TWI660990B - Siloxane resin composition, transparent hardened product using the same, transparent pixels, microlenses, solid-state imaging element - Google Patents

Abstract

A siloxane resin composition containing metal-containing particles, a siloxane resin, a polymerization initiator, and an ultraviolet absorber, and the solid content of the composition contains the metal-containing particles in an amount of 40% by mass or more and 80% by mass or less. The molar absorption coefficient of the ultraviolet absorber at 365 nm is 5000 mol ^-1 · L · cm ^-1 or more, and the molar absorption coefficient at 400 nm is 3500 mol ^-1 · L · cm ^-1 or less.

Description

Siloxane resin composition, transparent hardened product using the same, transparent pixels, microlenses, solid-state imaging element

The invention relates to a silicone resin composition, a transparent hardened product using the silicone resin composition, transparent pixels, microlenses, and a solid-state imaging element.

Examples of transparent materials incorporated in solid-state imaging devices include wafer-level lenses and microlenses. Alternatively, an anti-reflection film, a transparent pixel, a transparent insulating film, a flattening film, and the like, which are applied to these layers, may be mentioned. For each component, characteristics corresponding to its function are required. For example, for the above microlenses and transparent pixels, higher refractive index and higher light transmittance are required. In addition, recently, in order to achieve miniaturization of increasingly developed components, manufacturing adaptability of each material to fine processing accuracy is required.

Specifically, a technique of introducing high refractive index particles into a transparent resin is studied. Patent Document 1 proposes a positive-type photosensitive resin composition containing particles of titanium dioxide and the like in polyimide.

[Prior technical literature] [Patent Literature]

[Patent Document 1] International Publication No. 2005/088396

An object of the present invention is to provide a siloxane resin composition suitable as a material for transparent members such as lenses and transparent pixels. In addition, the purpose is to provide a siloxane resin composition that is not limited to a positive type, and can also be used as a heat-curable resin or a negative photosensitive resin, and can also appropriately cope with micro-processing of microlenses and transparent pixels. , Can optimize its manufacturing adaptability and hardened film characteristics according to needs. It is another object of the present invention to provide a transparent cured product, a transparent pixel, a microlens, and a solid-state imaging device using the above-mentioned siloxane resin composition.

The above problems are solved by the following means.

[1] A siloxane resin composition containing metal-containing particles, a siloxane resin, a polymerization initiator, and an ultraviolet absorber, wherein the solid content of the composition is 40% by mass or more and 80% by mass or less. The Mole absorption coefficient of the above metal-containing particles and the ultraviolet absorber at 365 nm is 5000 mol ^-1 . L. cm ^{-1 and} above, the molar absorption coefficient at 400nm is 3500mol ^-1 . L. cm ^-1 or less.

[2] The siloxane resin composition according to [1], which contains, as an element constituting the metal-containing particles, selected from the group consisting of Ti, Ta, W, Y, Ba, Hf, Zr, Sn, Nb, and V And Si metal.

[3] The siloxane resin composition according to [1] or [2], wherein the refractive index of the metal-containing particles is 1.75 or more and 2.90 or less.

[4] The siloxane resin composition according to any one of [1] to [3], wherein the number average particle diameter of the metal-containing particles is 3 nm or more and 30 nm or less.

[5] The silicone resin composition according to any one of [1] to [4], wherein the refractive index of the cured film that hardens the silicone resin composition is 1.6 or more and 2.0 or less.

[6] The siloxane resin composition according to any one of [1] to [5], wherein the element constituting the metal-containing particles includes Ti and Zr, and Ti / Zr is 3 or more and 30 or less.

[7] The siloxane resin composition according to any one of [1] to [6], which is a UV-curable resin composition.

[8] The siloxane resin composition according to any one of [1] to [7], further comprising a polymerizable compound.

[9] The siloxane resin composition according to any one of [1] to [8], wherein the ultraviolet absorber is selected from a benzotriazole compound, a benzophenone compound, a triazine compound, and a diene. A group of compounds, benzodithiols, and avobenzone compounds.

[10] The silicone resin composition according to any one of [1] to [9], wherein the polymerization initiator is selected from an organic halogen compound, an oxadiazole compound, a carbonyl compound, a ketal compound, and benzoin Compounds, acridine compounds, organic peroxides, azo compounds, coumarin compounds, azide compounds, metallocene compounds, hexaarylbisimidazole compounds, organic boric acid compounds, disulfonic acid compounds, oxime compounds, onium salt compounds , P-hydroxyacetophenone compound, aminoacetophenone compound, fluorenylphosphine oxide compound, trihalomethyltriazine compound, benzyldimethylketal compound, α-hydroxyketone compound, α-aminoketone compound, fluorene Phosphine compounds, phosphine oxide compounds, triarylimidazole dimers, onium compounds, benzothiazole compounds, benzophenone compounds, cyclopentadiene-benzene-iron complexes, halomethyloxadiazole compounds , 3-aryl-substituted coumarin compounds, α-aminoalkylphenyl ketone compounds, and benzoate compounds.

[11] The siloxane resin composition according to any one of [1] to [10], wherein the siloxane resin is a hydrolysis-condensation reaction product of an alkoxysilane compound.

[12] The siloxane resin composition according to any one of [1] to [11], wherein It is used in an amount of 1 to 60 parts by mass based on 100 parts by mass of the metal-containing particles.

[13] The siloxane resin composition according to any one of [1] to [12], wherein the solid content contains the ultraviolet absorber in an amount of 0.01% by mass or more and 20% by mass or less.

[14] The siloxane resin composition according to any one of [1] to [13], wherein the siloxane resin is obtained by performing a hydrolysis condensation reaction in the presence of the metal-containing particles.

[15] A transparent hardened material obtained by curing the siloxane resin composition according to any one of [1] to [14].

[16] A transparent pixel comprising the transparent hardened body according to [15].

[17] A microlens composed of the transparent hardened body according to [15].

[18] A solid-state imaging element including the transparent pixel according to [16], the microlens according to [17], or both.

In the description of the group (atomic group) in the present specification, unrepresented substitution and unsubstituted expression include both those having no substituent and those having a substituent. For example, "alkyl" includes not only an alkyl group (unsubstituted alkyl group) having no substituent, but also an alkyl group (substituted alkyl group) having a substituent.

The "radiation" in this specification refers to, for example, a bright line spectrum of a mercury lamp, an extreme ultraviolet (EUV light), an X-ray, an electron beam, and the like represented by an excimer laser. In the present invention, light means active light or radiation. Unless otherwise specified, "exposure" in this specification includes not only exposure by far-ultraviolet rays, X-rays, and EUV light typified by mercury lamps and excimer lasers, but also particle beams such as electron beams and ion beams. The description also includes Contained in exposure.

In addition, in the present specification, "(meth) acrylate" means both or any one of acrylate and methyl acrylate, and "(meth) acryl" means both or any of acrylic and methacrylic acid, "( "Meth) acrylfluorenyl" means both or any of acrylfluorenyl and methacrylfluorenyl.

In this specification, "monomer" and "monomer" have the same meaning. The monomers in this specification are distinguished from oligomers and polymers, and refer to compounds having a weight average molecular weight of 2,000 or less. In the present specification, the polymerizable compound refers to a compound having a polymerizable group, and may be a monomer or a polymer. Polymerizability refers to the group participating in the polymerization reaction.

The weight average molecular weight and the number average molecular weight can be determined by gel permeation chromatography (GPC).

In the present specification, Me in the chemical formula represents methyl, Et represents ethyl, Pr represents propyl, Bu represents butyl, and Ph represents phenyl.

The siloxane resin composition of the present invention is suitable as a material for transparent members such as lenses and transparent pixels. It is not limited to a positive-type photosensitive resin, and a heat-curable resin or a negative-type photosensitive resin can also be used, and it is also possible to appropriately cope with micro-processing of microlenses and transparent pixels. Furthermore, it is possible to optimize the manufacturing adaptability (especially, the pattern shape and the residue property) and the characteristics (light resistance) of the cured film when the pattern is formed as necessary. In addition, it is possible to provide a transparent hardened material, a transparent pixel, a microlens, and a solid-state imaging element that are excellent in quality using the above-mentioned siloxane resin composition.

1‧‧‧lens material

1a‧‧‧Micro lens

2‧‧‧leveling film

3‧‧‧ substrate

4‧‧‧ photoresist film

4a‧‧‧ patterned resist

4b‧‧‧ Hemispherical resist

10‧‧‧ micro lens array

(1) ‧‧‧Coating and curing steps

(2) ‧‧‧i-line photo resist coating

(3) ‧‧‧ Patterning and Lithography (Patteming by Litho.)

(4) ‧‧‧Thermal flow steps

(5) ‧‧‧Dry etching

FIG. 1 is an explanatory diagram schematically showing a manufacturing process of the lens array.

The siloxane resin composition of the present invention contains a specific amount of metal-containing particles, a siloxane resin, a polymerization initiator, and a specific ultraviolet absorber. Thereby, although inference is included, the reason for exhibiting the excellent effects described above can be considered as follows. In a photocurable siloxane resin using a polymerization initiator, metal-containing particles become foreign substances. When the metal-containing particles are contained in an amount exceeding a considerable amount, the developability and light resistance of the cured film, for example, are significantly reduced. In addition to the physical effects of metal-containing particles, light scattering characteristics are considered to be one of the reasons. In particular, when a considerable amount of metal-containing particles (such as TiO ₂ and the like) are contained, active oxygen is generated due to its photocatalytic activity, and the decomposition of the resin component caused by this is considered to be one of the causes of deterioration (coloring). On the other hand, if the amount of metal-containing particles is suppressed, it is difficult to achieve a desired high refractive index. On the other hand, by applying an ultraviolet absorbent having specific light absorption characteristics, not only can the balance of light absorption be optimized, but also the effects of scattering and photocatalytic activity described above can be effectively suppressed, and the transparency of the cured film can be maintained. In addition to the refractive index, the above-mentioned developability and light resistance are improved. Regarding this content, it has been experimentally confirmed that it is determined that the parameter of the specific wavelength of the ultraviolet absorber is accurately defined. Hereinafter, preferred embodiments will be described in detail.

<Metal-containing particles>

The metal-containing particles widely include particles containing a metal as a constituent element. Here, the word metal should be interpreted in the broadest sense, and it is assumed that metals such as boron, silicon, and arsenic are also included here. When the metal-containing particles are composed of oxygen atoms, they are particularly called metal oxide particles.

In the present invention, the metal-containing particles contain a material selected from the group consisting of Ti, Ta, W, Y, Ba, Hf, Zr, and S. Metals of n, Nb, V and Si are preferred. Among them, oxide particles containing a composite metal of two or more kinds thereof are preferred. For example, a combination of Ti and Zr (including Si as required), Ti and Sn (including Si as needed), Ti and Zr and Sn (including Si as needed) is preferred, and Ti, Zr, Sn, and The combination of Si is better.

Examples of the constituent material containing metal particles include titanium oxide, zirconia, silicon oxide, barium titanate, barium sulfate, barium oxide, hafnium oxide, tantalum oxide, tungsten oxide, and yttrium oxide. These constituent materials may contain two or more kinds, and it is preferable to contain at least titanium oxide and zirconia.

When titanium oxide is contained as a constituent material, rutile titanium oxide is preferably contained. Furthermore, it is preferable to contain 80% by mass or more of rutile titanium oxide with respect to the total amount of titanium oxide, more preferably 90% by mass or more, and even more preferably 95% by mass or more. The upper limit is 100% by mass.

From the viewpoint of obtaining a high refractive index, the refractive index of the metal-containing particles is preferably 1.75 or more, and more preferably 1.90 or more. The upper limit is preferably 2.90 or less, and more preferably 2.70 or less.

The average particle diameter of the metal-containing particles is preferably 500 nm or less, more preferably 200 nm or less, even more preferably 100 nm or less, even more preferably 50 nm or less, and most preferably 30 nm or less. The lower limit value is preferably 1 nm or more, and more preferably 3 nm or more. Since the transparency of a cured film improves by setting it as the said particle diameter range, it is preferable. In addition, insulation and durability can be provided in accordance with the homogeneity and needs of the cured film and the like, which is preferable. Regarding the metal-containing particles, powders of appropriate particles can be prepared and pulverized or dispersed using a disperser such as a bead mill.

~ Measurement of the refractive index of particles ~

The refractive index of the metal-containing particles can be measured by the following method. A mixed resin sample containing a matrix resin and a metal particle containing a solid content concentration of 10% and a metal particle-containing content adjusted to 0% by mass, 20% by mass, 30% by mass, 40% by mass, and 50% by mass was prepared. On the silicon chip, The thickness was 0.3 to 1.0 μm, followed by coating with a spin coater, followed by heating and drying at 200 ° C. for 5 minutes to obtain a coating film. Next, for example, the refractive index at a wavelength of 633 nm (25 ° C.) can be obtained using an ellipsometry (manufactured by Otsuka Electronics Co., Ltd.), and the value of 100% by mass of the metal-containing particles can be obtained by extrapolation.

~ Measurement of average particle size ~

The number-average particle diameter of the metal-containing particles (indicating the average particle diameter among the primary particle diameters) can be obtained from a photograph obtained by observing the particles with a transmission electron microscope. The projected area of the particles was determined, and the equivalent circle diameter was determined as the average particle diameter. In addition, in order to obtain an average particle diameter, arbitrary 100 particles were measured. The average particle diameter was determined as an average value of 80 pieces other than the 10 pieces on the maximum side and the 10 pieces on the minimum side. In this specification, the average particle diameter means a number average particle diameter unless otherwise specified.

Examples of commercially available metal-containing particles include T-BTO-020RF (barium titanate; manufactured by To da Kogyo Corporation), UEP-100 (zirconia; manufactured by DAIICHI KIGENSO KAGAKU KOGYO CO., LTD.), Or STR- 100N (titanium oxide; manufactured by Sakai Chemical Industry Co., Ltd.).

Metal-containing particles can also be obtained as a dispersion dispersed in a liquid. Examples of the silica-titanium oxide particles include "Optolake" (registered trademark) TR-502, "Optolake" TR-503, "Optolake" TR-504, "Optolake" TR-513, and "Optolake" TR-520 , "Optolake" TR-527, "Optolake" TR-528, "Optolake" TR-529, "Optolake" TR-544, or "Optolake" TR-550 (all manufactured by JGC Catalysts and Chemicals Ltd.) and are used as Examples of the silicon-coated titanium oxide particles include STR-100W and STR-100WLPT (both manufactured by Sakai Chemical Industry Co., Ltd.). Examples of the zirconia particles include "Bairaru" registered trademarks Zr-C20 (average particle size = 20nm; manufactured by Taki Chemical Co., Ltd.), ZSL-10A (average particle size = 60-100nm; manufactured by DAIICHI KIGENSO KAGAKU KOGYO CO., LTD.), "Nanouse "(Registered trademark) OZ-30M (average particle diameter = 7 nm; Nissan CHEMICAL Industries, manufactured by Limited), SZR-M (manufactured by Sakai Chemical Industry Co., Ltd.), or HXU-120JC (manufactured by SUMITOMO Osaka Cement Company, Limited).

As the content ratio (elemental composition) of the metal elements in the metal-containing particles, Ti and Zr are contained, and the ratio thereof is preferably 1 to 40 in terms of Ti / Zr ratio, 1 to 30 is more preferable, and 3 to 20 is more preferable. , 4 ~ 12 is even better, 4 ~ 9 is the best. When such a numerical range is satisfied, it is preferable because the storage property of the composition can be improved while maintaining a high refractive index. In addition, by setting Ti / Zr within this range, the light resistance of the cured product of the siloxane resin composition can be optimized, which is preferable. In particular, in the present invention, the interaction with the specific ultraviolet absorber is further improved, and the desired light resistance can be exhibited at a high level while maintaining the high refractive index of the cured product of the siloxane resin composition.

In addition, Ti and Si are preferably contained in a ratio of 1 to 40 in terms of Ti / Si ratio, more preferably 1 to 30, and even more preferably 1 to 10. In other words, it is preferable that Ti and Si are contained in a ratio of 1 or more in terms of Ti / Si ratio. The upper limit is preferably 40 or less, more preferably 30 or less, and even more preferably 10 or less.

The Ti / Sn ratio is preferably 10 or more, 13 or more is more preferable, 15 or more is further preferable, 17 or more is further preferable, 19 or more is further preferable, and 20 or more is more preferable. As the upper limit, 1,000 or less is preferred, 500 or less is preferred, 300 or less is further preferred, 100 or less is further preferred, 60 or less is further preferred, 50 or less is further preferred, and 40 or less is more preferred. By setting Ti / Sn within this range, the affinity of organic components used with metal-containing particles can be expected. Denseness (affinity) is preferred because of its good effect.

~ Measurement of Metal Element Content ~

In addition, regarding the content rate of the metal element containing the metal particles, the elemental composition (atomic%) determined by an X-ray fluorescence analysis method (Primus II X-ray fluorescence analyzer manufactured by Rigaku Co., Ltd.) was evaluated. About the ratio of a plurality of elements, each element composition (atomic%) was calculated | required, and it evaluated by the ratio of each element composition (atomic%). When the elemental composition ratio is obtained as the ratio of the mole number, the same meaning is obtained.

The surface treatment of the metal-containing particles may be in an arbitrary state, for example, a state of being treated with a surfactant described later, a state of being treated with a treating agent containing other metals, and the like. For example, a state in which specific metal-containing particles are formed, and another coating film such as a metal-containing substance is formed on the surface of the particles. Alternatively, another coating film such as a metal-containing substance may be made thicker as the core-shell type metal-containing particles. The ratio of the core to the shell is not particularly limited. When the entire particle is 100 parts by mass, the ratio of the core is preferably 85 parts by mass or more, more preferably 87 parts by mass or more, and even more preferably 90 parts by mass or more. The upper limit is actually 97 parts by mass or less. By setting the core-shell ratio to the above range, it is possible to optimize characteristics while maintaining a high refractive index.

The combination of the materials constituting the core and the shell is not particularly limited, and examples include an example in which the core is formed of particles containing Ti, Sn, and the like, and the shell is formed of a coating film containing Zr or Si. In order to increase the refractive index of the particles, the material constituting the shell is particularly preferably a high refractive index material. In addition, when titanium oxide is contained as the metal-containing particle component used in the core, the shell system is preferred to a light-stable material (such as zirconium) for the purpose of suppressing the photocatalytic activity of the titanium oxide component present on the surface of the particle. .

The content of the metal-containing particles in the solid content of the composition is 40% by mass or more, 45% by mass or more is preferred, 50% by mass or more is further preferred, and 55% by mass or more is particularly preferred. As The upper limit is preferably 80% by mass or less, more preferably 75% by mass or less, and even more preferably 70% by mass or less. By using more metal-containing particles, the refractive index of the cured film can be increased. On the other hand, when considering the compatibility with other performance, it is more preferable to make it below the said upper limit. In addition, it is considered that such a high concentration of the metal-containing particles is one of the causes of the deterioration of the cured film through the photocatalytic action described above. On the other hand, in the present invention, by using the specific ultraviolet absorber described above in combination, this problem can be improved without impeding other properties.

The metal-containing particles may be used alone or in combination of two or more.

In addition, in this specification, a solid content (solid content) is a component which does not disappear by volatilization or evaporation when drying processing is performed at 170 degreeC. Ingredients other than solvents and dispersion media are typically referred to.

The metal-containing particles used in the present invention can be produced by a conventional method. For example, as in the examples described later, a salt of a metal that becomes a constituent element is added to a medium forming a sol, and an alkali or an acid is further added as necessary to obtain a dispersed sol (filter cake). When the medium is an acid or an alkali, it is not necessary to add these. An example of heating and solidifying and pulverizing the sol may be mentioned. At this time, by adding a salt of a metal element to be mixed to the sol, particles of a composite metal can be obtained. Alternatively, the core particles may be formed once in advance, and at the same time, a sol containing a desired metal salt may be formed in the same manner as described above. Core-shell particles can be obtained by heating the sol and pulverizing the solidified one.

Examples of the metal salt used as a raw material include salts of the respective metals exemplified above. Specific examples include titanium tetrachloride, potassium stannate, zirconyl oxychloride, aluminum oxychloride, and aluminum chloride. Alternatively, various organometallic compounds, metal alkoxides, and the like can also be used.

Examples of the solvent for forming the sol include alkalis such as ammonia, potassium hydroxide, and sodium hydroxide. Aqueous solution; acidic aqueous solution such as hydrochloric acid, nitric acid, sulfuric acid, etc. Alternatively, a sol-gel method in which metal alkoxide is dissolved using water or various organic media can be mentioned.

As a method for producing the metal-containing particles that can be used in the present invention, for example, the methods described in paragraphs <0015> to <0043> of Japanese Patent Laid-Open No. 2008-69193 can be referred to. In addition, as the specific metal-containing particles, those described in paragraphs <0015> to <0043> of Japanese Patent Laid-Open No. 2008-69193 can be used in this specification by reference.

<Silicone resin>

The silicone resin is preferably a resin in which an alkoxysilane compound represented by any of the following formulae (1) to (3) (hereinafter, also simply referred to as a "silane compound") undergoes a hydrolytic condensation reaction. Further, it is also preferred that the silane compound represented by the formula (1) and the silane compound represented by the formula (2) undergo a hydrolysis condensation reaction together. Alternatively, the silane compound of the formula (1) and the silane compound of the formula (3) may be hydrolyzed and condensed together, and the silane compound of the formula (2) and the silane compound of the formula (3) or the formula ( A silane compound of 1) undergoes a hydrolytic condensation reaction with a silane compound of formula (2) and a silane compound of formula (3). In addition, one type of each type of silane compound may be used, and two or more types may be used.

(R ¹ ) _a Si (OR ² ) _4-a (1)

R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group. The hydrocarbon group is an alkyl group (1 to 12 carbon atoms is preferred, 1 to 6 is more preferred, 1 to 3 is more preferred), an alkenyl group (2 to 12 carbon atoms is preferred, 2 to 6 is more preferred), Alkynyl (carbon number 2-12 is preferred, 2-6 is more preferred), aryl (carbon number 6-22 is preferred, 6-14 is more preferred, 6-10 is more preferred), arane A group (carbon number 7 to 23 is more preferable, 7 to 15 is more preferable, and 7 to 11 is more preferable), and an alkyl group, an aryl group, or an alkenyl group is more preferable.

a is 0, 1, or 2. Among them, a is preferably 0 or 1, and 1 is more preferable.

R ³ Si (R ⁴ ) _C (OR ⁵ ) _3-C (2)

R ³ is a functional group-containing group. The functional group is preferably a group containing a hetero atom (S, O, N, P, Si, etc.) in the structure. Alternatively, it is preferable to contain a polymerizable group, an acidic group, or a basic group. (Meth) acrylic acid group, thiol group (Sulfanyl group), epoxy group, oxetanyl group, shrink group, glycidyloxy group, hydroxyl group, phenolic hydroxyl group, carboxyl group, A phosphate group, a sulfonic acid group, a phosphonic acid group, an amino group, an isocyanate group, a urea group, or a group having these substituents. When R ³ is bonded to Si via a linking group, examples of the linking group L described below can be cited, and among them, a hydrocarbon linking group is preferred. The carboxyl group, sulfonic acid group, phosphate group, and phosphonic acid group may form a salt or an ester, and an acid anhydride thereof. Amino groups can also form salts.

R ⁴ and R ⁵ are each independently a group having the same meaning as R ¹ .

c is 0 or 1.

R ⁶ ₃ Si-X- (SiR ⁷ ₃ ) _d (3)

R ⁶ and R ⁷ are each independently a group having the same meaning as the above-mentioned R ¹ , or an alkoxy group (the number of carbon atoms is preferably 1 to 12, the number of 1 to 6 is more preferred, and the number of 1 to 3 is particularly preferred), Alkenyloxy (2 to 12 carbon atoms is preferred, 2 to 6 is more preferred), alkynyloxy (2 to 12 carbon atoms is preferred, 2 to 6 is more preferred), aryloxy (carbon 6 to 22 atoms are preferred, 6 to 14 are more preferred, 6 to 10 are particularly preferred) or aralkyloxy (7 to 23 carbon atoms are preferred, 7 to 15 are more preferred, 7 to 11 are particularly preferred ). One to four of R ⁶ and R ⁷ may be a group of R ³ .

X is a divalent or more linking group. When X is a divalent linking group, examples of the linking group L described below can be cited. Specific examples include S, O, CO, NR ^N , polythio groups (S to 2 are S), and the like. When X is a trivalent linking group, an isocyanuric acid skeleton is mentioned, for example. d is an integer from 1 to 4, and 1 or 2 is preferred.

R ¹ to R ⁷ may each independently have an arbitrary substituent T. In addition, it can be bonded to the silicon atom together with the linking group L within a range where the effects of the present invention are exhibited. Or neighbors can be bonded to each other or even condensed to form a ring.

Examples of the silane compound represented by the formula (1): Examples of the trifunctional silane compound include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, and methyltriisocyanate. Propoxysilane, methyltri-n-butoxysilane, methyltri-tert-butoxysilane, methyltri-sec-tert-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyl Trimethoxysilane, butyltrimethoxysilane, pentyltrimethoxysilane, cyclopentyltrimethoxysilane, hexyltrimethoxysilane, cyclohexyltrimethoxysilane, octadecyltrimethoxysilane, ten Octyl triethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriisopropoxy, 1-naphthyltrimethoxysilane, 2-naphthyltrimethoxysilane, Heptafluorodecyltrimethoxysilane, heptafluorodecyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, p-styryltrimethoxysilane, allyltrimethyl Oxysilane and so on.

Examples of the bifunctional silane compound include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and methylbenzene. Dimethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, cyclohexylmethyldimethoxysilane, and the like.

Examples of the tetrafunctional silane compound include tetramethoxysilane and tetraethoxysilane.

Examples of silane compounds represented by formula (2): Examples of the trifunctional silane compound include 3-glycidyl ether propyltrimethoxy Silane, γ-methacryloxypropyltrimethoxysilane, γ-methallyloxypropyltriethoxysilane, γ-propenyloxytrimethoxysilane, γ-propenyloxy Propyltriethoxysilane, glycidyl ether methyltrimethoxysilane, glycidyl ether methyltriethoxysilane, α-glycidyl ether ethyltrimethoxysilane, α-glycidyl ether ethyltriyl Ethoxysilane, β-glycidyl ether ethyltrimethoxysilane, β-glycidyl ether ethyltriethoxysilane, α-glycidyl ether propyltrimethoxysilane, α-glycidyl ether propyltriol Ethoxysilane, β-glycidyl ether propyl trimethoxysilane, β-glycidyl ether propyl triethoxysilane, γ-glycidyl ether propyl trimethoxysilane, γ-glycidyl ether propyl tri Ethoxysilane, γ-glycidyl ether propyl tripropoxy silane, γ-glycidyl ether propyl triisopropoxy silane, γ-glycidyl ether propyl tri-n-butoxy silane, γ-glycidyl Etherpropyl tri-tert-butoxysilane, γ-glycidyl ether propyl tri-sec-butoxysilane, γ-glycidyl ether propyl trimethoxy Silane, α-glycidyl ether butyltrimethoxysilane, α-glycidyl ether tert-butyltrimethoxysilane, α-glycidyl ether tert-butyltriethoxysilane, α-glycidyl ether tert-butyltrisiloxane Ethoxysilane, β-glycidyl ether butyl trimethoxysilane, β-glycidyl ether butyl triethoxysilane, γ-glycidyl ether butyl trimethoxysilane, γ-glycidyl ether butyl tri Ethoxysilane, δ-glycidyl ether butyltrimethoxysilane, δ-glycidyl ether butyltriethoxysilane, (3,4-epoxycyclohexyl) methyltrimethoxysilane, (3, 4-epoxycyclohexyl) methyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethyl Oxysilane, 2- (3,4-epoxycyclohexyl) ethyltripropoxysilane, 2- (3,4-epoxycyclohexyl) ethyltri-tert-butoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltri-n-butoxysilane, 2- (3,4-epoxycyclohexyl) ethyltri-sec-butoxysilane, 3- (3,4-epoxycyclohexyl) propane Trimethoxysilane, 3- (3,4-epoxycyclohexyl) propyltriethoxysilane, 4- (3 4- epoxycyclohexyl) butyl trimethoxy Silane, 4- (3,4-epoxycyclohexyl) butyl triethoxy Silane, 3-aminopropyl Trimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-trimethoxy Methylsilylpropylsuccinic anhydride, 3-ureapropyltriethoxysilane and the like.

Examples of the bifunctional silane compound include γ-glycidyl ether propylmethyldimethoxysilane, γ-acrylic methoxypropylmethyldimethoxysilane, and γ-propylene methoxypropyl Methyldiethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, glycidyl ether methyldisiloxane Methoxysilane, glycidyl ether methylmethyldiethoxysilane, α-glycidyl ether ethylmethyldimethoxysilane, α-glycidyl ether ethylmethyldiethoxysilane, β- Glycidyl ether ethylmethyldimethoxysilane, β-glycidyl ether ethylmethyldiethoxysilane, α-glycidyl ether propyl methyldimethoxysilane, α-glycidyl ether propyl Methyldiethoxysilane, β-glycidyletherpropylmethyldimethoxysilane, β-glycidyletherpropylmethyldiethoxysilane, γ-glycidyletherpropylmethyldimethoxy Silane, γ-glycidyl ether propyl methyl diethoxy silane, γ-glycidyl ether propyl methyl dipropoxy silane, β-glycidyl ether propyl methyl di Butoxysilane, γ-glycidyletherpropylmethyldimethoxyethoxysilane, γ-glycidyletherpropylethyldimethoxysilane, γ-glycidyletherpropylethyldiethoxy Silane, γ-glycidyl ether propylvinyldimethoxysilane, γ-glycidyl ether propylvinyldiethoxysilane, 3-methacryloxypropyldimethoxysilane and the like.

Examples of the silane compound represented by the formula (3) include 1,3-bis (3-aminopropyl) tetramethyldisilaxane and 1,3-bis (3-aminoethyl) tetramethyl Disilaxane, 1,3-bis (3-aminopropyl) tetraethyldisilaxane, etc.

The siloxane resin can be obtained through a hydrolysis reaction and a condensation reaction using the alkoxysilane compound described above. As the hydrolytic condensation reaction, a known method can be used, and it can be used as required. Instead, catalysts such as acids or bases are used. The catalyst is not particularly limited as long as the pH is changed. Specifically, examples of the acid (organic acid, inorganic acid) include nitric acid, phosphoric acid, oxalic acid, acetic acid, formic acid, and hydrochloric acid. Examples of the base include ammonia, triethylamine, and ethylenediamine. The amount used is not particularly limited as long as the siloxane resin satisfies a predetermined molecular weight.

In the hydrolysis condensation reaction, a solvent may be added as needed. The solvent is not particularly limited as long as it is capable of carrying out a hydrolysis-condensation reaction, and examples of the solvent are mentioned below. Examples include alcohol compounds such as water, methanol, ethanol, propanol, diacetone alcohol, and tetrahydrofurfuryl alcohol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and dipropylene glycol methyl alcohol. Ether compounds such as ether; ester compounds such as methyl acetate, ethyl acetate, butyl acetate, γ-butyrolactone, and propylene glycol monomethyl ether acetate; ketones such as acetone, methyl ethyl ketone, and methyl isoamyl ketone Compound.

Regarding the conditions (temperature, time, solvent amount) of the hydrolytic condensation reaction, it is sufficient to appropriately select the preferable conditions according to the type of the materials used.

The weight average molecular weight of the siloxane resin used in this embodiment is preferably 2,000 or more, and more preferably 3,000 or more. The upper limit is preferably 500,000 or less, more preferably 450,000 or less, and even more preferably 250,000 or less.

In the present invention, the molecular weight of a polymer refers to a weight average molecular weight unless otherwise specified, and is measured by gel permeation chromatography (GPC) in standard polystyrene conversion. As a measuring device, a device manufactured by TOSOH CORPORATION was used. As a condition, the condition based on the following condition 1 was set. However, depending on the type of polymer, a better carrier (dissolution agent) and a chromatographic column suitable for the carrier can be further appropriately selected.

(Condition 1)

Column: Connect TOSOH TSKgel Super HZM-H, TOSOH TSKgel S uper HZ4000, TOSOH TSKgel Super HZ2000 columns

Carrier: Tetrahydrofuran

Measurement temperature: 40 ° C

Carrier flow: 1.0ml / min

Sample concentration: 0.1% by mass

Detector: RI (refractive index) detector

In the case of a siloxane resin, the siloxane resin was adjusted and measured with dimethylformamide so that the sample concentration became 0.3% by mass. However, depending on the kind and molecular weight, it can be measured according to the above Condition 1.

Although there are some overlapping portions, the following can be cited as the preferred siloxane resin.

Examples of the alkoxysilane having four or more alkoxy groups include tetramethoxysilane, tetraethoxysilane, tetraethoxysilane, tetraphenoxysilane, and tetramethoxydisilane. Siloxane, tetraethoxydisilaxane, bis (triethoxypropyl) tetrasulfide, tri- (3-methoxysilylpropyl) isocyanurate, tri- (3 -Triethoxysilylpropyl) isocyanurate. From the viewpoint of improving the chemical resistance of the cured film, in order to make a higher amount of the 9-functional silane and a 4-functional silane having a smaller steric hindrance react with each other, a mixture of the 4-functional silane and the 9-functional silane good.

The hydrolysate condensation reaction product of a siloxy resin type and a bifunctional or trifunctional alkoxysilane compound is preferable. Examples of the alkoxysilane compound constituting the siloxane resin include dimethoxydimethylsilane, diethoxydimethylsilane, dimethoxydiphenylsilane, and diethoxydiphenyl. Silane, dihydroxydiphenylsilane, dimethoxy (methyl) (phenyl) silane, Diethoxy (methyl) (phenyl) silane, dimethoxy (methyl) (phenethyl) silane, dicyclopentyldimethoxysilane or cyclohexyldimethoxy (methyl) silane , 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-propenyloxypropyltrimethoxysilane, or 3-propenyloxy Propyltriethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride, 3-triethoxysilylpropylsuccinic anhydride, 3-trimethoxysilylethylsuccinic anhydride, 3 -Trimethoxysilylbutyl succinic anhydride, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3- (3,4-epoxycyclohexyl ) Propyltrimethoxysilane, 3- (3,4-epoxycyclohexyl) propyltriethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, phenyltrimethoxysilane, benzene Ethyltrimethoxysilane, naphthyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, phenyltriethoxysilane, phenethyltriethoxysilane, naphthyltrimethoxysilane Ethoxysilane, Silane methoxy or tetraethyl orthosilicate.

Regarding the content of the siloxane resin, it is preferable to reduce the content of the siloxane resin when an alkali-soluble resin described later is contained in the composition, and to increase the content of the siloxane resin when the alkali-soluble resin is not contained. That is, when an alkali-soluble resin is contained in the composition, the content of the siloxane resin in the solid content of the composition is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 3% by mass or more. The upper limit is preferably 30% by mass or less, and more preferably 20% by mass or less.

In addition, when the alkali-soluble resin is not contained in the composition, the content of the siloxane resin in the solid content of the composition is preferably 10% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more. The upper limit is preferably 40% by mass or less, and more preferably 35% by mass or less.

The content of the siloxane resin relative to 100 parts by mass of the metal particles is preferably 1 part by mass or more, more preferably 10 parts by mass or more, and even more preferably 15 parts by mass or more. The upper limit is preferably 60 parts by mass or less, more preferably 50 parts by mass or less, and even more preferably 45 parts by mass or less. About Silicon Oxide The amount of the alkane resin is preferably used in an amount greater than or equal to the above lower limit from the viewpoints of film forming properties and film durability. On the other hand, it is preferable from the viewpoint that the high refractive index can be maintained by being suppressed to the above-mentioned upper limit value or less.

In addition, when it is referred to as a siloxane resin in this specification, it basically means a polymer obtained by the hydrolysis and condensation reaction of an alkoxy silane compound, but it also includes a polymer based on other reactions and a silane compound that is a raw material. What it means. However, in the present invention, a hydrolytic condensation reaction product of a siloxane resin-based silane compound is preferred. The hydrolysis and condensation reaction of the silane compound can be performed in the coexistence of metal-containing particles. At this time, a particle-resin matrix or core-shell structure that reacts with metal-containing particles on its surface can be formed.

<Ultraviolet absorbent>

The molar absorption coefficient (unit: mol ^-1 ‧L‧cm ^-1 ) of the ultraviolet absorber used in the present invention at a wavelength of 365 nm is more than 5000, more preferably 6500 or more, more preferably 8000 or more, and more than 10,000. Especially better. On the other hand, the molar absorption coefficient at a wavelength of 400 nm is 3500 or less, preferably 2500 or less, and more preferably 1500 or less. In addition, in this specification, unless otherwise specified, the Moire absorption coefficient is based on the conditions measured in the Example mentioned later.

Here, the action of the ultraviolet absorber in the present invention will be described. This effect is deduced as follows. For example, when the siloxane resin composition of the present invention is used as a negative-type photosensitive resin composition (ultraviolet-curing type), an example in which the siloxane resin composition is applied to a substrate can be cited. At this time, an active radiation (for example, i-ray) is irradiated through a light mask. As a result, the exposed portion is hardened by being exposed to light. By developing this with a predetermined developer, a pattern of the cured product of the siloxane resin composition is obtained.

On the other hand, when the transparency of the silicone resin composition is high, particularly when it is affected by particles in the composition, light may be scattered in the resin and the resin in the side periphery may be photosensitive. in this way At the same time, the resin around the side is also hardened, and Luan Guo is patterned in a state blurred with respect to the light mask.

On the other hand, in the silicone resin composition of the present invention, since an ultraviolet absorber having specific absorption characteristics is used, it is possible to obtain a hardened product with a sharp shape by suppressing exposure blur. Specifically, it can be understood that when ultraviolet rays (i-rays) are used for exposure, the siloxane resin and the matrix containing metal particles are liable to generate the above-mentioned light scattering. Therefore, it can be understood that the effect of the specific ultraviolet absorber used in the present invention becomes remarkable.

Further, in the siloxane resin composition of the present invention, excellent light resistance can also be achieved in the cured product. Although the reason is included, the ultraviolet absorbent having the specific absorption characteristics described above is adsorbed on the surface of the metal-containing particles in a specific state. It can be understood that, as a result, the scattering of ultraviolet rays on the particle surface is effectively suppressed, and this contributes to the suppression of the deterioration of the composition and the deterioration of its hardened material. In addition, it can be understood that as described above, the effect becomes more significant as the concentration of the metal-containing particles is higher.

The ultraviolet absorber can be widely selected as long as it has the above-mentioned optical characteristics, and specific examples thereof include (benzo) triazole compounds, benzophenone compounds, diene compounds, avobenzone compounds, and (benzo) dioxane. Thiazole compounds, (benzo) dithiol compounds, coumarin compounds, triazine compounds, and the like. () Here means that it may or may not be a benzo substituent. Among these, in consideration of high resolution and light resistance, a diene compound, an avobenzone compound, a benzodithiol compound, a triazole or a triazine compound is preferable.

The ultraviolet absorber used in the present invention preferably has at least one CO group (carbonyl group), CONH group (amido group), COO group (ester group), and CN group (cyano group) in its molecule (hereinafter, These groups are called specific adsorption groups). The above-mentioned specific adsorption group has two or more in the molecule Even better. There is no particular upper limit, but it is actually 8 or less. Although its effect includes an unclear part, it can be understood that it is effectively adsorbed or dispersed on the surface of the metal-containing particles as described above, thereby alleviating the effect of light scattering caused by the above-mentioned particles. In this respect, the above-mentioned metal-containing particles are preferably metal oxide fine particles having an M-O bond (M = metal).

The ultraviolet absorber used in the present invention is preferably composed of a compound having any one of the following formulae (a) to (g). Among them, it is more preferable to be composed of a compound having a skeleton of formulae (d) to (g). It is particularly preferred that it is composed of a compound having a skeleton of the formulae (d) to (f). As these skeletons, a compound having an arbitrary substituent within a predetermined range can be used. As an arbitrary substituent, the example of the substituent T mentioned later is mentioned. Among them, an alkyl group (1 to 24 carbon atoms is preferable, 1 to 12 is more preferable, 1 to 6 is more preferable, and 1 to 3 is particularly preferable), a hydroxyl group, and an alkoxy group (1 to 3 carbon atoms) 24 is better, 1 to 12 is better, 1 to 6 is more preferred, 1 to 3 is more preferred, fluorenyl (carbon number of 2 to 24 is better, 2 to 12 is better, 2 to 6 is further Preferably, 2 to 3 are preferred), aryl (6 to 22 carbon atoms is preferred, 6 to 14 is more preferred, 6 to 10 is more preferred), heterocyclyl (1 to 12 carbon atoms is preferred) , 2 ~ 5 is better). The heterocyclic group is preferably one containing N, O, and S, and among them, N is more preferable. The heterocyclic group is preferably a 5- to 7-membered ring, more preferably a 5- or 6-membered ring. In particular, it is preferred that the benzene ring of the formulae (a) to (f) have one or more of the above-mentioned substituents. When there are a plurality of arbitrary substituents on a benzene ring, a ring can be formed.

[Chemical Formula 1]

In the formula (f), R ^U1 and R ^U2 are each independently a substituent T, and among them, a cyano group or a fluorenyl group (with 1 to 24 carbon atoms being preferred, and 4 to 18 being more preferred) are more preferred. R ^U1 and R ^U2 may be the same or different.

In formula (g), R ^U3 and R ^U4 are each independently a substituent T. Among them, the alkyl group (the number of carbon atoms is 1 to 24 is preferable, 1 to 12 is more preferable, 1 to 6 is more preferable, and 1 to 6 3 is particularly preferred), and alkyl groups having a cyano group or a carboxyl group are more preferred. R ^U5 and R ^U6 are preferably the same as R ^U1 and R ^U2 .

R ^U1 and R ^U2 , R ^U3 and R ^U4 , R ^U5 and R ^U6 may be bonded or even condensed to form a ring.

Specific examples of the ultraviolet absorber include Uvinul A, Uvinul 3000, Uvinul 3008, Uvinul 3049, Uvinul 3050 (manufactured by BASF Ltd.), Sumisorb 130, Sumisorb 140, Sumisorb 200, Sumisorb 250, and Sumisorb 320. Sumisorb 340, Sumisorb 350 (SUMITOMO CHEMICALCOMPANY, manufactured by Limited), EVERSORB10, EVERSORB11, EVERSORB12 (EVERLIGHT CHEMICAL (Manufactured by INDUSTRIAl CORPORATION), Tomisob800 (manufactured by API CORPORATION), SEESORB100, SEESORB101, SEESORB101S, SEESORB102, SEESORB103, SEESORB105, SEESORB106, SEESORB107, SEESORB151 (manufactured by SHIPRO KASEI KAISHA. LTD. And other benzophenone compounds; Sumisorb200, Sumisorb250, Sumisorb300, Sumisorb320, Sumisorb340, Sumisorb350 (SUMITOMO CHEMICALCOMPANY, manufactured by LIMITED), JF77, JF78, JF79, JF80, JF83 (manufactured by JOHOKU CHEMICALCO., LTD), TINUVIN PS, TINUVIN 99- 2.TINUVIN 109, TINUVIN 171, TINUVIN 328, TINUVIN 384-2, TINUVIN 479, TINUVIN 900, TINUVIN 928, TINUVIN 1130 (manufactured by BASF Ltd.), TINUVIN 70, TINUVIN 71, TINUVIN 72, TINUVIN 73, TINUVIN 74, TINUVIN 75, TINUVIN 76, TINUVIN 234, TINUVIN 77, TINUVIN 78, TINUVIN 80, TINUVIN 81 (manufactured by Everlight Chemical Corporation), Tomisob100, Tomisob600 (made by API CORPORATION), SEESORB701, SEESORB702, SEESORB703, SEESORB704, SEESORB706, SEESORB707 (SEESORB707) KASEI KAISHA.LTD. ) And other benzotriazole compounds; Sumisorb400 (SUMITOMO CHEMICALCOMPANY, manufactured by LIMITED), benzoic acid compounds such as phenyl salicylate; TINUVIN400, TINUVIN405, TINUVIN460, TINUVIN477DW, TINUVIN479 (manufactured by BASF Ltd.) and other hydroxyphenyltriazines Compounds; coumarin compounds such as coumarin-4, 4-hydroxycoumarin, and 7-hydroxycoumarin.

As the diene compound, compounds in the columns of paragraphs 0144 to 0164 of Japanese Patent Laid-Open No. 2010-78729 can be used, and those contents can be referred to and incorporated into the present specification.

In the solid content of the silicone resin composition, the ultraviolet absorber is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and even more preferably 1% by mass or more. The upper limit is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less. With respect to 100 parts by mass of the metal-containing particles, 0.1 parts by mass or more is preferable, 0.5 parts by mass or more is more preferable, and 1 part by mass or more is more preferable. The upper limit is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and even more preferably 5 parts by mass or less. By applying the ultraviolet absorber at the above-mentioned lower limit value or more, the above-mentioned optimizing effects of developability and light resistance can be effectively obtained, so it is preferable. By making it below the said upper limit, it is possible to suppress an excessive influence on optical characteristics, such as transparency, and suppress a blurring phenomenon (B1oom) etc., and it also contributes to manufacturing adaptability, Therefore, it is preferable.

The ultraviolet absorbers may be used alone or in combination of two or more.

<Polymerization initiator>

The siloxane resin composition of the present invention contains a polymerization initiator. The polymerization initiator may be a thermal polymerization initiator or a photopolymerization initiator, but a photopolymerizable initiator is preferred. Examples include organic halogen compounds, oxadiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxides, azo compounds, coumarin compounds, azide compounds, metallocene compounds, six Arylbisimidazole compounds, organoboric acid compounds, disulfonic acid compounds, oxime compounds, onium salt compounds, hydroxyacetophenone compounds, aminoacetophenone compounds, fluorenylphosphine oxide compounds, trihalomethyltriazine compounds, benzyl Dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, fluorenyl phosphine compounds, phosphine oxide compounds, triarylimidazole dimers, onium compounds, benzothiazole compounds, benzophenone compounds, ring Pentadiene-benzene-iron complex, halomethyloxadiazole compound, 3-aryl substituted coumarin compound, α-aminoalkylphenyl ketone compound, benzoate compound.

As specific examples of these, reference can be made to the descriptions after paragraph <0135> of Japanese Patent Laid-Open No. 2010-106268 (corresponding to US Patent Application Publication No. 2011/0124824 specification <0163>), which are incorporated into this specification in.

Specific examples include an aminoacetophenone-based initiator described in Japanese Patent Laid-Open No. 10-291969 and a fluorenylphosphine oxide-based initiator described in Japanese Patent No. 4225898.

Examples of the hydroxyacetophenone-based initiator include IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (trade names: all manufactured by BASF Ltd.).

Examples of commercially available aminoacetophenone-based initiators include IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF Ltd.). In addition, a compound described in Japanese Patent Laid-Open No. 2009-191179 can be used in which the absorption wavelength is matched to a long-wave light source such as 365 nm or 405 nm.

As a commercially available fluorenyl phosphine-based initiator, IRGACURE-819, DAROCUR 4265, and DAROCUR-TPO (trade names: all manufactured by BASF Ltd.) can be used.

Examples of the azo compound include 2,2-azobisisobutyronitrile (AIBN), 3-carboxypropionitrile, azobismaleonitrile, and dimethyl-2,2'-azobis (2 -Methylpropionate) [V-601] (manufactured by Wako Pure Chemical Industries, Ltd.) and the like.

In the present invention, it is preferable to use an oxime compound. The oxime compound effectively functions as a polymerization initiator for initiating and promoting polymerization in the siloxane resin composition of the present invention. and, The oxime compound has less coloration in post-heating and has good hardenability. In particular, in the present invention, it is possible to optimize the resolution of the pattern and the light resistance of the cured product. Among them, commercially available products (all manufactured by BASF Ltd.) such as IRGACURE OXE01 (the following formula) and IRGACURE OXE02 (the following formula) can be appropriately used.

The oxime compound used as the polymerization initiator is preferably represented by the following formula (OX), and more preferably represented by the formula (OX-1).

‧A ¹

-AC or an alkyl group of the A ¹ formula (OX-1) is preferred. The alkyl-based carbon number is preferably 1 to 12, and more preferably 1 to 6. The alkyl group may have a substituent T described later. The substituent T may be substituted via a linking group L described later.

‧C

C represents Ar, -SAr, or -COAr.

‧R

R represents a monovalent substituent, and is preferably a monovalent non-metallic radical. Examples of the monovalent non-metal atomic group include an alkyl group (more preferably 1 to 12 carbon atoms, more preferably 1 to 6 and even more preferably 1 to 3), and an aryl group (more preferably 6 to 14 carbon atoms) , 6-10 is more preferred), fluorenyl (2-12 carbon atoms are preferred, 2-6 is more preferred, 2-3 is more preferred), arylfluorenyl (7-15 is preferred) 7 to 11 is more preferred), alkoxycarbonyl (2 to 12 carbon atoms is preferred, 2 to 6 is more preferred, 2 to 3 is particularly preferred), aryloxycarbonyl (7 to 15 carbon atoms is preferred) Better, 7 ~ 11 is better), heterocyclic group (2-12 carbon atoms is preferred, 2-6 is more preferred), alkylthiocarbonyl group (2-12 carbon atoms is better, 2 ~ 6 is more preferred, 2 to 3 is particularly preferred), arylthiocarbonyl (7 to 15 carbon atoms is preferred, 7 to 11 is more preferred), and the like. These groups may have a substituent of 1 or more. The aforementioned substituent may be further substituted with another substituent T. Among the substituents T, a halogen atom, an alkyl group (1 to 12 carbon atoms is preferred, 1 to 6 is more preferred, 1 to 3 is particularly preferred), and an aryl group (6 to 14 carbon atoms is preferred, 6 to 6 10 is more preferred), arylthio (6 to 14 carbon atoms is preferred, 6 to 10 is more preferred), arylfluorenyl (7 to 15 carbon atoms is preferred, 7 to 11 is more preferred)) Etc. is better. Among the linking group L, an alkylene group having 1 to 6 carbon atoms, O, S, CO, NR ^N, or a combination thereof is preferable.

‧B

B represents a monovalent substituent, an alkyl group (1 to 12 carbon atoms is preferred), an aryl group (6 to 14 carbon atoms is preferred, 6 to 10 carbon atoms is more preferred), a heterocyclic group (carbon 2 to 18 atoms are preferred, and 2 to 12 carbon atoms are more preferred). These groups may be bonded via a linking group L. These groups may have a substituent T of 1 or more. The substituent T may be substituted via any linking group L. Among them, the linking group L is also preferably an alkylene group having 1 to 6 carbon atoms, O, S, CO, NR ^N, or a combination thereof. Specific examples of B include the following. * Indicates a bonding position, and bonding can be performed at different positions. These groups may be further accompanied by a substituent T. Specific examples include benzamidine, phenylthio, and phenyloxy.

[Chemical Formula 4]

‧A

A is a single bond or linker. As a preferable example of the linking group, the above-mentioned linking group L or an arylene group (6 to 14 carbon atoms is preferred, and 6 to 10 carbon atoms is more preferred) or a heterocyclic linking group (aromatic heterocyclic linking group) For better) (2 to 18 carbon atoms is preferred, and 2 to 12 carbon atoms is more preferred).

‧Ar

Ar is aryl or heteroaryl (aromatic heterocyclic group). As the aryl group, 6 to 14 carbon atoms are preferred, 6 to 10 carbon atoms are more preferred, and phenyl and naphthyl are more preferred. The heteroaryl group is preferably 2 to 18 carbon atoms, more preferably 2 to 12 carbon atoms, and a carbazolyl group which may have a substituent such as an alkyl group at the N-position is more preferred.

As the oxime compound, Japanese Patent Application Laid-Open No. 2012-208494, paragraph 0513 (corresponding to US Patent Application Publication No. 2012/235099, <0632>) and the following formulae (OX-1), (OX- 2) or a description of the compound represented by (OX-3), which are incorporated into the present specification.

The polymerization initiator preferably has a maximum absorption wavelength in a wavelength region of 350 nm to 500 nm, and it is more preferable to have an absorption wavelength in a wavelength region of 360 nm to 480 nm, and it is more preferable to have a higher absorbance at 365 nm and 455 nm. From the point of sensitivity, the molar absorption coefficient at 365nm or 405nm is preferably 1,000 ~ 300,000, more preferably 2,000 ~ 300,000, and even more preferably 5,000 ~ 200,000. The measurement method of the Mohr absorption coefficient is the same as that of the ultraviolet absorber, and unless otherwise specified, it is based on the conditions measured in the examples described later.

The content of the polymerization initiator (the content of amidine in the case of two or more types) is relative to the total solid content of the composition. The volume content is preferably from 0.1% by mass to 10% by mass, more preferably from 0.3% by mass to 8% by mass, and even more preferably from 0.5% by mass to 5% by mass. Within this range, good curability and transparency can be obtained.

Moreover, a polymerization initiator can be used individually or in combination of 2 or more types.

<Solvent>

The siloxane resin composition of the present invention may contain a solvent. As for the solvent, the solvent used in the hydrolysis-condensation reaction of the silane compound may be directly used as a solvent for the composition, or the following solvents may be used in addition to or instead of the solvent.

Examples of the solvent include water, an aliphatic compound, a halogenated hydrocarbon compound, an alcohol compound, an ether compound, an ester compound, a ketone compound, a nitrile compound, a fluorene compound, a fluorene compound, and an aromatic compound. These solvents can be used in combination. Examples are listed below.

‧water

‧Aliphatic compounds

Hexane, heptane, cyclohexane, methylcyclohexane, octane, pentane, cyclopentane, etc.

‧Halogenated hydrocarbon compounds

Methyl chloride, chloroform, methylene chloride, dichloroethane, carbon tetrachloride, trichloroethylene, tetrachloroethylene, epichlorohydrin, monochlorobenzene, o-dichlorobenzene, chloropropene, HCFC, methyl chloroacetate, Ethyl chloroacetate, chloroacetic acid trichloroacetic acid, odor methane, methyl iodide, tris (tetra) chloroethylene, etc.

‧Alcohol compounds

Methanol, ethanol, 1-propanol, 2-propanol, 2-butanol, ethylene glycol, propylene glycol, glycerol, 1,6-hexanediol, cyclohexanediol, sorbitol, xylitol, 2-methyl-2,4-pentanediol, 1,3-butanediol, 1,4-butanediol, diacetone alcohol, tetrahydrofurfuryl alcohol, etc.

‧Ether compounds (including hydroxyl-containing ether compounds)

Dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, cyclohexyl methyl ether, anisole, tetrahydrofuran, alkylene glycol alkyl ether (ethylene glycol monomethyl ether, ethyl ether Glycol monobutyl ether, diethylene glycol, dipropylene glycol, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol, polyethylene glycol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol (Monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether, etc.)

‧Ester compound

Ethyl acetate, ethyl lactate, 2- (1-methoxy) propyl acetate, propylene glycol monomethyl ether acetate, etc.

‧Ketone compounds

Acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, cyclopentanone, etc.

‧Nitrile compound

Acetonitrile

‧Amine compounds

N, N-dimethylformamidine, 1-methyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolinone, 2-pyrrolidone, ε-caprolactam, formazan Ammonium amine, N-methylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropylamine, hexamethylphosphonium triamine, etc.

‧Asian compounds

Dimethyl sulfene

‧Aromatic compounds

Benzene, toluene, etc.

As the solvent, in order to uniformly dissolve each component of the composition, an alcohol compound, an ester compound, or an ether compound is preferable. Examples include propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diacetone alcohol, ethylene glycol monobutyl ether, 2-ethoxyethyl acetate, and 1-methoxypropyl-2-acetate. , 3-methoxy-3-methylbutanol, 3-methoxy-3-methylbutanol acetate, 3-methoxybutyl acetate, 1,3-butanediol diethyl Acid esters, ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether acetate, ethyl lactate, butyl lactate, ethyl acetate or γ-butyrolactone.

The amount of the solvent used is not particularly limited, but when used as a coating liquid, the solid content is preferably 5 mass% or more, more preferably 8 mass% or more, and even more preferably 10 mass% or more. The upper limit is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 35% by mass or less.

The solvents may be used alone or in combination of two or more.

<Polymerizable compound>

The silicone resin composition of the present invention may contain a polymerizable compound. The polymerizable compound is preferably an addition polymerizable compound having at least one polymerizable group such as an ethylenically unsaturated double bond, an epoxy group, and an oxetanyl group. The compound selected from the group having at least one polymerizable group is preferable, and the compound selected from the group having two or more polymerizable groups is more preferable. There is no particular upper limit, but it is actually 12 or less. For example, it may be a monomer, a prepolymer, that is, a polymer such as a dimer or a trimer, an oligomer, a mixture thereof, or a chemical form such as a copolymer thereof. Examples of the monomer and its copolymer include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or their esters and amidines . Phenamines using unsaturated carboxylic acid and aliphatic polyhydric alcohol compound, unsaturated carboxylic acid and aliphatic polyamine compound are preferred. In addition, an unsaturated carboxylic acid having a nucleophilic substituent such as a hydroxyl group, an amino group, or a mercapto group is also suitably used. Addition reactants of esters or unsaturated carboxylic acid amines and fluorinated or polyfunctional isocyanates or epoxy; and the aforementioned unsaturated carboxylic acid esters or unsaturated carboxylic acid amines and fluorinated or polyfunctional Dehydration condensation reactants of carboxylic acids and the like. In addition, unsaturated carboxylic acid esters or unsaturated carboxylic acid amines having an electrophilic substituent such as an isocyanate group or an epoxy group, and addition reactions with fluorene- or polyfunctional alcohols, amines, and thiols ; Unsaturated carboxylic acid esters or unsaturated carboxylic acid amines having a detachable substituent such as a halogen group or tosylateoxy group, and a substitution reaction with fluorene- or polyfunctional alcohols, amines, and thiols Things are also suitable. In addition, as another example, a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether, or the like can be used instead of the unsaturated carboxylic acid. As these specific compounds, the compounds described in paragraphs 0095 to 0108 of Japanese Patent Laid-Open No. 2009-288705 can be suitably used in the present invention.

The polymerizable compound is more preferably represented by the following formulae (MO-1) to (MO-6).

[Chemical Formula 5]

In the formula, n is 0-14, and m is 1-8. A plurality of R, T, and Z may be the same or different from each other in a molecule. When T is an oxyalkylene group, the terminal on the carbon atom side of the oxyalkylene group is bonded to R. At least one of R is a polymerizable group.

n is preferably from 0 to 5, more preferably from 1 to 3.

m is preferably from 1 to 5, more preferably from 1 to 3.

Specific examples of the polymerizable compound represented by the above formulae (MO-1) to (MO-6) For example, the compounds described in paragraphs 0248 to 0251 of Japanese Patent Laid-Open No. 2007-269779 can be suitably used in this embodiment.

Among them, as the polymerizable compound, dipentaerythritol triacrylate (KAYARAD D-330 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), and dipentaerythritol tetraacrylate (KAYARAD D-320 as a commercial product; Nippon Kayaku Co., Ltd.) dipentaerythritol penta (meth) acrylate (KAYARAD D-310; commercially available as Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (as Commercially available products include KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) and the structure of these (meth) acrylfluorenyl groups via ethylene glycol or propylene glycol residues or diglycerol EO (ethylene oxide) modification ( A meth) acrylate (M-460 as a commercial product; manufactured by Toagosei Company, Limited) is preferred. These oligomer types can also be used.

As the polymerizable compound, a compound represented by the following formula (i) or (ii) can also be used.

In the above formula, E represents-((CH ₂ ) _y CH ₂ O)-or-((CH ₂ ) _y CH (CH ₃ ) O)-, and-((CH ₂ ) _y CH ₂ O)-is more good.

y represents an integer from 1 to 10, an integer from 1 to 5 is preferred, and an integer from 1 to 3 is more preferred.

X represents a hydrogen atom, an acrylfluorenyl group, a methacrylfluorenyl group, or a carboxyl group, respectively. In formula (i), a total of 3 or 4 acrylfluorenyl and methacrylfluorenyl groups is more preferable, and 4 is more preferable. In formula (ii), the total number of acrylfluorenyl and methacrylfluorenyl is five or six, and six is preferable.

m represents an integer from 0 to 10, and an integer from 1 to 5 is preferred.

n represents an integer from 0 to 10, and an integer from 1 to 5 is preferred.

The polymerizable compound may have an acidic group such as a carboxyl group, a sulfonic acid group, or a phosphate group. Thereby, the ethylenic compound can be one having an unreacted carboxyl group as in the case of a mixture, and it can be used as it is. The acidic group can be introduced by reacting a hydroxyl group of the above-mentioned ethylenic compound with a non-aromatic carboxylic acid anhydride as necessary. In this case, specific examples of the non-aromatic carboxylic anhydride used include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and alkylated hexahydrophthalic anhydride. Phthalic anhydride, succinic anhydride, maleic anhydride.

The molecular weight of the polymerizable compound is not particularly limited, but it is preferably 300 or more and 1500 or less, and more preferably 400 or more and 700 or less.

The content of the polymerizable compound with respect to the total solid content in the composition is preferably in the range of 1% to 50% by mass, more preferably in the range of 3% to 40% by mass, and in the range of 5% to 30% by mass. The range of% is further preferred. If it is within this range, the refractive index and transparency are not excessively lowered, and hardenability is good, so it is preferable.

The polymerizable compound may be used singly or in combination of two or more kinds.

<Alkali-soluble resin>

The silicone resin composition of the present invention may contain an alkali-soluble resin. As the alkali-soluble resin, an alkali that can promote alkali solubility from a linear organic polymer and at least one of the molecules (acrylic copolymer and styrene copolymer-based molecules are preferred) is used. Soluble The resin is appropriately selected.

From the viewpoint of heat resistance, a polyhydroxystyrene resin, a polysiloxane resin, an acrylic resin, an acrylamide resin, and an acrylic / ammonium acrylic copolymer resin are preferred. From the viewpoint of developability control, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferred. Examples of the group that promotes alkali solubility (hereinafter also referred to as an acidic group) include a carboxyl group, a phosphate group, a sulfonic acid group, and a phenolic hydroxyl group. Those which are soluble in a solvent and can be developed with a weak alkaline aqueous solution are preferred, and (meth) acrylic acid is particularly preferred. These acidic groups may be only one kind, or two or more kinds.

As the linear organic polymer used as the alkali-soluble resin, a polymer having a carboxylic acid in a side chain is preferred, and examples thereof include a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, and a crotonic acid copolymer. , Maleic acid copolymers, partially esterified maleic acid copolymers, alkali-soluble phenolic resins such as phenolic resins, etc., acidic cellulose derivatives with carboxylic acids in side chains, and addition of acid anhydrides to polymers with hydroxyl groups By. In particular, a copolymer of (meth) acrylic acid and other monomers capable of being copolymerized therewith is suitable as the alkali-soluble resin. Examples of other monomers that can be copolymerized with (meth) acrylic acid include alkyl (meth) acrylate, aryl (meth) acrylate, and vinyl compounds. Examples of the alkyl (meth) acrylate and aryl (meth) acrylate include meth (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and n- (meth) acrylate. Butyl (meth) acrylate, isobutyl (meth) acrylate, (iso) pentyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (methyl ) Acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (Meth) acrylate, cyclohexyl (meth) acrylate, etc. Examples of the vinyl compound include styrene and α- Methyl styrene, vinyl toluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate Ester macromonomers and the like, as the N-substituted maleimide imide monomer described in Japanese Patent Laid-Open No. 10-300922, include jN-phenylmaleimide and N-cyclohexylmaleimide.醯 imine and so on.

As another monomer copolymerizable with (meth) acrylic acid, a repeating unit represented by the following formula (A1) is also preferable.

R ¹¹ represents a hydrogen atom or a methyl group. R ¹² represents an alkylene group having 2 or 3 carbon atoms, of which 2 is preferred. R ¹³ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. n1 represents an integer from 1 to 15, preferably from 1 to 12. The repeating unit represented by the above formula (A1) has good adsorption and / or orientation properties on the particle surface due to the effect of the π electrons of the benzene ring existing on the side chain. In particular, when the side chain portion adopts an ethylene oxide or propylene oxide structure of p-cumylphenol, the stereoscopic effect is also increased, and a better adsorption and / or orientation plane can be formed. Therefore, the effect is higher, so it is better.

R ¹³ is preferably an alkyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 1 to 10 carbon atoms. This is because when the number of carbon atoms of R ¹³ is large, the group becomes an obstacle to inhibit the resins from approaching each other and promotes adsorption and / or orientation. However, if it is too large, the effect may be hindered. As the alkyl group represented by R ¹³ , an unsubstituted alkyl group or an alkyl group substituted with a phenyl group is preferred.

As the silicone resin composition of the present invention, an alkali-soluble polyester resin can be used. on Although the action mechanism of the effect obtained by containing the alkali-soluble polyester resin is not clear, it is thought that those having an aromatic ring reduce the decomposability of the ester group and realize effective development.

As a method for synthesizing the alkali-soluble polyester resin, a method of undergoing an addition polymerization reaction of a polyfunctional epoxy compound and a polycarboxylic acid compound or an addition polymerization reaction of a polyol compound and a diacid anhydride is preferable. The polyhydric alcohol compound is preferably obtained by a reaction of a polyfunctional epoxy compound and a monobasic acid compound containing a radical polymerizable group. Examples of the catalyst used for addition polymerization reaction and addition reaction include ammonium catalysts such as tetrabutylammonium acetate; ammonia such as 2,4,6-tris (dimethylaminomethyl) phenol or dimethylbenzylamine; Based catalysts; phosphorus based catalysts such as triphenylphosphine; and chromium based catalysts such as acetoacetone chromium acetone or chromium chloride.

The alkali-soluble resin is preferably one which is soluble in a tetramethylammonium hydroxide (TMAH) aqueous solution at a concentration of 0.1% by mass or more at 23 ° C. A TMAH aqueous solution soluble in more than 1% by mass is further preferred, and a TMAH aqueous solution soluble in more than 2% is further preferred.

As the acid value of the alkali-soluble resin, 30 to 200 mgKOH / g is more preferable, 50 to 150 mgKOH / g is more preferable, and 70 to 120 mgKOH / g is more preferable. By setting it as such a range, the development residue of an unexposed part can be reduced effectively.

The weight-average molecular weight (Mw) of the alkali-soluble resin is preferably 2,000 to 50,000, more preferably 5,000 to 30,000, and particularly preferably 7,000 to 20,000.

The content of the alkali-soluble resin is preferably 10 to 50% by mass, more preferably 15 to 40% by mass, and even more preferably 20 to 35% by mass relative to the total solids content of the composition.

The alkali-soluble resin can be used singly or in combination of two or more kinds.

<Polymerization inhibitor>

The silicone resin composition of the present invention may contain a polymerization inhibitor. Examples of the polymerization inhibitor include phenolic hydroxy compounds, N-oxides, piperidine 1-oxy radical compounds, pyrrolidine 1-oxy radical compounds, and N-nitrosophenylammonium , Diazo compounds and cationic dyes, thioether-containing compounds, nitro-containing compounds, FeCl ₃ , CuCl ₂ and other transition metal compounds. As the polymerization inhibitor, for example, reference can be made to paragraphs 0260 to 0280 of Japanese Patent Laid-Open No. 2010-106268 (corresponding to US Patent Application Publication No. 2011/0124824, <0284> to <0296>), These contents are incorporated into this specification.

As a preferable addition amount of the polymerization inhibitor, 0.01 to 10 parts by mass is more preferable, and 0.01 to 8 parts by mass is more preferable to 0.05 parts by mass or more with respect to 100 parts by mass of the polymerization initiator. 5 The range below the mass part is the most preferable.

A polymerization inhibitor may be used individually by 1 type, and may use 2 or more types together.

<Dispersant>

As the dispersant, a high-molecular compound represented by the general formula (1) in Japanese Patent Application Laid-Open No. 2007-277514 (1) (corresponding to US2010 / 0233595 patent application scope 1) is preferred . Reference can be made to the description of Japanese Patent Laid-Open No. 2007-277514 (corresponding to US2010 / 0233595), which is incorporated into this specification.

The polymer compound represented by the general formula (1) is not particularly limited, but can be synthesized according to the synthesis methods described in paragraphs 0114 to 0140 and 0266 to 0348 of Japanese Patent Laid-Open No. 2007-277514.

The content of the dispersant is preferably 10 to 1,000 parts by mass, more preferably 30 to 1,000 parts by mass, and even more preferably 50 to 800 parts by mass relative to 100 parts by mass of the metal-containing particles. Moreover, it is more preferable that it is 10-30 mass% with respect to the total solid content of a composition. These dispersants may be used alone or in combination of two or more.

<Surfactant>

The siloxane resin composition of the present invention may contain a surfactant. Examples of the surfactant include a silicone-based surfactant, a silicone-based surfactant such as an organopolysiloxane, a fluorine-based surfactant, a polyoxyethylene dodecyl ether, and a polyoxyethylene oleyl ether. , Non-ionic surfactants such as polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol laurate or polyethylene glycol distearate, polyalkylene oxide interface An active agent, a poly (meth) acrylate-based surfactant, or a surfactant composed of an acrylic or methacrylic polymer. Examples of commercially available surfactants include "Megafac" (registered trademark) F142D, F172, F173, F183, F445, F470, F475, or F477 (all manufactured by DIC Corporation Co., Ltd.) or NBX- 15 or FTX-218 (all manufactured by NEOS COMPANYLIMITED) and other fluorine-based surfactants, BYK-333, BYK-301, BYK-331, BYK-345, or BYK-307 (all manufactured by BYK Additives & Instruments) and other silicones Department of surfactants.

The addition amount of the surfactant is not particularly limited, but in the solid content of the composition, 1% by mass or more is preferable, 1.5% by mass or more is more preferable, and 5% by mass or more is more preferable. The upper limit is not particularly limited, but 30% by mass or less is preferable, and 15% by mass or less is more preferable.

The surfactant may be used singly or in combination of two or more kinds.

The silicone resin composition of the present invention may contain other additives such as a dissolution inhibitor, a stabilizer, or an antifoaming agent as needed.

<Developer>

As the developing solution, an alkaline solution is preferably used. For example, the concentration of the basic compound is preferably 0.001 to 10% by mass, and more preferably 0.01 to 5% by mass. Examples of the basic compound include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, diamine Ethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxyl, benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine , 1,8-diazabicyclo [5.4.0] -7-undecene and so on. Among them, an organic base is preferred in the present invention. When an alkaline aqueous solution is used as the developing solution, a washing treatment is usually performed with water after development. Among these developing solutions, a fourth-order ammonium salt is preferred, and tetramethylammonium hydroxide (TMAH) or choline is more preferred.

The developer may be used alone or in combination of two or more.

In addition, the expression of a compound in the present specification (for example, when a compound is added at the end and referred to as the name) is used in addition to the above-mentioned compound as well as a meaning including a salt and an ion thereof. Moreover, it means the derivative which introduce | transduced a substituent etc. and changed a part within the range which can exhibit a desired effect.

In the present specification, unsubstituted and unsubstituted substituents (the same is true for a linking group) means that the group may have any substituent. This also has the same meaning for unlabeled, unsubstituted compounds. As a preferable substituent, the following substituent T is mentioned.

Examples of the substituent T include the following substituents.

Examples include alkyl (alkyl having 1 to 20 carbon atoms is preferred, for example, methyl, ethyl, isopropyl, third butyl, pentyl, heptyl, 1-ethylpentyl, benzyl , 2-ethoxyethyl, 1-carboxymethyl, etc.), alkenyl (alkenyl having 2 to 20 carbon atoms is preferred, for example, vinyl, allyl, olealkenyl, etc.), alkynyl (Alkynyl groups having 2 to 20 carbon atoms are preferred, for example, ethynyl, butadiynyl, phenylethynyl, etc.), cycloalkyl (cycloalkyl groups having 3 to 20 carbon atoms are preferred, for example , Cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, etc., but when it is recorded as an alkyl group, it usually includes the meaning of cycloalkyl group.), Aryl group (aryl group having 6 to 26 carbon atoms is Preferably, for example, phenyl, 1-naphthyl, 4-methoxyphenyl, 2-chlorophenyl, 3-methylphenyl, etc.), heterocyclic group (heterocyclic group having 2 to 20 carbon atoms) Preferably, a heterocyclic group having at least one oxygen atom, a sulfur atom, and a 5- or 6-membered ring of a nitrogen atom is preferred, for example, tetrahydropyran, tetrahydrofuran, 2-pyridyl, 4-pyridyl, 2 -Imidazolyl, 2-benzimidazolyl, 2-thiazolyl, 2-oxazolyl, pyrrolidone, etc.), alkoxy (carbon atom 1 to 20 alkoxy groups are preferred, for example, methoxy, ethoxy, isopropoxy, benzyloxy, etc.), aryloxy (aryloxy having 6 to 26 carbon atoms is preferred, For example, phenoxy, 1-naphthyloxy, 3-methylphenoxy, 4-methoxyphenoxy, etc.) and alkoxycarbonyl (alkoxycarbonyl having 2 to 20 carbon atoms are preferred) For example, ethoxycarbonyl, 2-ethylhexyloxycarbonyl, etc.), aryloxycarbonyl (aryloxycarbonyl having 6 to 26 carbon atoms is preferred, for example, phenoxycarbonyl, 1-naphthyl An oxycarbonyl group, a 3-methylphenoxycarbonyl group, a 4-methoxyphenoxycarbonyl group, etc.), an amino group (an amino group having 0 to 20 carbon atoms is preferred, and includes an alkylamino group and an arylamino group, for example, Ammonia, N, N-dimethylamino, N, N-diethylamino, N-ethylamino, aniline, etc.), sulfamoyl groups (aminesulfonyl groups having 0 to 20 carbon atoms are preferred) For example, N, N-dimethylaminosulfonyl, N-phenylaminesulfonyl, etc.), fluorenyl (fluorenyl having 1 to 20 carbon atoms is preferred, for example, ethylfluorenyl, propionyl Group, butyl fluorenyl, etc.), aryl fluorenyl (aryl fluorenyl having 7 to 23 carbon atoms is preferred, for example, benzamidine, etc.), fluorenyloxy (carbon number of carbon atoms) An alkoxy group of 1 to 20 is preferred, for example, ethoxy, etc.), an aryl alkoxy (group of 7 to 23 carbon atoms is preferred, for example, benzyloxy, etc.), Carbaminyl (carbamate having 1 to 20 carbon atoms is preferred, for example, N, N-dimethylaminocarbamate, N-phenylcarbamate, etc.), amidoamino (carbon atom Phenylamino groups having a number of 1 to 20 are preferred, for example, ethylamino, benzamidineamino, etc.), alkylthio (alkylthio groups having 1 to 20 carbon atoms are preferred, for example, methylthio, ethylthio Group, isopropylthio group, benzylthio group, etc.), arylthio group (arylthio group having 6 to 26 carbon atoms are preferred, for example, phenylthio group, 1-naphthylthio group, 3-methylphenylthio group, etc.) Group, 4-methoxyphenylthio, etc.), alkylsulfonyl (alkylsulfonyl having 1 to 20 carbon atoms is preferred, for example, methylsulfonyl, ethylsulfonyl, etc.) Arylsulfonyl (aryl sulfonyl having 6 to 22 carbon atoms is preferred, for example, benzenesulfonyl), alkylsilyl (alkylsilyl having 1 to 20 carbon atoms) Preferably, for example, monomethylsilyl, dimethylsilyl, trimethylsilyl, triethylsilyl, etc.), arylsilyl Alkyl groups (aryl silyl groups having 6 to 42 carbon atoms are preferred, for example, triphenylsilyl groups, etc.), and phosphinyl groups (phosphoranyl groups having 0 to 20 carbon atoms are preferred. For example, -OP (= O) (R ^P ) ₂ ), a phosphino group (a phosphino group having 0 to 20 carbon atoms is preferred, for example, -P (= O) (R ^P ) ₂ ), an oxophosphino group ( An phosphine group having 0 to 20 carbon atoms is preferred, for example, -P (R ^P ) ₂ ), (meth) acrylfluorenyl, (meth) acrylfluorenyloxy, (meth) acrylfluorenimino ((Meth) acrylfluorenylamino), a hydroxyl group, a thiol group, a carboxyl group, a phosphate group, a phosphonic acid group, a sulfonic acid group, a cyano group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.).

Further, among the groups listed in these substituents T, the above-mentioned substituent T may be further substituted.

When the substituent is an acidic group or a basic group, a salt thereof can be formed.

When a compound or even a substituent or a linking group includes an alkyl group, an alkylene group, an alkenyl group, an alkenylene group, an alkynyl group, an alkynylene group, etc., these may be cyclic or chain, and may be linear It may be branched, and may be substituted or unsubstituted as described above.

Each substituent specified in this specification may be substituted via the following linking group L within the range which exhibits the effect of this invention, and the linking group L may be interposed in the structure. For example, an alkyl group, an alkylene group, an alkenyl group, an alkenylene group, and the like may further include the following hetero linking group in the structure.

As the linking group L, a hydrocarbon linking group (an alkylene group having 1 to 10 carbon atoms (more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms), and an alkenylene group having 2 to 10 carbon atoms (carbon 2 to 6 atoms are more preferred, 2 to 4 are more preferred), alkynylene groups with 2 to 10 carbon atoms (2 to 6 carbon atoms are more preferred, 2 to 4 are more preferred), and 6 carbon atoms ~ 22 arylene (more preferably 6 to 10 carbon atoms), or a combination of these], hetero linking group [carbonyl (-CO-), thiocarbonyl (-CS-), ether (-O- ), Thioether group (-S-), imino group (-NR ^N- ), polythio group (the number of S is 1 to 8), imine linking group (R ^N -N = C <, -N = C (R ^N )-), sulfonyl (-SO _2- ), sulfinyl (-SO-), phosphate linking group (-OP (OH) (O) -O-), phosphonic linking group ( -P (OH) (O) -O-), or a combination of these], or a combination of these linking groups is preferred. In addition, when condensing to form a ring, the above-mentioned hydrocarbon linking group may be connected by suitably forming a double bond or a triple bond. The formed ring is preferably a 5-membered ring or a 6-membered ring. As the five-membered ring, a nitrogen-containing five-membered ring is preferred. When exemplified as a compound constituting the ring, examples include pyrrole, imidazole, pyrazole, indazole, indole, benzimidazole, piperidine, and imidazolidine. , Pyrazolidine, indololine, carbazole or derivatives thereof. Examples of the 6-membered ring include piperidine, morpholine, piperazine, and derivatives thereof. When aryl groups, heterocyclic groups, and the like are included, they may be a fluorene ring or a condensed ring, and may be substituted or unsubstituted in the same manner.

R ^N is a hydrogen atom or a substituent. As substituents, alkyl groups (1 to 24 carbon atoms are preferred, 1 to 12 are more preferred, 1 to 6 are further preferred, and 1 to 3 are particularly preferred), alkenyl (2 to 24 carbon atoms are preferred) Better, 2 ~ 12 is even better, 2 ~ 6 is even better, 2 ~ 3 is even better), alkynyl (carbon number 2 ~ 24 is better, 2 ~ 12 is better, 2 ~ 6 is further better Good, especially 2 to 3), aralkyl (7 to 22 carbon atoms is preferred, 7 to 14 is more preferred, 7 to 10 is more preferred), aryl (6 to 22 carbon atoms is more preferred) 6 to 14 is more preferable, and 6 to 10 is more preferable.

R ^P is a hydrogen atom, a hydroxyl group, or a substituent. As substituents, alkyl groups (1 to 24 carbon atoms are preferred, 1 to 12 are more preferred, 1 to 6 are further preferred, and 1 to 3 are particularly preferred), alkenyl (2 to 24 carbon atoms are preferred) Better, 2 ~ 12 is even better, 2 ~ 6 is even better, 2 ~ 3 is even better), alkynyl (carbon number 2 ~ 24 is better, 2 ~ 12 is better, 2 ~ 6 is further better Preferably, 2 to 3), aralkyl (7 to 22 carbon atoms is preferred, 7 to 14 is more preferred, 7 to 10 is more preferred), aryl (6 to 22 carbon atoms is more preferred) 6 to 14 is more preferred, 6 to 10 is particularly preferred), alkoxy (carbon number of 1 to 24 is preferred, 1 to 12 is more preferred, 1 to 6 is further preferred, 1 to 3 is particularly preferred), Alkenyloxy (2 to 24 carbon atoms is preferred, 2 to 12 is more preferred, 2 to 6 is more preferred, 2 to 3 is particularly preferred), alkynyloxy (2 to 24 carbon atoms is preferred) , 2 ~ 12 is more preferable, 2 ~ 6 is more preferable, 2 ~ 3 is more preferable, aralkoxy group (carbon number 7 ~ 22 is better, 7 ~ 14 is more preferable, 7 ~ 10 is more preferable ), Aryloxy (6 to 22 carbon atoms is preferred, 6 to 14 is more preferred, and 6 to 10 is particularly preferred).

The number of atoms constituting the linking group L is preferably from 1 to 36, more preferably from 1 to 24, even more preferably from 1 to 12, and even more preferably from 1 to 6. The number of connecting atoms of the linking group is preferably 10 or less, and more preferably 8 or less. The lower limit is 1 or more. The above-mentioned number of connected atoms refers to the minimum number of atoms that are connected to a path between predetermined structural parts and participate in the connection. For example, in the case of -CH ₂ -C (= O) -O-, the number of atoms constituting the linking group is 6, but the number of connecting atoms is 3.

Specifically, as a combination of a linking group, the following are mentioned. Oxycarbonyl (-OCO-), carbonate (-OCOO-), amido (-CONH-), urethane (-NHCOO-), urea (-NHCONH-), (poly) alkyleneoxy (-(Lr-O) x-), carbonyl (poly) oxyalkylene (-CO- (O-Lr) x-, carbonyl (poly) alkyleneoxy (-CO- (Lr-O) x -), Carbonyloxy (poly) alkyleneoxy (-COO- (Lr-O) x-), (poly) alkyleneimino (-(Lr-NR ^N ) x), alkylene (poly ) Iminoalkylene (-Lr- (NR ^N -Lr) x-), carbonyl (poly) iminoalkylene (-CO- (NR ^N -Lr) x-), carbonyl (poly) alkylene Imino (-CO- (Lr-NR ^N ) x-), (poly) ester (-(CO-O-Lr) x-,-(O-CO-Lr) x-,-(O-Lr- CO) x-,-(Lr-CO-O) x-,-(Lr-O-CO) x-), (poly) fluorenylamino (-(CO-NR ^N -Lr) x-,-(NR ^N -CO-Lr) x-,-(NR ^N -Lr-CO) x-,-(Lr-CO-NR ^N ) x-,-(Lr-NR ^N -CO) x-), etc. x is 1 or more An integer of 1 to 500 is preferable, and 1 to 100 is more preferable.

Lr is preferably an alkylene group, an alkenylene group, or a hydrocarbylene group. The carbon number of Lr is preferably from 1 to 12, more preferably from 1 to 6, and even more preferably from 1 to 3. The plurality of Lr and R ^N , R ^P , x and the like need not be the same. The orientation of the linking group is not limited to the above description, and can be understood as an orientation in which a predetermined chemical formula is appropriately combined.

<Container>

Regarding the siloxane resin composition of the present invention (whether it is a set or not), as long as corrosion resistance and the like are not a problem, it can be filled in any container, stored, transported, and used. In semiconductor applications, it is preferred that the cleanliness of the container is high and the elution of impurities is small. Examples of usable containers include "Clean bottle" series manufactured by AICELLO CORPORATION, "Pure bottle" manufactured by KODAMA PLASTICS Co., Ltd., and the like, but are not limited to these. The inner wall of the container and its accommodating portion is formed of a polyethylene resin, a polypropylene resin, a resin different from one or more resins selected from polyethylene-polypropylene resin, or a metal subjected to rust prevention and metal elution treatment. Is better.

<Filter out>

The siloxane resin composition of the present invention is preferably filtered with a filter in order to remove foreign matters, reduce defects, and the like. As long as it has been used for filtration applications and the like, it can be used without particular limitation. Examples include filters based on fluororesins such as PTFE (polytetrafluoroethylene); polyamide resins such as nylon; polyolefin resins (including high density and ultra-high molecular weight) such as polyethylene and polypropylene (PP) . Among these materials, polypropylene (including high-density polypropylene) and nylon are preferred.

The pore diameter of the filter is preferably about 0.1 to 7.0 μm, more preferably about 0.2 to 2.5 μm, more preferably about 0.2 to 1.5 μm, and even more preferably 0.3 to 0.7 μm. By setting this range, While filtering clogging is suppressed, fine foreign matters such as impurities or aggregates contained in the composition are reliably removed.

When using filters, different filters can be combined. In this case, the filtration in the first filter may be performed only once, or may be performed twice or more. When two or more filtrations are performed by combining different filters, the pore diameters of the second and subsequent pores are the same as or larger than those of the first pore diameter. Furthermore, a first filter having a different pore diameter within the above range may be combined. The pore size here can refer to the nominal value of the filter manufacturer. As commercially available filters, for example, various filters provided by Nihon Pall Manufacturing Ltd., ADVANTEC TOYO Roshi Kaisha, Ltd., Nihon Entegris K.K. (formerly Nihon Millipore Corporation), or KITZ MICRO FILTER CORPORATION can be selected.

The second filter can be formed from the same material as the first filter described above. The pore diameter of the second filter is suitable for about 0.2 to 10.0 μm, about 0.2 to 70 μm is preferable, and about 0.3 to 6.0 μm is more preferable. By setting it as this range, the foreign material can be removed in the state where the component particles contained in the mixed liquid remain.

For example, the filtration of the first filter may be performed using only the dispersion liquid, and the second filtration may be performed after mixing the other components.

This preferred embodiment of filtering is also the same as the filtering of the resist described later.

<Metal concentration>

The concentration of the metals (metal elements of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn) of the silicone resin composition of the present invention is preferably 5 ppm or less. With regard to the decrease in the concentration of such metals, the preferred embodiment is similar to the resist material described later. with.

<Formation of transparent hardened matter>

A method for forming a transparent hardened material (film) using the siloxane resin composition (ultraviolet-curable resin composition is preferred) of the present invention will be described by way of example. When the siloxane resin composition is used as a coating liquid, a micro gravure coating method, a spin coating method, a dip coating method, a curtain flow coating method, a roll coating method, a spray coating method, or a slit coating method can be used. A known method such as a cloth method is applied to the base substrate. After that, the film can be formed by pre-baking with a heating device such as a hot plate or an oven. The pre-baking is preferably performed at 50 to 150 ° C. for 30 seconds to 30 minutes. The film thickness after the pre-baking is preferably 0.1 to 15 μm.

After pre-baking, for example, using a stepper, mirror projection exposure machine (MPA), or parallel light lithography machine (hereinafter, PLA), an exposure machine is used to irradiate 10 to 4000 J / m with or without a desired mask. Around ² (converted to a wavelength of 365 nm). The exposure light source (active radiation) is not limited, and ultraviolet rays such as i-rays (wavelength 365nm), g-rays (wavelength 436nm) or h-rays (wavelength 405nm), KrF (wavelength 248nm) laser, or ArF (wavelength 193nm) laser can be used. Wait. After that, the film can also be subjected to post-exposure baking by heating the film at 150 to 450 ° C for about an hour by using a heating device such as a hot plate or an oven. In the present invention, it is preferable to use active radiation having a wavelength of 300 to 400 nm, and it is more preferable to use i-rays.

After patterned exposure, the non-exposed portion is dissolved by development, and a negative pattern can be obtained. As the developing method, a method such as spraying, dipping, or paddle immersion in the developing solution for 5 seconds to 10 minutes is preferable. Examples of the developer include those previously exemplified. After development, it is preferable to rinse the film with water. Then, it may be dried at 50 to 150 ° C. After that, the film is heated for about 1 hour at 120 to 280 ° C using a heating device such as a hot plate or an oven. By curing, a cured product (film) is obtained.

Transparent pixels and the like assembled on the solid-state imaging element can be formed on the substrate in this order.

The thickness of the obtained cured product (film) is preferably 0.1 to 10 μm. The leakage current is preferably 10 ^-6 A / cm ² or less, and the dielectric constant is preferably 6.0 or more.

The refractive index of the cured film of the siloxane resin composition of the present invention is preferably 1.6 or more, and more preferably 1.7 or more. There is no particular upper limit, but it is actually below 2.0. Regarding the refractive index, unless otherwise specified, it is based on the conditions measured in the examples described later.

The cured film of the siloxane resin composition of the present invention preferably has high transparency. The visible light transmittance is preferably 80% or more, more preferably 88% or more, and even more preferably 90% or more. There is no particular upper limit, but it is actually 99% or less. Regarding the transmittance of visible light, unless otherwise specified, it is assumed that it is based on the conditions measured in Examples described later.

The cured film obtained by curing the siloxane resin composition of the present invention can be suitably used particularly as a microlens or a transparent pixel of a solid-state imaging element.

<Method of Forming Microlens Array [See Figure 1]>

As one form of a method of forming a microlens, an example of a process of forming the microlens array 10 will be described. If necessary, the surface of the base material (element) 3 is filled with the unevenness on the transparent resin (planarizing film) 2 by a spin coating method in advance to flatten it. The lens material 1 is uniformly coated on the surface of the flattened substrate 3 (step 1). As the lens material, the above-mentioned siloxane resin composition can be used. A photoresist (photosensitive material) 4 is uniformly coated on the lens material 1 (step 2). As the photosensitive material, those commonly used in this kind of processing can be used. For the photoresist 4, ultraviolet rays were irradiated with a stepper using a reticle as a mask, and the space between the lenses was partially Line exposure. The photosensitive portion is decomposed and removed with a developing solution and patterned (step 3). The patterned resist 4a is heated, thereby obtaining a hemispherical pattern (hemispherical resist 4b) (step 4). At this time, the resist melts to become a liquid phase, and after changing to a hemispherical state, it changes to a solid phase. Thereafter, the lens material layer is etched by dry etching (step 5). Thereby, a microlens array 10 in which hemispherical lenses (microlenses 1a) are arranged can be formed.

As another embodiment of the lens array, a method of patterning a lens material by exposure without using the above-mentioned resist may be mentioned. In this embodiment, the patterned lens material is directly melted to obtain a hemispherical lens.

In addition, as the above-mentioned resist material, those that can be suitably used for such processing can be used. Examples include positive, negative, and both positive and negative photoresists. Specific examples of the positive resist include various photosensitive resin compositions such as vinyl cinnamate, cyclized polyisobutylene, azo-phenol resin, and diazolone-phenol resin. Specific examples of the negative resist include an azide-cyclized polyisoprene system, an azide-phenol resin system, and a chloromethyl polystyrene system. Specific examples of the positive-negative dual-purpose resist include various photosensitive resin compositions such as poly (p-butoxycarbonyloxystyrene). Among them, those disclosed in paragraph [Example 4] of Japanese Patent Laid-Open No. 1-142548 can be suitably used. Specifically, it is a photosensitive resin composition which contains a cresol novolak resin and naphthoquinonediazidesulfonate as a main component. More specifically, an esterification reaction product of 2,3,4,4'-tetrahydroxybenzophenone and naphthoquinone-1,2-diazide-5-sulfofluorene chloride (tri-ester) can be exemplified. Content is 85 mol%).

As the resist material, a positive resist containing a phenol resin is preferred. More specifically, a positive resist containing a resin having a repeating unit represented by the following formula (R-1) is mentioned.

In the formula, R ¹³ to R ¹⁶ each independently represent a hydrogen atom or an alkyl group (1 to 12 carbon atoms are preferred, 1 to 6 are more preferred, and 1 to 3 are particularly preferred). s represents an integer from 1 to 3. The molecular weight of the above-mentioned resin is not particularly limited, but in terms of polystyrene-equivalent weight average molecular weight, it is usually 1000 to 100 squares, preferably 2000 to 10 squares, and more preferably 3000 to 5 squares.

<Solid-state image sensor>

A solid-state imaging device according to a preferred embodiment of the present invention includes a transparent pixel and / or a microlens composed of a cured product of the siloxane resin composition of the present invention. The solid-state imaging element has a microlens array on a semiconductor light receiving element, and is assembled so that the microlens array is adjacent to a color filter. The light receiving element receives light that has passed through the transparent resin film, the lens, and the color filter in order and functions as an image sensor. Specifically, the transparent resin film functions as an anti-reflection film, improves the light collection efficiency of the microlenses, and the light efficiently collected by the microlenses is detected by a light receiving element through a color filter. These transfers work to detect all pixels of the light receiving element corresponding to each RGB light. Therefore, even when the pixels of the light receiving element and the lenses of the respective microlenses are arranged at a high density, an extremely sharp image can be obtained. As a transparent pixel intervening in the above-mentioned lens and RGB pixel arrangement, a cured product of the siloxane resin composition of the present invention can be suitably used.

As an example of a solid-state imaging element to which a lens array is applied, those described in Japanese Patent Laid-Open No. 2007-119744 can be cited. Specifically, a transfer electrode is provided between a CCD region or a photoelectric conversion portion formed on the surface of a semiconductor substrate, and a light-shielding film is formed thereon via an interlayer film. An interlayer insulation film based on BPSG (Boro-phospho-Silicate Glass), a passivation film, and a low-refractive-index transparent planarization film based on acrylic resin are laminated on the light-shielding film, and a combination of RGB is formed thereon Color filter. Further, a plurality of microlenses are formed by arranging a plurality of microlenses so as to be positioned above the photoelectric conversion portion through the protective film.

[Example]

Hereinafter, the present invention will be described in more detail with examples, but the present invention is not limited to these examples. In addition, in this embodiment, "part" and "%" are all based on quality unless otherwise specified.

<Synthesis example of dispersion composition A-1>

<Preparation of Water-dispersed Sol (AA-1) of Nuclear Particles>

7.6 kg of a titanium tetrachloride aqueous solution containing 7.8% by mass of titanium tetrachloride based on TiO ₂ conversion basis and 3.0 kg of ammonia water containing 15% by mass of ammonia were mixed to prepare a white slurry solution having a pH of 9.5. Next, the slurry was filtered, and then washed with ion-exchanged water to obtain 6.2 kg of a water-containing titanate filter cake having a solid content of 10% by mass.

Next, 7.1 kg of hydrogen peroxide water containing 35% by mass of hydrogen peroxide and 20.0 kg of ion-exchanged water were added to the filter cake, and the mixture was stirred and heated at 80 ° C. for 1 hour, and 28.9 kg of ion-exchanged water was added. Thus, 62.2 kg of a peroxytitanic acid aqueous solution containing 1% by mass of peroxytitanic acid based on TiO ₂ conversion was obtained. This aqueous solution of peroxytitanic acid was transparent yellow-brown and had a pH of 8.5.

Next, 3.0 kg of a cation exchange resin (manufactured by Mitsubishi Chemical Corporation) was mixed with 62.2 kg of the above-mentioned titanium peroxyacid aqueous solution, and potassium stannate containing 1% by mass of potassium stannate based on SnO ₂ conversion was slowly added thereto under stirring. 7.8 kg of aqueous solution. Next, the cation exchange resin introduced with potassium ions and the like was separated, and then heated in an autoclave at a temperature of 165 ° C. for 18 hours.

Next, the obtained mixed aqueous solution was cooled to room temperature, and then concentrated using an ultrafiltration membrane device (manufactured by Asahi Kasei Corporation., ACV-3010) to obtain a water-dispersed sol of core particles having a solid content of 10% by mass ( AA-1) (water-dispersed sol (AA-1) of metal oxide fine particles) 7.0 kg.

The water-dispersed sol (AA-1) of the metal oxide fine particles thus obtained was transparent milky white. When the content of the metal component contained in the metal oxide fine particles was measured, based on the oxide conversion of each metal component, TiO ₂ was 87.5% by mass, SnO ₂ was 10.6% by mass, and K ₂ O was 1.8% by mass. .

<Preparation of water-dispersed sol (AB-1) of surface-treated metal oxide particles>

To 7.0 kg of the water-dispersed sol (AA-1) of the nuclear particles obtained in the above, slowly adjust the pH to 7.0 with an aqueous potassium hydroxide solution, and slowly add a 3.6% concentration zirconium oxyzirconium chloride aqueous solution in terms of ZrO ₂ mass conversion. 1.5 kg was stirred and mixed at 40 ° C. for 1 hour to obtain an aqueous dispersion of metal oxide fine particles surface-treated with zirconium. At this time, the amount of zirconium was 5.0 mol% based on the oxide conversion basis with respect to the metal element contained in the core fine particles.

Next, 8.5 kg of the above-mentioned aqueous dispersion of the metal oxide fine particles surface-treated with zirconium was put into a spray-drying apparatus (NIRO ATOMIZER manufactured by NIRO Corporation) and spray-dried. Thereby, 0.9 kg of dry powder composed of surface-treated metal oxide fine particles having an average particle diameter of about 2 μm was obtained.

Next, 0.9 kg of the dried powder of the surface-treated metal oxide fine particles obtained in the above was fired at 500 ° C. for 2 hours in an air atmosphere to obtain surface-treated gold. Calcined powder of metal oxide fine particles 0.8kg. 0.2 kg of the calcined powder of the surface-treated metal oxide fine particles obtained in the above was dispersed in 0.2 kg of pure water, and 0.1 kg of a tartaric acid aqueous solution having a concentration of 28.6% and 0.06 kg of a KOH aqueous solution having a concentration of 50% by mass were added to the mixture. Stir. Next, alumina beads (high-purity alumina beads manufactured by TAIMEI ChemicalS Co., Ltd.) having a particle diameter of 0.1 mm were added to the stirred solution, and this was supplied to a wet powder mill (manufactured by KANSAI PAINT CO., LTD.). Batch type bench-type sand mill) for 180 minutes to perform powdering and dispersion treatment of the fired powder of the surface-treated metal oxide fine particles. Thereafter, alumina beads were separated and removed by a stainless steel filter having a pore diameter of 44 μm, and then 1.4 kg of pure water was added and stirred to obtain 1.7 kg of a surface-treated metal oxide fine particle aqueous dispersion having a solid content of 11% by mass. .

Next, after using an ultrafiltration membrane and washing with ion-exchanged water, 0.09 kg of an anion-exchange resin (manufactured by Mitsubishi Chemical Corporation: SANUPC) was added to perform deionization treatment, and then it was supplied to a centrifuge (manufactured by Hitachi Koki Co., Ltd.) CR-21G), and after processing at 12,000 rpm for 1 hour, ion-exchanged water was added to prepare 1.9 kg of a water-dispersed sol (AB-1) of surface-treated metal oxide fine particles having a solid content concentration of 10% by mass.

When measuring the content of metal components contained in the surface-treated metal oxide fine particles, based on the oxide conversion of each metal component, TiO ₂ was 82.6 mass%, SnO ₂ was 10.3 mass%, and ZrO ₂ was 4.9 mass%. K ₂ O was 2.2% by mass. The Ti / Zr ratio (elemental composition) at this time was 26. The number average particle diameter of the obtained metal oxide fine particles is about 5-20 nm.

<Preparation of methanol-dispersed sol (AC-1) of surface-treated metal oxide fine particles>

After adding 9.6 g of a cation exchange resin to 0.6 kg of the water-dispersed sol (AB-1) of the surface-treated metal oxide fine particles prepared in the above under stirring, the resin was separated to prepare a deionized surface-treated metal oxide fine particles. Water dispersion. Next, the above deionized table An aqueous dispersion of surface-treated metal oxide fine particles was obtained by using an ultrafiltration membrane device (a filtration membrane manufactured by Asahi Kasei Corporation., SIP-1013) to replace the dispersion medium from water with methanol and concentrating the surface-treated metal oxide fine particles. Methanol-dispersed sol (AC-1) 0.3 kg. As a result, the solid content concentration in the obtained methanol-dispersed sol was 30% by mass, and the water content was about 0.3% by mass.

<Preparation of Dispersion Composition A-1>

10.9 g (0.08 mol) of methyltrimethoxysilane, 63.5 g (0.32 mol) of phenyltrimethoxysilane, and methanol-dispersed sol AC-1 (solid content concentration 30% by mass, methanol 70) of surface-treated metal oxide fine particles (Mass%) 440.0 g and 370.0 g of DAA (diacetone alcohol) were placed in a reaction container, and while stirring, 32.0 g of water and 1.0 g of phosphoric acid were dropped into the solution so that the reaction temperature did not exceed 40 ° C. After the dropping, the flask was equipped with a distillation device, and the obtained solution was stirred and heated at a bath temperature of 105 ° C. for 2.5 hours, and the methanol produced by the hydrolysis was distilled while reacting. Thereafter, the solution was further heated and stirred at a bath temperature of 130 ° C. for 2 hours, and then cooled to room temperature to obtain a dispersion composition A-1.

(Example 1, Comparative Example 1)

Using the dispersion composition A-1 obtained in the above, the components are mixed or solvent substitution is performed so as to have the composition shown in the following table to obtain the siloxane resin compositions (thermosetting composition) of Examples and Comparative Examples. . Using each of the obtained thermosetting compositions of the examples and comparative examples, the following evaluations were performed.

<Test 100 series, 200 series, c01 ~ c06>

<Test 300 series>

(*) Omitted components in Table 1

(#) c06 No UV absorber added

PGMEA: propylene glycol monomethyl ether acetate

DAA: Diacetone alcohol

KAYARAD DPHA polymerizable compound (monomer) with unsaturated double bond

(Dipentaerythritol hexaacrylate)

Alkali-soluble resin (B-1) becomes 3 parts by mass based on 22 parts by mass of the siloxane resin. The system was adjusted (the total of both was 25 parts by mass) and added to thereby include the post-added resin B-1 in the table.

In the table, OXE01 indicates IRGACURE OXE01 (manufactured by BASF Ltd.), and OXE02 indicates IRGACURE OXE02 (manufactured by BASF Ltd.).

<Resolution test [1-1]>

An 8-inch silicon wafer with an undercoat layer was coated on the 8-inch silicon wafer with Act8 [trade name] manufactured by Tokyo Electron Limited by a spin coating method to obtain the film thickness after coating. Each curable composition was heated on a hot plate at 100 ° C. for 2 minutes to obtain a curable composition layer.

Next, the obtained hardenable composition layer was exposed through a mask using an i-ray step exposure device FPA-3000i5 + [trade name] (manufactured by Canon Marketing Japan Inc.) (exposure amount 50 to 1700 mJ / cm ² ) 1.1 μm square Bayer pattern.

Next, the hardenable composition layer after exposure was evaluated for developability using a developing device (Act8 [trade name] manufactured by Tokyo Electron Limited). As a developing solution, a tetramethylammonium hydroxide (TMAH) 0.3% aqueous solution was used, and spray development was performed at 23 ° C for 60 seconds. After that, a spin spray method using pure water was used for washing to obtain a pattern. The strain of the obtained pattern was evaluated with a scanning electron microscope (SEM) (S-4800H [trade name], manufactured by Hitachi High-Technologies) inspection (magnification: 20000 times). The lithographic performance was evaluated based on the following criteria. The resolution test was performed three times for each sample (hardening composition of each example and comparative example), and the results were combined to determine.

"5": The pattern is obvious and there is no residue.

"4": The pattern has a slightly tapered shape but no residue.

"3": The pattern is tapered, but there is less residue.

"2": The pattern has a tapered shape and there are many residues.

"1": Cannot be a pattern.

<Light resistance test [1-2]>

The composition was coated on a high-refractive-index glass (SFLD-6 [trade name] manufactured by SUMITA OPTICAL GLASS, Inc.) with a spin coater (H-360S [trade name] MIKASA CO., LTD.). Pre-baking was performed on a hot plate at 100 ° C for 2 minutes to obtain a coating film. Exposure was performed at 1000 mJ / cm ² by an ultra-high pressure mercury lamp "USH-500BY" [trade name] manufactured by USHIO INC. This coating film was heated at 200 ° C. for 5 minutes on a hot plate in an air atmosphere to obtain a cured film having a film thickness of 0.5 μm. The obtained cured film was irradiated with light of 500 square lxh for 50 hours using a light resistance tester (Xenon Weather Meter SX75 [trade name] manufactured by Suga Test Instruments Co., Ltd.), thereby performing a light resistance test. The temperature of the subject (the temperature in the test device) was set to 63 ° C. The relative humidity in the test apparatus was set to 50% RH. After the light resistance test, the transmittance of the cured film was measured, and the light resistance was evaluated according to the following criteria. The light resistance test was performed five times for each sample (the cured film of each of the examples and comparative examples), and the average value of the results obtained by removing the maximum and minimum values of the evaluation points three times was used.

"5": Transmissivity is less than ± 5%

"4": Transmissivity is more than ± 5% and less than ± 8%

"3": Transmissivity is over ± 8% to ± 10%

"2": Transmissivity is over ± 10% to ± 20%

"1": The transmissivity of the transmittance exceeds ± 20%

<Transparency test [1-3]>

~ Measurement of refractive index and visible transmittance ~

In the cured film used for evaluation of light resistance, the light transmittance of the cured film was measured at 400 nm to 700 nm using "MCPD-3000" manufactured by Otsuka Electronics Co., Ltd .. The minimum transmittance of 400 to 700 nm is used as the transmittance. The transparency test was performed five times for each sample (hardened films of each example and comparative example), and an average value of the results of three times in which the maximum value and the minimum value of the evaluation points were removed was used.

"5": transmittance exceeds 95%

"4": Transmittance exceeds 90% and less than 95%

"3": transmittance exceeds 85% and below 90%

"2": transmittance exceeds 80% and less than 85%

"1": 80% or less transmittance

In addition, at this time, the refractive index of a wavelength of 633 nm at a room temperature of 25 ° C. was measured using an ellipsometer (manufactured by Otsuka Electronics Co., Ltd.) with the same cured film sample. As a result, the refractive index of each of the cured films of the examples was about 1.8, and a desired high refractive index was achieved.

<Method for measuring Moire absorption coefficient>

A 1.00 × 10 ^-3 mol / L chloroform solution was prepared, and the absorbance was measured in the following order, thereby calculating the molar absorption coefficient of each ultraviolet absorber.

The chloroform solution adjusted to the above concentration was put in a glass tank having a width of 1 cm in the internal space, and the absorbance was measured using a UV-Vis-NIR spectrometer (Cary5000) [trade name] manufactured by Agilent Technologies, Inc. The measurement temperature was set at 25 ° C. The absorbance A obtained here was substituted into the following formula to calculate the Mohr absorption coefficient (mol ^-1 ‧L‧cm ^-1 ).

[Number 1]

In addition, in the above formula, ε represents a molar absorption coefficient (mol ^-1 ‧L · cm ^-1 ), A represents an absorbance, c represents a concentration (mol / L), and 1 represents an optical path length (cm). The concentration c was 1.00 × 10 ^-3 mol / L. The optical path length 1 corresponds to the width of the internal space of the above-mentioned glass tank, and thereby becomes 1 cm.

Matching: parts by mass

B-1: Alkali-soluble resin (B-1)

From the above results, it can be seen that the cured film obtained by using the siloxane resin composition of the present invention by using a specific ultraviolet absorber achieves good optical characteristics, has excellent resolution, and can exhibit high light resistance. performance.

(Example 1-2)

(Preparation of water-dispersed sol (E-1) of core particles)

7.60 kg of a titanium tetrachloride aqueous solution containing 7.75 mass% of titanium tetrachloride on a TiO ₂ conversion basis and 2.91 kg of ammonia water containing 15 mass% of ammonia were mixed, and these were dropped to ZrO ₂ over 24 hours while mixing these A mass conversion of 7.6 kg of a 1.23% concentration zirconium oxychloride octahydrate aqueous solution was prepared to prepare a white slurry solution having a pH of 8.8. Next, the slurry was diluted to 5 times with ion-exchanged water, and then filtered, and further washed with ion-exchanged water to obtain 5.2 kg of a hydrous titanic acid filter cake having a solid content of 10% by mass.

Next, 7.1 kg of hydrogen peroxide water and 20.0 kg of ion-exchanged water containing 35% by mass of hydrogen peroxide were added to the filter cake, and the mixture was stirred and heated at a temperature of 80 ° C for 1 hour, and ion-exchanged water was further added thereto 28.90 kg, thereby obtaining 61.39 kg of a titanium peroxyzirconate aqueous solution containing 1% by mass of titanium peroxyzirconate based on TiO ₂ conversion. This titanium peroxyzirconic acid aqueous solution was transparent yellow-brown and had a pH of 8.9.

Next, 4.00 kg of a cation exchange resin (manufactured by Mitsubishi Chemical Corporation) was mixed with 60.78 kg of the above-mentioned titanium peroxyzirconic acid aqueous solution, and stannic acid containing 1% by mass of potassium stannate based on SnO ₂ conversion was slowly added thereto under stirring. Potassium aqueous solution 8.01kg. Next, the cation exchange resin introduced with potassium ions and the like was separated and then heated in an autoclave at a temperature of 168 ° C for 20 hours.

Next, the obtained mixed aqueous solution was cooled to room temperature, and then concentrated using an ultrafiltration membrane device (manufactured by Asahi Kasei Corporation., ACV-3010) to obtain a water-dispersed sol of core particles having a solid content of 10% by mass ( Water-dispersed sol (E-1) of metal oxide fine particles) 6.89 kg. The water-dispersed sol (E-1) of the metal oxide fine particles thus obtained was transparent milky white. When measuring the content of metal components contained in the metal oxide fine particles, based on the oxide conversion of each metal component, TiO ₂ was 90.0% by mass, SnO ₂ was 4.2% by mass, K ₂ O was 0.5% by mass, and ZrO ₂ is 5.3% by mass.

(Preparation of Methanol-dispersed Sol (EM-1) of Metal Oxide Particles)

7.51 kg of the water-dispersed sol (E-1) of the metal oxide fine particles described above were spray-dried by a spray dryer. Thereby, 0.90 kg of dry powder composed of metal oxide fine particles having an average particle diameter of about 2 μm was obtained. Next, 0.90 kg of the dry powder of the metal oxide fine particles obtained in the above was fired at 500 ° C. for 2 hours in an air atmosphere to obtain 0.90 kg of a fired powder of the metal oxide fine particles. 0.20 kg of the calcined powder of the metal oxide fine particles obtained in the above was dispersed in 0.18 kg of pure water, and 0.13 kg of an aqueous tartaric acid solution at a concentration of 28.6% and 0.06 kg of an KOH aqueous solution at a concentration of 50% by mass were added to the mixture. Stir. Next, alumina beads (high-purity alumina beads manufactured by TAIMEI Chemicals Co., Ltd.) having a particle diameter of 0.1 mm were added to the solution after stirring, and this was supplied to a wet powder mill (manufactured by KANSAI PAINT CO., LTD.). Batch type bench-type sand mill) for 180 minutes for powdering and dispersion treatment of the fired powder of the metal oxide fine particles. Thereafter, alumina beads were separated and removed by a stainless steel filter having a pore diameter of 44 μm, and then 1.39 kg of pure water was added and stirred to obtain 1.70 kg of an aqueous dispersion of metal oxide fine particles having a solid content of 11.0% by mass. Next, after washing with ion exchange water using an ultrafiltration membrane, 0.09 kg of an anion exchange resin (manufactured by Mitsubishi Chemical Corporation: SANUPC) was added to perform deionization treatment, and it was then supplied to a centrifuge (CR-manufactured by Hitachi Koki Co., Ltd.) 21G), and after processing at 11,000 rpm for 1 hour, ion-exchanged water was added to prepare 1.86 kg of a water-dispersed sol (EZ-1) of metal oxide fine particles having a solid content concentration of 10% by mass.

Further, when the content of the metal component contained in the metal oxide fine particles was measured, each metal component was calculated on an oxide conversion basis, TiO ₂ was 88.9% by mass, SnO ₂ was 5.3% by mass, ZrO ₂ was 5.3% by mass, and K ₂ O is 0.5% by mass. (The TiO ₂ is 79.87 g / mol, the ZrO ₂ is 123.2 g / mol, and the Ti / Zr (molar ratio) in the above blend is 26.)

Next, after cooling, the ultra-filtration membrane device (filtration membrane manufactured by Asahi Kasei Corporation., SIP-1013) was used to replace the dispersion medium of the water-dispersed sol (EZ-1) of the metal oxide fine particles from water to methanol to obtain a metal. The methanol-dispersed sol (EM-1) of the oxide fine particles was 0.32 kg. As a result, the solid content concentration in the obtained methanol-dispersed sol (EM-1) was about 30% by mass, and the water content was 0.28% by mass.

(Preparation of methanol-dispersed sols (EM-2 and EM-3) of metal oxide fine particles with a changed ZrO ₂ ratio)

In addition to adjusting the amount of zirconium oxychloride added when preparing the water-dispersed sol (E-1) of the nuclear fine particles, a metal oxide having a different amount of ZrO ₂ was prepared according to the preparation of the water-dispersed sol (E-1) of the nuclear fine particles. Dispersions of fine particles (EM-2) and (EM-3). The Ti / Zr (molar ratio) of the particles contained in each dispersion (sol) is shown in Tables 1-3.

(Preparation of a methanol-dispersed sol (EM-4 ~ EM-7) of metal oxide fine particles with an average particle size changed)

By adjusting the heat treatment temperature and treatment time of the metal oxide particles, different preparations were made. Methanol-dispersed sols (EM-4) to (EM-7) of metal oxide fine particles having an average particle diameter. The number average particle diameter (Mn) of the particles contained in each dispersion (sol) is shown in Tables 1-3. The measurement method is as described above.

(Preparation of Silicic Acid Solution)

After diluting 0.31 kg of commercially available water glass (manufactured by AGC Si-Tech. Co., Ltd.) with pure water, debasing was performed using a cation exchange resin (manufactured by Mitsubishi Chemical Corporation) to obtain 2.0 containing SiO ₂ conversion basis. A mass% gallic acid silicic acid aqueous solution 3.00kg. The pH of the aqueous silicic acid solution was 2.3.

(Preparation of methanol-dispersed sol (CSTM-1) of core-shell metal oxide particles)

To 1.80 kg of the metal oxide fine particles in methanol-dispersed sol (EM-1), 12.3 kg of pure water was added and heated to a temperature of 90 ° C. while stirring, and then 2.39 kg of the aforementioned silicic acid aqueous solution was slowly added thereto. After the addition of the silicic acid aqueous solution, the mixture was further aged for 10 hours with stirring while maintaining the temperature at 90 ° C. At this time, the amount of the composite oxide coated with the metal oxide fine particles was 12 parts by mass based on 100 parts by mass of the surface-treated particles.

Next, this mixed solution was put into an autoclave (manufactured by Trirtsu Techno) and subjected to a heat treatment at a temperature of 165 ° C for 18 hours. Next, the obtained mixed solution was cooled to room temperature, and then concentrated using an ultrafiltration membrane (manufactured by Asahi Kasei Corporation., SIP-1013) to obtain a water-dispersed sol having a solid content of 10.0% by mass. As a result, a water-dispersed sol (CST-1) of core-shell type metal oxide particles coated with the surface of the metal oxide particles with an oxide containing silicon was obtained.

When measuring the content of metal components contained in the obtained core-shell metal oxide fine particles, based on the oxide conversion of each metal component, TiO ₂ was 86.3% by mass, SnO ₂ was 5.1% by mass, and ZrO ₂ was 5.1 The mass% and K ₂ O were 0.5 mass%. (TiO ₂ was 79.87 g / mol, ZrO ₂ was 123.2 g / mol, and the Ti / Zr (molar ratio) in the above blending was 26).

Next, after cooling, the dispersion medium was replaced with water by using an ultrafiltration membrane device (a filtration membrane manufactured by Asahi Kasei Corporation, SIP-1013) to obtain a methanol-dispersed sol (CSTM-1) of core-shell type metal oxide fine particles. ). As a result, the solid content concentration of the obtained methanol-dispersed sol (CSTM-1) was about 30% by mass, and the water content was 0.28% by mass.

<Preparation of Dispersion Composition E-1>

10.9 g (0.08 mol) of methyltrimethoxysilane, 63.5 g (0.32 mol) of phenyltrimethoxysilane, and a methanol-dispersed sol EM-1 of metal oxide fine particles (solid content concentration: 30% by mass, methanol: 70% by mass) ) 440.0 g and 370.0 g of DAA were put into the reaction vessel, and while stirring, 32.0 g of water and 1.0 g of phosphoric acid were dropped into the solution so that the reaction temperature did not exceed 40 ° C. After the dropping, a distillation apparatus was installed in the flask, and the obtained solution was heated and stirred at a bath temperature of 105 ° C. for 2.5 hours, thereby reacting while removing methanol produced by hydrolysis and distilling. Thereafter, the solution was further heated and stirred at a bath temperature of 130 ° C for 2 hours, and then cooled to room temperature to obtain a dispersed composition E-1 (solid content of 35.8% by mass, and the concentration of metal oxide particles in the solid content of the composition). 64% by mass).

<Preparation of dispersion composition (E-2 to E-7)>

In the preparation of the dispersion composition E-1, the metal particle-containing material used was changed to something other than Table 1-4, and dispersion compositions E-2 to E were prepared in the same manner as in the preparation of the dispersion composition E-1. -7.

<Preparation of dispersion composition C-1>

In the preparation of the dispersion composition E-1, the metal-containing material used was changed to other than CSTM-1, and the dispersion composition C-1 was prepared in the same manner as in the preparation of the dispersion composition E-1.

<Test 400 series>

The dispersion composition and / or ultraviolet absorber used were changed to those shown in Table 1-4, and a siloxane resin composition was obtained in the same manner as in Example 1. Using the obtained siloxane resin composition, the resolution, light resistance, and transparency were evaluated in the same manner as in Example 1.

The silicone resin compositions of Tests 401 to 409 shown in Table 1-4 show good resolution, light resistance, and transparency compared to the silicone resin composition of the Comparative Example shown in Table 1-2. . As a result, as long as Ti / Zr is 1 to 40 in Zr-containing titanium oxide (metal oxide fine particles), whether the shape is core-shell type (Test 101-302) or non-core-shell type (Test 401-408), Both show good results. In addition, the test 409 coated with silicon oxide also showed good results.

(Example 2)

In the preparation of the dispersion composition A-1, a siloxane resin composition was produced in the same manner as in Test 101 of Example 1 except that ethyltrimethoxysilane was used instead of methyltrimethoxysilane. In addition, a siloxane resin composition was produced in the same manner as in Example 1 except that a part of methyltrimethoxysilane was changed to tetramethoxysilane (both methyltrimethoxysilane and tetramethoxysilane were used simultaneously). The above-mentioned tests of resolution, light resistance, and applicability were performed using these silicone resin compositions, and it was confirmed that good results were obtained.

(Example 3)

In the preparation of the above-mentioned dispersed composition A-1, the composition ratio of TiO ₂ and ZrO ₂ was adjusted to other than the following Table 2 and each sample was prepared in the same manner as the dispersed composition A-1 (dispersed composition A-2 to A- 5).

A siloxane resin composition was prepared in the same manner as in Test 101 of Example 1 except that each of the above-mentioned dispersed compositions was used, and tests similar to those in Table 1 were performed. However, for the light resistance test [1-2], the light resistance test [1-2a] was performed under more severe conditions. Specifically, with respect to the conditions of the above-mentioned light resistance test [1-2], the temperature (inside the device) around the subject was set to 63 ° C, and the humidity was set to 90% RH. The light irradiation time was set to 50 hours.

As a result, the evaluation of the resolution test [1-1] and the evaluation of the transparency test [1-3] all showed good results. In the normal light resistance test [1-2], all the samples also showed approximately good results. On the other hand, in light resistance [1-2a] under severe conditions, a significant difference was confirmed as described below.

From the above results, it is understood that, in a preferred embodiment of the present invention, by using the Ti / Zr ratio of the metal oxide fine particles in an appropriate range, particularly high light resistance can be achieved when used in a severe environment.

(Example 4)

With respect to the dispersion composition A-1, the concentration of the metal oxide fine particles was changed to 40% by mass, 50% by mass, and 55% by mass, respectively, and the same test was performed. The refractive indices of the cured films were 1.67, 1.73, and 1.75, respectively. In addition, it was confirmed that good performance was shown in each item. On the other hand, when the concentration of the metal oxide fine particles is set to 10% by mass, the refractive index of the cured film falls significantly below 1.6. On the other hand, at this concentration, even if an ultraviolet absorber having a Molar absorption coefficient that does not have the Molar absorption coefficient specified in the present invention is used, no problems of resolution, light resistance, and transparency occur. From this result, it is understood that the ultraviolet absorber used in the present invention exhibits its usefulness when a considerable amount of metal oxide fine particles are used.

(Example 5)

The siloxane resin compositions prepared in the above-mentioned tests 101, 123, 124, and 201 were applied to a silicon wafer, respectively. Thereafter, pre-baking (100 ° C, 2 min) and post-baking (230 ° C, 10 min) were performed to form a coating film (lens material 1) having a film thickness of 1.1 µm (Fig. 1 (1)). Then, FHi-4750 ([trade name] FUJIFILM Electronic Materials FFEM CO., LTD. Resist solution) was applied so that the dry film thickness became 1.5 μm, and heated at 90 ° C. on a hot plate 1 Minutes to form a photoresist film 4 (FIG. 1 (2)). This photoresist film 4 was passed through a mask having a square lattice pattern with a side of 1.4 μm and a gap between the patterns of 0.35 μm, and an i-ray stepper (trade name: FPA-3000i5 +, Canon Marketing Japan Inc. (Manufactured) and exposed at 300 mJ / cm ² .

The alkaline development solution HPRD-429E (manufactured by FUJIFILM Electronic Materials CO., LTD.) Was used to perform a paddle development of the photoresist film at room temperature for 60 seconds, and then the solution was spin-coated with pure water. Rinse for 20 seconds. Thereafter, the substrate was further washed with pure water, and then the substrate was dried at a high speed to form a resist pattern (patterned photoresist 4a) (Fig. 1 (3)). When patterned, the separation width was 238.7 nm. The hot plate was subjected to a post-baking treatment at 145 ° C for 120 seconds, followed by a post-baking treatment at 160 ° C for 120 seconds, and a post-baking treatment at 175 ° C for 120 seconds to shape the resist into a lens. Shape (hemispherical shape) (Figure 1 (4)).

The substrate obtained as described above was subjected to a dry etching process using a dry etching apparatus (manufactured by Hitachi High-Technologies Corporation: U-621) under the following conditions to form a lens array (Fig. 1 (5)). The height of the lens body is 380 nm.

‧RF power: 800W

‧Antenna Bias: 400W

‧Wafer Bias: 400W

‧Internal pressure: 2Pa

‧Substrate temperature: 50 ℃

‧Type and flow of mixed gas: CF ₄ / C ₄ F ₆ / Ar = 350/25 / 800ml / min

‧Photoresist Etching Speed: 140nm / min

As a result of confirming the characteristics of each of the microlens array test bodies, it was confirmed that the excellent performance suitable for the use of the solid-state imaging element was shown.

Claims (59)

A siloxane resin composition containing metal-containing particles, a siloxane resin, a polymerization initiator, and an ultraviolet absorber, wherein the solid content of the composition contains the above-mentioned metal in an amount of 40% by mass or more and 80% by mass or less. The particles, as elements constituting the above-mentioned metal-containing particles, contain Ti and Zr, and Ti / Zr is 3 or more and 30 or less. The molar absorption coefficient of the ultraviolet absorber at 365 nm is 5000 mol ^-1 . L. Above cm ^-1 , the molar absorption coefficient at 400 nm is 3500 mol ^-1 . L. cm ^-1 or less. The siloxane resin composition according to item 1 of the scope of the patent application, wherein the element constituting the metal-containing particles contains a material selected from the group consisting of Ti, Ta, W, Y, Ba, Hf, Zr, Sn, Nb, and V. And Si metal. The siloxane resin composition according to item 1 of the scope of patent application, wherein the refractive index of the metal-containing particles is 1.75 or more and 2.90 or less. The siloxane resin composition according to item 1 of the scope of patent application, wherein the number average particle diameter of the metal-containing particles is 3 nm or more and 30 nm or less. The silicone resin composition according to item 1 of the scope of the patent application, wherein the refractive index of the cured film that hardens the silicone resin composition is 1.6 or more and 2.0 or less. The siloxane resin composition according to any one of claims 1 to 5 of the scope of application for a patent, which is a UV-curable resin composition. The siloxane resin composition according to any one of claims 1 to 5 of the patent application scope, further comprising a polymerizable compound. The siloxane resin composition according to any one of claims 1 to 5, wherein the ultraviolet absorber is selected from a benzotriazole compound, a benzophenone compound, a triazine compound, and a diene compound. Group consisting of benzodithiol and avobenzone compounds. The siloxane resin composition according to any one of claims 1 to 5, wherein the polymerization initiator is selected from an organic halogen compound, an oxadiazole compound, a carbonyl compound, a ketal compound, and a benzoin compound. , Acridine compound, organic peroxide, azo compound, coumarin compound, azide compound, metallocene compound, hexaarylbisimidazole compound, organic boric acid compound, disulfonic acid compound, oxime compound, onium salt compound, Hydroxyacetophenone compound, aminoacetophenone compound, fluorenylphosphine oxide compound, trihalomethyltriazine compound, benzyldimethylketal compound, α-hydroxyketone compound, α-aminoketone compound, fluorenylphosphine Compounds, phosphine oxide compounds, triarylimidazole dimers, onium compounds, benzothiazole compounds, benzophenone compounds, cyclopentadiene-benzene-iron complexes, halomethyloxadiazole compounds, 3 -An aryl-substituted coumarin compound, an α-aminoalkylphenyl ketone compound, and a benzoate compound. The siloxane resin composition according to any one of claims 1 to 5, wherein the siloxane resin is a hydrolysis-condensation reaction product of an alkoxysilane compound. The siloxane resin composition according to any one of claims 1 to 5 of the scope of patent application, wherein the siloxane resin composition is used in an amount of 1 part by mass to 60 parts by mass based on 100 parts by mass of the metal-containing particles. The siloxane resin composition according to any one of claims 1 to 5, wherein the solid content contains the ultraviolet absorber in an amount of 0.01% by mass or more and 20% by mass or less. The siloxane resin composition according to any one of claims 1 to 5, wherein the siloxane resin is obtained by performing a hydrolysis condensation reaction in the presence of the metal-containing particles. The siloxane resin composition according to any one of claims 1 to 3 and 5, in which the number-average particle diameter of the metal-containing particles is 1 nm or more and 200 nm or less. The siloxane resin composition according to any one of claims 1 to 3 and 5, in which the number-average particle diameter of the metal-containing particles is 1 nm or more and 50 nm or less. The siloxane resin composition according to any one of claims 1 to 5, wherein the metal-containing particles are core-shell particles. The siloxane resin composition according to any one of claims 1 to 5, wherein the metal-containing particles are core-shell particles and the core contains Ti or Sn. The siloxane resin composition according to any one of claims 1 to 5, wherein the metal-containing particles are core-shell particles and the core contains Ti. The siloxane resin composition according to any one of claims 1 to 5, wherein the metal-containing particles are core-shell particles and the core contains titanium oxide. The siloxane resin composition according to any one of claims 1 to 5, wherein the metal-containing particles are core-shell particles, and Zr is contained in the shell. The siloxane resin composition according to any one of claims 1 to 5, wherein the metal-containing particles are core-shell particles, and the shell contains zirconia. The siloxane resin composition according to any one of claims 1 to 5, wherein the Ti / Zr is 3 or more and 20 or less. The siloxane resin composition according to any one of claims 1 to 5, wherein the Ti / Zr is 4 or more and 9 or less. The siloxane resin composition according to any one of claims 1 to 5, wherein the polymerization initiator is an oxime or aminoacetophenone. The siloxane resin composition according to any one of claims 1 to 5, further comprising a polymerizable compound, wherein the polymerizable compound is any one of formulas (MO-1) to (MO-6) The compound represented by one, R = , , , -OH, -CH ₃ T =-(CH2) _m -,-OCH ₂ -,-O (CH ₂ ) ₂ -,-O (CH ₂ ) ₃ -,-O (CH ₂ ) _4- Z = In the formula, n is 0 to 14 and m is 1 to 8 respectively. In a molecule, a plurality of R, T and Z may be the same or different from each other. When T is an oxyalkylene group, the carbon of the oxyalkylene group is The terminal on the atom side is bonded to R, and at least one of R is a polymerizable group. The siloxane resin composition according to any one of claims 1 to 5, further comprising a solvent, wherein the solvent is diacetone alcohol. The siloxane resin composition according to any one of claims 1 to 5, further comprising a solvent, wherein the solvent is diacetone alcohol and propylene glycol monomethyl ether acetate. A siloxane resin composition containing metal-containing particles, a siloxane resin, a polymerization initiator, and an ultraviolet absorber, wherein the solid content of the composition contains the above-mentioned metal in an amount of 40% by mass or more and 80% by mass or less. The particles contain 0.01% by mass or more and 20% by mass or less of the above-mentioned ultraviolet absorber in a solid content, and the molar absorption coefficient of the ultraviolet absorber at 365 nm is 5000 mol ^-1 . L. Above cm ^-1 , the molar absorption coefficient at 400 nm is 3500 mol ^-1 . L. cm ^-1 or less. The siloxane resin composition according to item 28 of the scope of application for a patent, wherein the element constituting the metal-containing particles contains a material selected from the group consisting of Ti, Ta, W, Y, Ba, Hf, Zr, Sn, Nb, and V. And Si metal. The siloxane resin composition according to item 28 of the scope of application for a patent, wherein the refractive index of the metal-containing particles is 1.75 or more and 2.90 or less. The siloxane resin composition according to item 28 of the scope of application for a patent, wherein the number average particle diameter of the metal-containing particles is 3 nm or more and 30 nm or less. The silicone resin composition according to item 28 of the scope of application for a patent, wherein the refractive index of the cured film that hardens the silicone resin composition is 1.6 or more and 2.0 or less. The siloxane resin composition according to any one of claims 28 to 32 of the scope of application for a patent, wherein the element constituting the metal-containing particles includes Ti and Zr, and Ti / Zr is 3 or more and 30 or less. The siloxane resin composition according to any one of claims 28 to 32 of the scope of application for a patent, which is an ultraviolet curable resin composition. The siloxane resin composition according to any one of claims 28 to 32 in the scope of application for a patent, further comprising a polymerizable compound. The siloxane resin composition according to any one of claims 28 to 32, wherein the ultraviolet absorber is selected from a benzotriazole compound, a benzophenone compound, a triazine compound, and a diene compound. Group consisting of benzodithiol and avobenzone compounds. The siloxane resin composition according to any one of claims 28 to 32 in the patent application scope, wherein the polymerization initiator is selected from the group consisting of an organic halogen compound, an oxadiazole compound, a carbonyl compound, a ketal compound, and a benzoin compound. , Acridine compound, organic peroxide, azo compound, coumarin compound, azide compound, metallocene compound, hexaarylbisimidazole compound, organic boric acid compound, disulfonic acid compound, oxime compound, onium salt compound, Hydroxyacetophenone compound, aminoacetophenone compound, fluorenylphosphine oxide compound, trihalomethyltriazine compound, benzyldimethylketal compound, α-hydroxyketone compound, α-aminoketone compound, fluorenylphosphine Compounds, phosphine oxide compounds, triarylimidazole dimers, onium compounds, benzothiazole compounds, benzophenone compounds, cyclopentadiene-benzene-iron complexes, halomethyloxadiazole compounds, 3 -An aryl-substituted coumarin compound, an α-aminoalkylphenyl ketone compound, and a benzoate compound. The siloxane resin composition according to any one of items 28 to 32 of the scope of application for a patent, wherein the siloxane resin is a hydrolysis-condensation reaction product of an alkoxysilane compound. The siloxane resin composition according to any one of claims 28 to 32 in the scope of application for a patent, wherein the siloxane resin composition is used in an amount of 1 part by mass to 60 parts by mass based on 100 parts by mass of the metal-containing particles. The siloxane resin composition according to any one of claims 28 to 32 in the scope of application for a patent, wherein the siloxane resin is obtained by performing a hydrolysis condensation reaction in the presence of the metal-containing particles. According to the siloxane resin composition according to any one of claims 28 to 30 and 32 of the scope of application for a patent, the number average particle diameter of the metal-containing particles is 1 nm or more and 200 nm or less. The siloxane resin composition according to any one of claims 28 to 30 and 32, wherein the number-average particle diameter of the metal-containing particles is 1 nm or more and 50 nm or less. The siloxane resin composition according to any one of claims 28 to 32 in the scope of the patent application, wherein the metal-containing particles are core-shell particles. The siloxane resin composition according to any one of claims 28 to 32 in the scope of the patent application, wherein the metal-containing particles are core-shell particles and the core contains Ti or Sn. The siloxane resin composition according to any one of claims 28 to 32 in the scope of the patent application, wherein the metal-containing particles are core-shell particles and the core contains Ti. The siloxane resin composition according to any one of claims 28 to 32 in the scope of the application patent, wherein the metal-containing particles are core-shell particles and the core contains titanium oxide. The siloxane resin composition according to any one of claims 28 to 32 in the scope of the patent application, wherein the metal-containing particles are core-shell particles, and Zr is contained in the shell. The siloxane resin composition according to any one of claims 28 to 32 in the scope of the application patent, wherein the metal-containing particles are core-shell particles and the shell contains zirconia. The siloxane resin composition according to any one of claims 28 to 32 in the scope of the patent application, wherein the Ti / Zr is 1 or more and 30 or less. The siloxane resin composition according to any one of claims 28 to 32 in the scope of the patent application, wherein the Ti / Zr is 3 or more and 20 or less. The siloxane resin composition according to any one of claims 28 to 32 in the scope of the patent application, wherein the Ti / Zr is 4 or more and 9 or less. The siloxane resin composition according to any one of items 28 to 32 of the scope of application for a patent, wherein the polymerization initiator is an oxime or aminoacetophenone. The siloxane resin composition according to any one of claims 28 to 32 in the patent application scope, further comprising a polymerizable compound, wherein the polymerizable compound is any one of formulas (MO-1) to (MO-6) The compound represented by one, R = , , , -OH, -CH ₃ T =-(CH ₂ ) _m -,-OcH ₂ -,-O (CH ₂ ) ₂ -,-O (CH ₂ ) ₃ -,-O (CH ₂ ) _4- Z = In the formula, n is 0 to 14 and m is 1 to 8 respectively. In a molecule, a plurality of R, T and Z may be the same or different from each other. When T is an oxyalkylene group, the carbon of the oxyalkylene group is The terminal on the atom side is bonded to R, and at least one of R is a polymerizable group. The siloxane resin composition according to any one of claims 28 to 32 of the scope of application for a patent, further comprising a solvent, wherein the solvent is diacetone alcohol. The siloxane resin composition according to any one of claims 28 to 32 of the scope of application for a patent, further comprising a solvent, wherein the solvent is diacetone alcohol and propylene glycol monomethyl ether acetate. A transparent hardened material, which is obtained by hardening the siloxane resin composition described in any one of claims 1 to 55 of the scope of patent application. A transparent pixel is composed of a transparent hardened object as described in the 56th aspect of the patent application. A microlens composed of the transparent hardened object described in the 56th patent application. A solid-state imaging device includes a transparent pixel as described in claim 57, a microlens as described in claim 58 or both.