CN112368336A

CN112368336A - Resin composition and cured film thereof

Info

Publication number: CN112368336A
Application number: CN201980040304.1A
Authority: CN
Inventors: 日比野利保; 的羽良典; 诹访充史; 藤井真实
Original assignee: Toray Industries Inc
Current assignee: Toray Industries Inc
Priority date: 2018-08-31
Filing date: 2019-08-22
Publication date: 2021-02-12
Also published as: WO2020045214A1; JP7327163B2; TW202020024A; JPWO2020045214A1; KR20210052431A

Abstract

Provided is a resin composition having a low refractive index, excellent heat resistance, excellent chemical resistance, excellent coatability, and excellent pattern processability. A resin composition characterized by containing (A) a polysiloxane and (B) a solvent, wherein the polysiloxane (A) contains a structure represented by any one of specific general formulae (1) to (3) and a structure represented by any one of specific general formulae (4) or (5).

Description

Resin composition and cured film thereof

Technical Field

The present invention relates to a resin composition, a cured film thereof, and a solid-state imaging element, an organic EL element, and a display device provided with the same.

Background

In recent years, liquid crystal displays, organic EL televisions, and the like have been narrowed and thinned by introducing light from a side surface using an LED light source or the like. In particular, in recent years, as a new display device, a transparent liquid crystal display has been studied and developed by various companies. In this case, in order to efficiently guide light incident from the side surface in a certain direction, a novel material having a low refractive index, high transparency, excellent chemical resistance to chemicals used in a processing process, and good heat resistance without causing deterioration such as yellowing in a heating process is required. As a high-transparency and low-refractive index material, a silicone material is known as shown in

patent documents

1,2, and 3, and is widely used in liquid crystal displays, touch panels, solid-state imaging devices, and the like. However, in these materials, addition of a large amount of a fluorine-containing siloxane compound and addition of particles such as silica nanoparticles and hollow silica are carried out in order to obtain a low refractive index, and in the case of addition of a large amount of a fluorine-containing siloxane compound, it is inevitable to decrease chemical resistance and heat resistance, and in the case of addition of particles, fine irregularities on the surface and edges are inevitable when processing is carried out in a pattern. There is a strong demand for a low refractive index material having excellent heat resistance and chemical resistance without adding particles.

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. 2007-119744

Patent document 2: japanese patent laid-open publication No. 2013-014680

Patent document 3: japanese patent laid-open publication No. 2015-129908

Disclosure of Invention

Problems to be solved by the invention

In order to solve the above-described problems, an object of the present invention is to provide a resin composition which is a low refractive index material having excellent heat resistance and chemical resistance and also excellent pattern processability without adding particles.

Means for solving the problems

That is, the present invention is a resin composition containing (a) polysiloxane and (B) a solvent, wherein the (a) polysiloxane contains at least one of the structures represented by the following general formulae (1) to (3) and at least one of the structures represented by the following general formulae (4) to (5).

[ chemical formula 1]

(Y is an alicyclic or aromatic linking group having 5 to 10 carbon atoms R¹Represents a single bond or an alkylene group having 1 to 4 carbon atoms, R²Each independently represents hydrogen or an alkyl group having 1 to 4 carbon atoms, R³Each 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. )

ADVANTAGEOUS EFFECTS OF INVENTION

The present invention can provide a resin composition having a low refractive index, excellent heat resistance, excellent chemical resistance, excellent coatability, and excellent pattern processability.

Drawings

FIG. 1 is a process diagram showing an example of producing a cured film using a resin composition according to an embodiment of the present invention.

FIG. 2 is a process diagram showing an example of producing a cured film using the resin composition according to the embodiment of the present invention.

FIG. 3 is a process diagram showing an example of producing a cured film using the resin composition according to the embodiment of the present invention.

Detailed Description

The present invention will be described in detail below.

< A polysiloxane >

The resin composition of the present invention contains a polysiloxane containing at least one of the structures represented by the following general formulae (1) to (3) and at least one of the structures represented by the following general formulae (4) to (5). By including at least one of the structures shown in (1) to (3) and at least one of the structures shown in (4) to (5) in the polysiloxane, the alkali solubility of the polysiloxane can be improved, and the alkali dissolution suppressing effect by the interaction between the photosensitizer and silanol is exhibited, so that the contrast between exposed portions and unexposed portions before and after development can be improved, and a film with excellent resolution can be obtained.

[ chemical formula 2]

(Y is an alicyclic or aromatic linking group having 5 to 10 carbon atoms R¹Represents a single bond or an alkylene group having 1 to 4 carbon atoms, R²Each independently represents hydrogen or an alkyl group having 1 to 4 carbon atoms, R³Each independently represents an organic group having 1 to 8 carbon atoms, an X hydrogen atom or an acid-dissociable group, a represents an integer of 1 to 3, and n represents an integer of 1 to 10. )

In the structures represented by the general formulae (1) to (3), Y is an alicyclic or aromatic linking group having 5 to 10 carbon atoms. R¹Represents a single bond or an alkylene group having 1 to 4 carbon atoms, R²Each independently represents hydrogen or an alkyl group having 1 to 4 carbon atoms, R³Each 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.

As R¹Specific examples of the alkylene group include a methylene group, an ethylene group, an n-propenyl group, an isopropenyl group, an n-butenyl group, and a tert-butenyl group.

As R²Specific examples of the alkyl group of (3) include a methyl group, an ethyl group and an n-propyl groupIsopropyl, n-butyl, isobutoxy, t-butyl, and the like.

As R³Examples of the organic group of (2) include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclohexyl, phenyl and naphthyl groups.

X is a hydrogen atom or an acid-dissociable group, and when a plurality of X are present, X may be the same or different from each other. Here, the acid-dissociable group is a group that dissociates in the presence of an acid to form a polar group. The acid dissociable group has an acetal structure or a ketal structure which is relatively stable to alkali, and these are dissociated by the action of an acid. Specific examples thereof include, but are not limited to, alkoxycarbonyl, acetal, silyl, and acyl groups. Examples of the alkoxycarbonyl group include a tert-butoxycarbonyl group, a tert-pentyloxycarbonyl group, a methoxycarbonyl group, an ethoxycarbonyl group, and an isopropoxycarbonyl group. Examples of the acetal group include a methoxymethyl group, an ethoxyethyl group, a butoxyethyl group, a cyclohexyloxyethyl group, a benzyloxyethyl group, a phenethyloxyethyl group, an ethoxypropyl group, a benzyloxypropyl group, a phenethyloxypropyl group, an ethoxybutyl group, and an ethoxyisobutyl group. Examples of the silyl group include a trimethylsilyl group, an ethyldimethylsilyl group, a methyldiethylsilyl group, a triethylsilyl group, an isopropyldimethylsilyl group, a methyldiisopropylsilyl group, a triisopropylsilyl group, a tert-butyldimethylsilyl group, a methyl di-tert-butylsilyl group, a tri-tert-butylsilyl group, a phenyldimethylsilyl group, a methyldiphenylsilyl group, and a triphenylsilyl group. Examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, a heptanoyl group, a hexanoyl group, a pentanoyl group, a pivaloyl group, an isovaleryl group, a lauroyl group, a myristoyl group, a palmitoyl group, a stearoyl group, an oxalyl group, a malonyl group, a succinyl group, a glutaryl group, an adipoyl group, a piperonyl group, an suberoyl group, a azeloyl group, a sebacoyl group, an acryloyl group, a propioloyl group, a methacryloyl group, a crotonyl group, an oleoyl group, a maleoyl group, a fumaroyl group, a mesoconyl group, a camphoracyl group, a benzoyl group, a phthaloyl group, an isophthaloyl group, a terephthaloyl group, a naphthoyl group, a toluoyl group, a hydrogenated atoyl group, an atropic acyl group, a cinnamoyl group. These acid-dissociable groups may be those in which some or all of the hydrogen atoms are replaced with fluorine atoms. These acid-dissociable groups may be introduced into the polysiloxane compound (a) alone or in combination.

The structures represented by the general formulae (1) to (3) are the same, but may be described as (1 ') to (3') below.

[ chemical formula 2-1]

The structures represented by the general formulae (4) and (5) are the same, but may be described as (4 ') and (5') below.

[ chemical formula 2-2]

The structures represented by the general formulae (1) to (3) are preferably structures represented by the following general formulae (6) to (8). With the following structure, the compatibility of the photosensitizer with siloxane is improved, and therefore, the film can be prevented from clouding due to phase separation during thermal curing, and a cured film can be formed without impairing transparency.

[ chemical formula 3]

In a specific example of the moiety represented by the above general formula, a is an integer of 1 to 3, and a is preferably 1 to 2, and more preferably 1, from the viewpoint of solubility and chemical resistance.

Specific examples thereof are represented by general formulae, and the following structures are given.

[ chemical formula 4]

Wherein represents a group represented by¹A direct bond. R¹The single bond represents a bond directly bonded to a silicon atom. By containing these structures, a composition having a low refractive index, excellent coatability, and excellent pattern processability can be obtained. These structures are preferably contained in the polysiloxane (A) by 5 to 50 mol%, more preferably 5 to 30 mol%. The content ratio of the organosilane units represented by the above general formulae (1) to (3) can be measured²⁹Si-NMR was determined from the ratio of the peak area of Si to which the aromatic group is bonded to the peak area of Si derived from the organosilane unit to which the aromatic group is not bonded.

Further, as the organosilane unit represented by the general formulae (1) to (3), an organosilane unit can be used¹H-NMR、¹⁹F-NMR、¹³C-NMR, IR, TOF-MS, etc.

In addition, in the structure represented by the general formula (4) or (5), R in the formula²Each 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 (5) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, tetra-tert-butoxysilane, methyl silicate 51 (manufactured by Hibiscus chemical Co., Ltd.), M silicate 51, silicate 40, silicate 45 (manufactured by Moore chemical Co., Ltd.), methyl silicate 51, methyl silicate 53A, and ethyl silicate 48 (manufactured by COLCOAT CO., LTD.). By containing these organosilanes, chemical resistance can be improved. The preferable content is 5 to 50 mol%, more preferably 5 to 30 mol% in the polysiloxane as a hydrolysis condensation product. The content ratio of the organosilane unit represented by the general formula (4) or (5) can be determined by combination¹H-NMR、¹³C-NMR、²⁹Si-NMR, IR, TOF-MS, elemental analysis, ash content measurement, and the like.

The polysiloxane (a) may have structures represented by the following general formulae (9) to (11).

[ chemical formula 5]

(R²Each independently represents hydrogen or an alkyl group having 1 to 4 carbon atoms, R³Each independently represents an organic group having 1 to 8 carbon atoms, R⁴Represents an organic group having 1 to 10 carbon atoms and having a fluorine group. )

Specific examples of the fluorine-containing silane compound having the structure of the general formulae (9) to (11) include trifluoroethyl trimethoxysilane, trifluoroethyl triethoxysilane, trifluoroethyl triisopropoxysilane, trifluoropropyl trimethoxysilane, trifluoropropyl triethoxysilane, trifluoropropyl triisopropoxysilane, heptadecafluorodecyl trimethoxysilane, heptadecafluorodecyl triethoxysilane, heptadecafluorodecyl triisopropoxysilane, tridecafluorooctyl triethoxysilane, tridecafluorooctyl trimethoxysilane, tridecafluorooctyl triisopropoxysilane, trifluoroethyl methyldimethoxysilane, trifluoroethyl methyldiethoxysilane, trifluoroethyl methyldiisopropoxysilane, trifluoropropyl methyldimethoxysilane, trifluoropropyl methyldiethoxysilane, trifluoropropyl methyldiisopropyloxysilane, heptadecafluorodecyl methyldimethoxysilane, heptadecafluorodecyl triethoxysilane, heptadecafluoro, Heptadecafluorodecylmethyldiethoxysilane, heptadecafluorodecylmethyldiisopropoxysilane, tridecafluorooctylmethyldimethoxysilane, tridecafluorooctylmethyldiethoxysilane, tridecafluorooctylmethyldiisopropoxysilane, trifluoroethylethyldimethoxysilane, trifluoroethylethyldiethoxysilane, trifluoropropylethyldimethoxysilane, trifluoropropylethyldiethoxysilane, trifluoropropylethyldiisopropoxysilane, heptadecafluorodecylethyldiethoxysilane, heptadecafluorodecylethyldiisopropoxysilane, tridecafluorooctylethyldiethoxysilane, tridecafluorooctylethyldimethoxysilane, tridecafluorooctylethyldiethoxysilane, etc. More than 2 of these may be used.

Among these, trifluoroethyl trimethoxysilane, trifluoroethyl triethoxysilane, trifluoroethyl triisopropoxysilane, trifluoropropyl trimethoxysilane, trifluoropropyl triethoxysilane, trifluoropropyl triisopropoxysilane, heptadecafluorodecyl trimethoxysilane, heptadecafluorodecyl triethoxysilane, heptadecafluorodecyl triisopropoxysilane, tridecafluorooctyl triethoxysilane, tridecafluorooctyl trimethoxysilane, tridecafluorooctyl triisopropoxysilane are preferably used from the viewpoint of chemical resistance. In addition, trifluoroethyl trimethoxysilane, trifluoropropyl trimethoxysilane, heptadecafluorodecyl trimethoxysilane, and tridecafluorooctyl trimethoxysilane are particularly preferably used from the viewpoint of forming a uniform coating film. The content of the polysiloxane (a) is preferably 5 to 50 mol%, more preferably 10 to 40 mol%, from the viewpoint of chemical resistance.

In the polysiloxane (a) used in the resin composition of the present invention, in addition to the above-mentioned organosilane compound, another organosilane compound may be copolymerized. Specific examples of the copolymerizable organosilane compound include methyltrimethoxysilane, methyltriethoxysilane, methyltris (methoxyethoxy) silane, methyltripropoxysilane, methyltriisopropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (2 aminoethyl) -3-aminopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3- (N, N-glycidyl) aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-hydroxysilane, and the like, Gamma-aminopropyltriethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane, beta-cyanoethyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, alpha-glycidoxyethyltrimethoxysilane, alpha-glycidoxyethyltriethoxysilane, beta-glycidoxypropyltrimethoxysilane, beta-glycidoxypropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, gamma-glycidoxypropyltripropoxysilane, gamma-glycidoxypropyltriisopropoxysilane, gamma-glycidoxypropyltributoxysilane, gamma-glycidoxypropyltri (methoxyethoxy) silane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxyethyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxyethyl-trimethoxysilane, Alpha-glycidoxybutyltrimethoxysilane, beta-glycidoxybutyltrimethoxysilane, gamma-glycidoxybutyltrimethoxysilane, sigma-glycidoxybutyltriethoxysilane, (3, 4-epoxycyclohexyl) methyltrimethoxysilane, (3, 4-epoxycyclohexyl) methyltriethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltripropoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltributoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, beta-glycidoxybutyltrimethoxysilane, gamma-glycidoxybutyltrimethoxy, 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, dimethyldiethoxysilane, gamma-glycidoxypropylmethyldimethoxysilane, gamma-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, dimethyldimethoxysilane, glycidoxypropylmethyldimethoxysilane, dimethyldimethoxysilane, dimethyl, Glycidoxymethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, α -glycidoxyethylmethyldimethoxysilane, α -glycidoxyethylmethyldiethoxysilane, β -glycidoxyethylmethyldimethoxysilane, β -glycidoxyethylmethyldiethoxysilane, α -glycidoxypropylmethyldimethoxysilane, α -glycidoxypropylmethyldiethoxysilane, β -glycidoxypropylmethyldimethoxysilane, β -glycidoxypropylmethyldiethoxysilane, γ -glycidoxypropylmethyldimethoxysilane, γ -glycidoxypropylmethyldiethoxysilane, γ -glycidoxypropylmethyldipropaxysilane, β -glycidoxypropylmethyldibutoxysilane, β -glycidoxypropylmethyldibu, Gamma-glycidoxypropylmethyldi (methoxyethoxy) silane, gamma-glycidoxypropylethyldimethoxysilane, gamma-glycidoxypropylethyldiethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropylmethyldiethoxysilane, cyclohexylmethyldimethoxysilane, octadecylmethyldimethoxysilane, tetramethoxysilane, tetraethoxysilane, gamma-acryloylpropyltrimethoxysilane, gamma-acryloylpropyltriethoxysilane, gamma-acryloylpropyltri (methoxyethoxy) silane, gamma-methacryloylpropyltrimethoxysilane, gamma-methacryloylpropyltriethoxysilane, gamma-methacryloylpropyltri (methoxyethoxy) silane, gamma-methacryloylpropylmethyldimethoxysilane, gamma-glycidyloxypropylmethyldimethoxysilane, gamma-glycidyloxyethyldimethoxysilane, gamma-glycidyloxypropylmethyldimethoxysilane, gamma, Gamma-methacryloxypropylmethyldiethoxysilane, gamma-acrylopropylmethyldimethoxysilane, gamma-acrylopropylmethyldiethoxysilane, gamma-methacryloxypropyl (methoxyethoxy) silane, and the like.

These may be used in 2 or more kinds. Further, an organosilane compound having a hydrophilic group as a raw material of polysiloxane may be copolymerized as necessary. The organosilane compound having a hydrophilic group is preferably an organosilane compound having a carboxylic acid structure or an organosilane compound having a carboxylic acid anhydride structure, and more preferably an organosilane compound having a carboxylic acid anhydride structure.

Specific examples of the organic silane compound having a carboxylic anhydride structure include organic silane compounds represented by any one of the following general formulae (12) to (14). These may be used in 2 or more kinds.

[ chemical formula 6]

In the general formulae (12) to (14), R⁵～R⁷、R⁹～R¹¹And R¹³～R¹⁵Represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a phenyl group, a phenoxy group or an alkylcarbonyloxy group having 2 to 6 carbon atoms. R⁸、R¹²And R¹⁶Represents a single bond, or a chain 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, a carbonyl group, an ether group, an ester group, an amide group, an aromatic group, or a 2-valent group having any of these groups. These groups may be substituted. h and k represent an integer of 0 to 3.

As R⁸、R¹²And R¹⁶Specific examples of (1) include₂H₄-、-C₃H₆-、-C₄H₈-、-O-、-C₃H₆OCH₂CH(OH)CH₂O₂C-、-CO-、-CO₂-, -CONH-, the organic groups mentioned below, and the like.

[ chemical formula 7]

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

Specific examples of the organosilane compound represented by the general formula (13) include 3-trimethoxysilylpropylcyclohexylanhydride.

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, more preferably 20% by mass or more, relative to the total amount of solid components excluding the solvent. Further, 80 mass% or less is more preferable. When the siloxane compound is contained in this range, the transmittance and crack resistance of the coating film can be further improved.

The hydrolysis reaction is preferably carried out by adding an acid catalyst and water to the alkoxysilane compound in a solvent for 1 to 180 minutes and then reacting the mixture at room temperature to 110 ℃ for 1 to 180 minutes. By performing the hydrolysis reaction under such conditions, a rapid reaction can be suppressed. The reaction temperature is more preferably 40 to 105 ℃.

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

For example, the acid concentration, the reaction temperature, the reaction time, and the like are set in consideration of the scale of the reaction, the size of the reaction vessel, the shape of the reaction vessel, and the like, whereby physical properties suitable for the intended use can be obtained.

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 an acid anhydride thereof, and an acid catalyst such as an ion exchange resin. Particularly preferred is the use of acidic aqueous solutions of 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 further preferably 10 parts by mass or less, and more preferably 5 parts by mass or less, based on 100 parts by mass of the entire alkoxysilane compound used in the hydrolysis reaction. Here, the total alkoxysilane compound amount means an amount including all of the alkoxysilane compound, its hydrolysate, and its condensate, and the same applies hereinafter. The hydrolysis proceeds smoothly by setting the amount of the acid catalyst to 0.05 parts by mass or more, and the control of the hydrolysis reaction becomes easy by setting the amount to 10 parts by mass or less.

The weight average molecular weight (Mw) of the polysiloxane (a) used in the resin composition of the present invention is not particularly limited, and is preferably 1,000 or more, more preferably 2,000 or more, in terms of polystyrene measured by Gel Permeation Chromatography (GPC). Further, it is preferably 100,000 or less, and more preferably 50,000 or less. By setting Mw in the above range, good coating characteristics can be obtained, and solubility in a developer during pattern formation is also good.

The content of the polysiloxane (a) in the resin composition of the present invention is not particularly limited, and may be arbitrarily selected depending on the desired film thickness and application, and is usually 5 to 80% by mass in the resin composition. In addition, the content is preferably 5 to 50 mass%, more preferably 20 to 40 mass% in the solid content.

As water used in the hydrolysis reaction, ion-exchanged water is preferred. The amount of water is arbitrarily selected, and is preferably in the range of 1.0 to 4.0 moles per 1 mole of the alkoxysilane compound.

In addition, from the viewpoint of storage stability of the composition, it is preferable that the polysiloxane solution after hydrolysis and partial condensation does not contain the catalyst, and the catalyst can be removed as necessary. The removal method is not particularly limited, and water washing and/or treatment with an ion exchange resin is preferred in terms of ease of operation and removability. The water washing method comprises the following steps: after the polysiloxane solution is diluted with an appropriate hydrophobic solvent, the organic layer obtained by washing with water several times is concentrated with an evaporator or the like. Treatment with an ion exchange resin is a method of contacting the polysiloxane solution with a suitable ion exchange resin.

When the polysiloxane (a) used in the resin composition of the present invention is a compound obtained by hydrolyzing an organic silane compound derived from any one of the above general formulae (1) to (3), an organic silane compound derived from any one of the above general formulae (4) or (5), and preferably an organic silane compound derived from any one of the above general formulae (9) to (11) in the presence of metal compound particles described later and condensing the hydrolysate, the refractive index and hardness of the cured film are further improved. This is considered to be because: by polymerizing the polysiloxane in the presence of the metal compound particles, chemical bonding (covalent bonding) occurs between at least a part of the polysiloxane and the metal compound particles, and the metal compound particles are uniformly dispersed, thereby improving the storage stability of the coating liquid and the homogeneity of the cured film. The refractive index of the cured film obtained can be adjusted by the type of the metal compound particles. As the metal compound particles, those exemplified as metal compound particles described later can be used.

< solvent (B) >

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, an aromatic hydrocarbon solvent containing 1 or more kinds of hetero atoms is preferable. Although the aromatic hydrocarbon solvent having a hetero atom has high polarity, the solubility of the organic compound having a rigid skeleton such as naphthoquinone diazide is high, and therefore, the siloxane and naphthoquinone diazide interact with each other molecularly, and in the evaluation of the photosensitivity of the coating film, the reduction of the development film can be suppressed, and the contrast between the unexposed portion and the exposed portion can be improved. In addition, in order to improve the solvent handling, preferably at 23 degrees C, 1 atmospheric pressure liquid. If the melting point is higher than this, heating is necessary for use, and the solvent becomes difficult to handle. The boiling point of the solvent is preferably 100 ℃ to 300 ℃ and more preferably 120 ℃ to 250 ℃. By setting the boiling point to 100 ℃ or higher, the volatility of the solvent is appropriately suppressed, the leveling property during coating is improved, and a uniform coating film is easily formed. Further, by setting the boiling point to 300 ℃ or lower, the solvent is less likely to remain after the heat curing of the film, and the outgassing of the cured film can be reduced. Specific examples of the aromatic hydrocarbon solvent having a hetero atom include benzyl alcohol, 2-methylbenzyl alcohol, 3-methylbenzyl alcohol, 4-isopropylbenzyl alcohol, 1-phenylethyl alcohol, 2-phenyl-2-propanol, 2-ethylbenzyl alcohol, 3-ethylbenzyl alcohol, 4-ethylbenzyl alcohol, benzyl ether, 1, 2-dimethoxybenzene, 1, 3-dimethoxybenzene, 1, 4-dimethoxybenzene, phenyl ether, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, dibenzyl ether, methyl benzoate, ethyl benzoate, and 1, 4-bis (methoxymethyl) benzene.

The content of the solvent is preferably 10 to 50% by mass, and more preferably 20 to 40% by mass, based on the total amount of the solvent in the resin composition. When the content is 50% by mass or less, the drying property when the resin composition is applied and dried is improved. Further, when the content is 10% by mass or more, the compatibility between the siloxane and the photosensitizer is improved, and the coatability is improved.

Further, as a preferable solvent (B) used in the resin composition of the present invention, specific examples thereof include ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol mono-t-butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol dibutyl ether; acetic acid esters such as 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, butyl lactate, ethyl acetoacetate, methyl acetoacetate, propyl acetoacetate, butyl acetoacetate, and benzyl acetoacetate; ketones such as acetylacetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, cyclopentanone, and 2-heptanone; alcohols such as methanol, ethanol, propanol, butanol, isobutyl alcohol, amyl alcohol, 4-methyl-2-amyl alcohol, 3-methyl-2-butanol, 3-methyl-3-methoxy-1-butanol, diacetone alcohol and the like; aromatic hydrocarbons such as toluene and xylene; and gamma-butyrolactone, N-methylpyrrolidone, and the like. These may 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-t-butyl ether, diacetone alcohol, γ -butyrolactone, ethyl lactate, and the like. These may be used alone or in combination of 2 or more.

The content of the total solvent in the resin composition of the present invention is preferably in the range of 100 parts by mass to 9900 parts by mass, and more preferably in the range of 100 parts by mass to 5000 parts by mass, based on 100 parts by mass of the total alkoxysilane compound content.

< C) naphthoquinone diazide Compound >

The resin composition of the present invention preferably contains (C) a naphthoquinone diazide compound. The resin composition containing a naphthoquinone diazide compound forms a positive type in which exposed portions are removed by a developer. The naphthoquinone diazide compound to be used is not particularly limited, but is preferably a compound in which naphthoquinone diazide sulfonic acid is ester-bonded to a compound having a phenolic hydroxyl group, and a compound in which each of the ortho-position and the para-position of the phenolic hydroxyl group of the compound is independently hydrogen or a substituent represented by the general formula (15) can be used.

[ chemical formula 8]

In the formula, R¹⁷、R¹⁸、R¹⁹Each independently represents any one of an alkyl group having 1 to 10 carbon atoms, a carboxyl group, a phenyl group and a substituted phenyl group. In addition, can be represented by R¹⁷、R¹⁸、R¹⁹Forming a ring. The alkyl group may be unsubstituted or substituted, and may be selected according to the characteristics of the composition. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-hexyl group, a cyclohexyl group, an n-heptyl group, an n-octyl group, a trifluoromethyl group and a 2-carboxyethyl group. Examples of the substituent on the phenyl group include a hydroxyl group and a methoxy group. In addition, as represented by R¹⁷、R¹⁸、R¹⁹Specific examples of the ring-forming include cyclopentane, cyclohexane, adamantane, and fluorene rings.

When the ortho-position and the para-position of the phenolic hydroxyl group are other than the above groups, for example, methyl groups, oxidative decomposition occurs by heat curing to form a conjugated compound represented by a quinoid structure, and the cured film is colored to deteriorate colorless transparency. Note that these naphthoquinone diazide compounds can be synthesized by a known esterification reaction of a compound having a phenolic hydroxyl group with naphthoquinone diazide sulfonyl chloride.

Specific examples of the compound having a phenolic hydroxyl group include the following compounds (all manufactured by national chemical industry Co., Ltd.).

[ chemical formula 9]

[ chemical formula 10]

As the naphthoquinone diazide sulfonyl chloride as the raw material, 4-naphthoquinone diazide sulfonyl chloride or 5-naphthoquinone diazide sulfonyl chloride may be used. The 4-naphthoquinone diazide sulfonate compound has absorption in the i-line (wavelength 365nm) region, and is therefore suitable for i-line exposure. In addition, the 5-naphthoquinone diazide sulfonate compound has absorption in a wide range of wavelength region, and is therefore suitable for exposure at a wide range of wavelength. The 4-naphthoquinone diazide sulfonate compound and the 5-naphthoquinone diazide sulfonate compound are preferably selected according to the wavelength of exposure. The 4-naphthoquinone diazide sulfonate compound and the 5-naphthoquinone diazide sulfonate compound may be used in combination.

Examples of the naphthoquinone diazide compound preferably used in the present invention include compounds represented by the following general formula (16).

[ chemical formula 11]

In the formula, R²⁰Represents hydrogen or an alkyl group selected from the group consisting of 1 to 8 carbon atoms. R²¹、R²²、R²³Represents any one of a hydrogen atom, an alkyl group selected from the group consisting of 1 to 8 carbon atoms, an alkoxy group, a carboxyl group and an ester group. Each R²¹、R²²、R²³May be the same or different. Q represents any one of a 5-naphthoquinonediazidosulfonyl group and a hydrogen atom, and Q is not all a hydrogen atom. b. c, d, alpha and beta represent integers of 0-4. Wherein alpha + beta is more than or equal to 3. By using the naphthoquinone diazide compound represented by the general formula (16), sensitivity and resolution in pattern processing can be improved.

The amount of the naphthoquinone diazide compound to be added is not particularly limited, but is preferably 1 to 30 parts by mass, and more preferably 1 to 15 parts by mass, based on 100 parts by mass of the resin (polysiloxane). When the amount of the naphthoquinone diazide compound added is less than 1 part by mass, the solubility contrast between the exposed portion and the unexposed portion is too low, and thus a practically sufficient photosensitivity cannot be exhibited. In addition, in order to obtain a better dissolution contrast, it is preferably 5 parts by mass or more. On the other hand, when the amount of the naphthoquinone diazide compound added is more than 30 parts by mass, whitening of a coating film due to deterioration in compatibility between the polysiloxane and the naphthoquinone diazide compound or coloring due to decomposition of the naphthoquinone diazide compound occurring at the time of heat curing may be conspicuous, and thus colorless transparency of the cured film may be lowered. Further, in order to obtain a highly transparent film, it is preferably 15 parts by mass or less.

< metal compound particles >

In the present invention, metal compound particles are preferably contained. The metal compound particles are not particularly limited, and preferably contain (D) silica particles from the viewpoint of adjusting the refractive index. From the viewpoint of compatibility, the composite silicone resin with (D) silica particles is preferably prepared as follows: a silane compound having a structure derived from any one of the general formulae (1) to (3) and a silane compound having a structure derived from the general formulae (4) and (5) are hydrolyzed in the presence of (D) silica particles and (B) a solvent, and then subjected to a condensation reaction. (D) The number average particle diameter of the silica particles is preferably 1 to 200 nm. The number average particle diameter is more preferably 1 to 120nm in order to obtain a cured film having high visible light transmittance. In the case of hollow silica particles, the number average particle diameter is more preferably 30 to 100 nm. When the refractive index is 1nm or more, the low refractive index is sufficiently high, and when the refractive index is 200nm or less, reflection is sufficiently suppressed, and the film hardness is sufficiently high. (D) The number average particle diameter of the silica particles can be measured by a gas adsorption method, a dynamic light scattering method, a small-angle X-ray scattering method, a method of directly measuring the particle diameter by a transmission electron microscope or a scanning electron microscope, or the like. The number average particle diameter of the particles in the present invention is a value measured by a dynamic light scattering method.

Examples of the silica particles (D) used in the present invention include silica particles having a porous and/or hollow interior and silica particles having no porous and no hollow interior. Among these silica particles (D), silica particles having a porous and/or hollow interior are preferable in terms of reducing the refractive index of the coating film. Silica particles which are not porous and have no hollow inside have a small effect of reducing the refractive index because the refractive index of the particles themselves is 1.45 to 1.5. On the other hand, since the silica particles having a porous and/or hollow interior have a refractive index of 1.2 to 1.4, the effect of reducing the refractive index is large. That is, silica particles having a porous and/or hollow interior are preferably used in order to impart excellent hardness and low refractive index properties.

The silica particles having a hollow interior preferably used in the present invention mean silica particles having a hollow portion surrounded by a shell. The silica particles having a porous interior used in the present invention are silica particles having a plurality of hollow portions on the surface and inside of the particles. Among these, silica particles having a hollow structure and high strength of the particles themselves are preferable in view of the hardness of the transparent coating. (D) The refractive index of the silica particles is preferably 1.2 to 1.4, more preferably 1.2 to 1.35. These (D) silica particles can be produced by the methods disclosed in japanese patent No. 3272111 and japanese patent application laid-open No. 2001-233611. Examples of the (D) silica particles include those disclosed in japanese patent application laid-open No. 2001-233611 and those generally commercially available as disclosed in japanese patent No. 3272111.

(D) The refractive index of the silica particles can be measured by the following method. A sample of a mixed solution of the matrix resin having the content of the silica particles (D) adjusted to 10% in solid content concentration of 0% by mass, 20% by mass, 30% by mass, 40% by mass, and 50% by mass and the silica particles (D) was prepared, and the sample was coated on a silicon wafer so as to have a thickness of 0.3 to 1.0 μm using a spin coater, followed by heating and drying for 5 minutes using a hot plate at 200 ℃. Then, the refractive index at a wavelength of 633nm is determined using, for example, an ellipsometer (available from Otsuka Denshi Co., Ltd.), and the value of 100% by mass of the silica particles (D) can be determined by extrapolation.

When silica particles having a porous and/or hollow interior are introduced into the coating material, the refractive index of the film obtained from the coating material can be optimized, and the hardness of the film can be improved, which is preferable.

Examples of the silica particles which are not porous and have no hollow inside include: IPA-ST having a particle size of 12nm and using isopropanol as a dispersant, MIBK-ST having a particle size of 12nm and using methyl isobutyl ketone as a dispersant, IPA-ST-L having a particle size of 45nm and using isopropanol as a dispersant, IPA-ST-ZL having a particle size of 100nm and using isopropanol as a dispersant (trade name, manufactured by Nissan chemical industries, Ltd.), OSCAL 101 having a particle size of 12nm and using gamma-butyrolactone as a dispersant, OSCAL 105 having a particle size of 60nm and using gamma-butyrolactone as a dispersant, OSCAL 106 having a particle size of 120nm and using diacetone alcohol as a dispersant (trade name, manufactured by Nissan catalytic chemical industries, Co., Ltd.). Whether or not the hollow is present can be confirmed from the particle cross-sectional image by a TEM (scanning electron microscope) photograph.

Examples of commercially available silica particles (D) include "OSCAL" (manufactured by Nissan catalytic chemical Co., Ltd.) of an organic silica sol, colloidal silica "SNOWTEX", an organic silica sol (manufactured by Nissan chemical Co., Ltd.), high-purity colloidal silica, and a high-purity organosol "Quartron" (manufactured by Hibiscus chemical Co., Ltd.).

In addition, in order to obtain a cured film having a low refractive index, it is preferable to contain hollow silica particles. The presence or absence of hollowing can be confirmed from a cross-sectional image of the particle by a TEM (scanning electron microscope) photograph. The content of the silica particles (D) is not particularly limited, and may be appropriately used according to the application, and is usually about 1 to 80 mass% of the total solid content of the silicone resin composition.

The resin composition of the present invention is obtained by mixing at least the aforementioned (a) polysiloxane, (B) solvent, and preferably (C) naphthoquinone diazide compound. At this time, dilution with an arbitrary solvent is possible. The mixing temperature is not particularly limited, but is preferably in the range of 5 to 50 ℃ from the viewpoint of ease of operation.

The silicone resin composition of the present invention may contain various curing agents for accelerating or facilitating curing of the resin composition. Specific examples of the curing agent include nitrogen-containing organic compounds, silicone resin curing agents, various metal alkoxides, various metal chelates, isocyanate compounds and polymers thereof, methylolated melamine derivatives, methylolated urea derivatives, and the like, and these may contain one and/or 2 or more species. Among them, a metal chelate compound is preferably used in view of transparency of the coating film, stability of the curing agent, and the like.

Examples of the metal chelate compound include a titanium chelate compound, a zirconium chelate compound, an aluminum chelate compound and a magnesium chelate compound. These metal chelates can be easily obtained by reacting a chelating agent with a metal alkoxide. Examples of the chelating agent include β -diketones such as acetylacetone, benzoylacetone, and dibenzoylmethane; and beta-keto esters such as ethyl acetoacetate and ethyl benzoylacetate. Preferred specific examples of the metal chelate compound include aluminum chelate compounds such as ethyl acetoacetate aluminum diisopropyloxide, tris (ethylacetoacetate) aluminum, alkyl acetoacetate aluminum diisopropyloxide, monoacetoacetate bis (ethylacetoacetate) aluminum, tris (acetylacetonate) aluminum, and magnesium chelate compounds such as ethyl acetoacetate magnesium monoisopropoxide, bis (ethylacetoacetate) magnesium, alkyl acetoacetate magnesium monoisopropoxide, and bis (acetylacetonate) magnesium. The content of the curing agent is preferably 0.1 to 10% by mass, more preferably 0.5 to 6% by mass, in the solid content of the silicone resin composition.

Since the curing of the polysiloxane is accelerated by an acid, a curing catalyst such as a thermal acid generator may be contained in the resin composition of the present invention. Examples of the thermal acid generator include various onium salt compounds such as aromatic diazonium salts, sulfonium salts, diaryliodonium salts, triarylsulfonium salts, and triarylselenium salts, sulfonic acid esters, and halogen compounds.

Specific examples of the sulfonium salt include 4-hydroxyphenyldimethylsulfonium trifluoromethanesulfonate (product of prototype "W" made by Sanxin chemical industries Co., Ltd.), benzyl-4-hydroxyphenylmethylsulfanyl trifluoromethanesulfonate (product of prototype "O" made by Sanxin chemical industries Co., Ltd.), 2-methylbenzyl-4-hydroxyphenylmethylsulfanyl trifluoromethanesulfonate (product of prototype "N" made by Sanxin chemical industries Co., Ltd.), 4-methylbenzyl-4-hydroxyphenylmethylsulfanyl trifluoromethanesulfonate, 4-hydroxyphenylmethyl-1-naphthylmethylsulfanyl trifluoromethanesulfonate, 4-methoxycarbonyloxyphenyldimethylsulfonium trifluoromethanesulfonate (product of prototype "J" made by Sanxin chemical industries Co., Ltd.), benzyl-4-methoxycarbonyloxyphenylmethylsulfanyl trifluoromethanesulfonate (product of prototype "T" made by Sanxin chemical industries Co., Ltd.) 4-acetoxyphenyl benzylmethylsulfinium trifluoromethanesulfonate (manufactured by test "U" Sanxin chemical industries Co., Ltd.), 4-acetoxyphenyl methyl-4-methylbenzylsulfonium trifluoromethanesulfonate, 4-acetoxyphenyl dimethylsulfonium trifluoromethanesulfonate (manufactured by test "V" Sanxin chemical industries Co., Ltd.), 4-hydroxyphenyl dimethylsulfonium hexafluorophosphate, benzyl-4-hydroxyphenyl methylsulfinium hexafluorophosphate, 2-methylbenzyl-4-hydroxyphenyl methylsulfinium hexafluorophosphate, 4-hydroxyphenylmethyl-1-naphthylmethyl sulfonium hexafluorophosphate, 4-methoxycarbonyloxyphenyl dimethylsulfonium hexafluorophosphate, sodium iodonium, sodium thiosulfate, sodium iodonium, sodium iodo, Benzyl-4-methoxycarbonyloxyphenylmethylthioninium hexafluorophosphate, 4-acetoxyphenylbenzylmethylthioninium hexafluorophosphate (product "A" available from Sanxin chemical industries Co., Ltd.), 4-acetoxyphenylmethyl-4-methylbenzylsulfonium hexafluorophosphate, 4-acetoxyphenyldimethylsulfonium hexafluorophosphate (product name "SI-150" available from Sanxin chemical industries Co., Ltd.), "SI-180L" (product of Sanxin chemical industries Co., Ltd.), 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylthioninium hexafluoroantimonate, 2-methylbenzyl-4-hydroxyphenylmethylthioninium hexafluoroantimonate, 4-methylbenzyl-4-hydroxyphenylmethylthioninium hexafluoroantimonate, sodium hydrogen sulfide, sodium sulfide, potassium sulfide, 4-hydroxyphenylmethyl-1-naphthylmethylsulfinylhexafluoroantimonate, 4-methoxycarbonyloxyphenyldimethylsulfonium hexafluoroantimonate, benzyl-4-methoxycarbonyloxyphenylmethylsulfinylhexafluoroantimonate, 4-acetoxyphenylbenzylmethylsulfinylhexafluoroantimonate, 4-acetoxyphenylmethyl-4-methylbenzylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfinylhexafluoroantimonate and the like.

Examples of the aromatic diazonium salt include chlorophenyldiazonium hexafluorophosphate, dimethylaminobenzenediazonium hexafluoroantimonate, naphthyldiazonium hexafluorophosphate, and dimethylaminobenzenediazonium tetrafluoroborate.

Examples of diaryliodonium salts include diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, 4 '-di-tert-butyl-diphenyliodonium tetrafluoroborate, and 4, 4' -di-tert-butyl-diphenyliodonium hexafluorophosphate.

Examples of the triarylsulfonium salt include triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, tris (p-chlorophenyl) sulfonium tetrafluoroborate, tris (p-chlorophenyl) sulfonium hexafluorophosphate, tris (p-chlorophenyl) sulfonium hexafluoroantimonate, and 4-tert-butyltriphenylsulfonium hexafluorophosphate.

Examples of the triaryl selenium salt include triphenylselenium tetrafluoroborate, triphenylselenium hexafluorophosphate, triphenylselenium hexafluoroantimonate, bis (chlorophenyl) phenylseletetrafluoroborate, bis (chlorophenyl) phenylselenium hexafluorophosphate, and bis (chlorophenyl) phenylselenium hexafluoroantimonate.

Examples of the sulfonic acid ester include benzoin tosylate, p-nitrobenzyl-9, 10-ethoxyanthracene-2-sulfonate, 2-nitrobenzyl tosylate, 2, 6-dinitrobenzyl tosylate, and 2, 4-dinitrobenzyl tosylate.

Examples of the halogen compound include 2-chloro-2-phenylacetophenone, 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 (trichloromethyl) -s-triazine, bis-2- (4-chlorophenyl) -1,1, 1-trichloroethane, bis-1- (4-chlorophenyl) -2,2, 2-trichloroethanol, bis-2- (4-methoxyphenyl) -1,1, 1-trichloroethane, and the like.

Further, 5-norbornene-2, 3-dicarboximido trifluoromethanesulfonate (trade name "NDI-105" Midori Kagaku Co., manufactured by Ltd.), 5-norbornene-2, 3-dicarboximido toluenesulfonate (trade name "NDI-101" Midori Kagaku Co., manufactured by Ltd.), 4-methylphenylsulfonyloxyimino- α - (4-methoxyphenyl) acetonitrile (trade name "PAI-101" Midori Kagaku Co., manufactured by Ltd.), trifluoromethylsulfonyloxyimino- α - (4-methoxyphenyl) acetonitrile (trade name "PAI-105" Midori Kagaku Co., manufactured by Ltd.), 9-camphorsulfonyloxyimino- α -4-methoxyphenylacetonitrile (trade name "PAI-106" Midori Kagaku Co., manufactured by Ltd.), Ltd, Examples of the heat-generating agent include 1, 8-naphthalimide butane sulfonate (trade name "NAI-1004" manufactured by Midori Kagaku Co., Ltd.), 1, 8-naphthalimide toluene sulfonate (trade name "NAI-101" manufactured by Midori Kagaku Co., Ltd.), 1, 8-naphthalimide trifluoromethanesulfonate (trade name "NAI-105" Midori Kagaku Co., Ltd.), and 1, 8-naphthalimide nonafluorobutane sulfonate (trade name "NAI-109" Midori Kagaku Co., Ltd.).

The resin composition of the present invention may contain various surfactants such as various fluorine-based surfactants and silicone-based surfactants in order to improve the fluidity during coating. The kind of the surfactant is not particularly LIMITED, and examples thereof include "MEGAFACE (registered trademark)" F142D, MEGAFACE F172, MEGAFACE F173, MEGAFACE F183, MEGAFACE F430, MEGAFACE F444, MEGAFACE F445, MEGAFACE F470, MEGAFACE F475, MEGAFACE F477, MEGAFACE F553, MEGAFACE F554, MEGAFACE F555, MEGAFACE F556, MEGAFACE F559, MEGAFACE F560, MEGAFACE F563 (manufactured by Dainippon ink chemical Co., Ltd.), NBX-15, FTX-218, DFX-18 (manufactured by NEOS COMPANY LITED), LE-604, LE-605, LE-606, LE-607 (manufactured by Kyoho chemical Co., Ltd.), fluorine-based surfactants such as BYK-333, BYK-301, BYK-331, BYK-345, BYK-307 (manufactured by BYK Japan KK.), KL-403, KL-404, LE-302-303, LE-303, BYK-307 (manufactured by Kyok KK.), KL-403, KL-404, LE-302-303, and BYK-18, And silicone surfactants such as LE-304, LE-604, LE-605, LE-606, and LE-607 (available from Kyoeisha chemical Co., Ltd.), polyoxyalkylene surfactants, and poly (meth) acrylate surfactants. These may be used in 2 or more kinds.

The resin composition of the present invention may further contain additives such as a silane coupling agent, a crosslinking accelerator, a sensitizer, a thermal radical generator, a dissolution accelerator, a dissolution inhibitor, a stabilizer, and a defoaming agent, if necessary.

< method for Forming cured film >

The cured film of the present invention is obtained by curing the resin composition of the present invention or a photosensitive resin composition which is the resin composition of the present invention. Here, the photosensitive resin composition will be described in detail. The method for producing a cured film of a photosensitive resin composition preferably includes the following steps in 1 embodiment.

(I) A step of coating the photosensitive resin composition on a substrate to form a coating film,

(II) Process for exposing and developing the coating film, and

(III) heating the developed coating film.

The following examples are given.

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

After the pre-baking, an ultraviolet-visible exposure machine such as a stepper, a mirror projection mask aligner (MPA), a parallel light mask aligner (PLA) or the like is used to perform a process of 10 to 4000J/m through a desired mask²Left and right (in terms of 365nm wavelength exposure) pattern exposure.

After exposure, the (unexposed) portions are dissolved and removed by development, thereby obtaining a negative pattern or a positive pattern. The pattern resolution is preferably 15 μm or less. As a developing method, it is preferable to dip the developer in the developer by a method such as spraying, dipping, or stirring for 5 seconds to 10 minutes. As the developer, a known alkali developer can be used, and examples thereof include an aqueous solution of an inorganic base such as an alkali metal hydroxide, carbonate, phosphate, silicate, or borate, an amine such as 2-diethylaminoethanol, monoethanolamine, or diethanolamine, a quaternary ammonium salt such as tetramethylammonium hydroxide (TMAH), or choline. These may be used in 2 or more kinds. After the development, the developing solution is preferably rinsed with water, and if necessary, may be dehydrated, dried and baked at a temperature of 50 to 150 ℃ by a heating device such as a hot plate or an oven. If necessary, the film is heated (pre-baked) for 30 seconds to 30 minutes at a temperature of 50 to 300 ℃ by a heating device such as a hot plate or an oven, and then heated (cured) for about 30 seconds to 2 hours at a temperature of 150 to 450 ℃ by a heating device such as a hot plate or an oven, thereby obtaining a cured film.

The sensitivity of the photosensitive resin composition at the time of exposure is preferably 1500J/m from the viewpoint of productivity in pattern formation²Hereinafter, more preferably 1000J/m²The following. The sensitivity at the time of exposure was determined by the following method. The photosensitive resin composition was spin-coated on a silicon wafer at an arbitrary rotation speed using a spin coater, and prebaked at 120 ℃ for 3 minutes using a hot plate to prepare a prebaked film having a film thickness of 1 μm. After exposing the prebaked film to light through a gray scale mask having a line and space pattern of 1 to 10 μm for sensitivity measurement using PLA (PLA-501F manufactured by Canon inc., ltd.) by an ultra-high pressure mercury lamp, spray developing was performed for 90 seconds using an aqueous TMAH solution of 2.38 mass% using an automatic developing apparatus (AD-2000 manufactured by takiawa co., ltd.), followed by water-sprayingRinse for 30 seconds. In the formed pattern, the exposure amount of a line and space (line and space) pattern resolved by 10 μm in width of 1: 1 was obtained as sensitivity.

Thereafter, as a heat curing step, a cured film was produced by curing at 220 ℃ for 5 minutes using a hot plate, and the minimum pattern size in sensitivity was determined as the resolution after curing.

Fig. 1 shows a specific example of the method for producing a cured film according to the present embodiment. First, the resin composition of the present invention is applied to a substrate 1 to form a coating film 2. This was cured by heating, thereby obtaining a cured film 3.

Fig. 2 shows a specific example of the method for producing a cured film according to the present embodiment. The formation of the coating film 2 up to the first stage is carried out as described above. Subsequently, the coating film 2 is irradiated with active light 4 and exposed. This was cured by heating, thereby obtaining a cured film 3.

Fig. 3 shows a specific example of the method for producing a cured film according to the present embodiment. The formation of the coating film 2 up to the first stage is carried out as described above. Subsequently, the coating film 2 is irradiated with active rays 4 through the mask 5 to perform exposure. The exposed coating film is developed, thereby obtaining a pattern 6. This pattern is irradiated with an active ray 5 and cured by heating, thereby obtaining a cured film 3.

The cured film obtained by curing the grease composition of the present invention has a light transmittance of preferably 90% or more, more preferably 92% or more, relative to a1 μm film thickness at a wavelength of 400 nm. Such a high transmittance can be easily obtained by using, for example, a photosensitive resin composition containing polysiloxane having high transparency as a resin component.

The transmittance of the cured film at a wavelength of 400nm with respect to the 1 μm film thickness was determined by the following method. The photosensitive resin composition was spin-coated on a TEMPAX glass plate using a spin coater at an arbitrary rotation speed, and prebaked using a hot plate at 100 ℃ for 3 minutes. The resultant was thermally cured at 220 ℃ for 5 minutes in the air using a hot plate to prepare a cured film having a thickness of 1 μm. The UV-visible absorption spectrum of the obtained cured film was measured using MultiSpec-1500 (Shimadzu corporation) to determine the transmittance at a wavelength of 400 nm. As another method, the attenuation coefficient and the film thickness of the cured film to be measured at each wavelength by a spectroscopic ellipsometer FE5000 available from Otsuka Denshi K.K. can be determined by the following equations.

Transmittance of exp (-4 π kt/λ)

Where k represents an attenuation coefficient, t represents a film thickness, and λ represents a measurement wavelength.

The resin composition of the present invention and the cured film obtained by curing the same are suitably used for solid-state imaging devices, optical filters, organic EL devices, liquid crystal displays as display devices, organic EL televisions, particularly transparent liquid crystal televisions, and the like. More specifically, examples thereof include an antireflection film of an optical filter of a solid-state imaging element such as a back-illuminated CMOS image sensor, a color mixing prevention wall, a transparent pixel, a flattening material of a TFT substrate for a display, a color filter and a protective film thereof for a liquid crystal display, a transparent display, and the like, a phase shifter, an antireflection film, and the like. In addition, the film can also be used as a buffer coat, an interlayer insulating film, and various protective films of a semiconductor device.

Examples

The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to these examples. The following compounds used in synthesis examples and examples are abbreviated as compounds.

PGMEA: propylene glycol monomethyl ether acetate

CPN: cyclopentanone

And gBL: gamma-butyrolactone

BzOH: benzyl alcohol

BzME: benzyl methyl ether

MBz: benzoic acid methyl ester

MTMS: methyltrimethoxysilane

PhTMS: phenyltrimethoxysilane

TES: tetraethoxysilane

HfTMS: 4- (2-hydroxy-1, 1,1,3,3, 3-hexafluoroisopropyl) -1-triethoxysilylbenzene

CFTMS: trifluoropropyltrimethoxysilane.

< measurement of substituent ratio >

To carry out²⁹In the measurement of Si-NMR, the ratio of the integral value corresponding to each organosilane was calculated from the integral value of the whole, and the ratio was calculated. The sample (liquid) was injected into a 10mm diameter NMR sample tube made of "Teflon" (registered trademark) for measurement. Shown below²⁹Measurement conditions of Si-NMR.

The device comprises the following steps: JNM GX-270, manufactured by Nippon electronics Co., Ltd., measurement method: gated decoupling method

Measurement of nuclear frequency: 53.6693MHz (²⁹Si nuclei), spectral width: 20000Hz

Pulse width: 12 μ sec (45 ° pulse), pulse repetition time: 30.0sec

Solvent: acetone-d 6, standard: tetramethylsilane

Measuring temperature: room temperature, sample rotation speed: 0.0 Hz.

< measurement of solid content concentration >

The solid content concentration of the polysiloxane solution was determined by the following method. 1.5g of the polysiloxane solution was weighed into an aluminum cup and heated at 250 ℃ for 30 minutes using a hot plate 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)

To synthesize the Hf compound (H1), the following reaction was carried out.

[ chemical formula 12]

In a 300mL three-necked flask equipped with a reflux tube, 6.46g (20.0mmol) of the Hf compound (H-1), 7.38g (40.0mmol) of tetrabutylammonium iodide, and 0.2280g (0.60mmol) of bis (acetonitrile) (1, 5-cyclooctadiene) rhodium (I) tetrafluoroborate, which had been dried in advance, were collected at room temperature. Then, 120mL of dehydrated N, N-dimethylformamide, 11.1mL (80.0mmol) of dehydrated triethylamine and 7.40mL (40.0mmol) of triethoxysilane were added under an argon atmosphere, and the temperature was raised toStirring was carried out at 80 ℃ for 4 hours. After the reaction system was naturally cooled to room temperature, N-dimethylformamide as a solvent was distilled off, followed by addition of 200mL of diisopropyl ether. After diatomaceous earth was brought into contact with the resulting precipitate and filtered, the filtrate was washed with 100mL of water 3 times, and Na was added₂SO₄The mixture was dehydrated and dried, and further filtered, and then the solvent was distilled off. The residue as a reaction product was purified by distillation using a Kugelrohr apparatus at 140 to 190 ℃ and 200Pa to obtain HfTMS (Hf-1) as a colorless liquid. Method for producing HfTMS (Hf-1)¹The results of H-NMR measurement are shown below.

¹H-NMR (solvents CDCl3 (deuterated chloroform), TMS (tetramethylsilane)): δ 8.03(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 ═ 7.4 Hz).

Synthesis example 2 Synthesis of HfTMS (Hf-2)

To synthesize the Hf compound (H1), the following reaction was carried out.

[ chemical formula 13]

HfTMS (Hf-2) was obtained in the same manner as in Synthesis example 1, except that the Hf compound (H-1) was replaced with Hf compound (H-2). Method for producing HfTMS (Hf-1)¹The results of H-NMR measurement are shown below.

¹H-NMR (solvents CDCl3 (deuterated chloroform), TMS (tetramethylsilane)): δ 7.74(4H, dd, J ═ 18.6,18.3Hz),3.89(6H, q, J ═ 7.0Hz),3.57(1H, s),1.26(9H, t, J ═ 7.0 Hz).

Synthesis example 3 Synthesis of polysiloxane (P-1)

Into a 500ml three-necked flask, 109.25g (0.565mol) of MTMS, 84.67g (0.049mol) of HfTMS (Hf-1), 6.51g (0.014mol) of TES, and 191.75g of PGMEA were charged, and an aqueous phosphoric acid solution prepared by dissolving 1.00g (0.50 mass% based on the charged monomer) of phosphoric acid in 56.82g of water was added over 30 minutes while stirring at room temperature. Thereafter, the flask was oil-bathed at 70 deg.CAfter immersion and stirring for 90 minutes, the oil bath was warmed to 115 ℃ over 30 minutes. 1 hour after the start of the temperature rise, the internal temperature of the solution reached 100 ℃ and then the solution was heated and stirred for 2 hours (internal temperature 100 to 110 ℃) to obtain polysiloxane (P-1). While the temperature was increased and the mixture was stirred under heating, nitrogen gas was passed through the mixture at a flow rate of 0.05 l/min. 154.41g of methanol and water were distilled off as by-products during the reaction. The solid content concentration of the obtained polysiloxane (P-1) was 43.1% by mass. By passing²⁹The molar amounts of the structure represented by any of the general formulae (1) to (3) and the structure represented by any of the general formulae (4) or (5) in the polysiloxane (A) were 20 mol% and 3 mol%, respectively, as measured by Si-NMR.

Synthesis example 4 Synthesis of polysiloxane (P-2)

Polysiloxane (P-2) was obtained by charging 112.22g (0.551mol) of MTMS, 66.97g (0.037mol) of HfTMS (Hf-1), 22.88g (0.048mol) of TES, and 185.62g of PGMEA in the same procedure as in Synthesis example 1, and adding 1.01g (0.50 mass% based on the charged monomer) of phosphoric acid in 61.30g of water. The solid content concentration of the obtained polysiloxane (P-2) was 42.8% by mass. By passing²⁹The molar amounts of the structure represented by any of the general formulae (1) to (3) and the structure represented by any of the general formulae (4) or (5) in the polysiloxane (A) were 15 mol% and 10 mol%, respectively, as measured by Si-NMR.

Synthesis example 5 Synthesis of polysiloxane (P-3)

Polysiloxane (P-3) was obtained by charging 45.14g (0.257mol) of MTMS, 57.72g (0.037mol) of HfTMS (Hf-1), 98.61g (0.240mol) of TES, and 187.87g of PGMEA through the same procedure as in Synthesis example 1, and adding 1.01g (0.50 mass% based on the charged monomers) of phosphoric acid in 59.65g of water. The solid content concentration of the obtained polysiloxane (P-3) was 43.5% by mass. By passing²⁹The molar amounts of the structure represented by any of the general formulae (1) to (3) and the structure represented by any of the general formulae (4) or (5) in the polysiloxane (A) were 15 mol% and 50 mol%, respectively, as measured by Si-NMR.

Synthesis example 6 Synthesis of polysiloxane (P-4)

31.16g (0.184 m) of MTMS was charged through the same procedure as in Synthesis example 1ol), HfTMS (Hf-1)55.79g (0.037mol), TES 114.39g (0.288mol), and PGMEA 188.34g, and an aqueous phosphoric acid solution prepared by dissolving 1.01g (0.50 mass% relative to the charged monomer) of phosphoric acid in 59.31g of water was added to obtain polysiloxane (P-4). The solid content concentration of the obtained polysiloxane (P-4) was 42.5% by mass. By passing²⁹The molar amounts of the structure represented by any of the general formulae (1) to (3) and the structure represented by any of the general formulae (4) or (5) in the polysiloxane (A) were 15 mol% and 60 mol%, respectively, as measured by Si-NMR.

Synthesis example 7 Synthesis of polysiloxane (P-5)

Polysiloxane (P-5) was obtained by charging 66.18g (0.367mol) of MTMS, 59.24g (0.037mol) of HfTMS (Hf-1), 10.12g (0.024mol) of TES, 63.63g (0.137mol) of CFTMS, and 196.49g of PGMEA through the same procedure as in Synthesis example 1, and adding an aqueous phosphoric acid solution prepared by dissolving 1.00g (0.50 mass% based on the charged monomers) of phosphoric acid in 53.35g of water. The solid content concentration of the obtained polysiloxane (P-5) was 43.7% by mass. By passing²⁹The molar amounts of the structure represented by any of the general formulae (1) to (3) and the structure represented by any of the general formulae (4) or (5) in the polysiloxane (A) were 15 mol% and 5 mol%, respectively, as measured by Si-NMR.

Synthesis example 8 Synthesis of polysiloxane (P-6)

Polysiloxane (P-6) was obtained by charging 58.52g (0.330mol) of MTMS, 58.21g (0.037mol) of HfTMS (Hf-1), 19.89g (0.048mol) of TES, 62.52(0.137mol) of CFTMS, and 196.59g of PGMEA through the same procedure as in Synthesis example 1, and adding 1.00g (0.50 mass% based on the charged monomer) of phosphoric acid in 53.28g of water. The solid content concentration of the obtained polysiloxane (P-6) was 42.9% by mass. By passing²⁹The molar amounts of the structure represented by any of the general formulae (1) to (3) and the structure represented by any of the general formulae (4) or (5) in the polysiloxane (A) were 15 mol% and 10 mol%, respectively, as measured by Si-NMR.

Synthesis example 9 Synthesis of polysiloxane (P-7)

By the same procedure as in Synthesis example 1, MTMS 46.14g (0.257mol), HfTMS (Hf-1)59.01g (0.037mol), TES 30.24g (0.072mol), CFTMS 63.38(0.137mol), and PGMEA 197.97g were charged,an aqueous phosphoric acid solution prepared by dissolving 0.99g (0.50 mass% relative to the charged monomer) of phosphoric acid in 52.27g of water was added to obtain polysiloxane (P-7). The solid content concentration of the resulting polysiloxane (P-7) was 43.1% by mass. By passing²⁹The molar amounts of the structure represented by any of the general formulae (1) to (3) and the structure represented by any of the general formulae (4) or (5) in the polysiloxane (A) were 15 mol% and 20 mol%, respectively, as measured by Si-NMR.

Synthesis example 10 Synthesis of polysiloxane (P-8)

Polysiloxane (P-8) was obtained by charging 30.40g (0.184mol) of MTMS, 54.42g (0.037mol) of HfTMS (Hf-1), 55.78g (0.144mol) of TES, 58.45 g (0.137mol) of CFTMS, and 196.94g of PGMEA through the same procedure as in Synthesis example 1, and adding 1.00g (0.50 mass% based on the charged monomers) of phosphoric acid aqueous solution prepared by dissolving 53.02g of water. The solid content concentration of the obtained polysiloxane (P-8) was 43.2% by mass. By passing²⁹The molar amounts of the structure represented by any of the general formulae (1) to (3) and the structure represented by any of the general formulae (4) or (5) in the polysiloxane (A) were 15 mol% and 30 mol%, respectively, as measured by Si-NMR.

Synthesis example 11 Synthesis of polysiloxane (P-9)

Polysiloxane (P-9) was obtained by charging 5.71g (0.037mol) of MTMS, 51.09g (0.037mol) of HfTMS (Hf-1), 87.29g (0.240mol) of TES, 54.88(0.137mol) of CFTMS, and 197.24g of PGMEA through the same procedure as in Synthesis example 1, and adding an aqueous phosphoric acid solution prepared by dissolving 0.99g (0.50 mass% based on the charged monomers) of phosphoric acid in 52.80g of water. The solid content concentration of the obtained polysiloxane (P-9) was 42.8% by mass. By passing²⁹The molar amounts of the structure represented by any of the general formulae (1) to (3) and the structure represented by any of the general formulae (4) or (5) in the polysiloxane (A) were 15 mol% and 50 mol%, respectively, as measured by Si-NMR.

Synthesis example 12 Synthesis of polysiloxane (P-10)

54.02g (0.294mol) of MTMS, 40.30g (0.025mol) of HfTMS (Hf-1), 41.31g (0.096mol) of TES, 64.92(0.137mol) of CFTMS, and 191.35g of PGMEA were charged and 1.00g (0.50 mass% based on the charged monomer) of phosphoric acid was dissolved by addingThe resulting mixture was dissolved in 57.11g of water to obtain a phosphoric acid aqueous solution, polysiloxane (P-10). The solid content concentration of the resulting polysiloxane (P-10) was 43.1% by mass. By passing²⁹The molar amounts of the structure represented by any of the general formulae (1) to (3) and the structure represented by any of the general formulae (4) or (5) in the polysiloxane (A) were 10 mol% and 20 mol%, respectively, as measured by Si-NMR.

Synthesis example 13 Synthesis of polysiloxane (P-11)

Polysiloxane (P-11) was obtained by charging 35.26g (0.220mol) of MTMS, 70.13g (0.049mol) of HfTMS (Hf-1), 35.95g (0.096mol) of TES, 56.49(0.137mol) of CFTMS, and 201.48g of PGMEA through the same procedure as in Synthesis example 1, and adding an aqueous phosphoric acid solution prepared by dissolving 0.99g (0.50 mass% based on the charged monomers) of phosphoric acid in 49.70g of water. The solid content concentration of the resulting polysiloxane (P-11) was 43.4% by mass. By passing²⁹The molar amounts of the structure represented by any of the general formulae (1) to (3) and the structure represented by any of the general formulae (4) or (5) in the polysiloxane (A) were 20 mol% and 20 mol%, respectively, as measured by Si-NMR.

Synthesis example 14 Synthesis of polysiloxane (P-12)

Polysiloxane (P-12) was obtained by charging 20.80g (0.147mol) of MTMS, 93.11g (0.074mol) of HfTMS (Hf-1), 31.82g (0.096mol) of TES, 50.00 g (0.137mol) of CFTMS, and 209.29g of PGMEA through the same procedure as in Synthesis example 1, and adding an aqueous phosphoric acid solution prepared by dissolving 0.98g (0.50 mass% based on the charged monomers) of phosphoric acid in 43.99g of water. The solid content concentration of the obtained polysiloxane (P-12) was 43.0 mass%. By passing²⁹The molar amounts of the structure represented by any of the general formulae (1) to (3) and the structure represented by any of the general formulae (4) or (5) in the polysiloxane (A) were 30 mol% and 20 mol%, respectively, as measured by Si-NMR.

Synthesis example 15 Synthesis of polysiloxane (P-13)

Into a 500ml three-necked flask, 109.25g (0.565mol) of MTMS, 84.67g (0.049mol) of HfTMS (Hf-2), 6.51g (0.014mol) of TES, and 191.75g of PGMEA were charged, and an aqueous phosphoric acid solution prepared by dissolving 1.00g (0.50 mass% based on the charged monomer) of phosphoric acid in 56.82g of water was added over 30 minutes while stirring at room temperature. Then, the mixture is burnedAfter the flask was immersed in a 70 ℃ oil bath and stirred for 90 minutes, the oil bath was warmed to 115 ℃ over 30 minutes. 1 hour after the start of the temperature rise, the internal temperature of the solution reached 100 ℃ and then the solution was heated and stirred for 2 hours (internal temperature 100 to 110 ℃) to obtain polysiloxane (P-13). While the temperature was increased and the mixture was stirred under heating, nitrogen gas was passed through the mixture at a flow rate of 0.05 l/min. 154.41g of methanol and water were distilled off as by-products during the reaction. The solid content concentration of the obtained polysiloxane (P-1) was 43.0 mass%. By passing²⁹The molar amounts of the structure represented by any of the general formulae (1) to (3) and the structure represented by any of the general formulae (4) or (5) in the polysiloxane (A) were 20 mol% and 3 mol%, respectively, as measured by Si-NMR.

Synthesis example 16 Synthesis of polysiloxane (R-1)

Polysiloxane (R-1) was obtained by charging 188.82g (0.246mol) of HfTMS (Hf-1) and 235.14g of PGMEA through the same procedure as in Synthesis example 1, and adding an aqueous phosphoric acid solution prepared by dissolving 0.94g (0.50 mass% based on the charged monomers) of phosphoric acid in 25.09g of water. The solid content concentration of the obtained polysiloxane (R-1) was 43.2% by mass. By passing²⁹The molar amounts of the structure represented by any of the general formulae (1) to (3) and the structure represented by any of the general formulae (4) or (5) in the polysiloxane (A) were 100 mol% and 0 mol%, respectively, as measured by Si-NMR.

Synthesis example 17 Synthesis of polysiloxane (R-2)

Polysiloxane (R-2) was obtained by charging 41.54g (0.330mol) of MTMS, 151.49g (0.135mol) of HfTMS (Hf-1), and 219.40g of PGMEA through the same procedure as in Synthesis example 1, and adding 0.97g (0.50 mass% based on the charged monomers) of phosphoric acid in an aqueous phosphoric acid solution prepared by dissolving 36.60g of water in 0.97g of phosphoric acid. The solid content concentration of the obtained polysiloxane (R-2) was 43.5% by mass. By passing²⁹The molar amounts of the structure represented by any of the general formulae (1) to (3) and the structure represented by any of the general formulae (4) or (5) in the polysiloxane (A) were 55 mol% and 0 mol%, respectively, as measured by Si-NMR.

Synthesis example 18 Synthesis of polysiloxane (R-3)

MTMS 68.15g (0.330mol), CFTMS 133.47g (0.252mol), and PGMEA 187 were charged by the same procedure as in Synthesis example 1.34g of polysiloxane (R-3) was obtained by adding an aqueous phosphoric acid solution prepared by dissolving 1.01g (0.50 mass% based on the charged monomer) of phosphoric acid in 60.04g of water. The solid content concentration of the obtained polysiloxane (R-3) was 43.2% by mass. By passing²⁹The molar amounts of the structure represented by any of the general formulae (1) to (3) and the structure represented by any of the general formulae (4) or (5) in the polysiloxane (A) were 0 mol% and 0 mol%, respectively, as measured by Si-NMR.

Synthesis example 19 Synthesis of polysiloxane (R-4)

Polysiloxane (R-4) was obtained by charging 73.11g (0.330mol) of MTMS, 130.10g (0.277mol) of PhTMS130.10g and 181.36g of PGMEA through the same procedure as in Synthesis example 1, and adding 1.02g (0.50 mass% based on the charged monomers) of phosphoric acid in 64.42g of water. The solid content concentration of the obtained polysiloxane (R-4) was 42.8% by mass. By passing²⁹The molar amounts of the structure represented by any of the general formulae (1) to (3) and the structure represented by any of the general formulae (4) or (5) in the polysiloxane (A) were 0 mol% and 0 mol%, respectively, as measured by Si-NMR.

Synthesis example 20 Synthesis of polysiloxane (R-5)

Polysiloxane (R-5) was obtained by charging HfTMS 120.70g (0.111mol), PhTMS 71.98g (0.277mol), and PGMEA 220.71g in the same procedure as in Synthesis example 1, and adding an aqueous phosphoric acid solution prepared by dissolving 0.97g (0.50 mass% based on the charged monomers) of phosphoric acid in 35.64g of water. The solid content concentration of the obtained polysiloxane (R-5) was 43.2% by mass. By passing²⁹The molar amounts of the structure represented by any of the general formulae (1) to (3) and the structure represented by any of the general formulae (4) or (5) in the polysiloxane (A) were 45 mol% and 0 mol%, respectively, as measured by Si-NMR.

Synthesis example 21 Synthesis of polysiloxane (R-6)

Polysiloxane (R-6) was obtained by charging HfTMS 66.32g (0.049mol), PhTMS 129.44g (0.403mol) and PGMEA 209.20g in the same manner as in Synthesis example 1, and adding an aqueous phosphoric acid solution prepared by dissolving 0.98g (0.50 mass% based on the charged monomers) of phosphoric acid in 44.06g of water. The solid content concentration of the obtained polysiloxane (R-6) was 43.2% by mass. By passing²⁹The molar amounts of the structure represented by any of the general formulae (1) to (3) and the structure represented by any of the general formulae (4) or (5) in the polysiloxane (A) were 20 mol% and 0 mol%, respectively, as measured by Si-NMR. Table 1 shows the amounts of alkoxysilane to be charged as a raw material for the polysiloxane (A) obtained in Synthesis examples 1 to 18.

Synthesis example 22 Synthesis of polysiloxane (R-7)

Polysiloxane (R-7) was obtained by charging 15.46g (0.011mol) of MTMS, 19.27g (0.088mol) of CFTMS, 10.51g (0.050mol) of TES and 40.01g of PGMEA in the same manner as in Synthesis example 1, and adding an aqueous phosphoric acid solution prepared by dissolving 0.23g (0.50 mass% based on the charged monomers) of phosphoric acid in 14.53g of water. The solid content concentration of the obtained polysiloxane (R-6) was 43.2% by mass. By passing²⁹The molar amounts of the structure represented by any of the general formulae (1) to (3) and the structure represented by any of the general formulae (4) or (5) in the polysiloxane (A) were 0 mol% and 20 mol%, respectively, as measured by Si-NMR. Table 1 shows the amounts of alkoxysilane to be charged as a raw material for the polysiloxane (A) obtained in Synthesis examples 1 to 22.

[ Table 1]

Synthesis example 22 Synthesis of naphthoquinone diazide Compound (C-1)

21.23g (0.05mol) of TrisP-PA (trade name, manufactured by chemical industries, Ltd., Japan) having a phenolic hydroxyl group and 37.62g (0.14mol) of 5-naphthoquinonediazide sulfonyl chloride were dissolved in 450g of 1, 4-dioxane under a dry nitrogen stream to room temperature. 15.58g (0.154mol) of triethylamine mixed with 50g of 1, 4-dioxane was added dropwise thereto so that the temperature in the system did not become 35 ℃ or higher. After the dropwise addition, stirring was carried out at 30 ℃ for 2 hours. The triethylamine salt was filtered and the filtrate was added to water. Thereafter, the precipitated precipitate was collected by filtration. The precipitate was dried by a vacuum drier to obtain naphthoquinone diazide compound C-1 having the following structure.

[ chemical formula 14]

[ solvent replacement of Metal Compound particles ]

Solvent replacement example 1 solvent replacement of "THRULYA" 4110

As the metal oxide particles, the solvent of "THRULYA" 4110 (trade name, manufactured by NIGHTRO CATALYST FORMATION CO., LTD.) was replaced with PGMEA from isopropanol. 100g of isopropyl alcohol sol (solid content concentration 20%) of "THRULYA 4110 and 80g of PGMEA were put into a 500ml eggplant-shaped flask, and IPA was removed by reducing the pressure in an evaporator at 30 ℃ for 30 minutes. The solid content concentration of the PGMEA solution D-1 of THRULYA4110 obtained was determined to be 20.1%.

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

(1) Measurement of film thickness

The thicknesses of the pre-baked film, the developed film and the cured film were measured with a refractive index of 1.40 using Lambda Ace STM-602 (trade name, manufactured by Dainippon Screen).

(2) Measurement of refractive index

The obtained cured film was measured for its refractive index at 633nm at 22 ℃ using a spectroscopic ellipsometer FE5000 available from Otsuka Denshi.

(3) Evaluation of chemical resistance

The film thickness of the obtained cured film was measured (1) and recorded as film thickness t 1. Subsequently, the cured film was immersed in acetone for 5 minutes, and then heated at 100 ℃ for 1 minute using a hot plate (HP-1 SA, manufactured by AS ONE CORPORATION). After heating, the cured film thickness was measured by SURFACM and was designated as film thickness t 2. The film thickness change rate X before and after acetone immersion was calculated from the following formula, and chemical resistance was evaluated. Evaluation criteria are set as follows a to E.

Film thickness change rate X (%) (t1-t2)/t1 × 100

A: the change rate X of the film thickness is X < 5%

B: the change rate X of the film thickness is more than or equal to 5 percent and less than 15 percent

C: the change rate X of the film thickness is more than or equal to 15 percent and less than 30 percent

D: the change rate X of the film thickness is more than or equal to 30 percent and less than 60 percent

E: the film thickness change rate X is more than or equal to 60 percent and less than or equal to X.

(4) Evaluation of crack resistance

The obtained cured film was observed with a microscope to confirm the presence or absence of cracks.

Evaluation criteria are set as the following a to C.

A: no cracks were observed in the entire surface

B: cracks were seen only at the ends of the wafer substrate

C: cracks were seen throughout the face.

(5) Evaluation of coatability

The obtained cured film was observed with a microscope to evaluate the presence or absence of foreign matter and shrinkage.

A: no foreign matter and no shrinkage were observed on the entire surface.

B: foreign matter and shrinkage were observed only in the center of the wafer.

C: foreign matter and shrinkage were observed on the entire surface of the wafer.

(6) Measurement of transmittance (in terms of 1 μm at a wavelength of 400 nm)

The attenuation coefficient of the obtained cured film at a wavelength of 400nm was measured by a spectroscopic ellipsometer FE5000 available from Otsuka Denshi K.K., and the light transmittance (%) at a wavelength of 400nm as a film thickness of 1 μm was determined according to the following equation.

Light transmittance of exp (-4 pi kt/lambda)

Where k represents an attenuation coefficient, t represents a converted film thickness (μm), and λ represents a measurement wavelength (nm). In this measurement, t is 1(μm) in order to obtain a light transmittance in terms of 1 μm.

(7) Resolution ratio

The cured film obtained was observed for a square pattern at all exposure levels, and the minimum pattern size was observed as the resolution. Evaluation criteria were determined as follows.

A: minimum pattern size x <15 μm

B: minimum pattern size 15 μm x <50 μm

C: minimum pattern size 50 μm x <100 μm

D: the minimum pattern size is 100 mu m and x.

(8) Evaluation of reduction of developing film

The amount of film reduction during development was calculated for examples 19 to 40 and comparative examples 7 to 12.

Film thickness of pre-baked film/film thickness of pre-baked film × 100

The thickness of the prebaked film and the thickness after development were measured according to the method described in the above (1) measurement of film thickness.

Example 1

The resin compositions (I) shown in Table 2 were mixed at a ratio, and the mixture was stirred under a yellow lamp to prepare a homogeneous solution, which was then filtered through a 0.20 μm filter to prepare composition 1.

Immediately after the preparation, the composition 1 was spin-coated on a 4-inch silicon wafer using a spin coater (MIKASA co., LTD 1H-360S), and then heated at 120 ℃ for 3 minutes using a hot plate (SCW-636, manufactured by Dainippon Screen corporation) to prepare a prebaked film having a film thickness of 1.0 μm. Thereafter, the prebaked film was cured at 230 ℃ for 5 minutes using a hot plate to prepare a cured film 1.

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

Examples 2 to 18 and comparative examples 1 to 7

Compositions 2 to 24 having the compositions shown in Table 2 were prepared in the same manner as in the resin composition (I). Using each of the obtained compositions, a cured film 1 was produced and evaluated in the same manner as in example 1. The evaluation results are shown in table 3.

Example 19

The resin compositions (I) shown in Table 4 were mixed in the proportions shown below, and the mixture was stirred under a yellow lamp to prepare a homogeneous solution, which was then filtered through a 0.20 μm filter to prepare a composition 25.

Immediately after the preparation, the composition 25 was spin-coated on a 4-inch silicon wafer and a glass substrate with a spin coater (MIKASA co., LTD 1H-360S), and then heated at 120 ℃ for 3 minutes with a hot plate (SCW-636, manufactured by Dainippon Screen corporation) to prepare a pre-baked film, and (1) the film thickness was measured. The pre-baked film was subjected to spray development with a 2.38 mass% TMAH aqueous solution for 30 seconds using an automatic developing apparatus (TAKIZAWA co., ltd., AD-2000), followed by rinsing with water for 30 seconds to obtain a post-developed film 1 and a post-developed film 2 on a wafer and a glass substrate, respectively, and the film thickness of the post-developed film 1 was measured (1). Then, cured

films

2 and 3 were produced by aging

post-development films

1 and 2 at 230 ℃ for 5 minutes using a hot plate. The cured film 2 was subjected to (1) film thickness measurement.

The obtained prebaked film was exposed to light at 50msec intervals for 100msec to 1000msec using an i-line stepper (i 9C manufactured by Nikon Corporation), and then developed and cured in the same manner as described above to obtain a cured film 4.

The refractive index was measured (2) and the chemical resistance was evaluated (3) with the cured film 2, (6) the transmittance was measured with the cured film 3, and (7) the resolution was evaluated with the cured film 4. The results are shown in Table 5.

Examples 20 to 40 and comparative examples 8 to 12

Resin compositions 26 to 46 having the compositions shown in Table 4 were prepared in the same manner as the composition 25. In the resin compositions 44 to 46, PC-5 (manufactured by Toyo chemical Co., Ltd.) was used as a naphthoquinone diazide compound. Using the respective compositions thus obtained, pre-baked films and cured films 2 to 4 were produced and evaluated in the same manner as in example 19. The evaluation results are shown in table 5.

Cured films were produced and evaluated in the same manner as in example 1, except that (2) the refractive index was measured and (6) the transmittance was measured, and development was not performed when all the films were dissolved and could not be evaluated.

[ Table 2]

[ TABLE 2]

[ Table 3]

[ TABLE 3]

[ Table 4]

[ TABLE 4]

[ Table 5]

[ TABLE 5]

Description of the reference numerals

1 substrate

2 coating film

3 cured film

4 active ray

5 mask

6 Pattern

7 cured film pattern

Claims

1. A resin composition characterized by containing (A) a polysiloxane and (B) a solvent, wherein the (A) polysiloxane contains at least one of the structures represented by the following general formulas (1) to (3) and at least one of the structures represented by the following general formulas (4) to (5),

[ chemical formula 1]

Y is an alicyclic or aromatic linking group having 5 to 10 carbon atoms, R¹Represents a single bond or an alkylene group having 1 to 4 carbon atoms, R²Each is independentAnd R represents hydrogen or C1-4 alkyl³Each 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.

2. The resin composition according to claim 1, wherein the polysiloxane (A) comprises at least one of the structures represented by the following general formulae (6) to (8),

[ chemical formula 2]

R¹Represents a single bond or an alkylene group having 1 to 4 carbon atoms, R²Each independently represents hydrogen or an alkyl group having 1 to 4 carbon atoms, R³Each 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.

3. The resin composition according to claim 1 or 2, wherein (A) the polysiloxane skeleton has 5 to 50 mol% of at least one of the structures represented by the general formulae (4) to (5).

4. The resin composition according to any one of claims 1 to 3, wherein the polysiloxane (A) comprises at least one or more structures represented by the following general formulae (9) to (11),

[ chemical formula 3]

R²Each independently represents hydrogen or an alkyl group having 1 to 4 carbon atoms, R³Each independently represents an organic group having 1 to 8 carbon atoms, R⁴Represents an organic group having 1 to 10 carbon atoms and having a fluorine group.

5. The resin composition according to any one of claims 1 to 4, which comprises (C) a naphthoquinone diazide compound.

6. The resin composition according to claim 5, wherein the amount of the naphthoquinone diazide compound (C) is 1 to 15 parts by mass based on 100 parts by mass of the polysiloxane (A).

7. The resin composition according to any one of claims 1 to 6, which contains 1 or more kinds of aromatic hydrocarbon solvents (B) having hetero atoms.

8. The resin composition according to any one of claims 1 to 7, which contains (D) metal compound particles.

9. The resin composition according to claim 8, wherein the (D) metal compound particles are silica particles.

10. A cured film of the resin composition according to any one of claims 1 to 9.

11. A solid-state imaging element comprising the cured film according to claim 10.

12. An organic EL element comprising the cured film according to claim 10.

13. A display device comprising the cured film according to claim 10.