WO2020045214A1

WO2020045214A1 - Resin composition and cured film obtained therefrom

Info

Publication number: WO2020045214A1
Application number: PCT/JP2019/032782
Authority: WO
Inventors: 日比野利保; 的羽良典; 諏訪充史; 藤井真実
Original assignee: 東レ株式会社
Priority date: 2018-08-31
Filing date: 2019-08-22
Publication date: 2020-03-05
Also published as: KR20210052431A; JPWO2020045214A1; CN112368336A; JP7327163B2; TW202020024A

Abstract

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

Description

Resin composition, cured film thereof

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

In recent years, in a liquid crystal display, an organic EL television, and the like, light is introduced from the side using an LED light source or the like, thereby realizing a narrower frame and a thinner frame. In particular, recently, in liquid crystal displays, transparent liquid crystal displays have been intensively studied and developed by various companies as new display devices. At that time, the light incident from the side surface is efficiently guided in a certain direction, so it has a low refractive index, high transparency, excellent chemical resistance to chemicals used in the processing process, yellowing in the heating process, etc. There is a demand for a new material having good heat resistance, which does not cause deterioration of the material. As disclosed in

Patent Documents

1, 2, and 3, polysiloxane materials are known as highly transparent and low refractive index materials, and are widely used in liquid crystal displays, touch panels, solid-state imaging devices, and the like. However, in these materials, a large amount of fluorine-containing siloxane compound and particles such as silica nanoparticles and hollow silica are added in order to reduce the refractive index. In addition, a decrease in heat resistance was unavoidable, and when the particles were processed into a pattern, fine irregularities on the surface and edges were unavoidable. A low-refractive-index material excellent in heat resistance and chemical resistance without addition of particles was strongly demanded.

JP 2007-119744 A JP 2013-014680 A JP 2015-129908 A

In order to solve the problems described above, the present invention provides a resin composition which is a low refractive index material having excellent heat resistance, excellent chemical resistance, and excellent pattern workability without adding particles. With the goal.

That is, the present invention provides a resin composition containing (A) a polysiloxane and (B) a solvent, wherein the (A) polysiloxane has a structure represented by the following general formulas (1) to (3). A resin composition comprising at least one or more structures having at least one structure represented by the following general formulas (4) and (5).

(Y is an alicyclic or aromatic linking group having 5 to 10 carbon atoms. R ¹ is a single bond or an alkylene group having 1 to 4 carbon atoms, and R ² is independently hydrogen or 1 carbon atom. To 4 alkyl groups, R ³ are independently an organic group having 1 to 8 carbon atoms, X is a hydrogen atom or an acid dissociable group, a is an integer of 1 to 3, and n is an integer of 1 to 10. )

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

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

Hereinafter, the present invention will be described in detail.

<(A) polysiloxane>
The resin composition of the present invention has at least one structure represented by the following general formulas (1) to (3) and at least one structure represented by the following general formulas (4) to (5) It contains the polysiloxane contained above. By including at least one or more of the structures represented by (1) to (3) and at least one or more of the structures represented by (4) to (5) in the polysiloxane, Since the alkali dissolution inhibiting effect due to the interaction between the photosensitizer and the silanol can be exhibited while enhancing the alkali solubility, the contrast between the exposed and unexposed portions before and after development can be increased, and a film having excellent resolution can be obtained.

(Y is an alicyclic or aromatic linking group having 5 to 10 carbon atoms. R ¹ is a single bond or an alkylene group having 1 to 4 carbon atoms, and R ² is independently hydrogen or 1 carbon atom. To 4 alkyl groups, R ³ are independently an organic group having 1 to 8 carbon atoms, X is a hydrogen atom or an acid dissociable group, a is an integer of 1 to 3, and n is an integer of 1 to 10. )
In the structures represented by the general formulas (1) to (3), Y is an alicyclic or aromatic linking group having 5 to 10 carbon atoms. R ¹ is a single bond or an alkylene group having 1 to 4 carbon atoms; R ² is independently hydrogen or an alkyl group having 1 to 4 carbon atoms; R ³ is independently an organic group having 1 to 8 carbon atoms; Represents a hydrogen atom or an acid dissociable group, a represents an integer of 1 to 3, and n represents an integer of 1 to 10.

Specific examples of the alkylene group for R ¹ include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, and a t-butylene group.

Specific examples of the alkyl group for R ² include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutoxy group, a t-butyl group, and the like.

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

X is a hydrogen atom or an acid dissociable group, and when there are a plurality of Xs, the Xs may be the same or different. Here, the acid dissociable group is a group that dissociates in the presence of an acid to generate a polar group. The acid dissociable group has an acetal structure or a ketal structure which is relatively stable to alkali, and these are dissociated by the action of an acid. Specific examples include, but are not limited to, an alkoxycarbonyl group, an acetal group, a silyl group, and an acyl group. Examples of the alkoxycarbonyl group include a tert-butoxycarbonyl group, a tert-amyloxycarbonyl group, a methoxycarbonyl group, an ethoxycarbonyl group, an i-propoxycarbonyl group, and the like. As the acetal group, methoxymethyl group, ethoxyethyl group, butoxyethyl group, cyclohexyloxyethyl group, benzyloxyethyl group, phenethyloxyethyl group, ethoxypropyl group, benzyloxypropyl group, phenethyloxypropyl group, ethoxybutyl group, An ethoxyisobutyl group is exemplified. Examples of the silyl group include a trimethylsilyl group, an ethyldimethylsilyl group, a methyldiethylsilyl group, a triethylsilyl group, an i-propyldimethylsilyl group, a methyldi-i-propylsilyl group, a tri-i-propylsilyl group, and tert-butyl. Examples include a dimethylsilyl group, a methyldi-tert-butylsilyl group, a tri-tert-butylsilyl group, a phenyldimethylsilyl group, a methyldiphenylsilyl group, and a triphenylsilyl group. Examples of the acyl group include, for example, acetyl, propionyl, butyryl, heptanoyl, hexanoyl, valeryl, pivaloyl, isovaleryl, lauryloyl, myristoyl, palmitoyl, stearoyl, oxalyl, malonyl, succinyl Group, glutaryl group, adipoyl group, piperoyl group, suberoyl group, azeolaoyl group, sebacoil group, acryloyl group, propioloyl group, methacryloyl group, crotonoyl group, oleoyl group, maleoyl group, fumaroyl group, mesaconoyl group, camphoryl group, benzoyl group , Phthaloyl, isophthaloyl, terephthaloyl, naphthoyl, toluoyl, hydroatropoyl, atropoyl, cinnamoyl, furoyl, tenoyl, nicotinoyl, isonico It can be exemplified alkanoyl group. Those in which part or all of the hydrogen atoms of these acid dissociable groups are substituted with fluorine atoms can also be used. Further, a single kind of these acid dissociable groups may be introduced into the polysiloxane compound (A), or a plurality of kinds may be introduced.

構造 The structures represented by the general formulas (1) to (3) are the same, but are also represented by the following (1 ′) to (3 ′).

構造 Further, the structures represented by the general formulas (4) and (5) are the same, but are also represented by the following (4 ') and (5').

構造 The structures represented by the general formulas (1) to (3) are preferably the structures represented by the following general formulas (6) to (8). With the following structure, the compatibility between the photosensitive agent and the siloxane is improved, so that it is possible to prevent the film from becoming cloudy due to phase separation at the time of thermosetting, and to form a cured film without impairing the transparency.

As a specific example of the portion represented by the above general formula, a is an integer of 1 to 3, but from the viewpoint of solubility and chemical resistance, a is preferably 1 to 2, and more preferably a.
When these specific examples are represented by general formulas, the following structures can be mentioned.

Here, * indicates a bond directly connected to R ¹ . When R ¹ is a single bond, it represents a bond directly connected to a silicon atom. By containing these structures, it is possible to obtain a composition having a low refractive index, excellent coating properties, and excellent pattern processing properties. These structures are preferably contained in the polysiloxane (A) in an amount of 5 to 50 mol%, more preferably 5 to 30 mol%. The content ratio of the organosilane units represented by the general formulas (1) to (3) can be determined by measuring ²⁹ Si-NMR of polysiloxane, and determining the peak area of Si having an aromatic group bonded thereto and the ratio of the aromatic group being bonded. It can be determined from the ratio of the peak area of the Si derived from the untreated organosilane unit.

The organosilane units represented by the general formulas (1) to (3) can be identified using ¹ H-NMR, ¹⁹ F-NMR, ¹³ C-NMR, IR, TOF-MS, and the like.

Next, in the structure represented by the general formula (4) or (5), R ² independently represents hydrogen or an alkyl group having 1 to 4 carbon atoms. Specific examples of the siloxane having the structure represented by the general formula (4) or (5) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, tetratertiarybutoxysilane, Methyl silicate 51 (manufactured by Fuso Chemical Industry Co., Ltd.), M silicate 51, silicate 40, silicate 45 (manufactured by Tama Chemical Industry Co., Ltd.), methyl silicate 51, methyl silicate 53A, ethyl silicate 48 (manufactured by Colcoat Co., Ltd.) and the like. Can be By containing these organosilanes, the chemical resistance can be improved. A desirable content is 5 to 50 mol%, more preferably 5 to 30 mol%, in the polysiloxane that is a hydrolyzed condensate. The content ratio of the organosilane unit represented by the general formula (4) or (5) is determined by ¹ H-NMR, ¹³ C-NMR, ²⁹ Si-NMR, IR, TOF-MS, elemental analysis, ash measurement, and the like. Can be obtained in combination.

(A) The polysiloxane may further contain a structure represented by the following general formulas (9) to (11).

(R ² is independently hydrogen or an alkyl group having 1 to 4 carbon atoms, R ³ is independently an organic group having 1 to 8 carbon atoms, and R ⁴ is an organic group having 1 to 10 carbon atoms having a fluoro group. Represents a group.)
Specific examples of the fluorine-containing silane compound having the structure of the general formulas (9) to (11) include trifluoroethyltrimethoxysilane, trifluoroethyltriethoxysilane, trifluoroethyltriisopropoxysilane, and trifluoropropyltrisilane. Methoxysilane, trifluoropropyltriethoxysilane, trifluoropropyltriisopropoxysilane, heptadecafluorodecyltrimethoxysilane, heptadecafluorodecyltriethoxysilane, heptadecafluorodecyltriisopropoxysilane, tridecafluorooctyltriethoxysilane , Tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriisopropoxysilane, trifluoroethylmethyldimethoxysilane, trifluoroethylmethyl Ethoxysilane, trifluoroethylmethyldiisopropoxysilane, trifluoropropylmethyldimethoxysilane, trifluoropropylmethyldiethoxysilane, trifluoropropylmethyldiisopropoxysilane, heptadecafluorodecylmethyldimethoxysilane, heptadecafluorodecylmethyldimethoxysilane Ethoxysilane, heptadecafluorodecylmethyldiisopropoxysilane, tridecafluorooctylmethyldimethoxysilane, tridecafluorooctylmethyldiethoxysilane, tridecafluorooctylmethyldiisopropoxysilane, trifluoroethylethyldimethoxysilane, trifluoroethyl Ethyldiethoxysilane, trifluoroethylethyldiisopropoxysilane, trifluoropropylethyldimethyl Xysilane, trifluoropropylethyldiethoxysilane, trifluoropropylethyldiisopropoxysilane, heptadecafluorodecylethyldimethoxysilane, heptadecafluorodecylethyldiethoxysilane, heptadecafluorodecylethyldiisopropoxysilane, tridecafluorooctyl Examples include ethyldiethoxysilane, tridecafluorooctylethyldimethoxysilane, and tridecafluorooctylethyldiisopropoxysilane. Two or more of these may be used.

Among these, from the viewpoint of chemical resistance, trifluoroethyltrimethoxysilane, trifluoroethyltriethoxysilane, trifluoroethyltriisopropoxysilane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, trifluoropropyl Triisopropoxysilane, heptadecafluorodecyltrimethoxysilane, heptadecafluorodecyltriethoxysilane, heptadecafluorodecyltriisopropoxysilane, tridecafluorooctyltriethoxysilane, tridecafluorooctyltrimethoxysilane, tridecafluorooctyl Preferably, triisopropoxysilane is used. From the viewpoint of forming a uniform coating film, it is particularly preferable to use trifluoroethyltrimethoxysilane, trifluoropropyltrimethoxysilane, heptadecafluorodecyltrimethoxysilane, and tridecafluorooctyltrimethoxysilane. The content in the polysiloxane (A) is preferably from 5 to 50 mol%, more preferably from 10 to 40 mol%, from the viewpoint of chemical resistance.
The polysiloxane (A) used in the resin composition of the present invention may be copolymerized with another organosilane compound in addition to the above-mentioned organosilane compound. Specific examples of the copolymerizable organosilane compound include methyltrimethoxysilane, methyltriethoxysilane, methyltri (methoxyethoxy) silane, methyltripropoxysilane, methyltriisopropoxysilane, methyltributoxysilane, and ethyltrimethoxysilane. , Ethyltriethoxysilane, hexyltrimethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (2aminoethyl) -3-aminopropyltri Methoxysilane, 3-chloropropyltrimethoxysilane, 3- (N, N-glycidyl) aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, γ-aminopropyl Trimethoxysilane, γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, β-cyanoethyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxy Silane, α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxy Silane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltriisopropoxysilane, γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyltri (Methoxyet Xy) silane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltrimethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyl Trimethoxysilane, γ-glycidoxybutyltriethoxysilane, σ-glycidoxybutyltrimethoxysilane, σ-glycidoxybutyltriethoxysilane, (3,4-epoxycyclohexyl) methyltrimethoxysilane, (3 4- (epoxycyclohexyl) methyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltripropoxysilane, 2- (3,4-epoxycyclohexyl) ethyltributoxysilane, 2- (3,4-epoxycyclohexyl) Ethyltrimethoxysilane, 2- ( 3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriphenoxysilane, 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane, 3- (3,4-epoxycyclohexyl) ) Propyltriethoxysilane, 4- (3,4-epoxycyclohexyl) butyltrimethoxysilane, 4- (3,4-epoxycyclohexyl) butyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, γ-glycidoxy Propylmethyldimethyldimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, glycidoxymethyldimethoxy Sisilane, glycidoxymethylmethyldiethoxysilane, α-glycidoxyethylmethyldimethoxysilane, α-glycidoxyethylmethyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylmethyldi Ethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylmethyldiethoxysilane, γ-glycidoxy Propylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, β-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldi (methoxyethoxy) Orchid, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropylmethyldiethoxysilane, cyclohexylmethyldimethoxysilane, octadecylmethyldimethoxysilane, Tetramethoxysilane, tetraethoxysilane, γ-acryloylpropyltrimethoxysilane, γ-acryloylpropyltriethoxysilane, γ-acryloylpropyltri (methoxyethoxy) silane, γ-methacryloylpropyltrimethoxysilane, γ-methacryloylpropyltriethoxysilane , Γ-methacryloylpropyltri (methoxyethoxy) silane, γ-methacryloylpropylmethyldimethoxysilane, γ-methacryloylpropyl Methyl diethoxy silane, .gamma. acryloyl propyl methyl dimethoxy silane, .gamma. acryloyl propyl methyl diethoxy silane, .gamma.-methacryloxypropyltrimethoxysilane such as acryloyl propyl (methoxyethoxy) silane.

Two or more of these may be used. Further, an organosilane compound having a hydrophilic group may be copolymerized as a raw material of the polysiloxane, if necessary. As the organosilane compound having a hydrophilic group, an organosilane compound having a carboxylic acid structure or an organosilane compound having a carboxylic acid anhydride structure is preferable, and an organosilane compound having a carboxylic acid anhydride structure is more preferable.

具体 Specific examples of the organosilane compound having a carboxylic anhydride structure include an organosilane compound represented by any of the following formulas (12) to (14). Two or more of these may be used.

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

Specific examples of R ⁸ , R ¹² and R ¹⁶ include —C ₂ H ₄ —, —C ₃ H ₆ —, —C ₄ H ₈ —, —O—, —C ₃ H ₆ OCH ₂ CH (OH) Examples include CH ₂ O ₂ C—, —CO—, —CO ₂ —, and —CONH—, and the following organic groups.

Specific examples of the organosilane compound represented by the general formula (12) include 3-trimethoxysilylpropylsuccinic anhydride, 3-triethoxysilylpropylsuccinic anhydride, and 3-triphenoxysilylpropylsuccinic anhydride. Things.

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

具体 Specific examples of the organosilane compound represented by the general formula (14) include 3-trimethoxysilylpropyl phthalic anhydride.

The content of the component derived from the hydrolysis / condensation reaction product (siloxane compound) of the alkoxysilane compound in the resin composition is preferably at least 10% by mass, more preferably at least 20% by mass, based on the total solid content excluding the solvent. preferable. Further, the content is more preferably 80% by mass or less. By containing the siloxane compound in this range, the transmittance and crack resistance of the coating film can be further increased.

The hydrolysis reaction is preferably carried out at room temperature to 110 ° C. for 1 to 180 minutes after adding an acid catalyst and water to the above alkoxysilane compound in a solvent over 1 to 180 minutes. By performing the hydrolysis reaction under such conditions, a rapid reaction can be suppressed. The reaction temperature is more preferably from 40 to 105 ° C.

(4) After the silanol compound is obtained by the hydrolysis reaction, the reaction solution is preferably heated at 50 ° C. or higher and the boiling point of the solvent for 1 to 100 hours to conduct a condensation reaction. Further, in order to increase the degree of polymerization of the siloxane compound obtained by the condensation reaction, reheating or addition of a base catalyst can be performed.

Various conditions for hydrolysis are to obtain physical properties suitable for the intended use by setting, for example, acid concentration, reaction temperature, reaction time, etc. in consideration of the reaction scale, the size and shape of the reaction vessel, etc. Can be.

(4) Examples of the acid catalyst used in the hydrolysis reaction include acid catalysts such as hydrochloric acid, acetic acid, formic acid, nitric acid, oxalic acid, hydrochloric acid, sulfuric acid, phosphoric acid, polyphosphoric acid, polycarboxylic acids or anhydrides thereof, and ion exchange resins. Particularly, an acidic aqueous solution using formic acid, acetic acid or phosphoric acid is preferable.

The preferred content of the acid catalyst is preferably at least 0.05 part by mass, more preferably at least 0.1 part by mass, based on 100 parts by mass of all the alkoxysilane compounds used in the hydrolysis reaction. , Preferably 10 parts by mass or less, more preferably 5 parts by mass or less. Here, the total amount of the alkoxysilane compound refers to an amount including all of the alkoxysilane compound, its hydrolyzate, and its condensate, and hereinafter the same. When the amount of the acid catalyst is 0.05 parts by mass or more, the hydrolysis proceeds smoothly, and when the amount is 10 parts by mass or less, the control of the hydrolysis reaction becomes easy.

The weight average molecular weight (Mw) of the polysiloxane (A) used in the resin composition of the present invention is not particularly limited, but is preferably 1,000 or more in terms of polystyrene measured by gel permeation chromatography (GPC). More preferably, it is 2,000 or more. Further, it is preferably at most 100,000, more preferably at most 50,000. By setting Mw within the above range, good coating characteristics can be obtained, and the solubility in a developing solution at the time of pattern formation also becomes good.

In the resin composition of the present invention, the content of the polysiloxane (A) is not particularly limited and can be arbitrarily selected depending on the desired film thickness and intended use, but is generally 5% by mass to 80% by mass in the resin composition. It is. Further, the content is preferably from 5% by mass to 50% by mass, more preferably from 20% by mass to 40% by mass in the solid content.

水 Ion-exchanged water is preferable as the water used for the hydrolysis reaction. The amount of water can be arbitrarily selected, but is preferably used in the range of 1.0 to 4.0 mol per 1 mol of the alkoxysilane compound.

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 above catalyst, and the catalyst can be removed as necessary. Although there is no particular limitation on the removal method, water washing and / or treatment with an ion-exchange resin are preferred from the viewpoint of easy operation and removability. The water washing is a method of diluting a polysiloxane solution with an appropriate hydrophobic solvent, washing the resultant with water several times, and concentrating an organic layer obtained using an evaporator or the like. The treatment with an ion exchange resin is a method in which a polysiloxane solution is brought into contact with an appropriate ion exchange resin.

The polysiloxane (A) used in the resin composition of the present invention is an organosilane compound derived from any of the structures of the above general formulas (1) to (3), and any one of the above general formulas (4) and (5). Hydrolyzing an organosilane compound derived from such a structure, and preferably an organosilane compound derived from any of the structures represented by the general formulas (9) to (11) in the presence of metal compound particles described below; When obtained by condensation of the hydrolyzate, the refractive index and hardness of the cured film are further improved. By performing polymerization of the polysiloxane in the presence of the metal compound particles, a chemical bond (covalent bond) with the metal compound particles is generated in at least a part of the polysiloxane, and the metal compound particles are uniformly dispersed to preserve the coating liquid. It is considered that the stability and the uniformity of the cured film are improved. Further, the refractive index of the obtained cured film can be adjusted depending on the type of the metal compound particles. As the metal compound particles, those exemplified as metal compound particles described later can be used.

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

溶剤 The solvent used in the resin composition of the present invention is not particularly limited, but it is preferable to contain at least one aromatic hydrocarbon solvent having a hetero atom. Aromatic hydrocarbon solvents containing heteroatoms have high polarity but high solubility of organic compounds having a rigid skeleton such as naphthoquinonediazide. In the evaluation of the photosensitivity of the coating film, the reduction of the developed film can be suppressed, and the contrast between the unexposed portion and the exposed portion can be increased. Further, in order to improve the handleability as a solvent, it is preferable that the liquid be a liquid at 23 ° C. and 1 atm. If the melting point is higher than this, it is necessary to heat the material during use, and it becomes difficult to treat it as a solvent. Further, the boiling point of the solvent is preferably from 100 ° C to 300 ° C, more preferably from 120 ° C to 250 ° C. When the boiling point is 100 ° C. 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. When the boiling point is 300 ° C. or lower, the solvent hardly remains after the film is thermally cured, and the outgas 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-methylbenzyl alcohol, 4-isopropylbenzyl alcohol, 1-phenylethyl alcohol, 2-phenyl-2-propanol, 2-ethylbenzyl alcohol, 3-ethylbenzyl alcohol, 4-ethylbenzyl alcohol, anisole, 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.

含有 The content of these solvents is preferably from 10 to 50% by mass, more preferably from 20 to 40% by mass, based on all the solvents in the resin composition. When the content is 50% by mass or less, the drying property is improved when the resin composition is applied and dried. When the content is 10% by mass or more, the compatibility between the siloxane and the photosensitive agent is improved, and the coating property is improved.

Other preferred examples of the solvent (B) used in the resin composition of the present invention include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol monopropyl. Ethers such as ether, propylene glycol monobutyl ether, propylene glycol mono-t-butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether; ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propyl acetate, butyl Acetate, isobutyl acetate, 3-methoxybutyl acetate Acetates, such as acetate, 3-methyl-3-methoxybutyl acetate, methyl lactate, ethyl lactate, butyl lactate, ethyl acetoacetate, methyl acetoacetate, propyl acetoacetate, butyl acetoacetate, and benzyl acetoacetate; acetylacetone, methylpropyl Ketones such as ketone, methyl butyl ketone, methyl isobutyl ketone, cyclopentanone, 2-heptanone; methanol, ethanol, propanol, butanol, isobutyl alcohol, pentanol, 4-methyl-2-pentanol, 3-methyl-2 Alcohols such as -butanol, 3-methyl-3-methoxy-1-butanol and diacetone alcohol; aromatic hydrocarbons such as toluene and xylene; and γ-butyrolactone, N-methylpyrrolidinone and the like. These may be used alone or as a mixture.

Among these, particularly preferred examples of the solvent include 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, and diacetone alcohol. , Γ-butyrolactone, ethyl lactate and the like. These may be used alone or in combination of two 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, more preferably 100 parts by mass to 5000 parts by mass, based on 100 parts by mass of the total alkoxysilane compound content. Range.

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

In the formula, R ¹⁷ , R ¹⁸ , and R ¹⁹ each independently represent any one of an alkyl group having 1 to 10 carbon atoms, a carboxyl group, a phenyl group, and a substituted phenyl group. Further, R ¹⁷ , R ¹⁸ and R ¹⁹ may form a ring. The alkyl group may be either unsubstituted or substituted, and can be selected according to the characteristics of the composition. Specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-hexyl, cyclohexyl, n-heptyl, and n-butyl. Examples include an 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. Specific examples of the case where R ¹⁷ , R ¹⁸ , and R ¹⁹ form a ring include a cyclopentane ring, a cyclohexane ring, an adamantane ring, and a fluorene ring.

When the ortho-position and para-position of the phenolic hydroxyl group are other than those described above, for example, a methyl group, oxidative decomposition occurs by thermal curing, a conjugated compound represented by a quinoid structure is formed, and the cured film is colored to be colorless and transparent. Decrease. In addition, these naphthoquinonediazide compounds can be synthesized by a known esterification reaction between a compound having a phenolic hydroxyl group and naphthoquinonediazidesulfonic acid chloride.

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

As naphthoquinonediazidesulfonic acid chloride as a raw material, 4-naphthoquinonediazidesulfonic acid chloride or 5-naphthoquinonediazidesulfonic acid chloride can be used. The 4-naphthoquinonediazidosulfonic acid ester compound is suitable for i-line exposure because it has absorption in the i-line (wavelength 365 nm) region. Further, the 5-naphthoquinonediazidosulfonic acid ester compound has absorption in a wide range of wavelengths, and thus is suitable for exposure to a wide range of wavelengths. It is preferable to select a 4-naphthoquinonediazidesulfonic acid ester compound or a 5-naphthoquinonediazidosulfonic acid ester compound according to the wavelength of light to be exposed. It is also possible to use a mixture of a 4-naphthoquinonediazidesulfonic acid ester compound and a 5-naphthoquinonediazidosulfonic acid ester compound.
A naphthoquinonediazide compound preferably used in the present invention includes a compound represented by the following general formula (16).

In the formula, R ²⁰ represents hydrogen or an alkyl group selected from 1 to 8 carbon atoms. R ²¹ , R ²² , and R ^{23 each} represent a hydrogen atom, an alkyl group selected from 1 to 8 carbon atoms, an alkoxyl group, a carboxyl group, or an ester group. Each of R ²¹ , R ²² and R ²³ may be the same or different. Q represents either a 5-naphthoquinonediazidosulfonyl group or a hydrogen atom, and not all of Q is a hydrogen atom. b, c, d, α, and β represent an integer of 0 to 4. Here, α + β ≧ 3. By using the naphthoquinonediazide compound represented by the general formula (16), sensitivity and resolution in pattern processing are improved.

The addition amount of the naphthoquinonediazide compound is not particularly limited, but is preferably 1 to 30 parts by mass, more preferably 1 to 15 parts by mass, per 100 parts by mass of the resin (polysiloxane). When the addition amount of the naphthoquinonediazide compound is less than 1 part by mass, the dissolution contrast between the exposed and unexposed portions is too low and does not exhibit practically sufficient photosensitivity. In order to obtain a better dissolution contrast, the amount is preferably 5 parts by mass or more. On the other hand, when the addition amount of the naphthoquinonediazide compound is more than 30 parts by mass, whitening of the coating film occurs due to poor compatibility between the polysiloxane and the naphthoquinonediazide compound, or coloring due to decomposition of the quinonediazide compound which occurs during heat curing. Because it becomes remarkable, the colorless transparency of the cured film decreases. Further, in order to obtain a highly transparent film, the amount is preferably 15 parts by mass or less.

<(D) Metal compound particles>
The present invention preferably contains metal compound particles. The metal compound particles are not particularly limited, but preferably contain (D) silica particles from the viewpoint of adjusting the refractive index. (D) In the presence of silica particles and (B) a solvent, a silane compound derived from any of the structures of the above general formulas (1) to (3) and a structure of the above general formulas (4) and (5) From the viewpoint of compatibility, it is preferable to use a composite siloxane resin with silica particles (D) obtained by subjecting a derived silane compound to a condensation reaction after hydrolysis. (D) The silica particles preferably have a number average particle diameter of 1 to 200 nm. In order to obtain a cured film having high visible light transmittance, the number average particle diameter is more preferably from 1 to 120 nm. Among them, in the case of hollow silica particles, the number average particle diameter is more preferably 30 to 100 nm. If it is 1 nm or more, the low refractive index property is sufficient, and if it is 200 nm or less, the reflection is sufficiently suppressed, and the hardness of the film is sufficiently high. (D) The number average particle diameter of the silica particles should be measured by a gas adsorption method, a dynamic light scattering method, an X-ray small angle scattering method, a method of directly measuring the particle diameter by a transmission electron microscope or a scanning electron microscope, or the like. Can be. The number average particle diameter of the particles in the present invention refers to a value measured by a dynamic light scattering method.

(D) The silica particles (D) used in the present invention include silica particles having a porous and / or hollow inside and silica particles that are not porous and have no hollow inside. Among these (D) silica particles, silica particles having a porous and / or hollow inside are preferred for lowering the refractive index of the coating film. Silica particles that are not porous and do not have hollows have a small refractive index reduction effect because the particles themselves have a refractive index of 1.45 to 1.5. On the other hand, silica particles having a porous and / or hollow interior have a large effect of lowering the refractive index because the particles themselves have a refractive index of 1.2 to 1.4. That is, silica particles having a porous and / or hollow inside are preferably used because they can impart excellent hardness and can impart low refractive index.

シリカ Silica particles having a hollow inside, preferably used in the present invention, refer to silica particles having a hollow portion surrounded by an outer shell. Further, the silica particles having a porous inside used in the present invention refers to silica particles having a large number of cavities on the surface or inside of the particles. Among these, in consideration of the hardness of the transparent coating, silica particles having hollows with high strength of the particles themselves are preferable. (D) The silica particles themselves preferably have a refractive index of 1.2 to 1.4, more preferably 1.2 to 1.35. These silica particles (D) can be produced by the methods disclosed in Japanese Patent No. 3272111 and Japanese Patent Application Laid-Open No. 2001-233611. Examples of such (D) silica particles include, for example, those disclosed in JP-A-2001-233611 and those 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 mixed solution sample of (D) a matrix resin having a solid content concentration of 10% and a silica particle (D) prepared by adjusting the content of silica particles to 0% by mass, 20% by mass, 30% by mass, 40% by mass, and 50% by mass was prepared. Each of them was prepared and applied on a silicon wafer using a spin coater to a thickness of 0.3 to 1.0 μm, and then heated and dried on a hot plate at 200 ° C. for 5 minutes to form a coating film. Get. Next, the refractive index at a wavelength of 633 nm is determined using, for example, an ellipsometer (manufactured by Otsuka Electronics Co., Ltd.), and the value can be determined by extrapolating the value of (D) 100% by mass of the silica particles.

Introducing silica particles having a porous and / or hollow inside into the coating material can not only optimize the refractive index of the film obtained from the coating material but also increase the hardness of the film. preferable.

The silica particles which are not porous and have no hollow are, for example, IPA-ST using 12 nm particle size isopropanol as a dispersant, MIBK-ST using 12 nm particle size methyl isobutyl ketone as a dispersant, particles IPA-ST-L using isopropanol having a diameter of 45 nm as a dispersing agent, IPA-ST-ZL using isopropanol having a particle diameter of 100 nm as a dispersing agent (trade name, manufactured by Nissan Chemical Industries, Ltd.), γ having a particle diameter of 12 nm -Oscar 101 using butyrolactone as a dispersant, Oscar 105 using 60-nm-diameter γ-butyrolactone as a dispersant, and Oscar 106 using 120-nm-diameter diacetone alcohol as a dispersant. Co., Ltd.). In addition, the presence or absence of the hollow can be confirmed by a particle cross-sectional image by a TEM (scanning electron microscope) photograph.

Examples of commercially available (D) silica particles include organosilica sol “OSCAL” (manufactured by JGC Catalysts & Chemicals, Inc.), colloidal silica “Snowtex”, organosilica sol (manufactured by Nissan Chemical Industries, Ltd.), High-purity colloidal silica, high-purity organosol “Quartron” (Fuso Chemical Industry Co., Ltd.) and the like can be mentioned.

得る Further, 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 the hollow can be confirmed by a particle cross-sectional image by a TEM (scanning electron microscope) photograph. (D) The content of the silica particles is not particularly limited and may be an appropriate amount depending on the application, but is generally about 1 to 80% by mass of the total solids of the siloxane-based resin composition. .

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

シロキサン The siloxane resin composition of the present invention may contain various curing agents for accelerating the curing of the resin composition or facilitating the curing. Specific examples of the curing agent include nitrogen-containing organic substances, silicone resin curing agents, various metal alcoholates, various metal chelate compounds, isocyanate compounds and polymers thereof, methylolated melamine derivatives, methylolated urea derivatives, and the like. Or two or more kinds. Among them, a metal chelate compound is preferably used in view of transparency of a coating film, stability of a 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 chelate compounds can be easily obtained by reacting a metal alkoxide with a chelating agent. Examples of the chelating agent include β-diketones such as acetylacetone, benzoylacetone, and dibenzoylmethane; and β-keto acid esters such as ethyl acetoacetate and ethyl benzoylacetate. Preferred specific examples of the metal chelate compound include ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate), alkyl acetoacetate aluminum diisopropylate, aluminum monoacetyl acetate bis (ethyl acetoacetate), and aluminum tris ( Aluminum chelate compounds such as acetylacetonate), magnesium chelate compounds such as ethyl acetoacetate magnesium monoisopropylate, magnesium bis (ethyl acetoacetate), alkyl acetoacetate magnesium monosopropylate, and magnesium bis (acetylacetonate). . The content of the curing agent is preferably 0.1% by mass to 10% by mass, more preferably 0.5% by mass to 6% by mass, based on the solid content in the siloxane resin composition.

(4) Since curing of polysiloxane is accelerated by an acid, the resin composition of the present invention may contain a curing catalyst such as a thermal acid generator. 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.

As specific examples, as the sulfonium salt, 4-hydroxyphenyldimethylsulfonium triflate (prototype "W" manufactured by Sanshin Chemical Industry Co., Ltd.) and benzyl-4-hydroxyphenylmethylsulfonium triflate (prototype) “O” (manufactured by Sanshin Chemical Industry Co., Ltd.), 2-methylbenzyl-4-hydroxyphenylmethylsulfonium triflate (prototype “N” manufactured by Sanshin Chemical Industry Co., Ltd.), 4-methylbenzyl-4 -Hydroxyphenylmethylsulfonium triflate, 4-hydroxyphenylmethyl-1-naphthylmethylsulfonium triflate, 4-methoxycarbonyloxyphenyldimethylsulfonium triflate (prototype "J" Sansan Chemical Industry Co., Ltd. )), Benzyl-4-methoxycarbonyloxyphenyl Tylsulfonium triflate (prototype "T" @ Sanshin Chemical Industry Co., Ltd.), 4-acetoxyphenylbenzylmethylsulfonium triflate (prototype "U" @ Sanshin Chemical Industry Co., Ltd.), 4- Acetoxyphenylmethyl-4-methylbenzylsulfonium triflate, 4-acetoxyphenyldimethylsulfonium triflate (prototype "V" manufactured by Sanshin Chemical Industry Co., Ltd.), 4-hydroxyphenyldimethylsulfonium hexafluoro Phosphate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 2-methylbenzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 4-methylbenzyl-4-hydroxyphenylmethylsulfonium hexa full Lophosphate, 4-hydroxyphenylmethyl-1-naphthylmethylsulfonium hexafluorophosphate, 4-methoxycarbonyloxyphenyldimethylsulfonium hexafluorophosphate, benzyl-4-methoxycarbonyloxyphenylmethylsulfonium hexafluoro Phosphate, 4-acetoxyphenylbenzylmethylsulfonium hexafluorophosphate (prototype "A" manufactured by Sanshin Chemical Industry Co., Ltd.), 4-acetoxyphenylmethyl-4-methylbenzylsulfonium hexafluorophosphate, 4-acetoxyphenyldimethylsulfonium hexafluorophosphate (trade name “SI-150” manufactured by Sanshin Chemical Industry Co., Ltd.), “SI-180L” (manufactured by Sanshin Chemical Industry Co., Ltd.) ), 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 2-methylbenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 4- Methylbenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 4-hydroxyphenylmethyl-1-naphthylmethylsulfonium hexafluoroantimonate, 4-methoxycarbonyloxyphenyldimethylsulfonium hexafluoroantimonate, benzyl -4-methoxycarbonyloxyphenylmethylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylmethylsulfonate Hexafluoroantimonate, 4-acetoxyphenylmethyl-4-methylbenzylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexafluoroantimonate, Benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate;

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

Examples of the diaryliodonium salt include diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, diphenyliodonium triflate, 4,4′-di-t-butyl-diphenyliodonium triflate, 4,4'-di-t-butyl-diphenyliodonium tetrafluoroborate, 4,4'-di-t-butyl-diphenyliodonium hexafluorophosphate and the like.

Examples of the triarylsulfonium salt include triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, tri (p-chlorophenyl) sulfonium tetrafluoroborate, (P-chlorophenyl) sulfonium hexafluorophosphate, tri (p-chlorophenyl) sulfonium hexafluoroantimonate, 4-t-butyltriphenylsulfonium hexafluorophosphate, and the like.

Examples of triarylselenium salts include triphenylselenium tetrafluoroborate, triphenylselenium hexafluorophosphate, triphenylselenium hexafluoroantimonate, di (chlorophenyl) phenylselenium tetrafluoroborate, and di (chlorophenyl) phenylselenium hexafluoro Phosphate, di (chlorophenyl) phenyl selenium hexafluoroantimonate and the like can be mentioned.

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

Examples of the halogen compound include 2-chloro-2-phenylacetophenone, 2,2 ', 4'-trichloroacetophenone, 2,4,6-tris (trichloromethyl) -s-triazine, and 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-trichloro Ethane and the like.

In addition, 5-norbornene-2,3-dicarboximidyl triflate (trade name “NDI-105” manufactured by Midori Kagaku Co., Ltd.), 5-norbornene-2,3-dicarboximidyl tosylate (trade name “NDI -101 "manufactured by Midori Kagaku Co., Ltd.), 4-methylphenylsulfonyloxyimino-α- (4-methoxyphenyl) acetonitrile (trade name" PAI-101 "manufactured by Midori Kagaku Co., Ltd.), trifluoromethylsulfonyloxyimino -Α- (4-methoxyphenyl) acetonitrile (trade name “PAI-105” manufactured by Midori Kagaku Co., Ltd.), 9-camphorsulfonyloxyimino α-4-methoxyphenylacetonitrile (trade name “PAI-106”) Midori Chemical ( Co., Ltd.), 1,8-naphthalimidylbutanesulfonate ( Product name "NAI-1004" (manufactured by Midori Kagaku Co., Ltd.), 1,8-naphthalimidyl tosylate (trade name "NAI-101" manufactured by Midori Kagaku Co., Ltd.), 1,8-naphthalimidyl triflate ( Thermal acid generators such as NAI-105 (trade name, manufactured by Midori Kagaku Co., Ltd.) and 1,8-naphthalimidyl nonafluorobutane sulfonate (trade name "NAI-109," manufactured by Midori Kagaku Co., Ltd.) Can also be mentioned as an example.

樹脂 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 flowability at the time of application. There is no particular limitation on the type of surfactant, and for example, “MegaFac (registered trademark)” F142D, F172, F173, F183, F430, F444, F445, F470, F475, F477, F553, F554, F555, F556, F559, F560, F563 (all manufactured by Dainippon Ink and Chemicals, Inc.), NBX-15, FTX-218, DFX-18 (Neos Corporation) Fluorinated surfactants such as LE-604, LE-605, LE-606, LE-607 (manufactured by Kyoeisha Chemical Co., Ltd.), BYK-333, BYK-301, BYK-331, BYK-345, BYK-307 (manufactured by BYK Japan KK) KL-402, KL-403, KL-404, KL-700, LE-302, LE-30 , LE-304, LE-604, LE-605, LE-606, LE-607 (manufactured by Kyoeisha Chemical Co., Ltd.), silicone-based surfactants, polyalkylene oxide-based surfactants, poly (meth) acrylate-based surfactants Surfactants and the like can be used. Two or more of these may be used.

Furthermore, the resin composition of the present invention may contain, if necessary, a silane coupling agent, a crosslinking agent, a crosslinking accelerator, a sensitizer, a thermal radical generator, a dissolution accelerator, a dissolution inhibitor, a stabilizer, and an antifoaming agent. And the like.

<Method of forming cured film>
The cured film of the present invention is obtained by curing the resin composition of the present invention or the photosensitive resin composition which is the resin composition of the present invention. Here, the photosensitive resin composition will be described in detail. One embodiment of the method for producing a cured film of the photosensitive resin composition preferably includes the following steps.
(I) a step of applying a photosensitive resin composition on a substrate to form a coating film;
(II) a step of exposing and developing the coating, and (III) a step of heating the developed coating.
An example will be described below.

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

After pre-baking, using an ultraviolet-visible exposure machine such as a stepper, a mirror projection mask aligner (MPA), or a parallel light mask aligner (PLA), and passing through a desired mask, a pattern of about 10 to 4000 J / m ² (equivalent to a wavelength of 365 nm). Expose.

After exposure, the (un) exposed area is dissolved and removed by development to obtain a negative or positive pattern. The resolution of the pattern is preferably 15 μm or less. As a developing method, it is preferable to immerse in a developing solution for 5 seconds to 10 minutes by a method such as shower, dip, or paddle. As the developing solution, a known alkali developing solution can be used. For example, inorganic alkalis such as alkali metal hydroxides, carbonates, phosphates, silicates and borates, 2-diethylaminoethanol, Examples include aqueous solutions of amines such as ethanolamine and diethanolamine, and quaternary ammonium salts such as tetramethylammonium hydroxide (TMAH) and choline. Two or more of these may be used. After development, it is preferable to rinse with water. If necessary, dehydration and baking may be performed at a temperature in the range of 50 to 150 ° C. using a heating device such as a hot plate or an oven. The film is heated (soft bake) at a temperature of 50 to 300 ° C. for 30 seconds to 30 minutes using a heating device such as a hot plate or an oven if necessary, and then heated to 150 to 300 ° C. using a heating device such as a hot plate or an oven. By heating (curing) for about 30 seconds to 2 hours in a temperature range of 450 ° C., a cured film is obtained.

The photosensitive resin composition, from the viewpoint of productivity in the pattern formation, it is preferable that the sensitivity at the time of exposure is 1500 J / ^{m 2} or less, more preferably 1000 J / ^{m 2} or less. The sensitivity at the time of exposure is determined by the following method. The photosensitive resin composition is spin-coated on a silicon wafer at an arbitrary number of revolutions using a spin coater, and prebaked at 120 ° C. for 3 minutes using a hot plate to produce a prebaked film having a thickness of 1 μm. After exposing the prebaked film using a PLA (PLA-501F manufactured by Canon Inc.) through a gray scale mask having a line and space pattern of 1 to 10 μm for sensitivity measurement using an ultra-high pressure mercury lamp, automatic development is performed. Using a device (AD-2000, manufactured by Takizawa Sangyo Co., Ltd.), develop with a 2.38% by mass aqueous solution of TMAH for 90 seconds, and then rinse with water for 30 seconds. In the formed pattern, an exposure amount for resolving a 10 μm line and space pattern with a one-to-one width is obtained as sensitivity.

(5) Thereafter, as a thermal curing step, a cured film is prepared by curing at 220 ° C. for 5 minutes using a hot plate, and the minimum pattern dimension in sensitivity is determined as the post-curing resolution.

FIG. 1 shows a specific example of the method for manufacturing a cured film according to the present embodiment. First, the resin composition of the present invention is applied on a substrate 1 to form a coating film 2. This is overheat-cured to obtain a cured film 3.

FIG. 2 shows a specific example of the method for manufacturing a cured film according to the present embodiment. The steps up to the formation of the first coating film 2 are performed as described above. Next, the coating film 2 is exposed to actinic rays 4 and exposed. This is cured by heating to obtain a cured film 3.

FIG. 3 shows a specific example of the method for manufacturing a cured film according to the present embodiment. The steps up to the formation of the first coating film 2 are performed as described above. Next, the coating film 2 is exposed to actinic light 4 via the mask 5 to be exposed. The pattern 6 is obtained by developing the exposed coating film. The pattern is irradiated with actinic rays 5 and cured by heating, whereby a cured film 3 is obtained.

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

透過 The transmittance of the cured film per 1 μm of film thickness at a wavelength of 400 nm is determined by the following method. The photosensitive resin composition is spin-coated on a Tempax glass plate using a spin coater at an arbitrary rotation speed, and prebaked at 100 ° C. for 3 minutes using a hot plate. The composition is thermally cured at 220 ° C. for 5 minutes in the air using a hot plate to produce a cured film having a thickness of 1 μm. The ultraviolet-visible absorption spectrum of the obtained cured film is measured using MultiSpec-1500 manufactured by Shimadzu Corporation, and the transmittance at a wavelength of 400 nm is determined. As another method, the extinction coefficient and the film thickness of each target cured film at each wavelength can be measured by a spectroscopic ellipsometer FE5000 manufactured by Otsuka Electronics Co., Ltd., and can be obtained by the following equation.

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

The resin composition of the present invention and a cured film obtained by curing the resin composition are suitably used for a solid-state imaging device, an optical filter, an organic EL device, and a display device such as a liquid crystal display, an organic EL television, particularly a transparent liquid crystal television. More specifically, an antireflection film of a solid-state imaging device optical filter such as a backside illumination CMOS image sensor, a color mixing prevention wall, a transparent pixel, a flattening material for a display TFT substrate, a liquid crystal display, a color filter such as a see-through display, and the like. Examples thereof include a protective film, a phase shifter, and an antireflection film. Further, it can be used as a buffer coat of a semiconductor device, an interlayer insulating film, or various protective films.

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

<Measurement of ratio of substituents>
²⁹ Si-NMR was measured, and the ratio of the integrated value to each organosilane was calculated from the total integrated value to calculate the ratio. The sample (liquid) was injected into a 10 mm diameter “Teflon” (registered trademark) NMR sample tube and used for measurement. The measurement conditions of ²⁹ Si-NMR are shown below.

Apparatus: JNM GX-270 manufactured by JEOL Ltd. Measurement method: Gated decoupling method Measurement nuclear frequency: 53.6693 MHz ( ²⁹ Si nucleus), spectrum width: 20000 Hz
Pulse width: 12 μsec (45 ° pulse), pulse repetition time: 30.0 sec
Solvent: acetone-d6, reference substance: tetramethylsilane Measurement temperature: room temperature, sample rotation speed: 0.0 Hz.

<Measurement of solid content>
The solid concentration of the polysiloxane solution was determined by the following method. 1.5 g of the polysiloxane solution was weighed into an aluminum cup and heated at 250 ° C. for 30 minutes using a hot plate to evaporate the liquid. The solid content remaining in the heated aluminum cup was weighed to determine the solid content concentration of the polysiloxane solution.

Synthesis Example 1 Synthesis of HfTMS (Hf-1) The following reaction was performed to synthesize an Hf compound (H1).

In a 300 mL three-necked flask equipped with a reflux tube, 6.46 g (20.0 mmol) of the previously dried Hf compound (H-1), 7.38 g (40.0 mmol) of tetrabutylammonium iodide, and bis ( 0.2280 g (0.60 mmol) of acetonitrile) (1,5-cyclooctadiene) rhodium (I) tetrafluoroborate was collected at room temperature. Then, under an argon atmosphere, 120 mL of dehydrated N, N-dimethylformamide, 11.1 mL (80.0 mmol) of dehydrated triethylamine, and 7.40 mL (40.0 mmol) of triethoxysilane were added, and the mixture was heated to 80 ° C. The mixture was heated and stirred for 4 hours. After the reaction system was naturally cooled to room temperature, the solvent, N, N-dimethylformamide, was distilled off, and then 200 mL of diisopropyl ether was added. The resulting precipitate was contacted with celite and filtered, and the filtrate was washed three times with 100 mL of water, dried by adding Na2SO4, and filtered, and the solvent was distilled off. The residue as a reaction product was distilled and produced using a Kugelrohr apparatus under the conditions of 140 ° C. to 190 ° C. and 200 Pa to obtain HfTMS (Hf-1) as a colorless liquid. The result of ¹ H-NMR measurement of the obtained HfTMS (Hf-1) was as follows.

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

Synthesis Example 2 Synthesis of HfTMS (Hf-2) The following reaction was performed to synthesize an Hf compound (H1).

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

Synthesis Example 3 Synthesis of Polysiloxane (P-1) In a 500-ml three-necked flask, 109.25 g (0.565 mol) of MTMS, 84.67 g (0.049 mol) of HfTMS (Hf-1), and 6.51 g of TES ( 0.014 mol), 191.75 g of PGMEA were charged, and an aqueous phosphoric acid solution obtained by dissolving 1.00 g of phosphoric acid (0.50% by mass based on the charged monomers) in 56.82 g of water while stirring at room temperature was taken for 30 minutes. Was added. Thereafter, the flask was immersed in a 70 ° C. oil bath and stirred for 90 minutes, and then the temperature of the oil bath was raised to 115 ° C. over 30 minutes. One hour after the start of the temperature rise, the internal temperature of the solution reached 100 ° C., from which the solution was heated and stirred for 2 hours (the internal temperature was 100 to 110 ° C.) to obtain a polysiloxane (P-1). During the heating and stirring while heating, nitrogen was flowed at 0.05 l (liter) / minute. During the reaction, methanol and water as by-products were distilled out in total of 154.41 g. The solid concentration of the obtained polysiloxane (P-1) was 43.1% by mass. ^{According to} the measurement by ²⁹ Si-NMR, the (A) poly (A) having a structure represented by any of the general formulas (1) to (3) and a structure represented by any of the general formulas (4) or (5) The molar amount in the siloxane was 20 mol% and 3 mol%, respectively.

Synthesis Example 4 Synthesis of Polysiloxane (P-2) In the same manner as in Synthesis Example 1, 112.22 g (0.551 mol) of MTMS, 66.97 g (0.037 mol) of HfTMS (Hf-1), and TES were prepared. 22.88 g (0.048 mol), 185.62 g of PGMEA were charged, and an aqueous phosphoric acid solution obtained by dissolving 1.01 g of phosphoric acid (0.50% by mass based on charged monomers) in 61.30 g of water was added. A siloxane (P-2) was obtained. The solid content concentration of the obtained polysiloxane (P-2) was 42.8% by mass. ^{According to} the measurement by ²⁹ Si-NMR, the (A) poly (A) having a structure represented by any of the general formulas (1) to (3) and a structure represented by any of the general formulas (4) or (5) The molar amount in the siloxane was 15 mol% and 10 mol%, respectively.

Synthesis Example 5 Synthesis of Polysiloxane (P-3) In the same manner as in Synthesis Example 1, 45.14 g (0.257 mol) of MTMS, 57.72 g (0.037 mol) of HfTMS (Hf-1), and TES were prepared. 98.61 g (0.240 mol), 187.87 g of PGMEA were charged, and an aqueous solution of phosphoric acid obtained by dissolving 1.01 g of phosphoric acid (0.50% by mass based on charged monomers) in 59.65 g of water was added. A siloxane (P-3) was obtained. The solid concentration of the obtained polysiloxane (P-3) was 43.5% by mass. ^{According to} the measurement by ²⁹ Si-NMR, the (A) poly (A) having a structure represented by any of the general formulas (1) to (3) and a structure represented by any of the general formulas (4) or (5) The molar amount in the siloxane was 15 mol% and 50 mol%, respectively.

Synthesis Example 6 Synthesis of Polysiloxane (P-4) In the same manner as in Synthesis Example 1, 31.16 g (0.184 mol) of MTMS, 55.79 g (0.037 mol) of HfTMS (Hf-1), and TES were prepared. 114.39 g (0.288 mol), 188.34 g of PGMEA were charged, and an aqueous solution of phosphoric acid in which 1.01 g of phosphoric acid (0.50% by mass with respect to the charged monomers) was dissolved in 59.31 g of water was added. A siloxane (P-4) was obtained. The solid concentration of the obtained polysiloxane (P-4) was 42.5% by mass. ^{According to} the measurement by ²⁹ Si-NMR, the (A) poly (A) having a structure represented by any of the general formulas (1) to (3) and a structure represented by any of the general formulas (4) or (5) The molar amount in the siloxane was 15 mol% and 60 mol%, respectively.

Synthesis Example 7 Synthesis of Polysiloxane (P-5) In the same procedure as in Synthesis Example 1, 66.18 g (0.367 mol) of MTMS, 59.24 g (0.037 mol) of HfTMS (Hf-1), and TES 10.12 g (0.024 mol), 63.63 g (0.137 mol) of CFTMS, 196.49 g of PGMEA were charged, and 1.00 g of phosphoric acid was added to 53.35 g of water (0.50 mass% based on the charged monomer). The dissolved phosphoric acid aqueous solution was added to obtain a polysiloxane (P-5). The solid concentration of the obtained polysiloxane (P-5) was 43.7% by mass. ^{According to} the measurement by ²⁹ Si-NMR, the (A) poly (A) having a structure represented by any of the general formulas (1) to (3) and a structure represented by any of the general formulas (4) or (5) The molar amount in the siloxane was 15 mol% and 5 mol%, respectively.

Synthesis Example 8 Synthesis of Polysiloxane (P-6) By the same procedure as in Synthesis Example 1, 58.52 g (0.330 mol) of MTMS, 58.21 g (0.037 mol) of HfTMS (Hf-1), and TES 19.89 g (0.048 mol), 62.52 (0.137 mol) of CFTMS, 196.59 g of PGMEA were charged, and 1.00 g of phosphoric acid (0.50% by mass based on charged monomers) was added to 53.28 g of water. The dissolved phosphoric acid aqueous solution was added to obtain a polysiloxane (P-6). The solid concentration of the obtained polysiloxane (P-6) was 42.9% by mass. ^{According to} the measurement by ²⁹ Si-NMR, the (A) poly (A) having a structure represented by any of the general formulas (1) to (3) and a structure represented by any of the general formulas (4) or (5) The molar amount in the siloxane was 15 mol% and 10 mol%, respectively.

Synthesis Example 9 Synthesis of Polysiloxane (P-7) In the same procedure as in Synthesis Example 1, MTMS was 46.14 g (0.257 mol), HfTMS (Hf-1) was 59.01 g (0.037 mol), and TES was 30.24 g (0.072 mol), 63.38 (0.137 mol) of CFTMS, 197.97 g of PGMEA were charged, and 0.99 g of phosphoric acid was added to 52.27 g of water (0.50 mass% based on the charged monomer). The dissolved phosphoric acid aqueous solution was added to obtain a polysiloxane (P-7). The solid concentration of the obtained polysiloxane (P-7) was 43.1% by mass. ^{According to} the measurement by ²⁹ Si-NMR, the (A) poly (A) having a structure represented by any of the general formulas (1) to (3) and a structure represented by any of the general formulas (4) or (5) The molar amount in the siloxane was 15 mol% and 20 mol%, respectively.

Synthesis Example 10 Synthesis of Polysiloxane (P-8) In the same procedure as in Synthesis Example 1, 30.40 g (0.184 mol) of MTMS, 54.42 g (0.037 mol) of HfTMS (Hf-1), and TES were synthesized. 55.78 g (0.144 mol), 58.45 (0.137 mol) of CFTMS, 196.94 g of PGMEA were charged, and 1.00 g of phosphoric acid (0.50% by mass based on charged monomers) was added to 53.02 g of water. The dissolved phosphoric acid aqueous solution was added to obtain a polysiloxane (P-8). The solid concentration of the obtained polysiloxane (P-8) was 43.2% by mass. ^{According to} the measurement by ²⁹ Si-NMR, the (A) poly (A) having a structure represented by any of the general formulas (1) to (3) and a structure represented by any of the general formulas (4) or (5) The molar amount in the siloxane was 15 mol% and 30 mol%, respectively.

Synthesis Example 11 Synthesis of Polysiloxane (P-9) In the same procedure as in Synthesis Example 1, 5.71 g (0.037 mol) of MTMS, 51.09 g (0.037 mol) of HfTMS (Hf-1), and TES 87.29 g (0.240 mol), 54.88 (0.137 mol) of CFTMS, 197.24 g of PGMEA were charged, and 0.99 g of phosphoric acid was added to 52.80 g of water (0.50 mass% based on the charged monomer). The dissolved phosphoric acid aqueous solution was added to obtain a polysiloxane (P-9). The solid content of the obtained polysiloxane (P-9) was 42.8% by mass. ^{According to} the measurement by ²⁹ Si-NMR, the (A) poly (A) having a structure represented by any of the general formulas (1) to (3) and a structure represented by any of the general formulas (4) or (5) The molar amount in the siloxane was 15 mol% and 50 mol%, respectively.

Synthesis Example 12 Synthesis of Polysiloxane (P-10) In the same procedure as in Synthesis Example 1, 54.02 g (0.294 mol) of MTMS, 40.30 g (0.025 mol) of HfTMS (Hf-1), and TES were synthesized. 41.31 g (0.096 mol), 64.92 (0.137 mol) of CFTMS, 191.35 g of PGMEA were charged, and 1.00 g of phosphoric acid (0.50% by mass based on charged monomers) was added to 57.11 g of water. The dissolved phosphoric acid aqueous solution was added to obtain a polysiloxane (P-10). The solid content of the obtained polysiloxane (P-10) was 43.1% by mass. ^{According to} the measurement by ²⁹ Si-NMR, the (A) poly (A) having a structure represented by any of the general formulas (1) to (3) and a structure represented by any of the general formulas (4) or (5) The molar amount in the siloxane was 10 mol% and 20 mol%, respectively.

Synthesis Example 13 Synthesis of Polysiloxane (P-11) In the same manner as in Synthesis Example 1, 35.26 g (0.220 mol) of MTMS, 70.13 g (0.049 mol) of HfTMS (Hf-1), and TES 35.95 g (0.096 mol), 56.49 (0.137 mol) of CFTMS, 201.48 g of PGMEA were charged, and 0.99 g of phosphoric acid was added to 49.70 g of water (0.50% by mass based on charged monomers). The dissolved phosphoric acid aqueous solution was added to obtain a polysiloxane (P-11). The solid concentration of the obtained polysiloxane (P-11) was 43.4% by mass. ^{According to} the measurement by ²⁹ Si-NMR, the (A) poly (A) having a structure represented by any of the general formulas (1) to (3) and a structure represented by any of the general formulas (4) or (5) The molar amount in the siloxane was 20 mol% and 20 mol%, respectively.

Synthesis Example 14 Synthesis of Polysiloxane (P-12) In the same procedure as in Synthesis Example 1, MTMS was 20.80 g (0.147 mol), HfTMS (Hf-1) was 93.11 g (0.074 mol), and TES was 31.82 g (0.096 mol), 50.00 (0.137 mol) of CFTMS, 209.29 g of PGMEA were charged, and 0.98 g of phosphoric acid (43.99 g of water) was added to 43.99 g of water. The dissolved phosphoric acid aqueous solution was added to obtain a polysiloxane (P-12). The solid content concentration of the obtained polysiloxane (P-12) was 43.0% by mass. ^{According to} the measurement by ²⁹ Si-NMR, the (A) poly (A) having a structure represented by any of the general formulas (1) to (3) and a structure represented by any of the general formulas (4) or (5) The molar amount in the siloxane was 30 mol% and 20 mol%, respectively.

Synthesis Example 15 Synthesis of Polysiloxane (P-13) In a 500-ml three-necked flask, 109.25 g (0.565 mol) of MTMS, 84.67 g (0.049 mol) of HfTMS (Hf-2), and 6.51 g of TES ( 0.014 mol), 191.75 g of PGMEA were charged, and an aqueous phosphoric acid solution obtained by dissolving 1.00 g of phosphoric acid (0.50% by mass based on the charged monomers) in 56.82 g of water while stirring at room temperature was taken for 30 minutes. Was added. Thereafter, the flask was immersed in a 70 ° C. oil bath and stirred for 90 minutes, and then the temperature of the oil bath was raised to 115 ° C. over 30 minutes. One hour after the start of the temperature rise, the internal temperature of the solution reached 100 ° C., from which the solution was heated and stirred for 2 hours (the internal temperature was 100 to 110 ° C.) to obtain a polysiloxane (P-13). During the heating and stirring while heating, nitrogen was flowed at 0.05 l (liter) / minute. During the reaction, methanol and water as by-products were distilled out in total of 154.41 g. The solid concentration of the obtained polysiloxane (P-1) was 43.0% by mass. ^{According to} the measurement by ²⁹ Si-NMR, the (A) poly (A) having a structure represented by any of the general formulas (1) to (3) and a structure represented by any of the general formulas (4) or (5) The molar amount in the siloxane was 20 mol% and 3 mol%, respectively.

Synthesis Example 16 Synthesis of Polysiloxane (R-1) In the same manner as in Synthesis Example 1, 188.82 g (0.246 mol) of HfTMS (Hf-1) and 235.14 g of PGMEA were charged, and phosphorus was added to 25.09 g of water. An aqueous solution of phosphoric acid in which 0.94 g of acid (0.50% by mass based on the charged monomer) was dissolved was added to obtain a polysiloxane (R-1). The solid concentration of the obtained polysiloxane (R-1) was 43.2% by mass. ^{According to} the measurement by ²⁹ Si-NMR, the (A) poly (A) having a structure represented by any of the general formulas (1) to (3) and a structure represented by any of the general formulas (4) or (5) The molar amount in the siloxane was 100 mol% and 0 mol%, respectively.

Synthesis Example 17 Synthesis of Polysiloxane (R-2) In the same manner as in Synthesis Example 1, 41.54 g (0.330 mol) of MTMS, 151.49 g (0.135 mol) of HfTMS (Hf-1), and PGMEA were prepared. An aqueous solution of phosphoric acid in which 0.97 g of phosphoric acid (0.50% by mass based on the charged monomers) was added to 219.40 g of water and 36.60 g of water was added to obtain a polysiloxane (R-2). The solid concentration of the obtained polysiloxane (R-2) was 43.5% by mass. ^{According to} the measurement by ²⁹ Si-NMR, the (A) poly (A) having a structure represented by any of the general formulas (1) to (3) and a structure represented by any of the general formulas (4) or (5) The molar amount in the siloxane was 55 mol% and 0 mol%, respectively.

Synthesis Example 18 Synthesis of Polysiloxane (R-3) In the same procedure as in Synthesis Example 1, 68.15 g (0.330 mol) of MTMS, 133.47 g (0.252 mol) of CFTMS, and 187.34 g of PGMEA were charged. An aqueous phosphoric acid solution in which 1.01 g of phosphoric acid (0.50% by mass based on the charged monomers) was dissolved in 60.04 g of water was added to obtain a polysiloxane (R-3). The solid concentration of the obtained polysiloxane (R-3) was 43.2% by mass. ^{According to} the measurement by ²⁹ Si-NMR, the (A) poly (A) having a structure represented by any of the general formulas (1) to (3) and a structure represented by any of the general formulas (4) or (5) The molar amount in the siloxane was 0 mol% and 0 mol%, respectively.

Synthesis Example 19 Synthesis of Polysiloxane (R-4) In the same procedure as in Synthesis Example 1, 73.11 g (0.330 mol) of MTMS, 130.10 g (0.277 mol) of PhTMS, and 181.36 g of PGMEA were charged. An aqueous phosphoric acid solution in which 1.02 g of phosphoric acid (0.50% by mass based on the charged monomers) was dissolved in 64.42 g of water was added to obtain a polysiloxane (R-4). The solid concentration of the obtained polysiloxane (R-4) was 42.8% by mass. ^{According to} the measurement by ²⁹ Si-NMR, the (A) poly (A) having a structure represented by any of the general formulas (1) to (3) and a structure represented by any of the general formulas (4) or (5) The molar amount in the siloxane was 0 mol% and 0 mol%, respectively.

Synthesis Example 20 Synthesis of Polysiloxane (R-5) In the same procedure as in Synthesis Example 1, 120.70 g (0.111 mol) of HfTMS, 71.98 g (0.277 mol) of PhTMS, and 220.71 g of PGMEA were charged. An aqueous phosphoric acid solution obtained by dissolving 0.97 g of phosphoric acid (0.50% by mass based on the charged monomers) in 35.64 g of water was added to obtain a polysiloxane (R-5). The solid content of the obtained polysiloxane (R-5) was 43.2% by mass. ^{According to} the measurement by ²⁹ Si-NMR, the (A) poly (A) having a structure represented by any of the general formulas (1) to (3) and a structure represented by any of the general formulas (4) or (5) The molar amount in the siloxane was 45 mol% and 0 mol%, respectively.

Synthesis Example 21 Synthesis of Polysiloxane (R-6) In the same procedure as in Synthesis Example 1, 66.32 g (0.049 mol) of HfTMS, 129.44 g (0.403 mol) of PhTMS, and 209.20 g of PGMEA were charged. An aqueous phosphoric acid solution obtained by dissolving 0.98 g of phosphoric acid (0.50% by mass based on charged monomers) in 44.06 g of water was added to obtain a polysiloxane (R-6). The solid concentration of the obtained polysiloxane (R-6) was 43.2% by mass. ^{According to} the measurement by ²⁹ Si-NMR, the (A) poly (A) having a structure represented by any of the general formulas (1) to (3) and a structure represented by any of the general formulas (4) or (5) The molar amount in the siloxane was 20 mol% and 0 mol%, respectively. Table 1 shows the charged amounts of the alkoxysilanes, which are the raw materials for the polysiloxane (A) obtained in Synthesis Examples 1 to 18.

Synthesis Example 22 Synthesis of Polysiloxane (R-7) In the same procedure as in Synthesis Example 1, 15.46 g (0.011 mol) of MTMS, 19.27 g (0.088 mol) of CFTMS, and 10.51 g (0. 0.050 mol), 40.01 g of PGMEA, and an aqueous solution of phosphoric acid in which 0.23 g of phosphoric acid (0.50% by mass based on the charged monomer) was dissolved in 14.53 g of water, and polysiloxane (R-7) was added. ) Got. The solid concentration of the obtained polysiloxane (R-6) was 43.2% by mass. ^{According to} the measurement by ²⁹ Si-NMR, the (A) poly (A) having a structure represented by any of the general formulas (1) to (3) and a structure represented by any of the general formulas (4) or (5) The molar amount in the siloxane was 0 mol% and 20 mol%, respectively. Table 1 shows the charged amounts of the alkoxysilanes, which are the raw materials for the polysiloxane (A) obtained in Synthesis Examples 1 to 22.

Synthesis Example 22 Synthesis of naphthoquinonediazide compound (C-1) Under dry nitrogen stream, 21.23 g (0.05 mol) of compound TrisP-PA having a phenolic hydroxyl group (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) was added. 37.62 g (0.14 mol) of naphthoquinonediazidosulfonyl chloride was dissolved in 450 g of 1,4-dioxane, and the mixture was brought to room temperature. To this, 15.58 g (0.154 mol) of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature inside the system did not become 35 ° C. or higher. After the addition, the mixture was stirred at 30 ° C. for 2 hours. The triethylamine salt was filtered and the filtrate was poured into water. Thereafter, the deposited precipitate was collected by filtration. The precipitate was dried using a vacuum drier to obtain a naphthoquinonediazide compound C-1 having the following structure.

[Solvent replacement of metal compound particles]
Solvent Substitution Example 1 Solvent Substitution of "Surria" 4110 As metal oxide particles, the solvent of "Surria" 4110 (trade name, manufactured by JGC Catalysts & Chemicals, Inc.) was replaced with PGMEA from isopropanol. A 500 ml eggplant flask was charged with 100 g of Isopropanol sol (solid content concentration: 20%) of Sluria 4110 and 80 g of PGMEA, and the pressure was reduced at 30 ° C. for 30 minutes using an evaporator to remove IPA. The PGMEA solution of the resulting Sluria 4110 was obtained. The solid concentration of D-1 was measured and found to be 20.1%.

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

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

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

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

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

(4) Evaluation of crack resistance The presence or absence of cracks was confirmed by observing the obtained cured film with a microscope.
The evaluation criteria are A to C below.
A: No crack is observed on the entire surface. B: Crack is observed only on the edge of the wafer substrate. C: Crack is observed on the entire surface.

(5) Evaluation of coatability The obtained cured film was observed with a microscope to evaluate the presence or absence of foreign matter and cissing.
A: No foreign matter or cissing is observed on the entire surface.
B: Foreign matter and cissing are observed only at the center of the wafer.
C: Foreign matter and cissing are observed on the entire surface of the wafer.

(6) Measurement of transmittance (400 nm wavelength, 1 μm conversion)
The extinction coefficient of the obtained cured film at a wavelength of 400 nm was measured with a spectroscopic ellipsometer FE5000 manufactured by Otsuka Electronics Co., Ltd., and the light transmittance (%) at a wavelength of 400 nm in terms of a film thickness of 1 μm was determined by the following equation.
Light transmittance = exp (−4πkt / λ)
Here, k represents an extinction coefficient, t represents a converted film thickness (μm), and λ represents a measurement wavelength (nm). In this measurement, since the light transmittance in terms of 1 μm is obtained, t is 1 (μm).

(7) Resolution Regarding the obtained cured film, square patterns were observed at all exposure amounts, and observation was performed with the minimum pattern size as the resolution. The evaluation criteria were set as follows.
A: The minimum pattern dimension x is x <15 μm
B: The minimum pattern dimension x is 15 μm ≦ x <50 μm
C: The minimum pattern dimension x is 50 μm ≦ x <100 μm
D: The minimum pattern dimension x is 100 μm ≦ x.

(8) Evaluation of Reduction in Developed Film For Examples 19 to 40 and Comparative Examples 7 to 12, the amount of reduced film during development was calculated.
Reduction of developed film = (thickness of prebaked film−thickness of developed film) / thickness of prebaked film × 100
The thickness of the prebaked film and the thickness after development were measured according to the method described in (1) Measurement of Film Thickness.

Example 1
The mixture was prepared according to the ratio of the resin composition (I) in Table 2, mixed and stirred under a yellow light to form a uniform solution, and then filtered through a 0.20 μm filter to prepare Composition 1.

Immediately after the composition 1, spin coating is performed on a 4-inch silicon wafer using a spin coater (1H-360S manufactured by Mikasa Corporation), and then using a hot plate (SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.). Heating at 120 ° C. for 3 minutes produced a pre-baked film having a thickness of 1.0 μm. Thereafter, the pre-baked film was cured at 230 ° C. for 5 minutes using a hot plate to form a cured film 1.

Using the cured film 1, (2) measurement of refractive index, (3) evaluation of chemical resistance, (4) evaluation of crack resistance, and (5) evaluation of coating property were performed. Table 3 shows the results.

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

Example 19
The mixture was prepared at the ratio of the resin composition (I) in Table 4, mixed and stirred under a yellow light to form a uniform solution, and then filtered through a 0.20 μm filter to prepare a composition 25.

Immediately after the composition 25 was prepared, a 4-inch silicon wafer and a glass substrate were spin-coated using a spin coater (1H-360S, manufactured by Mikasa Co., Ltd.), and then heated on a hot plate (SCW-, manufactured by Dainippon Screen Mfg. Co., Ltd.). 636) and heated at 120 ° C. for 3 minutes to produce a pre-baked film, and (1) film thickness measurement was performed. The prebaked film was shower-developed with a 2.38% by mass TMAH aqueous solution for 30 seconds using an automatic developing device (AD-2000 manufactured by Takizawa Sangyo Co., Ltd.), rinsed with water for 30 seconds, and then on the wafer and the glass substrate. Then, after-development film 1 and post-development film 2 were obtained, and (1) film thickness measurement was performed on the post-development film 1. Thereafter, the post-development film 1 and the post-development film 2 were cured at 230 ° C. for 5 minutes using a hot plate to prepare cured

films

2 and 3 respectively. The cured film 2 was subjected to (1) film thickness measurement.

Further, the obtained prebaked film is exposed by using an i-line stepper (i9C manufactured by Nikon Corporation) at intervals of 50 msec from 100 msec to 1000 msec, and then developed and cured in the same manner as described above. I got

Using the cured film 2, (2) measuring the refractive index and (3) evaluating the chemical resistance, using the cured film 3, (6) measuring the transmittance, and using the cured film 4 (7) measuring the resolution. An evaluation was performed. Table 5 shows the results.

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

In (2) the measurement of the refractive index and (6) the measurement of the transmittance, when the developed film was completely dissolved and could not be evaluated, the cured film was prepared in the same manner as in Example 1 except that the development was not performed. Was prepared and evaluated.

Reference Signs List 1 substrate 2 coating film 3 cured film 4 actinic ray 5 mask 6 pattern 7 cured film pattern

Claims

A resin composition containing (A) a polysiloxane and (B) a solvent, wherein the (A) polysiloxane has at least one structure represented by the following general formulas (1) to (3), and And a resin composition comprising at least one structure represented by the following general formulas (4) and (5).

(Y is an alicyclic or aromatic linking group having 5 to 10 carbon atoms. R 1 is a single bond or an alkylene group having 1 to 4 carbon atoms, and R 2 is independently hydrogen or 1 carbon atom. To 4 alkyl groups, R 3 are independently an organic group having 1 to 8 carbon atoms, X is a hydrogen atom or an acid dissociable group, a is an integer of 1 to 3, and n is an integer of 1 to 10. )
The resin composition according to claim 1, wherein (A) the polysiloxane contains at least one structure represented by the following general formulas (6) to (8).

(R 1 is a single bond or an alkylene group having 1 to 4 carbon atoms, R 2 is independently of each other, hydrogen or an alkyl group having 1 to 4 carbon atoms, and R 3 is independently of each other an organic group having 1 to 8 carbon atoms. Group, X is a hydrogen atom or an acid dissociable group, a is an integer of 1 to 3, and n is an integer of 1 to 10.)
3. The resin composition according to claim 1, wherein the polysiloxane skeleton (A) has at least one of the structures represented by the general formulas (4) to (5) in an amount of 5 to 50 mol%.
4. The resin composition according to claim 1, wherein (A) the polysiloxane contains at least one structure represented by the following general formulas (9) to (11).

(R 2 is independently hydrogen or an alkyl group having 1 to 4 carbon atoms, R 3 is independently an organic group having 1 to 8 carbon atoms, and R 4 is an organic group having 1 to 10 carbon atoms having a fluoro group. Represents a group.)
The resin composition according to any one of claims 1 to 4, further comprising (C) a naphthoquinonediazide compound.
The resin composition according to claim 5, wherein the naphthoquinonediazide compound (C) is 1 to 15 parts by mass based on 100 parts by mass of the polysiloxane (A).
The resin composition according to any one of claims 1 to 6, further comprising one or more aromatic hydrocarbon-based (B) solvents having a hetero atom.
The resin composition according to any one of claims 1 to 7, further comprising (D) metal compound particles.
The resin composition according to claim 8, wherein the (D) metal compound particles are silica particles.
A cured film of the resin composition according to any one of claims 1 to 9.
A solid-state imaging device comprising the cured film according to claim 10.
An organic EL device comprising the cured film according to claim 10.
A display device comprising the cured film according to claim 10.