WO2016052307A1

WO2016052307A1 - Siloxane resin composition, transparent cured product using said composition, transparent pixel, microlens, and solid-state imaging element

Info

Publication number: WO2016052307A1
Application number: PCT/JP2015/076971
Authority: WO
Inventors: 祐継室; 高桑　英希; 久保田　誠; 翔一中村; 貴規田口; 上村　哲也
Original assignee: 富士フイルム株式会社
Priority date: 2014-10-03
Filing date: 2015-09-24
Publication date: 2016-04-07
Also published as: JP6013422B2; TW201614008A; JP2016074797A

Abstract

Provided is a siloxane resin composition containing a siloxane resin, mesityl oxide, a solvent, and metal-containing particles. Also provided are a transparent cured product, a transparent pixel, a microlens, and a solid-state imaging element that use the siloxane resin composition.

Description

Siloxane resin composition, transparent cured product, transparent pixel, microlens, and solid-state imaging device using the same

The present invention relates to a siloxane resin composition, a transparent cured product using the siloxane resin composition, a transparent pixel, a microlens, and a solid-state imaging device.

As a transparent material incorporated in a solid-state imaging device or the like, a wafer level lens or a microlens can be given. Alternatively, an antireflection film covering these, a transparent pixel located under the film, a transparent insulating film, a planarizing film, and the like can be given. Each member is required to have characteristics corresponding to its function. For example, the above-described microlens and transparent pixel are required to have a high refractive index and a high light transmittance. Also, in recent years, in order to realize ever-increasing miniaturization of elements, each material is required to have manufacturability suitable for fine processing accuracy.
Specifically, a technique for introducing high refractive index particles into a transparent resin has been studied. Patent Document 1 proposes a positive photosensitive resin composition in which particles such as titanium oxide are contained in polyimide.

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. It can be used not only as positive type but also as thermosetting resin or negative type photosensitive resin, and can also be suitably applied to micro-processing of micro lenses and transparent pixels, and is cured as necessary. An object of the present invention is to provide a siloxane resin composition capable of improving the characteristics of a film. Another object of the present invention is to provide a transparent cured product, a transparent pixel, a microlens, and a solid-state imaging device using the siloxane resin composition.

The above problems have been solved by the following means.
[1] A siloxane resin composition containing metal-containing particles, a siloxane resin, mesityl oxide, and a solvent.
[2] The siloxane resin composition according to [1], wherein the content of the mesityl oxide is 0.01% by mass or more and 15% by mass or less.
[3] The siloxane resin composition according to [1] or [2], wherein the content of the mesityl oxide is 0.09% by mass or less.
[4] The siloxane resin composition according to any one of [1] to [3], wherein the siloxane resin is a hydrolysis condensation reaction product of an alkoxysilane compound.
[5] The siloxane resin composition according to any one of [1] to [4], which contains 30 to 80 parts by mass of a siloxane resin with respect to 100 parts by mass of the metal-containing particles.
[6] The siloxane resin composition according to any one of [1] to [5], wherein the content of the metal-containing particles in the solid component of the siloxane resin composition is 10% by mass or more and 90% by mass or less. .
[7] As an element constituting the metal-containing particles, a metal selected from Ti, Ta, W, Y, Ba, Hf, Zr, Sn, Nb, V, and Si is contained. The siloxane resin composition according to any one of the above.
[8] As an element constituting the metal-containing particles, Ti and Zr are contained. In the elements constituting the metal-containing particles, the ratio of Ti to Zr, Ti / Zr, in the elemental composition ratio is 1 to 40. The siloxane resin composition according to any one of [1] to [7].
[9] As an element constituting the metal-containing particles, Ti and Zr are contained. In the elements constituting the metal-containing particles, the ratio of Ti to Zr, Ti / Zr, in terms of elemental composition ratio is 4 to 12 The siloxane resin composition according to any one of [1] to [8].
[10] The siloxane resin composition according to any one of [1] to [9], wherein the metal-containing particles have a number average particle diameter of 5 nm to 30 nm.
[11] The siloxane resin composition according to any one of [1] to [10], wherein the solvent contains diacetone alcohol.
[12] The siloxane resin composition according to any one of [1] to [11], wherein the siloxane resin is obtained by a hydrolytic condensation reaction in the presence of the metal-containing particles.
[13] A transparent cured product obtained by curing the siloxane resin composition according to any one of [1] to [12].
[14] A transparent pixel comprising the transparent cured product according to [13].
[15] A microlens comprising the transparent cured product according to [13].
[16] A solid-state imaging device comprising the transparent pixel according to [14] and / or the microlens according to [15].

In the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what does not have a substituent and what has a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In addition, “radiation” in the present specification means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams, and the like. In the present invention, light means actinic rays or radiation. Unless otherwise specified, “exposure” in this specification is not limited to exposure with an emission line spectrum of a mercury lamp, far ultraviolet rays typified by excimer laser, X-rays, EUV light, etc., but also particles such as electron beams and ion beams. Line drawing is also included in the exposure.
In this specification, “(meth) acrylate” represents both and / or acrylate and methacrylate, “(meth) acryl” represents both and / or acryl and “(meth) acrylic” ) "Acryloyl" represents both and / or acryloyl and methacryloyl.
In the present specification, “monomer” and “monomer” are synonymous. The monomer in this specification is distinguished from an oligomer and a polymer, and refers to a compound having a weight average molecular weight of 2,000 or less. In the present specification, the polymerizable compound means a compound having a polymerizable functional group, and may be a monomer or a polymer. The polymerizable functional group refers to a group that participates in a 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 a methyl group, Et represents an ethyl group, Pr represents a propyl group, Bu represents a butyl group, and Ph represents a phenyl group.
In this specification, the term “process” is not limited to an independent process, and is included in the term if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes. .

The siloxane resin composition of the present invention is suitable as a material for transparent members such as lenses and transparent pixels. Not only the positive type but also a thermosetting resin or a negative photosensitive resin can be used, and it can also be suitably applied to micro-processing of micro lenses and transparent pixels. Furthermore, according to a request | requirement, the characteristic (quality resulting from the surface condition at the time of manufacture) of a cured film can be improved. In addition, a high-quality transparent cured product, a transparent pixel, a microlens, and a solid-state imaging device using the siloxane resin composition can be provided.

The siloxane resin composition of the present invention contains metal-containing particles, a siloxane resin, a solvent, and mesityl oxide. Hereinafter, the preferred embodiment will be described in detail.

<Metal-containing particles>
The metal-containing particles widely include particles containing a metal as a constituent element. Here, the term “metal” is to be interpreted in the broadest sense, and includes semimetals such as boron, silicon, and arsenic. When the metal-containing particles are configured to include oxygen atoms, they may be particularly referred to as metal oxide particles.
In the present invention, the metal-containing particles preferably contain a metal selected from Ti, Ta, W, Y, Ba, Hf, Zr, Sn, Nb, V, and Si. Especially, it is preferable that it is the oxide particle of the composite metal containing 2 or more types of them. For example, a combination of Ti and Zr (more Si if necessary), Ti and Sn (more Si if necessary), Ti, Zr and Sn (more Si if necessary) is preferable, and a combination having Ti, Zr, Sn and Si is preferable. Further preferred.

Examples of the constituent material of the metal-containing particles include titanium oxide, zirconium oxide, 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, preferably contain at least titanium oxide and zirconium oxide, and more preferably contain titanium oxide, zirconium oxide, tin oxide and silicon oxide. In the case of containing titanium oxide as a constituent material, it is preferable to contain rutile type titanium oxide. Furthermore, it is preferable to contain 80% by mass or more of rutile type titanium oxide with respect to the total amount of titanium oxide, more preferably 90% by mass or more, and particularly preferably 95% by mass or more. The upper limit is 100% by mass.

The refractive index of the metal-containing particles is preferably 1.75 to 2.70, more preferably 1.90 to 2.70, from the viewpoint of obtaining a high refractive index.
The number average particle size of the metal-containing particles is preferably 500 nm or less, more preferably 200 nm or less, further preferably 100 nm or less, more preferably 50 nm or less, and particularly preferably 30 nm or less. The lower limit is preferably 1 nm or more, more preferably 3 nm or more, and particularly preferably 5 nm or more. By making it the range of the said number average particle diameter, the transparency of a cured film improves and it is preferable. Moreover, the homogeneity of a cured film etc., and insulation and durability can be imparted if necessary, which is preferable. The metal-containing particles can be pulverized or dispersed using a dispersing machine such as a bead mill by procuring appropriate particle powder.

-Measurement of refractive index of particles-
The refractive index of metal-containing particles can be measured by the following method. The content rate of the metal-containing particles is adjusted to 0% by mass, 20% by mass, 30% by mass, 40% by mass, and 50% by mass to prepare a mixed solution sample in which the metal-containing particles and the matrix resin are mixed. The solid content concentration of each mixed solution sample is 10%. Each mixed solution sample was applied on a silicon wafer so as to have a thickness of 0.3 to 1.0 μm using a spin coater, and then heated and dried on a 200 ° C. hot plate for 5 minutes, A coating film is obtained. Next, for example, the refractive index at a wavelength of 633 nm (25 ° C.) is obtained using an ellipsometer (manufactured by Otsuka Electronics Co., Ltd.), and the value of 100% by mass of the metal-containing particles can be extrapolated.

-Measurement of average particle size-
The number average particle size of the metal-containing particles (meaning the average particle size in the primary particle size) can be determined from the photograph obtained by observing the particles with a transmission electron microscope. The projected area of the particles is obtained, the equivalent circle diameter is obtained therefrom, and the number average particle diameter is calculated. In order to determine the average particle size, the particle size was measured for 100 particles, and the average value of 80 particles excluding the maximum 10 particles and the minimum 10 particles among the measured particle sizes was defined as the average particle size. .

Examples of commercially available metal-containing particles include T-BTO-020RF (barium titanate; manufactured by Toda Kogyo Co., Ltd.), UEP-100 (zirconium oxide; manufactured by Daiichi Rare Element Chemical Co., Ltd.), or STR-100N. STR-100W, STR-100WLPT (titanium oxide; both manufactured by Sakai Chemical Industry Co., Ltd.).
The metal-containing particles can also be obtained as a dispersion dispersed in a liquid. Examples of the silicon oxide-titanium oxide particles include “OPTRAIK” (registered trademark) TR-502, “OPTRAIK” TR-503, “OPTRAIK” TR-504, “OPTRAIK” TR-513, “OPTRAIK” "TR-520", "Optlake" TR-527, "Optlake" TR-528, "Optlake" TR-529, "Optlake" TR-544 or "Optlake" TR-550 Kogyo Co., Ltd.). Zirconium oxide particles include, for example, “Vilar” registered trademark Zr-C20 (average particle size = 20 nm; manufactured by Taki Chemical Co., Ltd.), ZSL-10A (average particle size = 60-100 nm; Daiichi Rare Element Co., Ltd.) ), “Nanouse” (registered trademark) OZ-30M (average particle size = 7 nm; manufactured by Nissan Chemical Industries, Ltd.), SZR-M (manufactured by Sakai Chemical Co., Ltd.) or HXU-120JC (Sumitomo Osaka Cement Co., Ltd.) ))).

The content ratio (element composition) of the metal element in the metal-containing particles includes Ti and Zr, and the ratio is preferably 1 to 40 in terms of the Ti / Zr ratio (ratio of Ti and Zr), more preferably 1 to 30. 3 to 20 is more preferable, 4 to 12 is still more preferable, and 4 to 9 is most preferable. When satisfying such a numerical range, it is preferable because the storage stability of the composition can be enhanced while maintaining the refractive index. In particular, in the present invention, it is preferable to combine mesityl oxide and fine particles containing Ti and Zr at the specific ratios from the viewpoint of improving the thermocycle characteristics. The reason is not clear, but is estimated as follows. When the thermocycle is repeated, it is considered that the adsorption and separation of the metal-containing particles are repeated, and agglomeration is likely to form defects. The behavior is expected to change depending on the ratio of metal elements. At this time, by coexisting a small amount of mesityl oxide, it is expected that this will coordinate with the surface of the metal-containing particle in a state peculiar, thereby exhibiting an aggregation suppressing action and the like.
Further, the content ratio (element composition) of the metal element in the metal-containing particles includes Ti and Si, and the ratio is preferably 1 to 40 in terms of Ti / Si ratio (ratio of Ti and Si). Is more preferable, and 1 to 10 is more preferable.
The Ti / Sn ratio (ratio of Ti and Sn) is preferably 10 or more, more preferably 13 or more, further preferably 15 or more, further preferably 17 or more, further preferably 19 or more, and particularly preferably 20 or more. preferable. As an upper limit, it is preferable that it is 1000 or less, 500 or less is more preferable, 300 or less is more preferable, 100 or less is more preferable, 60 or less is further more preferable, 50 or less is further more preferable, 40 or less is especially preferable. By making the Ti / Sn ratio within this range, it is preferable that the compatibility with the organic component used together with the metal-containing fine particles can be expected.

~ Measurement of metal element content ~
In addition, the content rate of the metal element of a metal containing particle | grain is evaluated by the element composition (atomic%) quantified by the fluorescent X ray analysis (Rigaku's PrimusII type | mold fluorescent X ray analyzer). The ratio of a plurality of elements is determined by obtaining each element composition (atomic%) and evaluating the ratio of each elemental composition (atomic%). The elemental composition ratio is synonymous even if it is obtained as a mole ratio.

The surface treatment of the metal-containing particles may be in any form, for example, an aspect of treatment with a surfactant described later, an aspect of treatment with a treatment agent containing another metal, or the like. For example, the aspect which forms a specific metal containing particle | grain and forms a film, such as another kind of metal containing material, on the surface is mentioned. Alternatively, a coating of another type of gold-containing material or the like may be thick and core-shell type metal-containing particles may be used. The ratio of the core to the shell is not particularly limited, but when the total 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 particularly preferably 90 parts by mass or more. The upper limit is practically 97 parts by mass or less. The combination of materials constituting the core and the shell is not particularly limited, but the core is composed of particles containing Ti, Sn, etc., and the shell is coated with Zr, coated with Si, or contains Zr and Si. An example comprising a coating is given.

The content of the metal-containing particles is preferably 10% by mass or more in the solid component of the composition, more preferably 20% by mass or more, and particularly preferably 30% by mass or more. As an upper limit, it is preferable that it is 90 mass% or less, It is more preferable that it is 80 mass% or less, It is especially preferable that it is 70 mass% or less.
A metal containing particle may be used individually by 1 type, or may be used in combination of 2 or more type.
In addition, in this specification, a solid component (solid content) means the component which does not lose | disappear by volatilizing or evaporating, when a drying process is performed at 100 degreeC. Typically, it refers to components other than solvents and dispersion media.

<Siloxane resin>
The siloxane resin is preferably a resin obtained by hydrolytic condensation reaction of an alkoxysilane compound represented by any of the following formulas (1) to (3). Furthermore, it is also preferable that the compound represented by the formula (1) and the compound represented by the formula (2) are both subjected to a hydrolytic condensation reaction. Alternatively, both the compound of formula (1) and the compound of formula (3) may be subjected to a hydrolytic condensation reaction. The compound of formula (2) and the compound of formula (3), or the compound of formula (1) and the formula The compound of (2) and the compound of formula (3) may be subjected to a hydrolytic condensation reaction. In addition, 1 type of compounds of each formula may be used, or 2 or more types may be used.

(R ¹ ) _a Si (OR ² ) _4-a (1)

R ¹ and R ² each independently represents a hydrogen atom or a hydrocarbon group. The hydrocarbon group is an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms), alkynyl A group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 14 carbon atoms, particularly preferably 6 to 10 carbon atoms), an aralkyl group (7 carbon atoms). To 23, more preferably 7 to 15, and particularly preferably 7 to 11, and more preferably an alkyl group, an aryl group, or an alkenyl group.
a is 0, 1 or 2.

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. Or it is preferable that a polymeric group, an acidic group, or a basic group is included. (Meth) acryloyloxy group, thiol group (sulfanyl group), epoxy group, oxetane group, glycidyl group, glycidoxy group, hydroxyl group, phenolic hydroxyl group, carboxyl group, phosphoric acid group, sulfonic acid group, phosphonic acid group, 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 are given, and among these, a hydrocarbon linking group is preferable. The carboxyl group, sulfonic acid group, phosphoric acid group, and phosphonic acid group may form a salt, ester, or anhydride thereof. The amino group may also form a salt. In the present specification, the term “acryl” or “acryloyl” broadly refers to not only an acryloyl group but also a derivative structure thereof, and includes a structure having a specific substituent at the α-position of the acryloyl group. However, in a narrow sense, the case where the α-position is a hydrogen atom may be referred to as acryl or acryloyl. Those having a methyl group at the α-position are called methacrylic, meaning either acryl (α-position is a hydrogen atom) or methacryl (α-position is a methyl group) Sometimes called.
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 R ¹ above, or an alkoxy group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 3 carbon atoms), an alkenyloxy group. (Preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms), alkynyloxy group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms), aryloxy group (preferably 6 to 22 carbon atoms, 6 To 14 are more preferable, and 6 to 10 are particularly preferable), or an aralkyloxy group (preferably 7 to 23 carbon atoms, more preferably 7 to 15 carbon atoms, and particularly preferably 7 to 11 carbon atoms). 1-4 of R ⁶ and R ⁷ may be R ³ groups.
X is a divalent or higher linking group. When X is a divalent linking group, examples of the linking group L described below are given. Specific examples include S, O, CO, NR ^N , and polysulfide groups (2 to 6 S). When X is a trivalent linking group, for example, an isocyanuric skeleton is exemplified. d is an integer of 1 to 4, preferably 1 or 2.

R ¹ to R ⁷ may each independently have an arbitrary substituent T. Moreover, you may couple | bond with the silicon atom with the coupling group L in the range with the effect of this invention. Further, adjacent ones may be bonded or condensed to form a ring.

Examples of silane compounds represented by formula (1):
Examples of the trifunctional silane compound include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, methyltri-n-butoxysilane, methyltri-t-butoxysilane, methyltri-sec-butoxy Silane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, butyltrimethoxysilane, pentyltrimethoxysilane, cyclopentyltrimethoxysilane, hexyltrimethoxysilane, cyclohexyltrimethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxy Silane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriisopropoxysilane, 1-naphthyltrimethoxysilane, - naphthyl trimethoxysilane, heptadecafluorodecyltrimethoxysilane, heptadecafluorodecyl triethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, p- styryl trimethoxysilane, and the like allyl trimethoxysilane.
Examples of the bifunctional silane compound include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, cyclohexylmethyldimethoxysilane, and the like. Can be mentioned.
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-glycidoxypropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloyloxytrimethoxysilane, and γ-acryloyloxy. Propyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β-glycidoxyethyltrimethoxysilane , Β-glycidoxyethyltriethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyl Liethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltriisopropoxysilane, γ-glycidoxy Propyltri-n-butoxysilane, γ-glycidoxypropyltri-t-butoxysilane, γ-glycidoxypropyltri-sec-butoxysilane, γ-glycidoxypropyltrimethoxysilane, α-glycidoxybutyl Trimethoxysilane, α-glycidoxy-t-butyltriethoxysilane, α-glycidoxy-t-butyltriethoxysilane, α-glycidoxy-t-butyltriethoxysilane, β-glycidoxybutyltrimethoxysilane, β-glyce Sidoxybutyltriethoxysilane, γ- Lysidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, δ-glycidoxybutyltrimethoxysilane, δ-glycidoxybutyltriethoxysilane, (3,4-epoxycyclohexyl) methyltrimethoxysilane, (3,4-epoxycyclohexyl) methyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3,4- Epoxycyclohexyl) ethyltripropoxysilane, 2- (3,4-epoxycyclohexyl) ethyltri-t-butoxysilane, 2- (3,4-epoxycyclohexyl) ethyltri-n-butoxysilane, 2- (3,4-epoxy (Cyclohexyl) ethyltri-s ec-butoxysilane, 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane, 3- (3,4-epoxycyclohexyl) propyltriethoxysilane, 4- (3,4-epoxycyclohexyl) butyltrimethoxysilane, 4- (3,4-epoxycyclohexyl) butyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3- Isocyanatopropyltriethoxysilane, 3-trimethoxysilylpropyl succinic anhydride, 3-ureidopropyltriethoxysilane and the like.
Examples of the bifunctional silane compound include γ-glycidoxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyldiethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, and γ-methacrylic. Oxypropylmethyldiethoxysilane, glycidoxymethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, α-glycidoxyethylmethyldimethoxysilane, α-glycidoxyethylmethyldiethoxysilane, β-glycidoxyethyl Methyldimethoxysilane, β-glycidoxyethylmethyldiethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyldiethoxysilane, β-glycidoxypro Rumethyldimethoxysilane, β-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, β- Glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldimethoxyethoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylvinyldimethoxysilane , Γ-glycidoxypropylvinyldiethoxysilane, 3-methacryloxypropyldimethoxysilane and the like.

Examples of the silane compound represented by the formula (3) include 1,3-bis (3-aminopropyl) tetramethyldisiloxane, 1,3-bis (3-aminoethyl) tetramethyldisiloxane, 1,3 -Bis (3-aminopropyl) tetraethyldisiloxane and the like.

The siloxane resin can be obtained through the hydrolysis reaction and the condensation reaction using the above-described alkoxysilane compound. A known method can be used as the hydrolysis-condensation reaction, and a catalyst such as an acid or a base may be used as necessary. 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, hydrochloric acid and the like. Examples of the alkali include ammonia, triethylamine, ethylenediamine, and the like. The amount to be used is not particularly limited as long as the siloxane resin satisfies a predetermined molecular weight.

If necessary, a solvent may be added to the reaction system of the hydrolysis condensation reaction. The solvent is not particularly limited as long as the hydrolysis-condensation reaction can be carried out, and examples of the solvent described below can be given. Among them, for example, alcohol compounds such as water, methanol, ethanol, propanol, diacetone alcohol (DAA), tetrahydrofurfuryl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, dipropylene glycol monomethyl Examples include ether compounds such as ether (DPM), ester compounds such as methyl acetate, ethyl acetate, butyl acetate, γ-butyrolactone, and propylene glycol monomethyl ether acetate, and ketone compounds such as acetone, methyl ethyl ketone, and methyl isoamyl ketone.

The conditions (temperature, time, amount of solvent) for the hydrolysis-condensation reaction may be appropriately selected according to the type of material used.

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

In the present invention, the molecular weight of a polymer (including a siloxane resin) means a weight average molecular weight unless otherwise specified, and is measured by gel permeation chromatography (GPC) in terms of standard polystyrene. The measurement conditions are based on the following condition 1. However, depending on the polymer type, an appropriate carrier (eluent) and a column suitable for it may be selected and used.
(Condition 1)
Column: TOSOH TSKgel Super HZM-H, TOSOH
TSKgel Super HZ4000, TOSOH TSKgel
A column connected with Super HZ2000 is used Carrier: Tetrahydrofuran Measurement temperature: 40 ° C.
Carrier flow rate: 1.0 ml / min
Sample concentration: 0.1% by mass
Detector: RI (refractive index) detector

Although there are some overlapping portions, preferred siloxane resins include the following.
Examples of the alkoxysilane having four or more alkoxy groups include tetramethoxysilane, tetraethoxysilane, tetraacetoxysilane, tetraphenoxysilane, tetramethoxydisiloxane, tetraethoxydisiloxane, and bis (triethoxysilylpropyl) tetrasulfide. , Tris- (3-trimethoxysilylpropyl) isocyanurate, and tris- (3-triethoxysilylpropyl) isocyanurate. From the viewpoint of improving the chemical resistance of the cured film, a mixture of tetrafunctional silane and 9 functional silane is used in order to allow bulky 9 functional silane and tetrafunctional silane with less steric hindrance to react with each other. Is preferred.

The siloxane resin is also preferably a hydrolyzate condensation reaction product with a bifunctional or trifunctional alkoxysilane compound. Examples of the alkoxysilane compound constituting the siloxane resin include dimethoxydimethylsilane, diethoxydimethylsilane, dimethoxydiphenylsilane, diethoxydiphenylsilane, dihydroxydiphenylsilane, dimethoxy (methyl) (phenyl) silane, and diethoxy (methyl) (phenyl). ) Silane, dimethoxy (methyl) (phenethyl) silane, dicyclopentyldimethoxysilane or cyclohexyldimethoxy (methyl) silane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane Or 3-acryloxypropyltriethoxysilane, 3-trimethoxysilylpropyl succinic anhydride, 3-triethoxysilylpropyl anhydride Acid, 3-trimethoxysilylethyl succinic anhydride, 3-trimethoxysilylbutyl succinic anhydride, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3- (3,4-epoxy (Cyclohexyl) propyltrimethoxysilane, 3- (3,4-epoxycyclohexyl) propyltriethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, phenyltrimethoxysilane, phenethyltrimethoxysilane, naphthyltrimethoxysilane, methyltriethoxy Examples include silane, ethyltriethoxysilane, phenyltriethoxysilane, phenethyltriethoxysilane, naphthyltriethoxysilane, tetramethoxysilane, and tetraethoxysilane.

The content of the siloxane resin is small when the alkali-soluble resin described later is contained, and is preferably increased when the alkali-soluble resin is not contained. That is, when the alkali-soluble resin is contained, the content of the siloxane resin is preferably 1% by mass or more, more preferably 2% by mass or more in the solid component of the composition, and 3% by mass. The above is particularly preferable. As an upper limit, it is preferable that it is 30 mass% or less, and it is more preferable that it is 20 mass% or less.
When the alkali-soluble resin is not contained, the content of the siloxane resin is preferably 10% by mass or more, more preferably 15% by mass or more, and more preferably 20% by mass or more in the solid component of the composition. It is particularly preferred that As an upper limit, it is preferable that it is 40 mass% or less, and it is more preferable that it is 35 mass% or less.
The amount is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and particularly preferably 30 parts by mass or more with respect to 100 parts by mass of the metal-containing particles. As an upper limit, it is preferable that it is 120 mass parts or less, It is more preferable that it is 100 mass parts or less, It is especially preferable that it is 80 mass parts or less. When the amount is made small, the upper limit is preferably 70 parts by mass or less, more preferably 60 parts by mass or less, and particularly preferably 50 parts by mass or less.

In the present specification, the term “siloxane resin” basically means a polymer obtained through a hydrolytic condensation reaction of an alkoxysilane compound. However, a polymer obtained by other reaction and a silane compound itself as a raw material are also included. Including meaning. However, in the present invention, the siloxane resin is preferably a hydrolytic condensation reaction product of a silane compound. The hydrolysis condensation reaction of the silane compound may be performed in the presence of metal-containing particles. At this time, a particle-resin matrix in which the silane compound reacts with the metal-containing particles on the surface thereof, or a core-shell structure in which the core is the metal-containing particles and the shell is the silane compound may be formed.

<Mesityl oxide>
The siloxane resin composition of the present invention contains mesityl oxide as an essential component. The concentration of mesityl oxide in the siloxane resin composition is preferably 0.01% by mass or more, and more preferably 0.02% by mass or more. As an upper limit, it is preferable that it is 15 mass% or less, It is more preferable that it is 12 mass% or less, It is more preferable that it is 10 mass% or less, It is further more preferable that it is 8 mass% or less, 4 mass% More preferably, it is more preferably 1% by mass or less, further preferably 0.1% by mass or less, and particularly preferably 0.09% by mass or less.
With respect to 100 parts by mass of the metal-containing particles, the mesityl oxide is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and particularly preferably 5 parts by mass or more. As an upper limit, it is preferable that it is 100 mass parts or less, It is more preferable that it is 80 mass parts or less, It is especially preferable that it is 50 mass parts or less.
Mesityl oxide is a compound represented by the following formula.

Since mesityl oxide is an impurity that affects the optical properties on one side, it is preferably suppressed to a small amount. On the other hand, the present invention is characterized in that the mesityl oxide is included even in a trace amount. In the present invention, the reason why a specific effect is obtained by adding mesityl oxide is not clear, but it is presumed to be due to the interaction with the metal-containing particles described above. The action appears particularly prominently as an effect on the thermocycle characteristics (see Examples below).

<Solvent>
The siloxane resin composition of the present invention contains a solvent. As the solvent, the solvent used in the hydrolysis condensation reaction of the silane compound may be used as it is as the solvent of the composition, or the following solvent may be used in addition to or in place of the solvent.
Examples of the solvent include water, aliphatic compounds, halogenated hydrocarbon compounds, alcohol compounds, ether compounds, ester compounds, ketone compounds, nitrile compounds, amide compounds, sulfoxide compounds, and aromatic compounds. These solvents may be used as a mixture. Examples of each are listed below.
Water / aliphatic compounds Hexane, heptane, cyclohexane, methylcyclohexane, octane, pentane, cyclopentane, etc.Halogenated hydrocarbon compounds Methylene chloride, chloroform, dichloromethane, ethane dichloride, carbon tetrachloride, trichloroethylene, tetrachloroethylene, epichlorohydride Phosphorus, monochlorobenzene, orthodichlorobenzene, allyl chloride, HCFC, monochloroacetic acid methyl, monochloroacetic acid ethyl, monochloroacetic acid trichloroacetic acid, methyl bromide, methyl hydride, tri (tetra) chloroethylene, etc., alcohol compounds methyl alcohol, ethyl alcohol, 1 -Propyl alcohol, 2-propyl alcohol, 2-butanol, ethylene glycol, propylene glycol, glycerin, 1,6-hexanedio , Cyclohexanediol, sorbitol, xylitol, 2-methyl-2,4-pentanediol, 1,3-butanediol, 1,4-butanediol, diacetone alcohol, tetrahydrofurfuryl alcohol, etc. Including compounds)
Dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, t-butyl methyl ether, cyclohexyl methyl ether, anisole, tetrahydrofuran, alkylene glycol alkyl ether (ethylene glycol monomethyl ether, ethylene 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 compounds 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 compounds Acetonitrile, etc. Amide compounds N, N-dimethylformamide, 1-methyl-2-pyrrolidone, 2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, 2-pyrrolidinone, ε-caprolactam, formamide, N-methylformamide, acetamide N-methylacetamide, N, N-dimethylacetamide, N-methylpropanamide, hexamethylphosphoric triamide, etc. ・ Sulphoxide compound Dimethylsulfoxy Etc. Aromatic compounds as benzene, toluene, etc.

As the solvent, an alcohol compound, an ester compound, or an ether compound is preferable from the viewpoint of uniformly dissolving each component of the composition and expressing the above-described action by the addition of mesityl oxide. For example, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diacetone alcohol, ethylene glycol mononormal butyl ether, 2-ethoxyethyl acetate, 1-methoxypropyl-2-acetate, 3-methoxy-3-methylbutanol, 3-methoxy -3-Methylbutanol acetate, 3-methoxybutyl acetate, 1,3-butylene glycol diacetate, ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether acetate, ethyl lactate, butyl lactate, ethyl acetoacetate or γ-butyrolactone. Among these, diacetone alcohol is particularly preferable from the above viewpoint.

The amount of the solvent used is not particularly limited, but in the case of a coating solution, the solid component is preferably 5% by mass or more, more preferably 10% by mass or more, It is particularly preferable that the content be 15% by mass or more. The upper limit is preferably 40% by mass or less, more preferably 35% by mass or less, and particularly preferably 30% by mass or less.
The solvent may be used alone or in combination of two or more.
About the siloxane resin composition of this invention, it is preferable to mix 2 or more types of solvents, For example, the combination of alcohol compound (DAA etc.) and ester compound (PEGMEA etc.) is mentioned. The mixing ratio is not particularly limited, but the alcohol compound (DAA or the like) is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and particularly preferably 30 parts by mass or more with respect to 100 parts by mass of the ester compound (PEGMEA or the like). preferable. As an upper limit, 100 mass parts or less are preferable, 90 mass parts or less are more preferable, and 80 mass parts or less are especially preferable. Mixing the above two solvents within this range is preferable because a cosolvent effect is obtained in combination with the addition of mesityl oxide.

<Ultraviolet absorber>
You may use a ultraviolet absorber for the siloxane resin composition of this invention. As the ultraviolet absorber, a benzotriazole compound, a benzophenone compound, or a triazine compound is preferably used.
Examples of the benzotriazole compounds include 2- (2H benzotriazol-2-yl) phenol, 2- (2H-benzotriazol-2-yl) -4,6-tert-pentylphenol, and 2- (2H benzotriazole). -2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol, 2 (2H-benzotriazol-2-yl) -6-dodecyl-4-methylphenol or 2- (2'- Hydroxy-5′-methacryloxyethylphenyl) -2H-benzotriazole.
Examples of benzophenone compounds include 2-hydroxy-4-methoxybenzophenone.
Examples of the ultraviolet absorber of the triazine compound include 2- (4,6-diphenyl-1,3,5 triazin-2-yl) -5-[(hexyl) oxy] -phenol.

<Polymerization initiator>
The siloxane resin composition of the present invention may contain a polymerization initiator. The polymerization initiator may be either a thermal polymerization initiator or a photopolymerization initiator, but a photopolymerization initiator is preferred. For example, organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, metallocene compounds, hexaarylbiimidazole compounds, organic boric acid Compound, disulfonic acid compound, oxime compound, onium salt compound, hydroxyacetophenone compound, aminoacetophenone compound, acylphosphine oxide compound, trihalomethyltriazine compound, benzyldimethyl ketal compound, α-hydroxyketone compound, α-aminoketone compound, acylphosphine compound , Phosphine oxide compound, metallocene compound, triallylimidazole dimer, onium compound, benzothiazole compound, benzo Examples include phenone compounds, cyclopentadiene-benzene-iron complex compounds, halomethyloxadiazole compounds, 3-aryl-substituted coumarin compounds, α-aminoalkylphenone compounds, and benzoate compounds.
As specific examples of these, the description after paragraph [0135] of JP 2010-106268 A (corresponding US Patent Application Publication No. 2011/0124824 [0163]) can be referred to. Incorporated into.

Specific examples include aminoacetophenone initiators described in JP-A-10-291969 and acylphosphine oxide initiators described in Japanese Patent No. 4225898.
Examples of the hydroxyacetophenone-based initiator include IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (trade names: all manufactured by BASF).
As commercially available aminoacetophenone initiators, IRGACURE-907, IRGACURE-369, IRGACURE-379 (trade names: all manufactured by BASF) and the like can be used. In addition, a compound described in JP-A-2009-191179 in which an absorption wavelength is matched with a long wave light source such as 365 nm or 405 nm can also be used.
As commercially available acylphosphine initiators, IRGACURE-819, Darocur 4265, DAROCUR-TPO (trade names: all manufactured by BASF) can be used.
Examples of the azo compound include 2,2-azobisisobutyronitrile (AIBN), 3-carboxypropionitrile, azobismaleonitrile, dimethyl-2,2′-azobis (2-methylpropionate) [V -601] (manufactured by Wako).

In the present invention, it is preferable to use an oxime compound. The oxime compound effectively functions as a polymerization initiator that initiates and accelerates polymerization in the siloxane resin composition of the present invention. In addition, the oxime compound is less colored by post-heating and has good curability. In particular, in the present invention, the addition of an oxime compound-based initiator is preferable because the characteristics after the thermocycle due to the action of the mesityl oxide and the metal-containing particles can be further improved. Among these, commercially available products (both manufactured by BASF) such as IRGACURE OXE01 (lower formula) and IRGACURE OXE02 (lower formula) can be suitably used.

As the oxime compound serving as a polymerization initiator, those represented by the following formula (OX) are preferred, and those represented by the formula (OX-1) are more preferred.

・ A ¹
A ¹ is preferably —AC or an alkyl group of the formula (OX-1). The alkyl group preferably has 1 to 12 carbon atoms, and more preferably 1 to 6 carbon atoms. The alkyl group may have a substituent T described later. Further, 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 nonmetallic atomic group. Examples of the monovalent nonmetallic atomic group include an alkyl group (preferably having a carbon number of 1 to 12, more preferably 1 to 6, particularly preferably 1 to 3), and an aryl group (preferably having a carbon number of 6 to 14, more preferably 6-10), an acyl group (preferably 2-12 carbon atoms, more preferably 2-6, particularly preferably 2-3), an aryloyl group (preferably 7-15 carbon atoms, more preferably 7-11). An alkoxycarbonyl group (preferably having a carbon number of 2 to 12, more preferably 2 to 6, particularly preferably 2 to 3), an aryloxycarbonyl group (preferably having a carbon number of 7 to 15, more preferably 7 to 11), a complex A cyclic group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms), an alkylthiocarbonyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, particularly preferably 2 to 3 carbon atoms), Over thiocarbonyl group include (preferably having 7 to 15, more preferably from 7 to 11 carbon atoms) and the like. Moreover, these groups may have one or more substituents. Further, the above-described substituent may be further substituted with another substituent T. Among the substituent T, a halogen atom, an alkyl group (preferably having a carbon number of 1 to 12, more preferably 1 to 6, particularly preferably 1 to 3), an aryl group (preferably having a carbon number of 6 to 14, more preferably 6). To 10), an arylthio group (preferably having 6 to 14 carbon atoms, more preferably 6 to 10), an aryloyl group (preferably having 7 to 15 carbon atoms, more preferably 7 to 11)) and the like. Among them, the linking group L is preferably an alkylene group having 1 to 6 carbon atoms, O, S, CO, NR ^N , or a combination thereof.

・ B
B represents a monovalent substituent, and is an alkyl group (preferably having 1 to 12 carbon atoms), an aryl group (preferably having 6 to 14 carbon atoms, more preferably having 6 to 10 carbon atoms), a heterocyclic group (preferably having carbon atoms). 2 to 18, more preferably 2 to 12 carbon atoms. These groups may be bonded via a linking group L. In addition, these groups may have one or more substituents T. The substituent T may also be substituted through an arbitrary linking group L. Here, 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, but may be bonded at different positions. Further, these groups may be further accompanied by a substituent T. Specific examples include a benzoyl group, a phenylthio group, and a phenyloxy group.

・ A
A is a single bond or a linking group. Preferred examples of the linking group include the linking group L or arylene group (preferably having 6 to 14 carbon atoms, more preferably 6 to 10 carbon atoms) or a heterocyclic linking group (preferably an aromatic heterocyclic linking group) (preferably Has 2 to 18 carbon atoms, more preferably 2 to 12 carbon atoms.

・ Ar
Ar is an aryl group or heteroaryl (aromatic heterocyclic group). The aryl group preferably has 6 to 14 carbon atoms, more preferably 6 to 10 carbon atoms, and is preferably a phenyl group or a naphthyl group. The heteroaryl group is preferably a carbazolyl group having preferably 2 to 18 carbon atoms, more preferably 2 to 12 carbon atoms, and optionally having a substituent such as an alkyl group at the N-position.

As an oxime initiator, Japanese Patent Application Laid-Open No. 2012-208494, paragraph 0513 (corresponding US Patent Application Publication No. 2012/235099, [0632]) and the following formulas (OX-1), (OX-2) or ( The description of the compound represented by OX-3) can be referred to, and the contents thereof are incorporated herein.

The polymerization initiator preferably has a maximum absorption wavelength in a wavelength region of 350 nm to 500 nm, more preferably has an absorption wavelength in a wavelength region of 360 nm to 480 nm, and particularly has a high absorbance at 365 nm and 455 nm. preferable. From the viewpoint of sensitivity, the molar extinction coefficient at 365 nm or 405 nm is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, and 5,000 to 200,000. It is particularly preferred.

The content of the polymerization initiator (total content in the case of two or more) is preferably 0.1% by mass or more and 10% by mass or less, more preferably 0.3% by mass with respect to the total solid content of the composition. % To 8% by mass, more preferably 0.5% 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.

<Polymerizable compound>
The siloxane resin composition of the present invention may contain a polymerizable compound. The polymerizable compound is preferably an addition polymerizable compound having a polymerizable group such as at least one ethylenically unsaturated double bond, an epoxy group, or an oxetanyl group. Preferably, it is selected from compounds having at least one polymerizable group, more preferably two or more. There is no particular upper limit, but 12 or less is practical. For example, it may have a chemical form such as a monomer, a prepolymer (that is, a polymer such as a dimer, a trimer, and an oligomer) or a mixture thereof and a copolymer thereof. Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, and amides. Preferably, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used. Further, an addition reaction product of an unsaturated carboxylic acid ester or unsaturated carboxylic acid amide having a nucleophilic substituent such as a hydroxyl group, an amino group or a mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and A dehydration condensation reaction product with a monofunctional or polyfunctional carboxylic acid is also preferably used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or unsaturated carboxylic acid amide having an electrophilic substituent such as an isocyanate group or an epoxy group and a monofunctional or polyfunctional alcohol, amine, or thiol; Furthermore, a substitution reaction product of an unsaturated carboxylic acid ester or unsaturated carboxylic acid amide having a leaving group such as a halogen group or a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. It is. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid. As these specific compounds, the compounds described in paragraph numbers 0095 to 0108 of JP-A-2009-288705 can be preferably used in the present invention.

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

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

n is preferably 0 to 5, and more preferably 1 to 3.
m is preferably 1 to 5, and more preferably 1 to 3.
As specific examples of the polymerizable compounds represented by the above formulas (MO-1) to (MO-6), the compounds described in Paragraph Nos. 0248 to 0251 of JP-A No. 2007-26979 are used in this embodiment. It can use suitably also in a form.

Among them, dipentaerythritol triacrylate (as a commercially available product, KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercially available product, KAYARAD D-320; Nippon Kayaku) as the polymerizable compound, etc. Dipentaerythritol penta (meth) acrylate (commercially available) KAYARAD D-310 (commercially available from Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available KAYARAD DPHA; Nippon Kayaku Co., Ltd.) And a structure in which these (meth) acryloyl groups are mediated by ethylene glycol and propylene glycol residues, diglycerin EO (ethylene oxide) -modified (meth) acrylate (commercially available product is M-460; Made sub-synthesis) is preferable. 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 formulae, E represents — ((CH ₂ ) _y CH ₂ O) — or — ((CH ₂ ) _y CH (CH ₃ ) O) —, and — ((CH ₂ ) _y CH ₂ O)-is preferred.
Each y represents an integer of 1 to 10, preferably an integer of 1 to 5, and more preferably an integer of 1 to 3.
X represents a hydrogen atom, an acryloyl group, a methacryloyl group, or a carboxyl group, respectively. In the formula (i), the total number of acryloyl groups and methacryloyl groups is preferably 3 or 4, more preferably 4. In the formula (ii), the total number of acryloyl groups and methacryloyl groups is 5 or 6, with 6 being preferred.
m represents an integer of 0 to 10 and is preferably an integer of 1 to 5.
n represents an integer of 0 to 10, and an integer of 1 to 5 is preferable.

As a polymeric compound, you may have acidic groups, such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Accordingly, the ethylenic compound may have an unreacted carboxyl group as in the case of a mixture, and this can be used as it is. If necessary, an acidic group may be introduced by reacting a hydroxyl group of the ethylenic compound with a non-aromatic carboxylic acid anhydride. In this case, specific examples of the non-aromatic carboxylic acid anhydride used include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, alkylated hexahydrophthalic anhydride, succinic anhydride, anhydrous Maleic acid is mentioned.

The molecular weight of the polymerizable compound is not particularly limited, but 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% by mass to 50% by mass, more preferably in the range of 3% by mass to 40% by mass, The range of 5% by mass to 30% by mass is more preferable. Within this range, the curability is good and preferable without excessively reducing the refractive index and transparency.
A polymeric compound may be used individually by 1 type, or may be used in combination of 2 or more type.

<Alkali-soluble resin>
The siloxane resin composition of the present invention may contain an alkali-soluble resin. The alkali-soluble resin is a linear organic polymer, and promotes at least one alkali-solubility in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be suitably selected from alkali-soluble resins having a group.
From the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferred. From the viewpoint of development 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 phosphoric acid 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 type or two or more types.

As the linear organic polymer used as the alkali-soluble resin, a polymer having a carboxylic acid in the side chain is preferable, such as 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 novolak resins, etc., acid cellulose derivatives having a carboxylic acid in the side chain, and acid anhydrides added to polymers having a hydroxyl group. Can be mentioned. In particular, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is suitable as the alkali-soluble resin. Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds. Examples of the alkyl (meth) acrylate and aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and (iso) pentyl (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) ) Acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, and other vinyl compounds include styrene, α-methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile , Vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, and the like, as N-substituted maleimide monomers described in JP-A-10-300922, jN-phenylmaleimide, N-cyclohexyl A maleimide etc. can be mentioned.

The other monomer copolymerizable with (meth) acrylic acid is preferably a repeating unit represented by the following formula (A1).

R ¹¹ represents a hydrogen atom or a methyl group. R ¹² represents an alkylene group having 2 or 3 carbon atoms, and among them, 2 carbon atoms are preferable. R ¹³ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. n1 represents an integer of 1 to 15, and preferably 1 to 12. The repeating unit represented by the above formula (A1) has good adsorption and / or orientation on the particle surface due to the effect of π electrons of the benzene ring present in the side chain. In particular, when this side chain portion has an ethylene oxide or propylene oxide structure of paracumylphenol, its steric effect is added, and a better adsorption and / or orientation plane can be formed. Therefore, it is more effective and preferable.
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 R ¹³ has a large number of carbon atoms, this group becomes an obstacle to suppress the approach between the resins and promote adsorption and / or orientation, but if it is too large, the effect may be hindered. Because. The alkyl group represented by R ¹³ is preferably an unsubstituted alkyl group or an alkyl group substituted with a phenyl group.

An alkali-soluble polyester resin may be used for the siloxane resin composition of the present invention. Although the action mechanism of the effect obtained by containing an alkali-soluble polyester resin is not clear, it is thought that those having an aromatic ring reduce the decomposability of the ester group and enable effective development.

As a method for synthesizing the alkali-soluble polyester resin, a method of undergoing a polyaddition reaction between a polyfunctional epoxy compound and a polycarboxylic acid compound or a polyaddition reaction between a polyol compound and a dianhydride is preferable. As a polyol compound, what was obtained by reaction of a polyfunctional epoxy compound and a radically polymerizable group containing monobasic acid compound is preferable. Examples of the catalyst used in the polyaddition reaction and the addition reaction include ammonium catalysts such as tetrabutylammonium acetate; amino catalysts such as 2,4,6-tris (dimethylaminomethyl) phenol or dimethylbenzylamine; triphenylphosphine And a phosphorus catalyst such as acetylacetonate chromium or chromium chloride.

The alkali-soluble resin is preferably soluble in a tetramethylammonium hydroxide (TMAH) aqueous solution at a concentration of 0.1% by mass or more at 23 ° C. Furthermore, it is preferable that it is soluble in 1% by mass or more of TMAH aqueous solution, and further it is soluble in 2% or more of TMAH aqueous solution.

The acid value of the alkali-soluble resin is preferably 30 to 200 mgKOH / g, more preferably 50 to 150 mgKOH / g, still more preferably 70 to 120 mgKOH / g. By setting it as such a range, the image 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 particularly preferably 20 to 35% by mass with respect to the total solid content of the composition.
An alkali-soluble resin may be used individually by 1 type, or may be used in combination of 2 or more type.

<Polymerization inhibitor>
The siloxane resin composition of the present invention may contain a polymerization inhibitor. Polymerization inhibitors include phenolic hydroxyl group-containing compounds, N-oxide compounds, piperidine 1-oxyl free radical compounds, pyrrolidine 1-oxyl free radical compounds, N-nitrosophenylhydroxylamines, diazonium compounds, and cations Examples include dyes, sulfide group-containing compounds, nitro group-containing compounds, transition metal compounds such as FeCl ₃ and CuCl ₂ . As the polymerization inhibitor, the description of JP 2010-106268 A paragraphs 0260 to 0280 (corresponding to [0284] to [0296] of the corresponding US Patent Application Publication No. 2011/0124824) can be referred to. The contents of which are incorporated herein by reference.

A preferable addition amount of the polymerization inhibitor is preferably 0.01 parts by mass or more and 10 parts by mass or less, and more preferably 0.01 parts by mass or more and 8 parts by mass or less with respect to 100 parts by mass of the polymerization initiator. It is most preferable that it exists in the range of 0.05 mass part or more and 5 mass parts or less.
A polymerization inhibitor may be used individually by 1 type, or may be used in combination of 2 or more type.

<Dispersant>
As the dispersant, a polymer compound represented by the general formula (1) of claim 1 (corresponding claim 1 of US2010 / 0233595) of JP-A-2007-277514 is preferable. The description of JP 2007-277514 A (corresponding US 2010/0233595) can be referred to, and the contents thereof are incorporated in the present 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 JP-A-2007-277514.

The content of the dispersing agent is preferably 10 to 1000 parts by mass, more preferably 30 to 1000 parts by mass, and further preferably 50 to 800 parts by mass with respect to 100 parts by mass of the metal-containing particles. The total solid content of the composition is preferably 10 to 30% by mass. 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 silicone surfactants, silicon surfactants such as organopolysiloxanes, fluorine surfactants, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, and polyoxyethylene octylphenyl ether. Nonionic surfactants such as polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate or polyethylene glycol distearate, polyalkylene oxide surfactants, poly (meth) acrylate surfactants, acrylic or methacrylic surfactants A surfactant made of a polymer is exemplified. Examples of commercially available surfactants include “Megafac” (registered trademark) F142D, F172, F173, F183, F445, F470, F475 or F477 (all manufactured by Dainippon Ink & Chemicals, Inc.) or NBX- 15 or FTX-218 (both manufactured by Neos Co., Ltd.) and other fluorine-based surfactants, BYK-333, BYK-301, BYK-331, BYK-345 or BYK-307 (all of which are Big Chemie Japan Co., Ltd.) And the like.

Although the addition amount of surfactant is not specifically limited, 1 mass% or more is preferable in a solid component of a composition, 1.5 mass% or more is more preferable, and 5 mass% or more is especially preferable. Although an upper limit is not specifically limited, 30 mass% or less is preferable and 15 mass% or less is more preferable.
Surfactant may be used individually by 1 type, or may be used in combination of 2 or more type.

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

<Developer>
As the developer, an alkaline solution is preferably used. For example, the concentration of the alkaline compound is preferably 0.001 to 10% by mass, and more preferably 0.01 to 5% by mass. Alkaline compounds include, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxy , Tetrabutylammonium hydroxy, benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene and the like. Among these, in this invention, an organic alkali is preferable. In the case where an alkaline aqueous solution is used as a developer, a washing treatment with water is generally performed after development. Among these developers, quaternary ammonium salts are preferable, and tetramethylammonium hydroxide (TMAH) or choline is more preferable.
One developer may be used alone, or two or more developers may be used in combination.

In addition, in this specification, it uses for the meaning containing the salt and its ion other than the said compound itself about the display of a compound (For example, when attaching | subjecting and attaching | subjecting a compound and an end). In addition, it is meant to include derivatives in which a part thereof is changed, such as introduction of a substituent, within a range where a desired effect is exhibited.
In the present specification, a substituent that does not specify substitution / non-substitution (the same applies to a linking group) means that the group may have an arbitrary substituent. This is also synonymous for compounds that do not specify substitution / non-substitution. Preferred substituents include the following substituent T.
Examples of the substituent T include the following.
An alkyl group (preferably an alkyl group having 1 to 20 carbon atoms, such as methyl, ethyl, isopropyl, t-butyl, pentyl, heptyl, 1-ethylpentyl, benzyl, 2-ethoxyethyl, 1-carboxymethyl, etc.), alkenyl A group (preferably an alkenyl group having 2 to 20 carbon atoms such as vinyl, allyl, oleyl and the like), an alkynyl group (preferably an alkynyl group having 2 to 20 carbon atoms such as ethynyl, butadiynyl, phenylethynyl and the like), A cycloalkyl group (preferably a cycloalkyl group having 3 to 20 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, etc., but the alkyl group usually means a cycloalkyl group), aryl Group (preferably having 6 to 2 carbon atoms) Aryl groups such as phenyl, 1-naphthyl, 4-methoxyphenyl, 2-chlorophenyl, 3-methylphenyl, etc.), heterocyclic groups (preferably heterocyclic groups having 2 to 20 carbon atoms, preferably at least 1 A 5- or 6-membered heterocyclic group having one oxygen atom, sulfur atom or nitrogen atom is preferred, and examples thereof include tetrahydropyran, tetrahydrofuran, 2-pyridyl, 4-pyridyl, 2-imidazolyl, 2-benzoimidazolyl, 2-thiazolyl, 2-oxazolyl, pyrrolidone group, etc.), alkoxy groups (preferably alkoxy groups having 1-20 carbon atoms, such as methoxy, ethoxy, isopropyloxy, benzyloxy etc.), aryloxy groups (preferably 6-26 carbon atoms). Aryloxy groups such as phenoxy, 1-naphthylo Si, 3-methylphenoxy, 4-methoxyphenoxy, etc.), alkoxycarbonyl groups (preferably alkoxycarbonyl groups having 2 to 20 carbon atoms, such as ethoxycarbonyl, 2-ethylhexyloxycarbonyl, etc.), aryloxycarbonyl groups (preferably Is an aryloxycarbonyl group having 6 to 26 carbon atoms, such as phenoxycarbonyl, 1-naphthyloxycarbonyl, 3-methylphenoxycarbonyl, 4-methoxyphenoxycarbonyl, etc., an amino group (preferably having 0 to 20 carbon atoms) Including amino group, alkylamino group, arylamino group, for example, amino, N, N-dimethylamino, N, N-diethylamino, N-ethylamino, anilino, etc.), sulfamoyl group (preferably having 0 to 20 carbon atoms) The sulfamoyl A group such as N, N-dimethylsulfamoyl, N-phenylsulfamoyl, etc.), an acyl group (preferably an acyl group having 1 to 20 carbon atoms such as acetyl, propionyl, butyryl, etc.), an aryloyl group ( Preferably an aryloyl group having 7 to 23 carbon atoms, such as benzoyl, an acyloxy group (preferably an acyloxy group having 1 to 20 carbon atoms, such as acetyloxy), an aryloyloxy group (preferably having a carbon number) 7 to 23 aryloyloxy groups such as benzoyloxy), carbamoyl groups (preferably carbamoyl groups having 1 to 20 carbon atoms such as N, N-dimethylcarbamoyl, N-phenylcarbamoyl etc.), acylamino groups ( Preferably an acylamino group having 1 to 20 carbon atoms, such as acetylamino Benzoylamino and the like), an alkylthio group (preferably an alkylthio group having 1 to 20 carbon atoms, such as methylthio, ethylthio, isopropylthio, benzylthio and the like), an arylthio group (preferably an arylthio group having 6 to 26 carbon atoms, such as Phenylthio, 1-naphthylthio, 3-methylphenylthio, 4-methoxyphenylthio, etc.), alkylsulfonyl groups (preferably alkylsulfonyl groups having 1 to 20 carbon atoms, such as methylsulfonyl, ethylsulfonyl, etc.), arylsulfonyl groups (Preferably an arylsulfonyl group having 6 to 22 carbon atoms, such as benzenesulfonyl), an alkylsilyl group (preferably an alkylsilyl group having 1 to 20 carbon atoms, such as monomethylsilyl, dimethylsilyl, trimethylsilyl, Ethylsilyl, etc.), arylsilyl groups (preferably arylsilyl groups having 6 to 42 carbon atoms, such as triphenylsilyl), phosphoryl groups (preferably phosphoryl groups having 0 to 20 carbon atoms, such as —OP (= O) (R ^P ) ₂ ), a phosphonyl group (preferably a phosphonyl group having 0 to 20 carbon atoms, such as —P (═O) (R ^P ) ₂ ), a phosphinyl group (preferably having 0 to 20 carbon atoms). Phosphinyl groups such as —P (R ^P ) ₂ ), (meth) acryloyl groups, (meth) acryloyloxy groups, (meth) acryloylimimino groups ((meth) acrylamido groups), hydroxyl groups, thiol groups, carboxyl groups , Phosphoric acid group, phosphonic acid group, sulfonic acid group, cyano group, halogen atom (eg fluorine atom, chlorine atom, bromine atom, iodine atom) Is mentioned.
In addition, each of the groups listed as the substituent T may be further substituted with the substituent T described above.
Moreover, when the said substituent is an acidic group or a basic group, the salt may be formed.
When a compound or a substituent / linking group includes an alkyl group / alkylene group, an alkenyl group / alkenylene group, an alkynyl group / alkynylene group, etc., these may be cyclic or linear, and may be linear or branched These may be substituted as described above or may be unsubstituted.
Each substituent defined in the present specification may be substituted through the following linking group L within the scope of the effects of the present invention, or the linking group L may be present in the structure thereof. For example, the alkyl group / alkylene group, alkenyl group / alkenylene group and the like may further have the following hetero-linking group interposed in the structure.
The linking group L includes a hydrocarbon linking group [an alkylene group having 1 to 10 carbon atoms (more preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms), an alkenylene group having 2 to 10 carbon atoms (more preferably carbon atoms). 2 to 6, more preferably 2 to 4), an alkynylene group having 2 to 10 carbon atoms (more preferably 2 to 6, more preferably 2 to 4 carbon atoms), and an arylene group having 6 to 22 carbon atoms (more preferably Is a carbon number 6-10), or a combination thereof], hetero-linking group [carbonyl group (—CO—), thiocarbonyl group (—CS—), ether group (—O—), thioether group (—S—) , Imino group (—NR ^N —), polysulfide group (the number of S is 1 to 8), imine linking group (R ^N —N═C <, —N═C (R ^N ) —), sulfonyl group (— SO ₂ -), a sulfinyl group (-SO- , A phosphate linking group (—O—P (OH) (O) —O—), a phosphonic acid linking group (—P (OH) (O) —O—), or a combination thereof), or a combination thereof A linking group is preferred. In addition, when condensing and forming a ring, the said hydrocarbon coupling group may form the double bond and the triple bond suitably, and may connect. The ring to be formed is preferably a 5-membered ring or a 6-membered ring. As the five-membered ring, a nitrogen-containing five-membered ring is preferable, and examples of the compound forming the ring include pyrrole, imidazole, pyrazole, indazole, indole, benzimidazole, pyrrolidine, imidazolidine, pyrazolidine, indoline, carbazole, or these And derivatives thereof. Examples of the 6-membered ring include piperidine, morpholine, piperazine, and derivatives thereof. Moreover, when an aryl group, a heterocyclic group, etc. are included, they may be monocyclic or condensed and may be similarly substituted or unsubstituted.
^RN is a hydrogen atom or a substituent. Examples of the substituent include an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms), and an alkenyl group (preferably having 2 to 24 carbon atoms and 2 carbon atoms). To 12 is more preferable, 2 to 6 is more preferable, and 2 to 3 is particularly preferable, and an alkynyl group (2 to 24 carbon atoms is preferable, 2 to 12 is more preferable, 2 to 6 is more preferable, and 2 to 3 is Particularly preferred), an aralkyl group (preferably 7 to 22 carbon atoms, more preferably 7 to 14 carbon atoms, particularly preferably 7 to 10 carbon atoms), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 14 carbon atoms, 6 to 14 carbon atoms). 10 is particularly preferred).
^RP is a hydrogen atom, a hydroxyl group, or a substituent. Examples of the substituent include an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms), and an alkenyl group (preferably having 2 to 24 carbon atoms and 2 carbon atoms). To 12 is more preferable, 2 to 6 is more preferable, and 2 to 3 is particularly preferable, and an alkynyl group (2 to 24 carbon atoms is preferable, 2 to 12 is more preferable, 2 to 6 is more preferable, and 2 to 3 is Particularly preferred), an aralkyl group (preferably 7 to 22 carbon atoms, more preferably 7 to 14 carbon atoms, particularly preferably 7 to 10 carbon atoms), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 14 carbon atoms, 6 to 14 carbon atoms). 10 is particularly preferred), an alkoxy group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12, more preferably 1 to 6 and particularly preferably 1 to 3), an alkenyloxy group (having carbon number). To 24, more preferably 2 to 12, more preferably 2 to 6, particularly preferably 2 to 3, and an alkynyloxy group (preferably having 2 to 24 carbon atoms, more preferably 2 to 12 and more preferably 2 to 6). More preferably, 2 to 3 are particularly preferred), an aralkyloxy group (preferably 7 to 22 carbon atoms, more preferably 7 to 14 carbon atoms, particularly preferably 7 to 10 carbon atoms), an aryloxy group (preferably 6 to 22 carbon atoms, 6 to 14 are more preferable, and 6 to 10 are particularly preferable.
The number of atoms constituting the linking group L is preferably 1 to 36, more preferably 1 to 24, still more preferably 1 to 12, and particularly preferably 1 to 6. The number of linking atoms in the linking group is preferably 10 or less, and more preferably 8 or less. The lower limit is 1 or more. The number of connected atoms refers to the minimum number of atoms that are located in a path connecting predetermined structural portions and are involved 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 linking atoms is 3.
Specific examples of combinations of linking groups include the following. Oxycarbonyl group (—OCO—), carbonate group (—OCOO—), amide group (—CONH—), urethane group (—NHCOO—), urea group (—NHCONH—), (poly) alkyleneoxy group (— ( Lr-O) x-), carbonyl (poly) oxyalkylene group (-CO- (O-Lr) x-, carbonyl (poly) alkyleneoxy group (-CO- (Lr-O) x-), carbonyloxy ( Poly) alkyleneoxy group (—COO— (Lr—O) x—), (poly) alkyleneimino group (— (Lr—NR ^N ) x), alkylene (poly) iminoalkylene group (—Lr— (NR ^N —) lr) x-), carbonyl (poly) iminoalkylene group ^{(-CO- (NR N -Lr) x-} ), carbonyl (poly) alkyleneimino group (-CO- ^(lr-NR N) -), (Poly) ester group (-(CO-O-Lr) x-,-(O-CO-Lr) x-,-(O-Lr-CO) x-,-(Lr-CO-O) x-,-(Lr-O-CO) x-), (poly) amide group (-(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 an integer of 1 or more, preferably 1 to 500, 1 to 100 is more preferable.
Lr is preferably an alkylene group, an alkenylene group or an alkynylene group. The carbon number of Lr is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3. A plurality of Lr, R ^N , R ^P , x, etc. need not be the same. The direction of the linking group is not limited by the above description, and may be understood as appropriate according to a predetermined chemical formula.

<Formation of transparent cured product>
An example is given and demonstrated about the formation method of transparent hardened | cured material (film | membrane) using the siloxane resin composition of this invention. When the siloxane resin composition is used as a coating solution, it can be applied on a base substrate by a known method such as microgravure coating, spin coating, dip coating, curtain flow coating, roll coating, spray coating or slit coating. . Then, it can pre-bake with heating apparatuses, such as a hot plate or oven, and a film | membrane can be formed. Prebaking is preferably performed at 50 to 150 ° C. for 30 seconds to 30 minutes. The film thickness after pre-baking is preferably 0.1 to 15 μm.

After pre-baking, for example, using an exposure machine such as a stepper, mirror projection mask aligner (MPA) or parallel light mask aligner (hereinafter referred to as PLA), light of about 10 to 4000 J / m ² (wavelength 365 nm exposure amount conversion) is desired. Irradiate through or without the mask. The exposure light source (active radiation) is not limited, and ultraviolet rays such as i-line (wavelength 365 nm), g-line (wavelength 436 nm), or h-line (wavelength 405 nm), KrF (wavelength 248 nm) laser, ArF (wavelength 193 nm) laser, etc. Can be used. Thereafter, post-exposure baking may be performed by heating the film at 150 to 450 ° C. for about 1 hour using a heating device such as a hot plate or an oven. In the present invention, it is particularly preferable to use i-line.

After patterning exposure, the unexposed portion is dissolved by development, and a negative pattern can be obtained. As a developing method, a method of immersing in a developing solution for 5 seconds to 10 minutes by a method such as shower, dipping or paddle is preferable. Examples of the developer include those exemplified above. After development, the film is preferably rinsed with water. Subsequently, dry baking may be performed at 50 to 150 ° C. Thereafter, the film is thermally cured at 120 to 280 ° C. for about 1 hour using a heating device such as a hot plate or an oven to obtain a cured product (film).
Transparent pixels and the like incorporated in the solid-state imaging device can be formed on the substrate in such a procedure.

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

The refractive index of the cured product (film) of the siloxane resin composition of the present invention is preferably 1.65 or more, more preferably 1.70 or more, and particularly preferably 1.75 or more. Although there is no upper limit in particular, it is practical that it is 2.20 or less. Unless otherwise specified, the refractive index is based on the conditions measured in 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 90% or more, more preferably 93% or more, and particularly preferably 95% or more. There is no particular upper limit, but it is practical that it is 99% or less. Unless otherwise specified, the visible light transmittance is based on the conditions measured in the examples described later.

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

<Method for forming microlens array>
An example of a microlens array forming process will be described as an embodiment of a microlens forming method. If necessary, the surface of an uneven element is filled with a transparent resin spin coat and planarized. A lens material is uniformly applied to the flattened surface. A resist is uniformly applied on the lens material. The stepper device irradiates ultraviolet rays using the reticle as a mask to expose the space between the lenses. A pattern is formed by disassembling and removing the portion exposed to the developer. A hemispherical pattern is obtained by heating. At this time, the resist melts into a liquid phase, becomes a hemispherical state, and then changes to a solid phase. Thereafter, the lens material layer is etched by dry etching. In this way, a lens array in which hemispherical lenses are arranged can be formed.
As another embodiment of the lens array forming step, there is a method in which the use of the resist is omitted and the lens material is patterned by exposure. In this embodiment, the patterned lens material is melted as it is to obtain a hemispherical lens.

<Solid-state imaging device>
A solid-state imaging device according to a preferred embodiment of the present invention includes a transparent pixel and / or a microlens made of a cured product of the siloxane resin composition of the present invention. A lens unit is provided on the semiconductor light receiving unit, and the lens array member and the color filter are incorporated so as to be adjacent to each other. The light receiving element receives light passing through the transparent resin film, the lens, and the color filter in this order, and functions as an image sensor. Specifically, the transparent resin film functions as an antireflection film, improves the light collection efficiency of the lens, and the light efficiently collected by the lens is detected by the light receiving element via the color filter. These function over the whole element which detects the light corresponding to RGB. Therefore, even when the light receiving elements and the lenses are arranged with high density, an extremely clear image can be obtained. The cured product of the siloxane resin composition of the present invention can be suitably used as a transparent pixel interposed in the lens or RGB pixel array.

Examples of solid-state imaging devices to which a lens array is applied include those described in Japanese Patent Application Laid-Open No. 2007-119744. Specifically, a transfer electrode is provided between a CCD region and a photoelectric conversion unit formed on the surface of the semiconductor substrate, and a light shielding film is formed thereon via an interlayer film. On the light shielding film, an interlayer insulating film made of BPSG (Boro-Phospho-Silicate Glass), a passivation film, a transparent planarizing film having a low refractive index made of acrylic resin, and the like are laminated. G. B. Are combined to form a color filter. Further, a large number of microlenses are arranged so as to be positioned above the photoelectric conversion portion which is a light receiving region via a protective film.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not construed as being limited to these examples. In this example, “part” and “%” are based on mass unless otherwise specified.

<Example 1 and Comparative Example 1>
(Preparation of fine particle water dispersion sol (E-1))
A white slurry liquid having a pH of 9.5 was prepared by mixing 7.60 kg of an aqueous titanium tetrachloride solution containing 7.75% by mass of titanium tetrachloride on a TiO ₂ basis and 2.91 kg of aqueous ammonia containing 15% by mass of ammonia. . Next, this white slurry was filtered and then washed with ion-exchanged water to obtain 6.21 kg of a hydrous titanate cake having a solid content of 10% by mass.
Next, 7.10 kg of hydrogen peroxide containing 35% by mass of hydrogen peroxide and 20.00 kg of ion exchange water were added to this cake, and then heated at 80 ° C. for 1 hour with stirring. Further, 28.90 kg of ion-exchanged water was added to obtain 62.24 kg of an aqueous solution of titanic acid peroxide containing 1% by mass of titanic acid peroxide in terms of TiO ₂ . This aqueous solution of titanic acid peroxide was transparent yellowish brown and had a pH of 8.5.
Next, 62.20 kg of the above-mentioned aqueous solution of titanic acid titanate was mixed with 3.00 kg of a cation exchange resin (manufactured by Mitsubishi Chemical Corporation), and stannic acid containing 1% by mass of potassium stannate in terms of SnO ₂ conversion. 7.79 kg of aqueous potassium solution was gradually added with stirring.
Next, after separating the cation exchange resin which took in potassium ion etc., this mixed aqueous solution was heated in the autoclave at the temperature of 168 degreeC for 20 hours.
Next, the obtained mixed aqueous solution was cooled to room temperature and then concentrated with an ultrafiltration membrane device to obtain 7.02 kg of an aqueous dispersion sol (E-1) of fine particles having a solid content of 10% by mass. .
The water-dispersed sol (E-1) containing the metal oxide fine particles thus obtained was transparent and milky white.
When the content of the metal component contained in the metal oxide fine particles was measured, TiO ₂ 87.5% by mass, SnO ₂ 10.6% by mass, and K ₂ O It was 8 mass%.

(Preparation of water-dispersed sol (EZ-1) of surface-treated metal oxide fine particles)
The aqueous dispersion sol (E-1) of fine particles obtained as described above was added to 7.02 kg of zirconium oxychloride octahydrochloride having a concentration of 3.6% in terms of ZrO ₂ while adjusting the pH to 7.0 with an aqueous potassium hydroxide solution. 1.54 kg of the aqueous solution of the hydrate was gradually added and 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% in terms of oxide with respect to the metal element contained in the fine particles.
Subsequently, 8.51 kg of an aqueous dispersion of surface-treated metal oxide fine particles with zirconium was spray-dried with a spray dryer (NIRO ATOMIZER manufactured by NIRO). As a result, 0.90 kg of a dry powder composed of surface-treated 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 surface-treated metal oxide fine particles obtained above was calcined for 2 hours at a temperature of 500 ° C. in an air atmosphere, and the calcined powder of the surface-treated metal oxide fine particles 0 .83 kg was obtained.
0.20 kg of the sintered powder of the surface-treated metal oxide particles obtained above was dispersed in 0.18 kg of pure water, and 0.13 kg of a 28.6% concentration tartaric acid aqueous solution and a 50% by mass KOH aqueous solution were added thereto. 0.06 kg was added and sufficiently stirred.
Next, alumina beads having a particle diameter of 0.1 mm (Daimei Chemical Co., Ltd. high-purity alumina beads) were added, and this was subjected to a wet pulverizer (Batch type tabletop sand mill manufactured by Campe Co., Ltd.) for 180 minutes. The fired powder of the surface-treated metal oxide fine particles (titania composite oxide fine particles) was pulverized and dispersed. Thereafter, the alumina beads were separated and removed using a stainless steel filter having an opening of 44 μm, and further 1.38 kg of pure water was added and stirred, and the surface-treated metal oxide having a solid content of 11.0% by mass 1.70 kg of an aqueous dispersion of fine particles was obtained. Next, this aqueous dispersion was washed with ion exchange water using an ultrafiltration membrane, and then 0.09 kg of an anion exchange resin (manufactured by Mitsubishi Chemical Corporation: SANUPC) was added for deionization treatment. Next, the sample was subjected to a centrifuge (CR-21G manufactured by Hitachi Koki Co., Ltd.) for 1 hour at a speed of 11,000 rpm, and then ion-exchanged water was added to the surface-treated metal oxide having a solid content concentration of 10% by mass. 1.86 kg of water-dispersed sol (EZ-1) of fine particles was prepared.
Furthermore, when the content of the metal component contained in the surface-treated metal oxide fine particles was measured, 82.6% by mass of TiO ₂ , 10.3% by mass of SnO ₂ , ZrO based on the oxide conversion standard of each metal component. ₂ 4.9% by mass and K ₂ O 2.2% by mass (TiO ₂ was 79.87 g / mol, ZrO ₂ was 123.2 g / mol, Ti / Zr (molar ratio) in the above formulation) Becomes 26).
Next, after cooling, the dispersion medium is replaced with methanol by using an ultrafiltration membrane device (a filtration membrane manufactured by Asahi Kasei Co., Ltd., SIP-1013), and a methanol dispersion of core-shell inorganic oxide fine particles (EM- 1) 0.32 kg was obtained. As a result, the solid content concentration contained in the obtained methanol dispersion was about 30% by mass, and the water content was 0.28% by mass.
Next, 0.095 kg of propylene glycol monomethyl ether acetate (PGMEA) and 0.038 kg of diacetone alcohol (DAA) were added to 0.30 kg of this methanol dispersion (EM-1), and then heated and stirred at a bath temperature of 100 ° C. Then, methanol in the dispersion was removed, and 0.30 kg of PGMEA / DAA dispersion (EP-1) was prepared. The solid content concentration in the dispersion at this time was 40% by mass.

(Preparation of PGMEA / DAA dispersions (EP-2) to (EP-5) with different ratios of ZrO ₂ )
Except for adjusting the addition amount of the zirconium oxychloride octahydrate aqueous solution at the time of preparation of the water dispersion sol (EZ-1), the amount of ZrO ₂ in accordance with the preparation method of the PGMEA / DAA dispersion (EP-1) Dispersions shown in Table 1 below were prepared. The number average particle diameter (Mn) of the particles contained in each dispersion is shown in the table. The measurement method was as described above.

The components of the following formulation 1 were placed in a reaction vessel, and 16.1 g of water and 0.26 g of phosphoric acid were added dropwise to this solution while stirring so that the reaction temperature did not exceed 40 ° C. After the dropwise addition, a distillation apparatus was attached to the flask, and the resulting solution was heated and stirred at a bath temperature of 105 ° C. for 2.5 hours, and reacted while distilling off the methanol produced by hydrolysis. Thereafter, the solution was further heated and stirred at a bath temperature of 115 ° C. for 2 hours and then cooled to room temperature to obtain a polymer solution S-1 (solid content: 30% by mass).
[Prescription 1]
Methyltrimethoxysilane 20.4g
(0.15 mol 136.2 g / mol)
Phenyltrimethoxysilane 69.4g
(0.35 mol 198.3 g / mol)
PGMEA / DAA dispersion (EP-1) (solid content 40% by mass) 243 g
PGMEA 127g
DAA 51g

10 g of mesityl oxide was added to 90 g of this polymer solution S-1, and 0.5 g of IRGACURE OXE02 was added as a photoinitiator. Furthermore, each sample of the siloxane resin composition was prepared by changing the additional solvent as shown in Table 2 below. In sample 113, IR369 was added as a photoinitiator.

The following thermocycle test was performed on each sample of the siloxane resin composition produced above. The results are shown in Table 3.

<Thermocycle test [TC test]> Each completed sample was stored in a glass sealed container. Then, using a thermocycle tester (manufactured by Hutech, LTS-150-W [trade name]), a thermocycle at 5 ° C. for 4 hours and 25 ° C. for 2 hours was repeated for 90 days to obtain a sample for thermocycle test It was created.
A sample for thermo cycle test was applied to high refractive index glass (SFLD-6 [trade name] manufactured by Sumita Optical Glass Co., Ltd.) with a spine coater (1H-360S (Mikasa Co., Ltd.)), and a hot plate And prebaked at 100 ° C. for 2 minutes to obtain a coating film. This coating film was further heated at 200 ° C. for 5 minutes on a hot plate in an air atmosphere to obtain a cured film having a thickness of 0.6 μm.
About the obtained cured film, the 1 mm square of the central portion was magnified 100 times with an optical microscope, the defects were visually observed, and the number in 1 mm square was counted and used as an evaluation standard. The average value of five samples was adopted for evaluation.

1 Number of defects 50 or more 2 Number of defects 25 or more and less than 50 3 Number of defects 10 or more and less than 25 4 Number of defects 5 or more and less than 10 5 Number of defects 1 or more and less than 5 6 Didn't exist

Formulation: parts by mass Ti / Zr is the elemental composition ratio (molar ratio)
Siloxane resin: Hydrolysis condensation of MTMS / PTMS MTMS: Methyltrimethoxysilane PTMS: Phenyltrimethoxysilane PGMEA: Propylene glycol monomethyl ether acetate DAA: Diacetone alcohol MeOH 20: Means that 20 parts of methanol was used instead of DAA To do.
OXE02: IRGACURE OXE02
IR369: IRGACURE-369

-Aspect in which titanium particles are not coated-
<Example 2>
(Preparation of fine particle water dispersion sol (E-21))
7.60 kg of titanium tetrachloride aqueous solution containing 7.75% by mass of titanium tetrachloride in terms of TiO ₂ and 2.91 kg of aqueous ammonia containing 15% by mass of ammonia were mixed, and these were mixed in terms of ZrO _{2 by} mass. 7.6 kg of a 1.23% concentration zirconium oxychloride octahydrate aqueous solution was added dropwise over 24 hours to prepare a white slurry having a pH of 8.8. Next, the white slurry was diluted 5 times with ion-exchanged water, filtered, and further washed with ion-exchanged water to obtain 5.2 kg of a hydrous titanium zirconate cake having a solid content of 10% by mass. .
Next, 7.10 kg of hydrogen peroxide containing 35% by mass of hydrogen peroxide and 20.0 kg of ion exchange water were added to the cake, and then heated at 80 ° C. for 1 hour with stirring. Further, 28.90 kg of ion-exchanged water was added to obtain 61.39 kg of an aqueous titanium zirconate solution containing 1% by mass of titanium zirconate in terms of TiO ₂ . This aqueous solution of titanium zirconate acid was transparent yellowish 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 titanium peroxide zirconate aqueous solution, and tin containing 1% by mass of potassium stannate in terms of SnO ₂ conversion standard was added thereto. 8.01 kg of potassium acid aqueous solution was gradually added with stirring. Next, after separating the cation exchange resin which took in potassium ion etc., this mixed aqueous solution was heated in the autoclave at the temperature of 168 degreeC for 20 hours.
Next, the obtained mixed aqueous solution was cooled to room temperature and then concentrated with an ultrafiltration membrane device to obtain 6.89 kg of a fine particle water dispersion sol (E-21) having a solid content of 10% by mass. .
The water-dispersed sol (E-21) containing the metal oxide fine particles thus obtained was transparent and milky white.
When the content of the metal component contained in the metal oxide fine particles was measured, it was 90.0% by mass of TiO ₂ , 4.2% by mass of SnO ₂ , 0.2% by mass of K ₂ O, based on the oxide conversion standard of each metal component. 5 wt%, and was _ZrO 2 5.3% by mass.

(Preparation of metal oxide fine particle water dispersion sol (EZ-21))
7.51 kg of the water-dispersed sol (E-21) containing the above metal oxide fine particles was spray-dried with a spray dryer (NIRO ATOMIZER manufactured by NIRO). As a result, 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 dried powder of metal oxide fine particles obtained above was fired at 500 ° C. for 2 hours in an air atmosphere to obtain 0.90 kg of fired powder of metal oxide fine particles. It was.
0.20 kg of the fired powder of metal oxide fine particles obtained above was dispersed in 0.18 kg of pure water. 06 kg was added and stirred thoroughly.
Next, alumina beads having a particle diameter of 0.1 mm (Daimei Chemical Co., Ltd. high-purity alumina beads) were added, and this was subjected to a wet pulverizer (Batch type tabletop sand mill manufactured by Campe Co., Ltd.) for 180 minutes. The fired powder of metal oxide fine particles was pulverized and dispersed. Thereafter, the alumina beads were separated and removed using a stainless steel filter having an opening of 44 μm, and further 1.39 kg of pure water was added and stirred to obtain metal oxide fine particles having a solid content of 11.0% by mass. 1.70 kg of aqueous dispersion was obtained.
Next, this aqueous dispersion was washed with ion exchange water using an ultrafiltration membrane, and then 0.09 kg of an anion exchange resin (manufactured by Mitsubishi Chemical Corporation: SANUPC) was added for deionization treatment. Next, the resultant was subjected to a centrifuge (CR-21G manufactured by Hitachi Koki Co., Ltd.) for 1 hour at a speed of 11,000 rpm, and then ion-exchanged water was added to form metal oxide fine particles having a solid content concentration of 10% by mass. 1.86 kg of an aqueous dispersion sol (EZ-21) was prepared.
Furthermore, when the content of the metal component contained in the metal oxide fine particles was measured, TiO ₂ 88.9% by mass, SnO ₂ 5.3% by mass, ZrO ₂ 5 based on the oxide conversion standard of each metal component. 0.3 wt% and K ₂ O 0.5 wt% (TiO ₂ was 79.87 g / mol, ZrO ₂ was 123.2 g / mol, and Ti / Zr (molar ratio) in the above composition was 26 Becomes).
Next, after cooling the water dispersion sol (EZ-21), the dispersion medium was replaced from water to methanol using an ultrafiltration membrane device (a filtration membrane manufactured by Asahi Kasei Co., Ltd., SIP-1013). 0.32 kg of a fine particle methanol dispersion (EM-21) was obtained. As a result, the solid content concentration contained in the obtained methanol dispersion was about 30% by mass, and the water content was 0.28% by mass.
Next, 0.095 kg of propylene glycol monomethyl ether acetate (PGMEA) and 0.038 kg of diacetone alcohol (DAA) were added to 0.30 kg of this methanol dispersion (EM-21), and then heated and stirred at a bath temperature of 100 ° C. Then, methanol in the dispersion was removed, and 0.30 kg of PGMEA / DAA dispersion (EP-21) was prepared. The solid content concentration in the dispersion at this time was 40% by mass.

(Preparation of PGMEA / DAA dispersions (EP-22) to (EP25) with different ratios of ZrO ₂ )
Except for adjusting the addition amount of the zirconium oxychloride octahydrate aqueous solution at the time of preparing the water dispersion sol (E-21), the amount of ZrO ₂ was determined according to the preparation method of the PGMEA / DAA dispersion (EP-21). Dispersions shown in Table 4 below were prepared. Table 4 shows the number average particle diameter (Mn) of the particles contained in each dispersion.

In the preparation of the polymer solution S-1, a PEGMEA / DAA dispersion (EP-21) (solid content 40% by mass) was used instead of the PEGMEA / DAA dispersion (EP-1) (solid content 40% by mass). In the same manner as above, a polymer solution S-2 (solid content: 30% by mass) was obtained.

10 g of mesityl oxide was added to 90 g of this polymer solution S-2, and 0.5 g of IRGACURE OXE02 was added as a photoinitiator. Furthermore, each sample of the siloxane resin composition was prepared by changing the additional solvent as shown in Table 5 below. In sample 213, IR369 was added as a photoinitiator.

The thermocycle test was conducted in the same manner as in Example 1 for each sample of the siloxane resin composition produced above. The results are shown in Table 6.

<Example 3>
(Preparation of PGMEA / DAA dispersions (EP-31) to (EP-35) with different number average particle diameters)
When preparing the water-dispersed sol (E-21), the average particle size was adjusted by increasing the heat treatment temperature and treatment time of the metal oxide fine particles. Except for adjusting the average particle size, the dispersions shown in Table 7 below were prepared by changing the amount of ZrO ₂ in accordance with the method for preparing the PEGMEA / DAA dispersion (EP-21). Table 7 shows the number average particle diameter (Mn) of the particles contained in each dispersion. The measuring method is as described above.

In the preparation of the polymer solution S-1, a PEGMEA / DAA dispersion (EP-31) (solid content 40% by mass) was used instead of the PEGMEA / DAA dispersion (EP-1) (solid content 40% by mass). In the same manner as above, a polymer solution S-3 (solid content: 30% by mass) was obtained.

10 g of mesityl oxide was added to 90 g of this polymer solution S-3, and 0.5 g of IRGACURE OXE02 was added as a photoinitiator. Furthermore, each sample of the siloxane resin composition was prepared by changing the additional solvent as shown in Table 8 below. In sample 313, IR369 was added as a photoinitiator.

The thermocycle test was conducted in the same manner as in Example 1 for each sample of the siloxane resin composition produced above. The results are shown in Table 9.

-Aspect where titanium particles are coated with Si-
<Example 4>
(Preparation of silicic acid solution)
After diluting 0.31 kg of commercially available water glass (manufactured by AGC S-Tech Co., Ltd.) with pure water, it is dealkalized using a cation exchange resin (manufactured by Mitsubishi Chemical Corporation) to convert silicic acid into SiO ₂ As a result, 3.00 kg of an aqueous silicic acid solution containing 2.0% by weight was obtained. The silicic acid aqueous solution had a pH of 2.3.

(Preparation of aqueous dispersion sol (E-41) of core (Ti and Zr) shell (Si) type inorganic oxide fine particles)
After adding 12.3 kg of pure water to 1.80 kg of water-dispersed sol (E-21) containing metal oxide fine particles, stirring and heating to 90 ° C., 2.39 kg of aqueous silicic acid solution is gradually added thereto. After the addition, this mixed solution was aged for 10 hours under stirring while maintaining the temperature at 90 ° C. At this time, the amount of the composite oxide covering the metal oxide fine particles was 12 parts by mass with respect to 100 parts by mass of the metal oxide fine particles.
Next, this mixed solution was put in an autoclave (manufactured by Pressure Glass Industrial Co., Ltd.) and subjected to heat treatment at a temperature of 165 ° C. for 18 hours.

Next, the obtained mixed solution was cooled to room temperature and then concentrated with an ultrafiltration device to obtain an aqueous dispersion sol (E-41). This water-dispersed sol (E-41) was subjected to ultrafiltration membrane (SIP-1013, manufactured by Asahi Kasei Co., Ltd.), and the dispersion medium was replaced with water to methanol to obtain a metal oxide fine particle methanol dispersion (EM- 41) 0.31 kg was obtained. As a result, the solid content concentration contained in the obtained methanol dispersion was about 30% by mass, and the water content was 0.25% by mass.
Next, 0.095 kg of propylene glycol monomethyl ether acetate (PGMEA) and 0.038 kg of diacetone alcohol (DAA) were added to 0.30 kg of this methanol dispersion (EM-41), and then heated and stirred at a bath temperature of 100 ° C. Then, methanol in the dispersion was removed, and 0.30 kg of PGMEA / DAA dispersion (EP-41) was prepared. The solid content concentration in the dispersion at this time was 40% by mass.

As a result, core (Ti and Zr) shell (Si) type metal oxide fine particles obtained by coating the surface of the metal oxide fine particles with an oxide containing silicon were obtained. When the content of the metal component contained in the obtained core-shell type metal oxide fine particles was measured, TiO _{2 was} 86.3% by mass, SnO ₂ 5.1% by mass, ZrO based on the oxide conversion standard of each metal component. ₂ 5.1% by mass and K ₂ O 0.5% by mass (TiO ₂ was 79.87 g / mol, ZrO ₂ was 123.2 g / mol, Ti / Zr (molar ratio) in the above formulation) Becomes 26).

(Preparation of PGMEA dispersions (EP-42) to (EP-45) with different ratios of ZrO ₂ )
The PGMEA / DAA dispersion (EP- In accordance with 41), dispersions shown in Table 10 below with varying amounts of ZrO ₂ were prepared. Table 10 shows the number average particle diameter (Mn) of the particles contained in each dispersion.

In the preparation of the polymer solution S-1, PGMEA / DAA dispersion (EP-41) (solid content 40% by mass) was used instead of PEGMEA / DAA dispersion (EP-1) (solid content 40% by mass). In the same manner as above, a polymer solution S-4 (solid content: 30% by mass) was obtained.

10 g of mesityl oxide was added to 90 g of this polymer solution S-4, and 0.5 g of IRGACURE OXE02 was added as a photoinitiator. Furthermore, each sample of the siloxane resin composition was prepared by changing the additional solvent as shown in Table 11 below. In sample 413, IR369 was added as a photoinitiator.

The thermocycle test was conducted in the same manner as in Example 1 for each sample of the siloxane resin composition produced above. The results are shown in Table 12.

<Example 5>
(Preparation of PGMEA / DAA dispersions (EP-51) to (EP-55) with different number average particle diameters)
When preparing the water-dispersed sol (E-21), the average particle size was adjusted by increasing the heat treatment temperature and treatment time of the metal oxide fine particles. Except for adjusting the average particle diameter, a dispersion shown in Table 13 below was prepared in which the amount of ZrO ₂ was changed in accordance with the method for preparing a PEGMEA / DAA dispersion (EP-41). Table 13 shows the number average particle diameter (Mn) of the particles contained in each dispersion. The measuring method is as described above.

In the preparation of the polymer solution S-1, PGMEA / DAA dispersion (EP-51) (solid content 40% by mass) was used instead of PEGMEA / DAA dispersion (EP-1) (solid content 40% by mass). In the same manner as above, a polymer solution S-5 (solid content: 30% by mass) was obtained.

10 g of mesityl oxide was added to 90 g of this polymer solution S-5, and 0.5 g of IRGACURE OXE02 was added as a photoinitiator. Further, each sample of the siloxane resin composition was prepared by changing the additional solvent as shown in Table 14 below. In sample 513, IR369 was added as a photoinitiator.

The thermocycle test was conducted in the same manner as in Example 1 for each sample of the siloxane resin composition produced above. The results are shown in Table 15.

From the above results, it can be seen that the siloxane resin composition of the present invention achieves excellent thermocycle characteristics and contributes to improving the manufacturing suitability and manufacturing quality.

When the optical properties of the transparent cured film of Test 101 were confirmed, the refractive index was 1.8 and the light transmittance was 90% or more. The optical characteristics of other test films were confirmed in the same manner, and it was confirmed that all of the films of the examples exhibited a desired high refractive index and high light transmittance. The refractive index and light transmittance were measured as follows.

-Measurement of refractive index and visible light transmittance-
A sample for thermocycle test was applied to a high refractive index glass (SFLD-6 manufactured by Sumita Optical Glass Co., Ltd.) for 10 seconds at 700 rpm, 30 seconds at 1100 rpm, and a spin coater (1H-360S [trade name] (Mikasa Corporation). )))). Using a hot plate (SCW-636 [trade name] manufactured by Dainippon Screen Mfg. Co., Ltd.), the coating film was obtained by prebaking at 120 ° C. for 3 minutes. This coating film was heated on a hot plate in an air atmosphere at 230 ° C. for 5 minutes to obtain a cured film having a thickness of 0.5 μm. About the obtained cured film, the refractive index in wavelength 633nm in 25 degreeC room temperature was measured using the ellipsometer (made by Otsuka Electronics Co., Ltd.). At this time, the light transmittance of this coating film (test transparent film) was measured from 400 nm to 700 nm. As the transmittance, a minimum transmittance value of 400 to 700 nm was adopted. The test was performed 5 times for each sample, and the average value of 3 results excluding the maximum and minimum values was adopted.

In the above formulation 1, a resin composition was similarly prepared by replacing methyltrimethoxysilane with ethyltrimethoxysilane. Further, a siloxane resin composition was similarly prepared by replacing part of methyltrimethoxysilane with tetramethoxysilane. When the thermocycle test was implemented using these siloxane resin compositions, it was confirmed that good results were obtained in all cases.

Claims

Metal-containing particles, siloxane resin, mesityl oxide, solvent,
A siloxane resin composition containing
The siloxane resin composition according to claim 1, wherein the content of the mesityl oxide is 0.01 mass% or more and 15 mass% or less.
The siloxane resin composition according to claim 1 or 2, wherein the content of the mesityl oxide is 0.09% by mass or less.
The siloxane resin composition according to any one of claims 1 to 3, 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 4, comprising 30 parts by mass or more and 80 parts by mass or less of a siloxane resin with respect to 100 parts by mass of the metal-containing particles.
The siloxane resin composition according to any one of claims 1 to 5, wherein the content of the metal-containing particles in the solid component of the siloxane resin composition is 10% by mass or more and 90% by mass or less.
The element according to any one of claims 1 to 6, comprising a metal selected from Ti, Ta, W, Y, Ba, Hf, Zr, Sn, Nb, V, and Si as an element constituting the metal-containing particle. The siloxane resin composition described.
As elements constituting the metal-containing particles, Ti and Zr are contained,
The siloxane resin composition according to any one of claims 1 to 7, wherein, in the elements constituting the metal-containing particles, the ratio of Ti and Zr, Ti / Zr, is 1 to 40 in terms of elemental composition ratio.
As elements constituting the metal-containing particles, Ti and Zr are contained,
The siloxane resin composition according to any one of claims 1 to 8, wherein, in the elements constituting the metal-containing particles, the ratio of Ti and Zr, Ti / Zr, is 4 to 12 in terms of elemental composition ratio.
The siloxane resin composition according to any one of claims 1 to 9, wherein the metal-containing particles have a number average particle diameter of 5 nm to 30 nm.
The siloxane resin composition according to any one of claims 1 to 10, wherein the solvent contains diacetone alcohol.
The siloxane resin composition according to any one of claims 1 to 11, wherein the siloxane resin is obtained by a hydrolytic condensation reaction in the presence of the metal-containing particles.
A transparent cured product obtained by curing the siloxane resin composition according to any one of claims 1 to 12.
A transparent pixel comprising the transparent cured product according to claim 13.
A microlens made of the transparent cured product according to claim 13.
A solid-state imaging device comprising the transparent pixel according to claim 14 and / or the microlens according to claim 15.