hz), 3.89 (6H, q, J=7.0Hz), 3.57 (1H, s), 1.26 (9H, t, J=7.0Hz).

Synthesis Example 3 Synthesis of polysiloxane (P-1) In a 500 ml three-necked flask, 109.25 g (0.565 mol) of MTMS, 84.67 g (0.049 mol) of HfTMS (Hf-1), 6.51 g (0.014 mol) were put in ) And 191.75 g of PGMEA, a phosphoric acid aqueous solution in which 1.00 g of phosphoric acid was dissolved in 56.82 g of water (0.50% by mass relative to the monomer input) was added over 30 minutes while stirring at room temperature. Thereafter, the flask was immersed in an oil bath at 70°C and stirred for 90 minutes, and then the oil bath was heated to 115°C over 30 minutes. One hour after the temperature increase started, the internal temperature of the solution reached 100°C, and then superheated stirring was performed for 2 hours (internal temperature was 100°C to 110°C) to obtain polysiloxane (P-1). Furthermore, nitrogen gas was circulated at a temperature of 0.05 l (liter)/minute while heating and stirring. A total of 154.41 g of methanol and water as by-products were distilled off during the reaction. The solid content concentration of the obtained polysiloxane (P-1) was 43.1% by mass. By the measurement of ²⁹ Si-NMR, the structure represented by any one of the general formula (1) to the general formula (3), and the structure represented by any one of the general formula (4) or the general formula (5) is: (A) The molar amounts of polysiloxane are 20 mol% and 3 mol%, respectively.

Synthesis Example 4 Synthesis of polysiloxane (P-2) In the same order as Synthesis Example 1, 112.22 g (0.551 mol) of MTMS, 66.97 g (0.037 mol) of HfTMS (Hf-1), 22.88 g ( 0.048 mol) of TES and 185.62 g of PGMEA were added to 61.30 g of water, and a phosphoric acid aqueous solution in which 1.01 g of phosphoric acid (0.50% by mass relative to the input monomer) was dissolved to obtain polysiloxane (P-2). The solid content concentration of the obtained polysiloxane (P-2) was 42.8% by mass. By the measurement of ²⁹ Si-NMR, the structure represented by any one of the general formula (1) to the general formula (3), and the structure represented by any one of the general formula (4) or the general formula (5) is: (A) The molar amounts of polysiloxane are 15 mol% and 10 mol%, respectively.

Synthesis Example 5 Synthesis of polysiloxane (P-3) In the same order as Synthesis Example 1, 45.14 g (0.257 mol) of MTMS, 57.72 g (0.037 mol) of HfTMS (Hf-1), 98.61 g ( 0.240 mol) of TES and 187.87 g of PGMEA, and a phosphoric acid aqueous solution in which 1.01 g of phosphoric acid (0.50% by mass relative to the monomer input) was dissolved in 59.65 g of water was added to obtain polysiloxane (P-3). The solid content concentration of the obtained polysiloxane (P-3) was 43.5% by mass. By the measurement of ²⁹ Si-NMR, the structure represented by any one of the general formula (1) to the general formula (3), and the structure represented by any one of the general formula (4) or the general formula (5) is: (A) The molar amounts of polysiloxane are 15 mol% and 50 mol%, respectively.

Synthesis Example 6 Synthesis of polysiloxane (P-4) In the same order as Synthesis Example 1, 31.16 g (0.184 mol) of MTMS, 55.79 g (0.037 mol) of HfTMS (Hf-1), 114.39 g ( 0.288 mol) of TES and 188.34 g of PGMEA were added to 59.31 g of water, and a phosphoric acid aqueous solution in which 1.01 g of phosphoric acid (0.50% by mass relative to the input monomer) was dissolved to obtain polysiloxane (P-4). The solid content concentration of the obtained polysiloxane (P-4) was 42.5% by mass. By the measurement of ²⁹ Si-NMR, the structure represented by any one of the general formula (1) to the general formula (3), and the structure represented by any one of the general formula (4) or the general formula (5) is: (A) The molar amounts of polysiloxane are 15 mol% and 60 mol%, respectively.

Synthesis Example 7 Synthesis of polysiloxane (P-5) In the same order as Synthesis Example 1, 66.18 g (0.367 mol) of MTMS, 59.24 g (0.037 mol) of HfTMS (Hf-1), 10.12 g ( 0.024 mol) of TES, 63.63 g (0.137 mol) of CFTMS, 196.49 g of PGMEA, and 53.35 g of water were dissolved in phosphoric acid aqueous solution of 1.00 g of phosphoric acid (0.50% by mass relative to the input monomer) to obtain poly Siloxane (P-5). The solid content concentration of the obtained polysiloxane (P-5) was 43.7% by mass. By the measurement of ²⁹ Si-NMR, the structure represented by any one of the general formula (1) to the general formula (3), and the structure represented by any one of the general formula (4) or the general formula (5) is: (A) The molar amounts of polysiloxane are 15 mol% and 5 mol%, respectively.

Synthesis Example 8 Synthesis of polysiloxane (P-6) In the same order as Synthesis Example 1, 58.52 g (0.330 mol) of MTMS, 58.21 g (0.037 mol) of HfTMS (Hf-1), 19.89 g ( 0.048 mol) of TES, 62.52 (0.137 mol) of CFTMS, 196.59 g of PGMEA, and a phosphoric acid aqueous solution in which 1.00 g of phosphoric acid (0.50% by mass relative to the input monomer) was dissolved in 53.28 g of water to obtain polysilicon Oxane (P-6). The solid content concentration of the obtained polysiloxane (P-6) was 42.9% by mass. By the measurement of ²⁹ Si-NMR, the structure represented by any one of the general formula (1) to the general formula (3), and the structure represented by any one of the general formula (4) or the general formula (5) is: (A) The molar amounts of polysiloxane are 15 mol% and 10 mol%, respectively.

Synthesis Example 9 Synthesis of polysiloxane (P-7) In the same order as Synthesis Example 1, 46.14 g (0.257 mol) of MTMS, 59.01 g (0.037 mol) of HfTMS (Hf-1), and 30.24 g ( 0.072 mol) of TES, 63.38 (0.137 mol) of CFTMS, 197.97 g of PGMEA, and a phosphoric acid aqueous solution in which 0.99 g of phosphoric acid (0.50% by mass relative to the input monomer) was dissolved in 52.27 g of water to obtain polysilicon Oxane (P-7). The solid content concentration of the obtained polysiloxane (P-7) was 43.1% by mass. By the measurement of ²⁹ Si-NMR, the structure represented by any one of the general formula (1) to the general formula (3), and the structure represented by any one of the general formula (4) or the general formula (5) is: (A) The molar amounts of polysiloxane are 15 mol% and 20 mol%, respectively.

Synthesis Example 10 Synthesis of polysiloxane (P-8) In the same order as Synthesis Example 1, 30.40 g (0.184 mol) of MTMS, 54.42 g (0.037 mol) of HfTMS (Hf-1), 55.78 g ( 0.144 mol) of TES, 58.45 (0.137 mol) of CFTMS, 196.64 g of PGMEA, and a phosphoric acid aqueous solution in which 1.00 g of phosphoric acid (0.50% by mass relative to the input monomer) was dissolved in 53.02 g of water to obtain polysilicon Oxane (P-8). The solid content concentration of the obtained polysiloxane (P-8) was 43.2% by mass. By the measurement of ²⁹ Si-NMR, the structure represented by any one of the general formula (1) to the general formula (3), and the structure represented by any one of the general formula (4) or the general formula (5) is: (A) The molar amounts of polysiloxane are 15 mol% and 30 mol%, respectively.

Synthesis Example 11 Synthesis of polysiloxane (P-9) In the same order as Synthesis Example 1, 5.71 g (0.037 mol) of MTMS, 51.09 g (0.037 mol) of HfTMS (Hf-1), 87.29 g ( 0.240 mol) of TES, 54.88 (0.137 mol) of CFTMS, 197.24 g of PGMEA, and a phosphoric acid aqueous solution in which 0.99 g of phosphoric acid (0.50% by mass relative to the input monomer) was dissolved in 52.80 g of water to obtain polysilicon Oxane (P-9). The solid content concentration of the obtained polysiloxane (P-9) was 42.8% by mass. By the measurement of ²⁹ Si-NMR, the structure represented by any one of the general formula (1) to the general formula (3), and the structure represented by any one of the general formula (4) or the general formula (5) is: (A) The molar amounts of polysiloxane are 15 mol% and 50 mol%, respectively.

Synthesis Example 12 Synthesis of polysiloxane (P-10) In the same order as Synthesis Example 1, 54.02 g (0.294 mol) of MTMS, 40.30 g (0.025 mol) of HfTMS (Hf-1), 41.31 g ( 0.096 mol) of TES, 64.92 (0.137 mol) of CFTMS, 191.35 g of PGMEA, and a phosphoric acid aqueous solution in which 1.00 g of phosphoric acid (0.50% by mass relative to the input monomer) was dissolved in 57.11 g of water to obtain polysilicon Oxane (P-10). The solid content concentration of the obtained polysiloxane (P-10) was 43.1% by mass. By the measurement of ²⁹ Si-NMR, the structure represented by any one of the general formula (1) to the general formula (3), and the structure represented by any one of the general formula (4) or the general formula (5) is: (A) The molar amounts of polysiloxane are 10 mol% and 20 mol%, respectively.

Synthesis Example 13 Synthesis of polysiloxane (P-11) In the same order as Synthesis Example 1, 35.26 g (0.220 mol) of MTMS, 70.13 g (0.049 mol) of HfTMS (Hf-1), 35.95 g ( 0.096 mol) of TES, 56.49 (0.137 mol) of CFTMS, and 201.48 g of PGMEA, and added to 49.70 g of water, a phosphoric acid aqueous solution in which 0.99 g of phosphoric acid (0.50% by mass relative to the input monomer) was dissolved to obtain polysilicon Oxane (P-11). The solid content concentration of the obtained polysiloxane (P-11) was 43.4% by mass. By the measurement of ²⁹ Si-NMR, the structure represented by any one of the general formula (1) to the general formula (3), and the structure represented by any one of the general formula (4) or the general formula (5) is: (A) The molar amounts of polysiloxane are 20 mol% and 20 mol%, respectively.

Synthesis Example 14 Synthesis of polysiloxane (P-12) In the same order as Synthesis Example 1, 20.80 g (0.147 mol) of MTMS, 93.11 g (0.074 mol) of HfTMS (Hf-1), 31.82 g ( 0.096 mol) of TES, 50.00 (0.137 mol) of CFTMS, 209.29 g of PGMEA, and a phosphoric acid aqueous solution in which 0.98 g of phosphoric acid (0.50% by mass relative to the input monomer) was dissolved in 43.99 g of water to obtain polysilicon Oxane (P-12). The solid content concentration of the obtained polysiloxane (P-12) was 43.0% by mass. By the measurement of ²⁹ Si-NMR, the structure represented by any one of the general formula (1) to the general formula (3), and the structure represented by any one of the general formula (4) or the general formula (5) is: (A) The molar amounts of polysiloxane are 30 mol% and 20 mol%, respectively.

Synthesis Example 15 Synthesis of polysiloxane (P-13) In a 500 ml three-necked flask, 109.25 g (0.565 mol) of MTMS, 84.67 g (0.049 mol) of HfTMS (Hf-2), 6.51 g (0.014 mol) were put in ) And 191.75 g of PGMEA, a phosphoric acid aqueous solution in which 1.00 g of phosphoric acid was dissolved in 56.82 g of water (0.50% by mass relative to the monomer input) was added over 30 minutes while stirring at room temperature. Thereafter, the flask was immersed in an oil bath at 70°C and stirred for 90 minutes, and then the oil bath was heated to 115°C over 30 minutes. One hour after the temperature increase started, the internal temperature of the solution reached 100°C, and then superheated stirring was performed for 2 hours (internal temperature was 100°C to 110°C) to obtain polysiloxane (P-13). Furthermore, nitrogen gas was circulated at a temperature of 0.05 l (liter)/minute while heating and stirring. A total of 154.41 g of methanol and water as by-products were distilled off during the reaction. The solid content concentration of the obtained polysiloxane (P-1) was 43.0% by mass. By the measurement of ²⁹ Si-NMR, the structure represented by any one of the general formula (1) to the general formula (3), and the structure represented by any one of the general formula (4) or the general formula (5) is: (A) The molar amounts of polysiloxane are 20 mol% and 3 mol%, respectively.

Synthesis Example 16 Synthesis of polysiloxane (R-1) In the same order as Synthesis Example 1, 188.82 g (0.246 mol) of HfTMS (Hf-1) and 235.14 g of PGMEA were added to 25.09 g of water A phosphoric acid aqueous solution in which 0.94 g of phosphoric acid (0.50% by mass relative to the monomer input) was dissolved was dissolved to obtain polysiloxane (R-1). The solid content concentration of the obtained polysiloxane (R-1) was 43.2% by mass. By the measurement of ²⁹ Si-NMR, the structure represented by any one of the general formula (1) to the general formula (3), and the structure represented by any one of the general formula (4) or the general formula (5) is: (A) The molar amounts of polysiloxane are 100 mol% and 0 mol%, respectively.

Synthesis Example 17 Synthesis of polysiloxane (R-2) In the same order as Synthesis Example 1, 41.54 g (0.330 mol) of MTMS, 151.49 g (0.135 mol) of HfTMS (Hf-1), and 219.40 g of PGMEA was added to a phosphoric acid aqueous solution in which 0.97 g of phosphoric acid (0.50% by mass relative to the input monomer) was dissolved in 36.60 g of water to obtain polysiloxane (R-2). The solid content concentration of the obtained polysiloxane (R-2) was 43.5% by mass. By the measurement of ²⁹ Si-NMR, the structure represented by any one of the general formula (1) to the general formula (3), and the structure represented by any one of the general formula (4) or the general formula (5) is: (A) The molar amounts of polysiloxane are 55 mol% and 0 mol%, respectively.

Synthesis Example 18 Synthesis of polysiloxane (R-3) In the same order as Synthesis Example 1, 68.15 g (0.330 mol) of MTMS, 133.47 g (0.252 mol) of CFTMS, and 187.34 g of PGMEA were added and added to In 60.04 g of water, 1.01 g of phosphoric acid (0.50% by mass relative to the monomer input) was dissolved in phosphoric acid aqueous solution to obtain polysiloxane (R-3). The solid content concentration of the obtained polysiloxane (R-3) was 43.2% by mass. By the measurement of ²⁹ Si-NMR, the structure represented by any one of the general formula (1) to the general formula (3), and the structure represented by any one of the general formula (4) or the general formula (5) is: (A) The molar amounts of polysiloxane are 0 mol% and 0 mol%, respectively.

Synthesis Example 19 Synthesis of polysiloxane (R-4) In the same order as Synthesis Example 1, 73.11 g (0.330 mol) of MTMS, 130.10 g (0.277 mol) of PhTMS, and 181.36 g of PGMEA were added and added to In 64.42 g of water, a phosphoric acid aqueous solution in which 1.02 g of phosphoric acid (0.50% by mass relative to the input monomer) was dissolved was obtained as polysiloxane (R-4). The solid content concentration of the obtained polysiloxane (R-4) was 42.8% by mass. By the measurement of ²⁹ Si-NMR, the structure represented by any one of the general formula (1) to the general formula (3), and the structure represented by any one of the general formula (4) or the general formula (5) is: (A) The molar amounts of polysiloxane are 0 mol% and 0 mol%, respectively.

Synthesis Example 20 Synthesis of polysiloxane (R-5) In the same order as Synthesis Example 1, 120.70 g (0.111 mol) of HfTMS, 71.98 g (0.277 mol) of PhTMS, and 220.71 g of PGMEA were added and added to In 35.64 g of water, a phosphoric acid aqueous solution in which 0.97 g of phosphoric acid (0.50% by mass relative to the input monomer) was dissolved was obtained as polysiloxane (R-5). The solid content concentration of the obtained polysiloxane (R-5) was 43.2% by mass. By the measurement of ²⁹ Si-NMR, the structure represented by any one of the general formula (1) to the general formula (3), and the structure represented by any one of the general formula (4) or the general formula (5) is: (A) The molar amounts of polysiloxane are 45 mol% and 0 mol%, respectively.

Synthesis Example 21 Synthesis of polysiloxane (R-6) In the same order as Synthesis Example 1, 66.32 g (0.049 mol) of HfTMS, 129.44 g (0.403 mol) of PhTMS, and 209.20 g of PGMEA were added and added to In 44.06 g of water, 0.98 g of phosphoric acid (0.50% by mass relative to the input monomer) was dissolved in phosphoric acid aqueous solution to obtain polysiloxane (R-6). The solid content concentration of the obtained polysiloxane (R-6) was 43.2% by mass. By the measurement of ²⁹ Si-NMR, the structure represented by any one of the general formula (1) to the general formula (3), and the structure represented by any one of the general formula (4) or the general formula (5) is: (A) The molar amounts of polysiloxane are 20 mol% and 0 mol%, respectively. Table 1 shows the input amount of alkoxysilane as the raw material of (A) polysiloxane obtained in Synthesis Example 1 to Synthesis Example 18.

Synthesis Example 22 Synthesis of polysiloxane (R-7) In the same order as Synthesis Example 1, 15.46 g (0.011 mol) of MTMS, 19.27 g (0.088 mol) of CFTMS, and 10.51 g (0.050 mol) of TES were added 40.01 g of PGMEA, and a phosphoric acid aqueous solution in which 0.23 g of phosphoric acid (0.50% by mass relative to the input monomer) was dissolved in 14.53 g of water to obtain polysiloxane (R-7). The solid content concentration of the obtained polysiloxane (R-6) was 43.2% by mass. By the measurement of ²⁹ Si-NMR, the structure represented by any one of the general formula (1) to the general formula (3), and the structure represented by any one of the general formula (4) or the general formula (5) is: (A) The molar amounts of polysiloxane are 0 mol% and 20 mol%, respectively. Table 1 shows the input amount of alkoxysilane as the raw material of (A) polysiloxane obtained in Synthesis Example 1 to Synthesis Example 22.

[Table 1] [Table 1]

Synthesis Example 22 Synthesis of Naphthoquinone Diazide Compound (C-1) Under a stream of dry nitrogen, 21.23 g (0.05 mol) of a compound having a phenolic hydroxyl group TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 37.62 g of 5-naphthoquinonediazidesulfonyl acid chloride ( 0.14 mol) dissolved in 450 g of 1,4-dioxane and set to room temperature. In it, 15.58 g (0.154 mol) of triethylamine mixed with 1,4-dioxane 50 g was added dropwise in such a way that the system would not become higher than 35°C. After the dropwise addition, the mixture was stirred at 30°C for 2 hours. The triethylamine salt was filtered, and the filtrate was poured into water. Thereafter, the deposited precipitate was collected by filtration. This precipitate was dried with a vacuum dryer to obtain a naphthoquinonediazide compound C-1 having the following structure.

[化14]

[Solvent replacement of metal compound particles] Solvent replacement example 1 "Sururia" 4110 solvent replacement As the metal oxide particles, the solvent of "Sururia" 4110 (trade name, manufactured by Nichiwa Catalyst Co., Ltd.) was replaced from isopropyl alcohol to PGMEA. In a 500 ml eggplant-shaped flask, put 100 g of Sururua 4110 isopropanol sol (solid content concentration is 20%) and 80 g of PGMEA, and reduce the pressure at 30°C for 30 minutes using an evaporator. To remove isopropyl alcohol (IPA). The solid content concentration of the obtained PUREA solution D-1 of Sururia 4110 was measured and found to be 20.1%.

Each evaluation of the obtained resin composition was performed by the following method.

(1) Film thickness measurement For a film formed on a silicon wafer, using Lambda Ace (Lambda Ace) STM-602 (trade name, manufactured by Dainippon Screen), the prebaked film was measured with a refractive index of 1.40, and developed The thickness of the film and the cured film.

(2) Measurement of refractive index The refractive index at 633 nm at 22° C. was measured on the obtained hardened film using a spectroscopic ellipsometer FE5000 manufactured by Otsuka Electronics Co., Ltd.

(3) Evaluation of chemical resistance The film thickness of the obtained cured film was measured by (1) film thickness, and it was set as the film thickness t1. Next, the hardened film was immersed in acetone for 5 minutes, and then heated at 100° C. for 1 minute using a hot plate (HP-1SA manufactured by Asone Co., Ltd.). After heating, the film thickness of the cured film was measured by Surfcom and set as the film thickness t2. The film thickness change rate X before and after acetone immersion was calculated by the following formula, and the chemical resistance was evaluated. The evaluation criteria are set to the following A to E.

Film thickness change rate X (%) = (t1-t2)/t1×100 A: The film thickness change rate X is X<5% B: The film thickness change rate X is 5%≦X＜15% C: The rate of film thickness change X is 15%≦X＜30% D: The film thickness change rate X is 30%≦X＜60% E: The film thickness change rate X is 60%≦X.

(4) Evaluation of crack resistance The obtained cured film was observed with a microscope to confirm the presence or absence of cracks. The evaluation criteria are set to the following A to C. A: No cracks were observed on the entire surface B: Only cracks were seen at the end of the wafer substrate C: Cracks were seen on the entire surface.

(5) Evaluation of coatability The obtained cured film was observed with a microscope to evaluate the presence or absence of foreign matter and depressions. A: No foreign objects or depressions were observed on the entire surface. B: Only foreign objects and depressions are seen in the center of the wafer. C: Foreign objects and depressions are seen on the entire surface of the wafer.

(6) Measurement of transmittance (400 nm wavelength, 1 μm conversion) The extinction coefficient of the obtained cured film at 400 nm wavelength was measured by a spectroscopic ellipsometer FE5000 manufactured by Otsuka Electronics Co., Ltd., and the light at 400 nm wavelength converted to a film thickness of 1 μm was obtained by the following formula Transmittance (%). Light transmittance = exp (-4πkt/λ) Among them, k represents the extinction coefficient, t represents the converted film thickness (μm), and λ represents the measurement wavelength (nm). In addition, in this measurement, the light transmittance converted to 1 μm is obtained, so t is 1 (μm).

(7) Resolution With respect to the obtained cured film, the square pattern at all exposures was observed, and the minimum pattern size was observed as the resolution. Set the evaluation criteria as follows. A: The minimum pattern size x is x＜15 μm B: The minimum pattern size x is 15 μm≦x＜50 μm C: The minimum pattern size x is 50 μm≦x<100 μm D: The minimum pattern size x is 100 μm≦x.

(8) Evaluation of thinning of developed film For Examples 19 to 40 and Comparative Examples 7 to 12, the amount of film thinning during development was calculated. Thinning of developed film = (film thickness of prebaked film-film thickness after developed) / film thickness of prebaked film × 100 In addition, the film thickness of the prebaked film and the film thickness after development were performed according to the method described in (1) Film thickness measurement.

Example 1 It was prepared at the ratio of the resin composition (I) in Table 2 and was mixed and stirred under a yellow lamp to prepare a uniform solution. After that, it was filtered with a 0.20 μm filter to prepare Composition 1.

Immediately after preparing Composition 1, a spin coater (1H-360S manufactured by Mikasa Co., Ltd.) was used for spin coating on a 4-inch silicon wafer, and then a heating plate (Dainippon Screen) was used. ) The SCW-636 manufactured by Co., Ltd.) was heated at 120°C for 3 minutes to produce a pre-baked film with a thickness of 1.0 μm. After that, the prebaked film was cured at 230° C. for 5 minutes using a hot plate to produce a cured film 1.

The cured film 1 was used to perform (2) measurement of refractive index, (3) evaluation of chemical resistance, (4) evaluation of crack resistance, and (5) evaluation of coating properties. The results are shown in Table 3.

Example 2 to Example 18, Comparative Example 1 to Comparative Example 7 In the same manner as the resin composition (I), Compositions 2 to 24 of the composition shown in Table 2 were prepared. Using each obtained composition, the cured film 1 was produced and evaluated in the same manner as in Example 1. Table 3 shows the evaluation results.

Example 19 It was prepared at the ratio of (I) resin composition in Table 4 and was mixed and stirred under a yellow lamp to make a uniform solution. After that, it was filtered with a 0.20 μm filter to prepare composition 25.

Immediately after preparing the composition 25, a spin coater (1H-360S manufactured by Mikasa Co., Ltd.) was spin-coated on each of a 4-inch silicon wafer and a glass substrate, and then a hot plate (Great Japan) was used. SCW-636 manufactured by Dainippon Screen Co., Ltd. was heated at 120°C for 3 minutes to prepare a pre-baked film, and (1) film thickness measurement was performed. An automatic developing device (AD-2000 manufactured by Takizawa Industries Co., Ltd.) was used for the pre-baked film, and spray development was performed in a 2.38% by mass TMAH aqueous solution for 30 seconds, followed by 30 seconds rinse with water to apply to the wafer The developed film 1 and the developed film 2 were obtained on the upper and glass substrates, respectively, and (1) film thickness measurement was performed on the developed film 1. Thereafter, the developed film 1 and the developed film 2 were cured at 230° C. for 5 minutes using a hot plate to produce a cured film 2 and a cured film 3, respectively. (1) Film thickness measurement was performed on the cured film 2.

In addition, the obtained prebaked film was exposed using an i-ray stepper (i9C manufactured by Nikon Co., Ltd.) from 50 msec to 1000 msec in units of 50 msec, and then used as described above. Developed and cured to obtain the cured film 4.

The cured film 2 was used to perform (2) refractive index measurement and (3) chemical resistance evaluation, the cured film 3 was used to perform (6) transmittance measurement, and the cured film 4 was used to perform (7) resolution evaluation. These results are shown in Table 5.

Example 20 to Example 40, Comparative Example 8 to Comparative Example 12 In the same manner as composition 25, resin composition 26 to resin composition 46 having the compositions shown in Table 4 were prepared. In the resin composition 44 to the resin composition 46, PC-5 (manufactured by Toyo Synthetic Co., Ltd.) was used as a naphthoquinonediazide compound. Using each obtained composition, the prebaked films and the cured films 2 to 4 were prepared in the same manner as in Example 19 and evaluated. Table 5 shows the evaluation results.

In addition, in the measurement of (2) refractive index and the measurement of (6) transmittance, when development was performed and the film was completely dissolved and evaluation was impossible, a cured film was produced in the same manner as in Example 1 except that development was not performed. And evaluate it.

[Table 2] [Table 2]

[Table 3] [Table 3]

[Table 4] [Table 4]

[Table 5] [Table 5]

1: substrate 2: coating 3: hardened film 4: Actinic rays 5: Mask 6: Pattern 7: Hardened film pattern

FIG. 1 is a step diagram showing a production example of a cured film using the resin composition of the embodiment of the present invention. FIG. 2 is a step diagram showing a production example of a cured film using the resin composition of the embodiment of the present invention. 3 is a step diagram showing an example of production of a cured film using the resin composition of the embodiment of the present invention.

Claims (13)

A resin composition containing (A) polysiloxane and (B) a solvent, wherein the resin composition is characterized in that the (A) polysiloxane contains at least one or more of the following general formulas (1) to The structure represented by the general formula (3), and at least one or more structures represented by the following general formula (4) to general formula (5),

Y is an alicyclic or aromatic linking group having 5 to 10 carbon atoms; R ¹ represents a single bond or an alkylene group having 1 to 4 carbon atoms, and R ² independently represents hydrogen or an alkyl group having 1 to 4 carbon atoms R ³ independently represents an organic group having 1 to 8 carbon atoms, X represents a hydrogen atom or an acid dissociable group, a represents an integer of 1 to 3, and n represents an integer of 1 to 10. The resin composition as described in item 1 of the patent application scope, wherein (A) the polysiloxane contains at least one or more structures represented by the following general formulas (6) to (8),

R ¹ represents a single bond or an alkylene group having 1 to 4 carbon atoms, R ² independently represents hydrogen or an alkyl group having 1 to 4 carbon atoms, R ³ independently represents an organic group having 1 to 8 carbon atoms, and X represents A hydrogen atom or an acid dissociable group, a represents an integer of 1 to 3, and n represents an integer of 1 to 10. The resin composition as described in item 1 or item 2 of the patent application scope, wherein (A) the polysiloxane skeleton has 5 mol% to 50 mol% of the general formula (4) to general formula (5) At least one or more of the structures shown. The resin composition according to any one of claims 1 to 3, wherein (A) the polysiloxane contains at least one or more of the following general formulas (9) to (11) Structure,

R ² independently represents hydrogen or a C 1-4 alkyl group, R ³ independently represents a C 1-8 organic group, and R ⁴ represents a C 1-10 organic group having a fluorine group. The resin composition according to any one of items 1 to 4 of the patent application scope, which contains (C) a naphthoquinone diazide compound. The resin composition as described in item 5 of the patent application scope, wherein (C) the naphthoquinonediazide compound is 1 to 15 parts by mass relative to (A) 100 parts by mass of polysiloxane. The resin composition according to any one of claims 1 to 6, which contains one or more aromatic hydrocarbon-based (B) solvents having heteroatoms. The resin composition according to any one of the first to seventh patent application ranges, which contains (D) metal compound particles. The resin composition as described in item 8 of the patent application, wherein the (D) metal compound particles are silica particles. A cured film, which is a cured film of the resin composition according to any one of claims 1 to 9. A solid-state imaging element includes a cured film as described in item 10 of the patent application. An organic electroluminescent element including the cured film as described in item 10 of the patent application. A display device includes a cured film as described in item 10 of the patent application.

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