WO2021193221A1

WO2021193221A1 - Resin composition, cured film, method for producing microlens, solid state imaging device, microlens, and touch panel

Info

Publication number: WO2021193221A1
Application number: PCT/JP2021/010522
Authority: WO
Inventors: 石川世志美; 日比野利保; 鳴戸真之; 諏訪充史
Original assignee: 東レ株式会社
Priority date: 2020-03-24
Filing date: 2021-03-16
Publication date: 2021-09-30
Also published as: JPWO2021193221A1; TW202136421A

Abstract

The present invention provides a high refractive index resin composition that exhibits excellent heat resistance and dry etching properties by not containing a fused polycyclic aromatic compound and lowering the quantity of a metal compound that is difficult to etch. This resin composition contains: a polysiloxane (A) having a structure represented by formula (1); particles (B) of a composite oxide of titanium and one or more elements selected from the group consisting of aluminum, tin, zirconium and silicon; and a solvent (C). R¹ denotes an alkyl group having 1-4 carbon atoms or an alkoxy group having 1-4 carbon atoms. n is 0 or 1, and ＊ denotes a direct bond to a silicon atom.

Description

Resin composition, cured film, manufacturing method of microlens, solid-state image sensor, microlens, touch panel

The present invention relates to a resin composition, a cured film, a method for manufacturing a microlens, a solid-state image sensor, a microlens, and a touch panel.

In recent years, with the rapid development of digital cameras, camera-equipped mobile phones, etc., there is a demand for smaller size and higher pixel count of solid-state image sensors. Since the miniaturization of the solid-state image sensor causes a decrease in sensitivity due to a decrease in light utilization efficiency, a microlens is formed on each pixel on the color filter of the light intake port to efficiently collect light. It prevents the decrease in sensitivity.

As a general method for manufacturing a microlens, a material for forming a microlens is applied, cured, a photoresist is applied on the upper part, exposed and developed, a pattern is processed to the size of the microlens, and then the photoresist is used. Is used as a mask, and the material for forming a microlens is processed into a microlens shape by dry etching.

The material for forming a microlens is required to have a high refractive index in order to efficiently collect light, and at the same time, it is required to have excellent moisture resistance, chemical resistance, etc. while maintaining high transmittance. .. A polysiloxane resin is used as a resin that satisfies such a requirement.

For example, Patent Document 1 reports a siloxane resin composition for forming a microlens, which contains a siloxane resin having a condensed polycyclic aromatic group and a composite oxide such as aluminum, titanium, tin or zirconium.

International Publication No. 2015/002183

The siloxane resin composition for forming a microlens containing a siloxane resin having a condensed polycyclic aromatic group and metal compound particles described in Patent Document 1 contains a composite oxide such as aluminum, titanium, tin or zirconium. Therefore, it is difficult to dry etch, and there is a problem in the process compatibility of microlens formation. Further, there are problems that the heat resistance is insufficient and the chemical resistance of the cured film is insufficient due to the thermal decomposition of the condensed polycyclic aromatic group at a high temperature.

In order to solve the above problems, the present invention has the following configurations.
(1) Titanium composite oxide particles (B1) having a total content of one or more elements selected from the group consisting of resin (A), aluminum, tin and zirconium of 2% by weight or more and 15% by weight or less, and aluminum. , Two types of particles of titanium composite oxide particles (B2) having a total content of one or more elements selected from the group consisting of tin and zirconium of less than 2% by weight, and a solvent (C). Resin composition.
(2) Particles (B) which are a composite oxide of one or more types of polysiloxane (a1) having a structure represented by the formula (1), aluminum, tin, zirconium and silicon selected from the group and titanium, and A resin composition containing the solvent (C).

R ¹ represents an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. n is 0 or 1, and * means a bond directly connected to a silicon atom.

The resin composition of the present invention is excellent in high heat resistance, etching property and chemical resistance.

The resin composition of the present invention is a titanium composite oxide particle having a total content of one or more elements selected from the group consisting of resin (A), aluminum, tin and zirconium of 2% by weight or more and 15% by weight or less. Two types of particles, B1), titanium composite oxide particles (B2) having a total content of one or more elements selected from the group consisting of aluminum, tin and zirconium of less than 2% by weight, and a solvent (C). ), Contains.

Further, the resin composition of another aspect of the present invention is one or more selected from the group consisting of polysiloxane (a1) having a structure represented by the formula (1), aluminum, tin, zirconium and silicon, and titanium. It contains particles (B) which are composite oxides and a solvent (C). The polysiloxane (a1) having the structure represented by the formula (1) may be hereinafter referred to as polysiloxane (a1). Particles (B) which are a composite oxide of one or more kinds and titanium selected from the group consisting of aluminum, tin, zirconium and silicon may be hereinafter referred to as particles (B).

<Resin (A)>
Examples of the resin (A) in the present invention include general resins (those having a repeating unit structure) such as acrylic resins, epoxy resins, polyethylenes, polyimides, and polysiloxanes, but with the particles (B) described later. It is particularly desirable that the resin (A) is polysiloxane (A1) from the viewpoint of compatibility, heat resistance of the formed cured film, and chemical resistance. Further, since the cured film has a high refractive index and good chemical resistance, the refractive index of the polysiloxane (A1) at a wavelength of 633 nm is preferably 1.60 or more and less than 1.80.

Further, it is desirable that the polysiloxane (A1) is a polysiloxane (a1) having a structure represented by the formula (1).

Since the polysiloxane (a1) has the structure of the formula (1), it is possible to impart high refractive index, high heat resistance and good etching property to the cured film.

The mol ratio of the structure represented by the formula (1) in the polysiloxane (a1) is preferably 10 to 90 mol% with respect to 100 mol% of all Si atoms contained in the polysiloxane (a1). Within the above range, the refractive index, heat resistance and etching property of the cured film can be further improved. As the lower limit, the mol ratio of the structure represented by the formula (1) in the polysiloxane (a1) is more preferably 20 mol% or more with respect to 100 mol% of all Si atoms contained in the polysiloxane (a1). More preferably, it is 30 mol% or more. As an upper limit, the mol ratio of the structure represented by the formula (1) in the polysiloxane (a1) is more preferably 85 mol or less with respect to 100 mol% of all Si atoms contained in the polysiloxane (a1), and further. It is preferably 80 mol or less.

Further, from the viewpoint of chemical resistance of the cured film, the polysiloxane (A1) or polysiloxane (a1) preferably has a structure represented by the formula (2) and / or a structure represented by the formula (3).

R ² represents an alkylene group having 1 to 4 carbon atoms or a divalent aromatic group having 1 to 8 carbon atoms. * Means a bond that is directly linked to a silicon atom.

The mol ratio of the formulas (2) and (3) in the polysiloxane (A1) or polysiloxane (a1) to 100 mol% of all Si atoms contained in the polysiloxane (A1) or polysiloxane (a1). The total is preferably 1 to 30 mol%, more preferably 5 to 20 mol%. Within this range, the chemical resistance of the cured film can be improved.

Polysiloxane (A1) or polysiloxane (a1) can be obtained by a known method of hydrolyzing an alkoxysilane compound as a raw material in an organic solvent and partially condensing it. At this time, an arbitrary substituent can be introduced into the polysiloxane by selecting the type of the raw material alkoxysilane.

The structure of the formula (1) can be introduced by using the alkoxysilane compound represented by the formula (4).

R ¹ represents an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. n is 0 or 1, and R ³ is an alkyl group having 1 to 4 carbon atoms. R ⁴ is a hydrocarbon group having 1 to 10 carbon atoms. m is 0 or 1.

Examples of the alkoxysilane compound represented by the formula (4) include biphenyltrimethoxysilane, biphenyltriethoxysilane, biphenylmethyldimethoxysilane, biphenylmethyldiethoxysilane, 4-methylbiphenyltrimethoxysilane, and 4-methylbiphenyltriethoxysilane. Examples thereof include 4-methoxybiphenyltrimethoxysilane and 4-methoxybiphenyltriethoxysilane. These alkoxysilane compounds may be used alone or in combination of two or more.

The structure represented by the formula (2) and / or the structure represented by the formula (3) can be introduced by using the alkoxysilane compound represented by the formula (5).

R ² represents an alkylene group having 1 to 4 carbon atoms or a divalent aromatic group having 1 to 8 carbon atoms. R ⁵ is an alkyl group having 1 to 4 carbon atoms. R ⁶ is a hydrocarbon group having 1 to 10 carbon atoms. l is 0 or 1.

Examples of the alkoxysilane compound represented by the formula (5) include 3-trimethoxysilylpropyl succinic anhydride, 3-triethoxysilylpropyl succinic anhydride, 3-triphenyloxysilylpropyl succinic anhydride, and 3-tri. Examples thereof include methoxycisilylpropylphthalic anhydride, 3-trimethoxycyclylpropylcyclohexyldicarboxylic anhydride, and the like. These alkoxysilane compounds may be used alone or in combination of two or more.

Further, the polysiloxane (A1) or the polysiloxane (a1) may contain an alkoxysilane compound other than the above as a raw material. Examples of alkoxysilane compounds other than the above include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, and hexyltrimethoxysilane. Octadecyltrimethoxysilane, octadecyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriisopropoxysilane, 1-naphthyltrimethoxysilane, 1-naphthyltriethoxysilane, 3-aminopropyltriethoxysilane, N- (2-Aminoethyl) -3-aminopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3- (N, N-diglycidyl) aminopropyltrimethoxysilane, 3-glycidoxysipropyltrimethoxysilane, vinyltri Methoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -Γ-Aminopropyltrimethoxysilane, β-cyanoethyltriethoxysilane, trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, perfluoropropylethyltrimethoxy Silane, Perfluoropropylethyltriethoxysilane, Perfluoropentylethyltrimethoxysilane, Perfluoropentylethyltriethoxysilane, Tridecafluorooctyltrimethoxysilane, Tridecafluorooctyltriethoxysilane, Tridecafluorooctyllippropoxysilane, Tridecafluorooctyl triisopropoxysilane, heptadecafluorodecyltrimethoxysilane, heptadecafluorodecyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, methylvinyl Dimethoxysilane, methylvinyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, N- (2) -Aminoethyl) -3-aminopropylmethyldimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, trifluoropropylmethyldimethoxysilane, trifluoropropylmethyldiethoxysilane, trifluoropropyl Ethyldimethoxysilane, trifluoropropylethyldiethoxysilane, trifluoropropylvinyldimethoxysilane, trifluoropropylvinyldiethoxysilane, heptadecafluorodecylmethyldimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropylmethyldiethoxy Examples thereof include silane, cyclohexylmethyldimethoxysilane, octadecylmethyldimethoxysilane, tetramethoxysilane, tetraethoxysilane, and tetrapropoxysilane.

Among the alkoxysilane compounds, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane are preferable from the viewpoint of chemical resistance of the obtained cured film. These alkoxysilane compounds may be used alone or in combination of two or more.

The content of the polysiloxane (A1) and / or the polysiloxane (a1) is based on the total amount of the solid content of the resin composition excluding the solvent (C) from the viewpoint of further enhancing the light transmittance and crack resistance of the cured film. 10% by weight or more is preferable, and 20% by weight or more is more preferable. The content of polysiloxane (A1) and / or polysiloxane (a1) is the total amount of solids excluding the solvent (C) of the resin composition from the viewpoint of further enhancing the light transmittance and crack resistance of the cured film. 80% by weight or less is more preferable.

Next, a method for producing polysiloxane (A1) or polysiloxane (a1) will be described.

Polysiloxane (A1) or polysiloxane (a1) can be obtained by hydrolyzing and condensing an alkoxysilane compound as a raw material.

In the hydrolysis reaction, an acid catalyst and water are added to the above-mentioned alkoxysilane compound in a solvent to generate a silanol group. It is preferable to add an acid catalyst and water to the alkoxysilane compound over 1 to 180 minutes, and then react at room temperature to 110 ° C. for 1 to 180 minutes. By carrying out the hydrolysis reaction under such conditions, a rapid reaction can be suppressed. A more preferable reaction temperature is 40 to 105 ° C.

Further, after the hydrolysis reaction, a condensation reaction is carried out to obtain polysiloxane. The condensation reaction is preferably carried out by heating the reaction solution at 50 ° C. or higher and below the boiling point of the solvent for 1 to 100 hours. It is also effective to reheat or add a base catalyst in order to increase the degree of polymerization of the polysiloxane compound obtained by the condensation reaction.

Various conditions in the hydrolysis / condensation reaction are suitable for the intended use by setting, for example, the acid concentration, reaction temperature, reaction time, etc. in consideration of the reaction scale, size, shape, etc. of the reaction vessel. Can be obtained.

Examples of the acid catalyst used in the hydrolysis reaction include acid catalysts such as hydrochloric acid, acetic acid, formic acid, nitrate, oxalic acid, hydrochloric acid, sulfuric acid, phosphoric acid, polyphosphoric acid, polyvalent carboxylic acid or its anhydride, and ion exchange resin. In particular, an acidic aqueous solution using formic acid, acetic acid or phosphoric acid is preferable.

The preferable content of these acid catalysts is preferably 0.05 parts by weight or more, more preferably 0.1 parts by weight or more, based on 100 parts by weight of the total polysiloxane compound before the hydrolysis reaction. Further, it is preferably 10 parts by weight or less, more preferably 5 parts by weight or less. Here, the total amount of the polysiloxane compound is a compound having a silicon atom and includes all of the alkoxysilane compound which is a raw material of the polysiloxane, its hydrolyzate, and the polysiloxane which is a condensate thereof. To tell. The definition is the same below. When the amount of the acid catalyst is 0.05 parts by weight or more, the hydrolysis proceeds smoothly, and when the amount is 10 parts by weight or less, the hydrolysis reaction can be easily controlled.

The solvent used for the hydrolysis / condensation reaction is not particularly limited, but is appropriately selected in consideration of the stability, wettability, volatility, etc. of the resin composition. Not only one type of solvent but also two or more types can be used. The solvent used for the hydrolysis / condensation reaction may be contained as it is as the solvent (C) of the resin composition.

Specific examples of the solvent include the following. Methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl-3-methoxy-1-butanol, di Alcohols such as acetone alcohol.

Glycols such as ethylene glycol and propylene glycol.
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol mono-t-butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, Ethers such as ethylene glycol dibutyl ether and diethyl ether.

Ketones such as methyl ethyl ketone, acetylacetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, and 2-heptanone.

Amides such as dimethylformamide and dimethylacetamide.
Ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl lactate, ethyl lactate, butyl lactate, etc. Acetic acids; aromatic or aliphatic hydrocarbons such as toluene, xylene, hexane, cyclohexane.

In addition, γ-butyrolactone, N-methyl-2-pyrrolidone, dimethyl sulfoxide, etc.

Of these, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and propylene glycol mono-t are considered in terms of the permeability of the cured film and crack resistance. -Butyl ether, γ-butylollactone and the like are preferably used.

It is also preferable to adjust the concentration or viscosity of the resin composition to an appropriate level by further adding a solvent after the completion of the hydrolysis / condensation reaction. It is also possible to distill and remove all or part of vaporizable hydrolysis products such as alcohol produced by heating and / or under reduced pressure after hydrolysis, and then add a suitable solvent.

The amount of the solvent used in the hydrolysis reaction is preferably 50 parts by weight or more, more preferably 80 parts by weight or more, and preferably 500 parts by weight or less, based on 100 parts by weight of the total polysiloxane compound. Preferably, it is 200 parts by weight or less. Gel formation can be suppressed by setting the amount of the solvent to 50 parts by weight or more. Further, when the content is 500 parts by weight or less, the hydrolysis reaction proceeds rapidly.

Further, as the water used for the hydrolysis reaction, ion-exchanged water is preferable. The amount of water can be arbitrarily selected, but it is preferably used in the range of 1.0 to 4.0 mol with respect to 1 mol of the alkoxysilane compound.

<Particle (B)>
The resin composition of the present invention contains titanium composite oxide particles (B1) having a total content of one or more elements selected from the group consisting of aluminum, tin and zirconium of 2% by weight or more and 15% by weight or less (hereinafter, (Sometimes referred to as particles (B1)) and titanium composite oxide particles (B2) having an elemental layer content of less than 2% by weight selected from the group consisting of aluminum, tin and zirconium (hereinafter, referred to as “B1)”. It contains two types of particles (sometimes referred to as particles (B2)). By containing these two types of particles, the refractive index and etching processability can be improved.

The total element content refers to the ratio (% by weight) of the total content of the relevant element to the total weight of the relevant particle, and when a dispersant containing the particles (B1) or (B2) is used, the ratio thereof is used. The ratio of the total content of the corresponding elements shall be calculated with the total amount of solids as the weight of the particles.

The total content of one or more elements selected from the group consisting of aluminum, tin and zirconium of the particles (B2) is preferably less than 0.5% by weight, more preferably 0.1% by weight, from the viewpoint of etchability. More preferably, it is less than%. Furthermore, it is desirable that the amount is as small as possible, and ideally 0% by weight.

The mixed weight ratio (B1 / B2) of these particles (B1) and the particles (B2) is preferably 0.25 to 4. Being in this range improves the etching property.

The content of the corresponding element of the particle (B1) or the particle (B2) can be measured by a fluorescent X-ray analysis method, an ICP emission spectroscopic analysis method, an ICP weight analysis method, or an atomic absorption spectrometry method. The total amount of aluminum, tin and zirconium contained in the resin composition is preferably 0.01% by weight or more and less than 1% by weight with respect to 100% by weight of the total amount of the resin composition. For example, by adjusting the mixing ratio of the particles (B1) and the particles (B2) as described above, the total amount of aluminum, tin, and zirconium contained in the resin composition can be adjusted.

The total content of the particles (B1) and the particles (B2) is preferably 35 to 70% by weight with respect to the solid content in the resin composition. Within the above range, high refractive index, crack resistance and transparency can be achieved at the same time. As a lower limit, the total content of the particles (B1) and the particles (B2) is more preferably 40% by weight or more, still more preferably 45% by weight or more, based on the solid content in the resin composition. As an upper limit, the total content of the particles (B1) and the particles (B2) is more preferably 65% by weight or less, still more preferably 60% by weight or less, based on the solid content in the resin composition.

Further, the resin composition of another aspect of the present invention contains particles (B) which are composite oxides of titanium and one or more selected from the group consisting of aluminum, tin, zirconium and silicon. The above-mentioned particles (B1) and particles (B2) are also assumed to be a kind of particles (B).

Particle (B) has a high refractive index and stability, and is preferably used. Among them, particles which are a composite oxide of tin and / or zirconium and titanium have a high refractive index and are more preferable.

Further, the particles (B) are one or more selected from the group consisting of aluminum, tin and zirconium, the particles (B3) which are composite oxides of titanium, and the particles (B4) which are composite oxides of silicon and titanium. ), It is more preferable to contain two types of particles. Etching property is improved by containing two kinds of particles, the particles (B3) and the particles (B4). One or more kinds selected from the group consisting of aluminum, tin and zirconium, and particles (B3) which are composite oxides of titanium may be hereinafter referred to as particles (B3). Particles (B4) which are composite oxides of silicon and titanium may be hereinafter referred to as particles (B4). It is assumed that the particle (B3) and the particle (B4) are a kind of the particle (B).

The number average particle size of the particles (B) is preferably 1 to 200 nm. In order to obtain a cured film having high transmittance, the number average particle diameter of the particles (B) is more preferably 1 nm to 70 nm. Here, the number average particle diameter of the particles (B) can be measured by a gas adsorption method, a dynamic light scattering method, a small-angle X-ray scattering method, a transmission electron microscope, or a scanning electron microscope.

The content of the particles (B) is preferably 35 to 70% by weight with respect to the solid content in the resin composition. Within the above range, high refractive index, crack resistance and transparency can be achieved at the same time. As a lower limit, the content of the particles (B) is more preferably 40% by weight or more, still more preferably 45% by weight or more, based on the solid content in the resin composition. As an upper limit, the content of the particles (B) is more preferably 65% by weight or less, still more preferably 60% by weight or less, based on the solid content in the resin composition. The total content of the particles (B3) and the particles (B4) is preferably 35 to 70% by weight with respect to the solid content in the resin composition. As a lower limit, the total content of the particles (B3) and the particles (B4) is more preferably 40% by weight or more, still more preferably 45% by weight or more, based on the solid content in the resin composition. As an upper limit, the total content of the particles (B3) and the particles (B4) is more preferably 65% by weight or less, still more preferably 60% by weight or less, based on the solid content in the resin composition.

The content of aluminum, tin, zirconium and silicon in the composite oxide is not particularly limited, but the total amount of aluminum, tin and zirconium contained in the resin composition is 100% by weight based on the total amount of the resin composition. , 0.01% by weight or more and less than 1% by weight. Within this range, the etching property is improved and it becomes easier to form a lens.

Titanium oxide includes those having different crystal structures, such as anatase-type titanium oxide and rutile-type titanium oxide, but the crystal structure of the particles (B) is not particularly limited, and particles (B) having an appropriate structure depending on the application are not particularly limited. ) Can be used.

Further, the surface of the particles (B) may be coated with a polymer, a dispersant, or the like. The dispersed state of the surface-coated particles (B) is stabilized, and aggregation and precipitation tend to be suppressed even if the content of the particles (B) in the resin composition is increased.

There are no particular restrictions on the polymer or dispersant that coats the surface of the particles (B). On the other hand, the polysiloxane (A1) in the resin composition also contributes to the dispersion stabilization of the particles (B). The polysiloxane (A1) and the particles (B) easily interact with each other, and the dispersion stability can be improved by simply mixing them.

When the polysiloxane (A1) is polymerized, the polysiloxane (A1) and the particles (B) are bonded by mixing the particles (B) in the process of hydrolysis / condensation reaction of the alkoxysilane compound as a raw material. A complex (E) of polysiloxane and particles can be formed. Similarly, when polymerizing polysiloxane (A1), particles (B1) or particles (B2) are mixed in the process of hydrolysis / condensation reaction of the alkoxysilane compound as a raw material to obtain polysiloxane (A1). A composite (E) of a polysiloxane and a particle in which the particle (B1) or the particle (B2) is bonded can be formed. The resin composition of the present invention preferably contains a polysiloxane (A1) and a composite (E) of the polysiloxane and the particles in which the particles (B1) or the particles (B2) are bonded.

Similarly, for the polysiloxane (a1) having the structure represented by the formula (1), a complex (E1) of the polysiloxane and the particles in which the polysiloxane (a1) and the particles (B) are bonded is formed. Is preferable. The resin composition of the present invention preferably contains a polysiloxane (a1) and a complex (E1) of the polysiloxane and the particles to which the particles (B) are bonded.

By containing the complex (E) or (E1) in the resin composition of the present invention, the dispersion stability of the particles (B1) or the particles (B2) or the particles (B) is further improved. be able to.

Examples of commercially available particles (B) are "Optrake®" TR-502, "Optrake" TR-503, "Optrake" TR-504, "Optrake®" TR-502, "Optrake" TR-504, "Optrake®" TR-502, "Optrake" TR-504, which are silicon oxide-titanium oxide composite particles. Optrake "TR-513", "Optrake" TR-520, "Optrake" TR-527, "Optrake" TR-528, "Optrake" TR-529, Zirconium oxide-tin oxide-silicon oxide-titanium oxide Composite particle "Optrake" TR-550, titanium oxide particle "Optrake" TR-505 (trade name, manufactured by Catalysis Chemical Industry Co., Ltd.), zirconium oxide particle (manufactured by High Purity Chemical Laboratory Co., Ltd.) ), Tin oxide-zinc oxide composite particles (manufactured by Catalysis Chemical Industry Co., Ltd.), and the like.

Examples of particles (B1) include the above-mentioned "Optrake" TR-550 (trade name, manufactured by Catalysis Chemical Industry Co., Ltd.), zirconium oxide particles (manufactured by High Purity Chemical Laboratory Co., Ltd.), tin oxide-oxidation. Zirconium composite particles (manufactured by Catalysis Chemical Industry Co., Ltd.), etc. can be mentioned.

Further, as an example of the particle (B2), the above-mentioned "Optrake (registered trademark)" TR-502, "Optrake" TR-503, "Optrake" TR-504, "Optrake" TR-513, " "Optrake" TR-520, "Optrake" TR-527, "Optrake" TR-528, "Optrake" TR-529, "Optrake" TR-505 (above, trade name, Catalytic Chemical Industry Co., Ltd.) Made), etc.

Examples of particles (B3) include the above-mentioned "Optrake" TR-550 (trade name, manufactured by Catalysis Chemical Industry Co., Ltd.), zirconium oxide particles (manufactured by High Purity Chemical Laboratory Co., Ltd.), tin oxide-oxidation. Zirconium composite particles (manufactured by Catalysis Chemical Industry Co., Ltd.), etc. are mentioned, and examples of the particles (B4) include the above-mentioned "Optrake (registered trademark)" TR-502, "Optrake" TR-503, ". "Optrake" TR-504, "Optrake" TR-513, "Optrake" TR-520, "Optrake" TR-527, "Optrake" TR-528, "Optrake" TR-529, "Optrake" "TR-505 (above, trade name, manufactured by Catalysis Chemical Industry Co., Ltd.), etc. can be mentioned.

<Chinone diazide compound (D)>
In order to impart positive photosensitivity to the resin composition of the present invention, it is preferable to further contain the quinone diazide compound (D). By containing the quinonediazide compound, a positive relief pattern can be obtained by improving the solubility of the exposed portion in the aqueous solution of tetramethylammonium hydroxide.

As the quinone diazide compound (D), the compound represented by any of the formula (6) is preferable. It is a compound in which a sulfonic acid of naphthoquinonediazide is ester-bonded to a compound having a phenolic hydroxyl group.

R ⁷ indicates the residue after esterification of the compound having a phenolic hydroxyl group.

Examples of the compound having a phenolic hydroxyl group used here include 4,4'-Cyclohexylidenobis phenol, 4,4'-Cyclohexylidenebis [2-methylphenol], 5,5'-(1,1'-Cyclohexylidene) bis-. [1,1'-(biphenyl) -2-ol], 4,4'-Cyclopendylidephenol, 4,4'-Cyclohexylphenol [2,6-dimethylphenol], 4,4'-Cyclohexylridebis [2- (1,1,) 1-dimethylphenol], 4,4'-Cyclohexylphenol [2-cyclohexylphenol], 4,4'-Cyclopentylphenol [2-methylphenol], 4,4'-(4-Methylcylide4 2,6-dimethylphenol], 4,4'-[4- (1-Methylphenol) cyclohexylphenol] bisphenol, 4,4'-[4- (1-methylphenol) cyclohexylphenol] bis [2-methylphenol], 4,4' -[4- (1-Methylly) cyclohexylphenol] bis [2-cyclohexylphenol], 4,4'-Cyclopentylylenebis [2- (1-methyltyl) phenol), 4,4'-[4- (1-Methylly") bis [2,6-dimethylphenol], 4,4'-Cyclopentylidenebis [2- (1,1-dimethyl) phenol], 4,4,4', 4'Tetracis [(1-methylylide) bis (1,4) -Cyclohexylidene)] phenol), 4,4', 4''-Ethylidenetris phenol, 4,4'-[1- [4- [4- [4-Hydroxyphenyl) -1-methylyl] phenol] ethylylene] phenol, Cyclohy [2-fl uoro phenol], 4,6-Bis [(4-hydroxyphenyl) methyl] -1,3-benzenediol, 4,6-Bis [(3,5-dimethyl-4-hydroxyphenyl) methyl] -1,2,3- phenol, 2,4,6-Tris (4-hydroxyphenylphenol) -1,3-benzenediol, 2,4-Bis [(3-methyl-4-hydroxyphenyl) methyl] -6-cyclohexylphenol, 2,4-Bis [( 5-methyl-2-hydoxyphenyl) methyl] -6-cyclohexylphenol, 2,4-Bis [(2,5-dimethyl-4-hydroxyphenyl) methyl] -6-cyclohexylphenol, 2,4-Bis [(3,5) -Dimethyl-4-hydroxyphenol] methyl] -6-cyclohexylphenol, 2,4-Bis [(4-hydroxy-3-cyclohexylphenyl) methyl] -6-methylphenol, 2,4-Bis [(2,3,6-) Trimethyl-4-hydroxyphenyl) methyl] -6-cycrohexyl phenol, 4,6-Bis [3,5-dimethyl-4-hydroxyphenyl] methyl] -1,3-benzenediol, 2,4-Biz [(2,4-2,4-) dihydroxyphenyl) methyl] -6-cyclohexyl phenol, 4- [1- (4-Hydroxyphenyl) -1-phenyl] -1,2-benzenedol, BIR-OC, BIP-PC, 2,6-Bis (2,4-Bis) dihydroxybenzal) -4-methylphenol, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A (trade name, manufactured by Asahi Organic Materials Industry Co., Ltd.), Examples thereof include 4,4'-sulfonyldiphenol (manufactured by Wako Pure Chemical Industries, Ltd.) and 9,9-Biz (4-hydroxyphenyl) fluorolene (trade name, manufactured by JFE Chemical Co., Ltd.).

Among these, the following are examples of compounds having a preferable phenolic hydroxyl group.

4,4'-Cyclohexylidobis phenol, 4,4,4', 4'Tetracis [(1-methylthylide) bis (1,4-cyclohexylidene)] phenol, 4,4', 4''-Ethylidenellis phenol, 4,4 '-[1- [4- [1- (4-Hydroxyphenyl) -1-methylly] phenyl] ethylide] bisphenol, 4,4'-Cyclohexylphenol [2-cyclohexylphenol], 4,4'-(4-Methyllic) bis phenol, 4,4'-[4- (1-Methyrethyl) cyclohexylphenol] bis phenol, 4,4'-[4- (1-Methyl thyll) cyclohexylphenol] bis [2-cyclohexylphenol], 4,4'-C phenol, 4,6-Bis [(4-hydroxyphenyl) methyl] -1,3-benzenediol, 2,4,6-Tris (4-hydroxyphenylmethyl) -1,3-benzenediol, 2,4-Bis [(5-5-bisphenol)] methyl-2-hydroxyphenyl) methyl] -6-cyclohexylphenol, 4,6-Bis [3,5-dimethyl-4-hydroxyphenyl] methyl] -1,3-benzenediol, 4- [1- (4-Hydroxyphenol) -Phenylphenol] -1,2-phenendiol, BIP-PC, 2,6-Bis (2,4-dihydroxybenzyl) -4-methylphenol, BIR-PTBP, BIR-BIPC-F, 9,9-Biz (4-hydroxyphenyl) ) Phenol.

Among these, compounds having a particularly preferable phenolic hydroxyl group include, for example, 4,4'-Cyclohexylidobis phenol, 4,4,4', 4'Tetracis [(1-methylthylide) bis (1,4-cyclohexylide)]. phenol, 4,4', 4''-Ethylidephenol, 4,4'-[1- [4- [1- (4-Hydroxyphenyl) -1-methylly] phenyl] etheridene] phenol, 4,6-Bis [ (4-Hydroxyphenyl) methyl] -1,3-benzenediol, 2,4,6-Tris (4-hydroxyphenylmethyl) -1,3-benzenedil, 4- [1- (4-Hydroxyphenyl) -1-phenyl] -1 , 2-benzenediol, 2,6-Bis (2,4-dihydroxybenzyl) -4-methylphenol, BIR-PTBP, BIR-BIPC-F, 4,4'-sulfonyldiphenol, 9,9-Biz (4-hydroxyphenyl) ) Phenol and the like.

A compound obtained by introducing 4-naphthoquinonediazide sulfonic acid or 5-naphthoquinone diazidosulfonic acid into the compound having a phenolic hydroxyl group described above by an ester bond can be exemplified as a preferable compound. Other compounds can also be used.

The content of the quinone diazide compound (D) is 1 to 50 parts by weight, more preferably 2 to 10 parts by weight, based on the resin (A) and / or the polysiloxane (A1). The content of the quinone diazide compound (D) is preferably 1 to 50 parts by weight, more preferably 2 to 10 parts by weight, based on the polysiloxane (a1). By setting the amount to 1 part by weight or more, pattern formation can be performed with practical sensitivity. Further, when the content is 50 parts by weight or less, a resin composition having excellent transmittance and pattern resolution can be obtained.

The preferable molecular weight of the quinonediazide compound (D) is 300 or more, more preferably 350 or more. Further, it is 1000 or less, more preferably 800 or less. By setting the molecular weight to 300 or more, the effect of suppressing dissolution of the unexposed portion can be obtained. Further, by setting the molecular weight to 1000 or less, a relief pattern without scum can be obtained in a portion developed after exposure and from which the photosensitive resin composition has been removed.

Since the quinone diazide compound (D) is added, naphthoquinone diazide groups remain in the coating film in the unexposed area, which may cause coloration of the film after heat curing. In order to obtain a transparent cured film, it is preferable to irradiate the entire surface of the developed film with ultraviolet rays to decompose the naphthoquinone diazide compound, and then perform heat curing.

<Solvent (C)>
The resin composition of the present invention contains a solvent (C). Examples of the solvent (C) include the following.

Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol mono-t-butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, Ether-based compounds such as ethylene glycol dibutyl ether.
Ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propyl acetate, butyl acetate, isobutyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate and other acetate compounds.
Lactate SL such as methyl lactate, ethyl lactate, and butyl lactate. Ketone compounds such as acetylacetone, methylpropylketone, methylbutylketone, methylisobutylketone, cyclopentanone, 2-heptanone, and mesityl oxide. Alcohols such as methanol, ethanol, propanol, butanol, isobutyl alcohol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl-3-methoxy-1-butanol, diacetone alcohol, etc. Compound. Aromatic hydrocarbon compounds such as toluene and xylene. In addition, γ-butyrolactone, N-methylpyrrolidinone, etc. These may be contained alone or in two or more kinds.

Among these, examples of particularly preferable solvents are propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol mono-t-butyl ether, and diacetone alcohol. , Gamma-butylollactone. These may be contained alone or in two or more kinds.

The content of the solvent (C) in the resin composition is preferably in the range of 100 parts by weight to 9900 parts by weight, more preferably in the range of 100 parts by weight to 5000 parts by weight, based on 100 parts by weight of the total polysiloxane compound. be.

<Other ingredients>
The resin composition of the present invention may contain various surfactants in order to improve the flowability and the uniformity of the film thickness at the time of coating. The type of surfactant is not particularly limited, and for example, a fluorine-based surfactant, a silicone-based surfactant, a polyalkylene oxide-based surfactant, a poly (meth) acrylate-based surfactant, or the like can be used. Of these, a fluorine-based surfactant is particularly preferably used from the viewpoint of flowability and film thickness uniformity.

Specific examples of the fluorine-based surfactant include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether and 1,1,2,2-tetrafluorooctyl. Hexyl ether, octaethylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1) , 1,2,2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecylsulfonate, 1,1,2,2 , 8,8,9,9,10,10-decafluorodecan, 1,1,2,2,3,3-hexafluorodecane, N- [3- (perfluorooctane sulfonamide) propyl] -N, N'-dimethyl-N-carboxymethyleneammonium betaine, perfluoroalkylsulfonamide propyltrimethylammonium salt, perfluoroalkyl-N-ethylsulfonylglycine salt, bis phosphate (N-perfluorooctylsulfonyl-N-ethylaminoethyl) , Monoperfluoroalkylethyl phosphate, etc. Fluorescent surfactants comprising compounds having a fluoroalkyl or fluoroalkylene group at at least any of the terminal, main chain and side chains can be mentioned.

As commercially available products, "Megafuck" (registered trademark) F142D, F172, F173, F183, F410, F477, F553, F554, F556, F557, F559, F560, etc. F563, RS-72-K, DS-21, R-41 (all manufactured by Dainippon Ink and Chemicals Co., Ltd.), "Ftop" (registered trademark) EF301, 303, 352 (Shin-Akita Kasei (Shin-Akita Kasei) (Manufactured by Sumitomo Co., Ltd.), "Florard" FC-430, FC-431 (manufactured by Sumitomo 3M Co., Ltd.), "Asahi Guard" (registered trademark) AG710, "Surfron" (registered trademark) S-382, SC-101 , SC-102, SC-103, SC-104, SC-105, SC-106 (manufactured by Asahi Glass Co., Ltd.), BM-1000, BM-1100 (manufactured by Yusho Co., Ltd.), NBX -15, FTX-218 (manufactured by Neos Co., Ltd.) and other fluorosurfactants can be mentioned. Among these, the above-mentioned "Mega Fvck" (registered trademark) F477, F556, F563, BM-1000, BM-1100, NBX-15, and FTX-218 are particularly preferable from the viewpoint of flowability and film thickness uniformity.

Commercially available silicone-based surfactants include SH28PA, SH7PA, SH21PA, SH30PA, and ST94PA (all manufactured by Toray Dow Corning Silicone Co., Ltd.), BYK-333, and BYK-352 (manufactured by Big Chemie Japan Co., Ltd.). ), KL-700, LE-302, LE-303, LE-304 (Kyoeisha Chemical Co., Ltd.) and the like. Examples of other surfactants include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene distearate and the like.

The content of the surfactant is usually 0.001 to 10 parts by weight with respect to 100 parts by weight of the total polysiloxane compound content in the resin composition. These may be used alone or in combination of two or more at the same time.

Further, the resin composition may contain a polymerization inhibitor for the purpose of suppressing thermal polymerization at the time of prebaking for vaporizing the solvent, for example. Examples of the polymerization inhibitor include catechols such as phenol, hydroquinone, p-methoxyphenol, benzoquinone, methoxybenzoquinone, 1,2-naphthoquinone, cresol, and pt-butylcatechol, alkylphenols, alkylbisphenols, phenothiazine, and the like. 2,5-di-t-butylhydroquinone, 2,6-di-t-butylphenol, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, N, N'-hexamethylene Bis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide), 2,2'methylenebis (4-methyl-6-t-butylphenol), 4,4'methylenebis (2,6-di- t-Butylphenol), 4,4'butylidenebis (3-methyl-6-t-butylphenol), 2,6-bis (2'-hydroxy-3'-t-butyl-5'-methylbenzyl) 4-methylphenol , 1,1,3-Tris (2'-methyl-5'-t-butyl-4'-hydroxyphenyl) butane, 1,3,5-trimethyl-2,4,6-Tris (3'-5') -Di-t-butyl-4'-hydroxybenzyl) benzene, triethylene glycol bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], pentaerythrityltetrax [3- (3) , 5-di-t-butyl-4-hydroxyphenyl) propionate], 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2, Phenols such as 4-dimethyl-6-t-butylphenol and 2-t-butyl-4-methoxyphenol, 6-t-butyl-m-cresol, 2,6-di-t-butyl-p-cresol, 2 -T-Butyl hydroquinone, methylene blue, dimethyl dithiocarbamic acid copper salt, diethyl dithiocarbamic acid copper salt, dipropyl dithiocarbamic acid copper salt, dibutyl dithiocarbamic acid copper salt, dibutyl dithiocarbamate copper, dibutyl dithiocarbamate copper, salicylate copper, thiodipropionic acid esters, mercaptobenz Imidazole or phosphites Examples thereof include the combined use of these compounds with an oxygen-containing gas such as air. The content of the polymerization inhibitor in the resin composition of the present invention is preferably 0.000005 to 0.2% by weight, preferably 0.00005 to 0.1% by weight, based on the entire resin composition. More preferred. Further, 0.0001 to 0.5% by weight is preferable, and 0.001 to 0.2% by weight is more preferable with respect to all the components other than the organic solvent.

Further, the resin composition of the present invention can contain a viscosity regulator, a stabilizer, a colorant, an ultraviolet absorber and the like, if necessary.

<Cured film>
The resin composition of the present invention is applied onto a substrate to obtain a coating film. A cured film can be formed by drying and curing this by heating.

As the coating method of the resin composition of the present invention, microgravure coating, spin coating, dip coating, curtain flow coating, roll coating, spray coating, slit coating, sink coating method and the like can be preferably used.

The heat-drying and curing conditions are appropriately selected depending on the substrate to be applied and the resin composition, but usually, the treatment is carried out at a temperature of room temperature or higher and 400 ° C. or lower for 0.5 to 240 minutes. Is preferable. A particularly preferable curing temperature is 100 to 400 ° C, more preferably 150 to 400 ° C.

The film thickness of the coating film and the cured film is not particularly limited, but both are generally in the range of 0.001 to 100 μm.

When the above resin composition has photosensitivity, the method for producing a cured film preferably includes the following steps.
(I) A step of applying a resin composition onto a substrate to form a coating film,
(II) Step of exposing the coating film (III) Step of heating the coating film after the exposure.

Each of the above steps will be described in order.

(I) Step of Applying Resin Composition to Substrate to Form Coating Film The above resin composition is applied to the substrate by a known method such as spin coating or slit coating, and heated in a hot plate, oven or the like. Heat using the device. This is called prebake. Prebaking is preferably carried out in a temperature range of 50 to 150 ° C. for 30 seconds to 30 minutes. The film thickness after prebaking is preferably 0.1 to 15 μm.

(II) Step of exposing the coating film After prebaking, an ultraviolet-visible exposure machine such as a stepper, a mirror projection mask aligner (MPA), or a parallel light mask aligner (PLA) is used to expose ^{about 10 to 4000 J / m 2} (wavelength 365 nm exposure). The entire surface of the coating film is exposed with an exposure amount of (quantity conversion).

(III) The coating film that has undergone the step (I) of heating and curing the coating film, or the coating film that has undergone (I) and (II) is heated at 150 to 450 ° C. using a heating device such as a hot plate or an oven. A cured film is obtained by heating (curing) for about 30 seconds to 2 hours in the temperature range of.

Further, when the above resin composition has photosensitive property and a patterned cured film is produced, it is preferable to include the following steps.
(I) A step of applying a resin composition onto a substrate to form a coating film,
(Ii) A step of removing an exposed portion of the coating film by developing the coating film with a developing solution after a pattern exposure step.
(Iii) A step of exposing the coating film remaining after development,
(Iv) A step of heating the coating film after the exposure.

Each of the above processes will be explained in order.

(I) Step of applying the resin composition on the substrate to form a coating film The above resin composition is applied on the substrate by a known method such as spin coating or slit coating, and heated in a hot plate, an oven, or the like. Heat using the device. This is called prebake. Prebaking is preferably carried out in a temperature range of 50 to 150 ° C. for 30 seconds to 30 minutes. The film thickness after prebaking is preferably 0.1 to 15 μm.

(Ii) A step of removing an exposed portion of the coating film by developing the coating film with a developing solution after a pattern exposure step. After prebaking, a stepper, a mirror projection mask aligner (MPA), and a parallel light mask aligner (pla). ^{A pattern exposure is performed with an exposure amount of about 10 to 4000 J / m 2} (equivalent to an exposure amount of 365 nm wavelength) through a desired mask using an ultraviolet visible exposure machine such as the above.

After exposure, the film in the exposed area is dissolved and removed by development to obtain a positive pattern. The resolution of the pattern is preferably 15 μm or less. Examples of the developing method include methods such as showering, dipping, and paddle, and it is preferable to immerse the film in a developing solution for 5 seconds to 10 minutes. As the developing solution, a known alkaline developing solution can be used, and examples thereof include an aqueous solution of the following alkaline components. Inorganic alkaline components such as alkali metal hydroxides, carbonates, phosphates, silicates and borates, amines such as 2-diethylaminoethanol, monoethanolamine and diethanolamine, tetramethylammonium hydroxide (TMAH) , Colin and other quaternary ammonium salts. Two or more of these may be used as the alkaline developer.

Further, it is preferable to rinse with water after development, and if necessary, dehydration drying baking may be performed in a temperature range of 50 to 150 ° C. with a heating device such as a hot plate or an oven. Further, if necessary, heating is performed in a heating device such as a hot plate or an oven in a temperature range of 50 to 300 ° C. for 30 seconds to 30 minutes. This is called soft bake.

(Iii) Step of exposing the coating film remaining after the development After the development, an ultraviolet visible exposure machine such as a stepper, a mirror projection mask aligner (mpa), a parallel light mask aligner (pla) is used, and the coating film remains through a desired mask. Pattern exposure is performed at an exposure amount of about 10 to 4000 J / m ^{2 (wavelength 365 nm exposure amount conversion).}

(Iv) A step of heating the coating film after the exposure.

A cured film is obtained by heating (curing) the coating film that has undergone (iii) in a heating device such as a hot plate or an oven in a temperature range of 150 to 450 ° C. for about 30 seconds to 2 hours.

In the steps of (ii) exposure and development, the resin composition of the present invention ^{preferably has a sensitivity of 1500 J / m 2} or less, preferably 1000 J / m ² or less, from the viewpoint of productivity in pattern formation. Is more preferable.

The sensitivity at the time of exposure is obtained by the following method. The photosensitive resin composition is spin-coated on a silicon wafer at an arbitrary rotation speed using a spin coater. The coating film is prebaked at 120 ° C. for 3 minutes using a hot plate to prepare a prebaked film having a film thickness of 1 μm. Using PLA (PLA-501F manufactured by Canon Inc.), which is a mask aligner, an ultra-high pressure mercury lamp is used, and a grayscale mask having a line and space pattern of 1 to 10 μm, which is a mask for sensitivity measurement, is used. The pre-baked film is exposed. Then, using an automatic developing device (AD-2000 manufactured by Takizawa Sangyo Co., Ltd.), shower development is performed with a 2.38 wt% TMAH aqueous solution for 90 seconds, and then rinse with water for 30 seconds. Among the formed patterns, the one with the lowest exposure amount (hereinafter referred to as the optimum exposure amount) among the exposure amounts formed on the substrate without peeling off after development of a square pattern having a design dimension of 100 μm is defined as the sensitivity. ..

Then, as a thermosetting 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 obtained as the post-cure resolution.

The cured film of the present invention is a cured film obtained by curing the resin composition of the present invention.

The resin composition of the present invention and its cured film are suitably used as index matching materials for optical devices such as solid-state image sensors, optical filters, and displays, and touch panels. More specifically, a light-collecting microlens and an optical waveguide formed on a solid-state image sensor such as a back-illuminated CMOS image sensor, an antireflection film installed as an optical filter, and a flattening material for a TFT substrate for a display. Examples thereof include a color filter such as a liquid crystal display, a protective film thereof, and a phase shifter. Among these, since it is possible to achieve both high transparency and high refractive index, it is particularly preferably used as a condensing microlens formed on a solid-state image sensor or an optical waveguide connecting a condensing microlens and an optical sensor unit. .. Further, the resin composition of the present invention and the cured film thereof can also be used as a buffer coat of a semiconductor device, an interlayer insulating film, and various protective films.

<Solid image sensor>
The solid-state image sensor of the present invention comprises the cured film of the present invention. As an example, there is a form in which a transparent resin layer such as a color filter, a microlens (array), and an antireflection film is sequentially provided on a substrate having a semiconductor light receiving element from the substrate side. Light from the outside passes through the transparent resin layer, the microlens, and the color filter in this order, reaches the light receiving element, and is detected. At this time, by applying the cured film formed from the resin composition of the present invention as a microlens, efficient light collection to the light receiving element becomes possible. It functions over the pixels of the light receiving element that detects light corresponding to each of RGB, and obtains an extremely clear image even when the pixels of the light receiving element and the individual lenses of the microlens are arranged at high density. Can be done.

Further, as another form, a resin layer that functions as an optical waveguide, a color filter, a microlens (array), and a resin layer such as an antireflection film are sequentially formed on a substrate having a light receiving element. At this time, the cured film formed from the resin composition of the present invention can be suitably used as a microlens or an optical waveguide.

<Micro lens>
The microlens of the present invention comprises the cured product of the present invention. As one form of the microlens forming method, an example of the microlens array forming step will be described. If necessary, the unevenness of the element is embedded and flattened by spin coating with a transparent resin. The lens material is uniformly applied to the flattened surface to form a cured film by the method described above. Further, the resist is uniformly applied on it. Using a stepper device, the resist is irradiated with ultraviolet rays using a reticle as a mask to expose a portion of the space between lenses. The exposed part is decomposed and removed with a developing solution to form a pattern. Obtained by heating a hemispherical pattern. At this time, the resist melts into a liquid phase, becomes a hemispherical state, and then changes to a solid phase. Then, the hemispherical pattern layer of the resist material and the layer of the lens material are etched by dry etching. In this way, a lens array in which hemispherical lenses are arranged can be formed. Since the cured film of the present invention has excellent dry etching properties, patterning in the dry etching step is easy. Etching gases used for dry etching include fluorogas such as CF _4, C ₄ F _6, C ₄ F _8, C ₄ F _8, CHF _3, SF ₆ , and NF ₃ gas, O ₂ gas, Ar gas, and N. ₂ Gas or the like can be used.

Further, as another embodiment of the microlens, there is a method of omitting the use of the resist material described above and directly patterning the lens material by exposure. In this embodiment, the patterned lens material is melted by a heating step to obtain a hemispherical lens. When the resin composition of the present invention has positive photosensitivity, it can be suitably used for such an embodiment. At this time, since it is not necessary to form a pattern by the etching method, the work can be simplified and deterioration of the wiring portion due to the etching chemical solution or plasma can be avoided.

<Touch panel>
The touch panel of the present invention comprises the cured film of the present invention. Further, the cured film of the present invention is suitably used for an on-cell type or film type touch panel. The touch panel referred to here is a capacitive touch panel. The sensor layer of the capacitive touch panel has wiring in which ITO (Indium Tin Oxide) and metal (silver, molybdenum, aluminum, etc.) are patterned on a base material such as glass or film, and other wiring intersections. A structure having an insulating film and a protective film for protecting ITO and metal is common. The touch panel method is an on-cell method in which a sensor layer is formed on a liquid crystal panel, an OGS (One Glass Solution) method in which a touch panel layer is directly laminated on a cover glass, and a sensor layer is provided between the cover glass and the liquid crystal panel. Examples include an out-cell method of forming, and a film method using a sensor layer having a film as a support layer. One form of these touch panels includes a form in which an index matching layer is provided below or above the ITO or metal wiring pattern layer in order to suppress the phenomenon in which the ITO or metal wiring is visually recognized (bone visibility phenomenon). The cured film formed from the resin composition of the present invention can be suitably used as an index matching layer (or a high refractive index layer in the layer). Further, since the on-cell method forms the touch panel layer directly on the liquid crystal panel, the wiring, the protective film, the insulating film material, and the index matching layer need to be processed and formed at a low temperature equal to or lower than the heat resistant temperature of the liquid crystal. Further, in the case of the film method, it is necessary to process and form the wiring, the protective film, the insulating film material, and the index matching layer at a low temperature below the heat resistant temperature of the film. In these cases, it is difficult to apply an inorganic material formed by high-temperature film formation by CVD (Chemical Vapor Deposition), and the cured film of the present invention can be preferably used.

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

<Alkoxysilane compound>
MTMS: Methyltrimethoxysilane BPTMS: Biphenyltrimethoxysilane BPDMS: Biphenylmethyldimethoxysilane SuTMS: 3-Trimethoxysilylpropyl succinic acid anhydride NaPTMS: 1-naphthyltrimethoxysilane.

<Solvent>
PGMEA: Propylene glycol monomethyl ether acetate DAA: Diacetone alcohol MeOH: Methanol.

<Chinone diazide compound>
THP-17: (Sulfonic acid ester of 4,4', 4 "-Ethylidine-tris phenol and 1,2-naphthoquinone-2-diazide-5-sulfonic acid) (manufactured by Daito Chemix Co., Ltd.).

The measurement method performed in this example is as follows.

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

<Creation of cured film>
A resin composition was applied onto an 8-inch silicon wafer substrate using a spin coater (model name: Clean Track Mark 7 manufactured by Tokyo Electron Limited). After coating, the film was prebaked at 100 ° C. for 3 minutes, exposed to the entire surface with an I-line stepper exposure machine at an exposure amount of 400 mJ / cm ² , and finally heated and cured at 230 ° C. for 5 minutes to obtain a cured film of about 1 μm.

<Analysis of metal content>
The amounts of aluminum, tin and zirconium contained in the resin composition were quantified by fluorescent X-ray analysis. A sample was collected in a 30 mmΦ plane on a filter paper, and measurement was performed using a sample cell for measurement.
Equipment: ZSX PrimusII (manufactured by Rigaku Denki Kogyo)
Measurement conditions: Tube Rh
Measurement atmosphere Measurement surface in vacuum 30 mmΦ
Measuring range 5B-92U.

<Measurement of refractive index of cured film>
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.

<Evaluation of heat resistance of cured film>
The film thickness (T1) of the obtained cured film was measured. Next, the substrate with the cured film was additionally cured at 280 ° C. for 10 minutes on a hot plate, and then the film thickness (T2) of the cured film was measured. The film thickness change rate before and after the additional cure was calculated from the following formula, the film thickness change rate was calculated by the following formula, and a pass / fail judgment was made.
Film thickness change rate (%) = (T1-T2) / T1 × 100
A: Film thickness change rate (%) ≤ 3%
B: 3% <Film thickness change rate (%) ≤ 5%.
C: Film thickness change rate (%)> 5%.

<Chemical resistance evaluation of cured film>
The film thickness (T1) of the obtained cured film was measured. Next, the substrate with the cured film was immersed in N-methylpyrrolidone at room temperature for 5 minutes, then dried on a hot plate at 100 ° C. for 1 minute, and then the film thickness (T3) of the cured film was measured. The film thickness change rate before and after the additional cure was calculated from the following formula, the film thickness change rate was calculated by the following formula, and a pass / fail judgment was made.
Film thickness change rate (%) = (T1-T3) / T1 × 100
A: Film thickness change rate (%) ≤ 5%
B: 5% <Film thickness change rate (%) ≤ 10%
C: Film thickness change rate (%)> 10%.

<Dry etching evaluation>
The obtained cured film was evaluated by dry etching under the following equipment and conditions, and the film surface roughness Ra after etching was measured with a surfcom stylus film thickness measuring device. The obtained surface roughness Ra was determined as follows.
Dry etching equipment: RIE-10N
Dry etching conditions: Output 200W
Pressure 15Pa
Gas CF ₄
Flow rate 30ccm
Time 3 minutes Surface roughness Ra (nm):
AA: Ra <5 nm
A: 5 nm ≤ Ra <8 nm
B: 8 nm ≤ Ra <14 nm
C: 14 ≦ Ra <20 nm.
D: Ra> 20 nm.

<Patterning evaluation>
A resin composition was applied onto an 8-inch silicon wafer substrate using a spin coater (model name: Clean Track Mark 7 manufactured by Tokyo Electron Limited). After coating, it was prebaked at 80 ° C. for 1 minute and exposed with an I-line stepper exposure machine at an exposure amount of 400 mJ / cm ² through a photomask. As the photomask, a light-shielding mask having 50 μm, 30 μm, and 10 μm line & space openings was used. The exposed substrate was then immersed in 2.38% TMAH for 90 seconds and then rinsed with water for 30 seconds. Further, the residual film portion was entirely exposed with an I-line stepper at an exposure amount of 400 mJ / cm ² , and then heated at 230 ° C. for 5 minutes to obtain a pattern film of about 1 μm. The square pattern of the obtained pattern film was observed, and the smallest pattern dimension (the size of the side of the square) in which the missing pattern was observed was taken as the resolution. The evaluation criteria were set as follows.
resolution:
A: Resolution ≤ 10 μm
B: 10 μm <resolution ≤ 30 μm
C: 30 μm <resolution ≤ 50 μm
D: Resolution> 50 μm.

The polymer synthesis method used in the examples is as follows.

<Synthesis Example 1> Preparation of Polysiloxane Solution X-1 27.24 g (0.20 mol) of MTMS, 54.82 g (0.20 mol) of BPTMS, and 101.14 g of DAA were placed in a 500 mL three-necked flask and stirred at room temperature. While doing so, a mixed solution of 21.6 g of water and 0.41 g of phosphoric acid was added over 30 minutes. Then, the flask was immersed in an oil bath at 70 ° C. and stirred for 1 hour, and then the temperature of the oil bath was raised to 120 ° C. Thirty minutes after the start of temperature rise, the internal temperature of the solution reached 100 ° C., and the mixture was heated and stirred for 2 hours. The temperature inside the flask was 100 to 110 ° C. During the reaction, a total of 49 g of methanol and water, which are by-products, were distilled off. The solution of the polysiloxane and the composite oxide particles remaining in the flask was used as a mixed solution X-1. The solid content concentration of this was 34.9% by weight.

<Synthesis Example 2> Preparation of Polysiloxane Solution X-2 27.24 g (0.20 mol) of MTMS, 51.68 g (0.20 mol) of BPDMS, and 103.85 g of DAA were placed in a 500 mL three-necked flask and stirred at room temperature. While doing so, a mixed solution of 18.00 g of water and 0.39 g of phosphoric acid was added over 30 minutes. Then, the flask was immersed in an oil bath at 70 ° C. and stirred for 1 hour, and then the temperature of the oil bath was raised to 120 ° C. Thirty minutes after the start of temperature rise, the internal temperature of the solution reached 100 ° C., and the mixture was heated and stirred for 2 hours. The temperature inside the flask was 100 to 110 ° C. During the reaction, a total of 40 g of methanol and water, which are by-products, were distilled off. The solution of the polysiloxane and the composite oxide particles remaining in the flask was used as a mixed solution X-2. The solid content concentration of this was 34.6% by weight.

<Synthesis Example 3> Preparation of Polysiloxane Solution X-3 21.79 g (0.16 mol) of MTMS, 54.82 g (0.20 mol) of BPTMS, and 10.49 g (0.04 mol) of SuTMS in a 500 mL three-necked flask. , DAA was charged in an amount of 111.85 g, and a mixed solution of 22.32 g of water and 0.44 g of phosphoric acid was added over 30 minutes while stirring at room temperature. Then, the flask was immersed in an oil bath at 70 ° C. and stirred for 1 hour, and then the temperature of the oil bath was raised to 120 ° C. Thirty minutes after the start of temperature rise, the internal temperature of the solution reached 100 ° C., and the mixture was heated and stirred for 2 hours. The temperature inside the flask was 100 to 110 ° C. During the reaction, a total of 49 g of methanol and water, which are by-products, were distilled off. The solution of the polysiloxane and the composite oxide particles remaining in the flask was used as a mixed solution X-3. The solid content concentration of this was 34.8% by weight.

<Synthesis Example 4> Preparation of mixed solution X-4 of polysiloxane and composite oxide particles 10.90 g (0.08 mol) of MTMS, 27.41 g (0.10 mol) of BPTMS, and 5 of SuTMS in a 500 mL three-necked flask. .25 g (0.02 mol), 111.85 g DAA, methanol sol TR-550 (solid content concentration 20.5% by weight, manufactured by JGC Catalysts and Chemicals) of composite oxide particles of tin, zirconium, silicon and titanium 73. 09.09 g, methanol sol TR-527 (solid content concentration 20.5% by weight, manufactured by JGC Catalysts and Chemicals), which is a composite oxide particle of silicon and titanium, was charged, and 11.16 g of water and 0 phosphoric acid were charged while stirring at room temperature. .22 g of the mixture was added over 30 minutes. Then, the flask was immersed in an oil bath at 70 ° C. and stirred for 1 hour, and then the temperature of the oil bath was raised to 120 ° C. Thirty minutes after the start of temperature rise, the internal temperature of the solution reached 100 ° C., and the mixture was heated and stirred for 2 hours. The temperature inside the flask was 100 to 110 ° C. A total of 139 g of methanol and water, which are by-products, were distilled off during the reaction. The solution of the polysiloxane and the composite oxide particles remaining in the flask was used as a mixed solution X-4. The solid content concentration of this was 34.7% by weight.

<Synthesis Example 5> Preparation of mixed solution X-5 of polysiloxane and composite oxide particles 8.17 g (0.06 mol) of MTMS, 27.41 g (0.10 mol) of BPTMS, and 10 SuTMS in a 500 mL three-necked flask. .49 g (0.04 mol), 122.55 g DAA, methanol sol TR-550 (solid content concentration 20.5% by weight, manufactured by JGC Catalysts and Chemicals) of composite oxide particles of tin, zirconium, silicon and titanium was 80. 09.09 g, methanol sol TR-527 (solid content concentration 20.5% by weight, manufactured by JGC Catalysts and Chemicals), which is a composite oxide particle of silicon and titanium, was charged, and 80.09 g was charged. .23 g of the mixture was added over 30 minutes. Then, the flask was immersed in an oil bath at 70 ° C. and stirred for 1 hour, and then the temperature of the oil bath was raised to 120 ° C. Thirty minutes after the start of temperature rise, the internal temperature of the solution reached 100 ° C., and the mixture was heated and stirred for 2 hours. The temperature inside the flask was 100 to 110 ° C. During the reaction, a total of 150 g of methanol and water, which are by-products, were distilled off. The solution of the polysiloxane and the composite oxide particles remaining in the flask was used as a mixed solution X-5. The solid content concentration of this was 34.7% by weight.

The polymer used in the comparative example was synthesized as follows.

<Synthesis Example 6> Preparation of Polysiloxane Solution R-1 27.24 g (0.20 mol) of MTMS, 49.67 g (0.20 mol) of NaPTMS, and 91.58 g of DAA were placed in a 500 mL three-necked flask and stirred at room temperature. While doing so, a mixed solution of 21.6 g of water and 0.38 g of phosphoric acid was added over 30 minutes. Then, the flask was immersed in an oil bath at 70 ° C. and stirred for 1 hour, and then the temperature of the oil bath was raised to 120 ° C. Thirty minutes after the start of temperature rise, the internal temperature of the solution reached 100 ° C., and the mixture was heated and stirred for 2 hours. The temperature inside the flask was 100 to 110 ° C. During the reaction, a total of 49 g of methanol and water, which are by-products, were distilled off. The solution of the polysiloxane and the composite oxide particles remaining in the flask was used as a mixed solution R-1. The solid content concentration of this was 34.8% by weight.

The resin composition was prepared and evaluated as follows.

<Example 1>
X-1 (solid content concentration 34.9% by weight) was 7.16 g, TR-550 (solid content concentration 20.6% by weight, manufactured by JGC Catalysts and Chemicals) was 12.14 g, and DAA was 0. 44 g and 0.26 g of MeOH were mixed under a yellow lamp, stirred with shaking, and then filtered through a filter having a diameter of 0.45 μm to obtain Composition 1. The metal content in the obtained resin composition was 1.03% by weight. Further, with respect to the obtained resin composition, a cured film was formed according to the above-mentioned method, and refractive index measurement, heat resistance evaluation, chemical resistance evaluation and dry etching evaluation were performed. The composition of the resin composition is shown in Table 2, and the evaluation results are shown in Table 3. Since it does not have photosensitivity, patterning evaluation was not performed, and the patterning evaluation was set to "-".

<Example 2>
X-2 (solid content concentration 34.6% by weight) is 7.23 g, TR-550 (solid content concentration 20.6% by weight, manufactured by JGC Catalysts and Chemicals) is 12.14 g, DAA is 0.38 g, and MeOH is 0. .26 g was mixed under a yellow light, stirred with shaking, and then filtered through a filter having a diameter of 0.45 μm to obtain Composition 2. The metal content in the obtained resin composition was 1.03% by weight. Further, with respect to the obtained resin composition, a cured film was formed according to the above-mentioned method, and refractive index measurement, heat resistance evaluation, chemical resistance evaluation and dry etching evaluation were performed. The composition of the resin composition is shown in Table 2, and the evaluation results are shown in Table 3. Since it does not have photosensitivity, patterning evaluation was not performed, and the patterning evaluation was set to "-".

<Example 3>
X-1 (solid content concentration 34.9% by weight) was 7.16 g, TR-550 (solid content concentration 20.6% by weight, manufactured by JGC Catalysts and Chemicals) was 1.10 g, and TR-527 (solid content concentration 20. 11.06 g (5% by weight, manufactured by JGC Catalysts and Chemicals), 0.42 g of DAA, 0.26 g of MeOH, mixed under a yellow light, stirred with shaking, and filtered through a filter having a diameter of 0.45 μm to form a composition. I got 3. The metal content in the obtained resin composition was 0.11% by weight. Further, with respect to the obtained resin composition, a cured film was formed according to the above-mentioned method, and refractive index measurement, heat resistance evaluation, chemical resistance evaluation and dry etching evaluation were performed. The composition of the resin composition is shown in Table 2, and the evaluation results are shown in Table 3. Since it does not have photosensitivity, patterning evaluation was not performed, and the patterning evaluation was set to "-".

<Example 4>
X-1 (solid content concentration 34.9% by weight) was 7.16 g, TR-550 (solid content concentration 20.6% by weight, manufactured by JGC Catalysts and Chemicals) was 6.07 g, and TR-527 (solid content concentration 20. (5% by weight, manufactured by JGC Catalysts and Chemicals), 6.07 g, DAA (0.44 g), MeOH (0.26 g), mixed under a yellow light, stirred with shaking, and filtered through a filter having a diameter of 0.45 μm to form a composition. I got 4. The metal content in the obtained resin composition was 0.54% by weight. Further, with respect to the obtained resin composition, a cured film was formed according to the above-mentioned method, and refractive index measurement, heat resistance evaluation, chemical resistance evaluation and dry etching evaluation were performed. The composition of the resin composition is shown in Table 2, and the evaluation results are shown in Table 3. Since it does not have photosensitivity, patterning evaluation was not performed, and the patterning evaluation was set to "-".

<Example 5>
X-1 (solid content concentration 34.9% by weight) was 7.16 g, TR-550 (solid content concentration 20.6% by weight, manufactured by JGC Catalysts and Chemicals) was 10.42 g, and TR-527 (solid content concentration 20. 1.72 g (5% by weight, manufactured by JGC Catalysts and Chemicals), 0.44 g of DAA, 0.26 g of MeOH, mixed under a yellow light, stirred with shaking, and filtered through a filter having a diameter of 0.45 μm to form a composition. I got 5. The metal content in the obtained resin composition was 0.86% by weight. Further, with respect to the obtained resin composition, a cured film was formed according to the above-mentioned method, and refractive index measurement, heat resistance evaluation, chemical resistance evaluation and dry etching evaluation were performed. The composition of the resin composition is shown in Table 2, and the evaluation results are shown in Table 3. Since it does not have photosensitivity, patterning evaluation was not performed, and the patterning evaluation was set to "-".

<Example 6>
7.18 g of X-3 (solid content concentration 34.8% by weight), 6.07 g of TR-550 (solid content concentration 20.6% by weight, manufactured by JGC Catalysts and Chemicals), TR-527 (solid content concentration 20. (5% by weight, manufactured by JGC Catalysts and Chemicals), 6.07 g, DAA (0.42 g), MeOH (0.26 g), mixed under a yellow light, stirred with shaking, and filtered through a filter having a diameter of 0.45 μm to form a composition. I got 6. The metal content in the obtained resin composition was 0.54% by weight. Further, with respect to the obtained resin composition, a cured film was formed according to the above-mentioned method, and refractive index measurement, heat resistance evaluation, chemical resistance evaluation and dry etching evaluation were performed. The composition of the resin composition is shown in Table 2, and the evaluation results are shown in Table 3. Since it does not have photosensitivity, patterning evaluation was not performed, and the patterning evaluation was set to "-".

<Example 7>
7.18 g of X-3 (solid content concentration 34.8% by weight), 6.07 g of TR-550 (solid content concentration 20.6% by weight, manufactured by JGC Catalysts and Chemicals), TR-527 (solid content concentration 20. (5% by weight, manufactured by JGC Catalysts and Chemicals) was mixed at 6.07 g, DAA at 0.28, THP-17 at 0.40 g under a yellow light, stirred with shaking, and then filtered through a filter having a diameter of 0.45 μm. Composition 7 was obtained. The metal content in the obtained resin composition was 0.51% by weight. Further, a cured film was formed on the obtained resin composition according to the above-mentioned method, and refractive index measurement, heat resistance evaluation, chemical resistance evaluation, dry etching evaluation and patterning evaluation were performed. The composition of the resin composition is shown in Table 2, and the evaluation results are shown in Table 3.

<Example 8>
After mixing 14.41 g of X-4 (solid content concentration 34.7% by weight), 1.59 g of DAA, 3.60 g of PGMEA, 0.40 g of THP-17 under a yellow light, and shaking and stirring. The composition 8 was obtained by filtering with a filter having a diameter of 0.45 μm. The metal content in the obtained resin composition was 0.53% by weight. Further, a cured film was formed on the obtained resin composition according to the above-mentioned method, and refractive index measurement, heat resistance evaluation, chemical resistance evaluation, dry etching evaluation and patterning evaluation were performed. The composition of the resin composition is shown in Table 2, and the evaluation results are shown in Table 3.

<Example 9>
After mixing 14.33 g of X-5 (solid content concentration 34.7% by weight), 1.67 g of DAA, 3.60 g of PGMEA, 0.40 g of THP-17 under a yellow light, and shaking and stirring. The composition 9 was obtained by filtering with a filter having a diameter of 0.45 μm. The metal content in the obtained resin composition was 0.52% by weight. Further, a cured film was formed on the obtained resin composition according to the above-mentioned method, and refractive index measurement, heat resistance evaluation, chemical resistance evaluation, dry etching evaluation and patterning evaluation were performed. The composition of the resin composition is shown in Table 2, and the evaluation results are shown in Table 3.

<Comparative example 1>
R-1 (solid content concentration 34.8% by weight) is 7.23 g, TR-550 (solid content concentration 20.6% by weight, manufactured by JGC Catalysts and Chemicals) is 12.14 g, DAA is 0.38 g, and MeOH is 0. .26 g was mixed under a yellow light, stirred with shaking, and then filtered through a filter having a diameter of 0.45 μm to obtain composition 10. The metal content in the obtained resin composition was 1.03% by weight. Further, a cured film was formed on the obtained resin composition according to the above-mentioned method, and refractive index measurement, heat resistance evaluation, chemical resistance evaluation, and dry etching evaluation were performed. The composition of the resin composition is shown in Table 2, and the evaluation results are shown in Table 3.

From the comparison between Examples 1 to 9 and Comparative Example 1, it can be seen that the resin composition of the present invention is a composition having excellent heat resistance and dry etching properties. Further, it can be seen that Examples 3 to 9 are excellent in etching properties, and Examples 8 and 9 are particularly excellent. Further, it was found that Examples 6 to 9 were excellent in chemical resistance. Photosensitivity patterning was possible for Examples 7-9.

Claims

Resin (A),
From the group consisting of titanium composite oxide particles (B1) having a total content of one or more elements selected from the group consisting of aluminum, tin and zirconium of 2% by weight or more and 15% by weight or less, and the group consisting of aluminum, tin and zirconium. A resin composition containing two types of titanium composite oxide particles (B2) having a total content of one or more selected elements of less than 2% by weight, and a solvent (C).
The resin composition according to claim 1, wherein the total content of one or more elements selected from the group consisting of aluminum, tin and zirconium of the particles (B2) is less than 0.5% by weight.
The resin composition according to claim 1, wherein the total content of one or more elements selected from the group consisting of aluminum, tin and zirconium of the particles (B2) is less than 0.1% by weight.
The resin composition according to any one of claims 1 to 3, wherein the mixed weight ratio (B1 / B2) of the particles (B1) and the particles (B2) is 0.25 to 0.25 to 4. Twice
7. Resin composition.
The resin composition according to any one of claims 1 to 5, wherein the resin (A) is a polysiloxane (A1).
The resin composition according to claim 6, wherein the polysiloxane (A1) has a refractive index of 1.60 or more and less than 1.80 at a wavelength of 633 nm.
The resin composition according to claim 6 or 7, which contains the polysiloxane (A1) and the composite (E) of the polysiloxane and the particles in which the particles (B1) or the particles (B2) are bonded.
The resin composition according to any one of claims 6 to 8, wherein the polysiloxane (A1) is a polysiloxane (a1) having a structure represented by the formula (1).

(R 1 represents an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. N is 0 or 1, and * means a bond directly bonded to a silicon atom.)
The resin composition according to any one of claims 6 to 9, wherein the polysiloxane (A1) has a structure represented by the formula (2) and / or a structure represented by the formula (3).

(R 2 represents an alkylene group having 1 to 4 carbon atoms or a divalent aromatic group having 1 to 8 carbon atoms. * Means a bond directly linked to a silicon atom.)
Polysiloxane (a1) having the structure represented by the formula (1),
One or more selected from the group consisting of aluminum, tin, zirconium and silicon, and particles (B) which are composite oxides of titanium,
A resin composition containing the solvent (C).

(R 1 represents an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. N is 0 or 1, and * means a bond directly bonded to a silicon atom.)
The resin composition according to claim 11, wherein the total amount of aluminum, tin and zirconium contained in the resin composition is 0.01% by weight or more and less than 1% by weight with respect to 100% by weight of the total amount of the resin composition.
The particles (B) are one or more selected from the group consisting of aluminum, tin and zirconium, and the particles (B3) which are composite oxides of titanium.
The resin composition according to claim 11 or 12, which contains two types of particles, particles (B4) which are composite oxides of silicon and titanium.
The resin composition according to any one of claims 11 to 13, wherein the polysiloxane (a1) has a structure represented by the formula (2) and / or a structure represented by the formula (3).

(R 2 represents an alkylene group having 1 to 4 carbon atoms or a divalent aromatic group having 1 to 8 carbon atoms. * Means a bond directly linked to a silicon atom.)
The resin composition according to any one of claims 1 to 14, further containing the quinone diazide compound (D).
The resin composition according to any one of claims 11 to 15, which contains a composite (E1) of polysiloxane and particles in which polysiloxane (a1) and particles (B) are bonded.
A cured film obtained by curing the resin composition according to any one of claims 1 to 16.
A method for manufacturing a microlens, wherein the cured film according to claim 17 is processed by dry etching.
A solid-state image sensor comprising the cured film according to claim 17.
The microlens made of the cured film according to claim 17.
An on-cell type or film type touch panel provided with the cured film according to claim 17.