TWI663478B - Siloxane resin composition, transparent hardened product using the same, transparent pixels, microlenses, solid-state imaging element - Google Patents

Abstract

A siloxane resin composition comprising metal-containing particles, a siloxane resin, a solvent A having a boiling point of 210 ° C or higher and 270 ° C or lower at 1 atmosphere and a solvent B having a boiling point lower than 210 ° C at 1 atmosphere The silicone resin composition contains the above-mentioned metal-containing particles in a solid content of 40% by mass or more and 80% by mass or less.

Description

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

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

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

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

[Previous Technical Literature]

[Patent Literature]

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

An object of the present invention is to provide a siloxane resin composition suitable as a material for transparent members such as lenses and transparent pixels. In addition, an object of the present invention is to provide a silicone resin composition, which is not limited to a positive type, and can also be applied to a heat-curable resin or a negative photosensitive resin, and can also appropriately respond to micro Fine processing of lenses and transparent pixels, and the properties of the cured film can be optimized as required. 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 above-mentioned siloxane resin composition.

The above-mentioned problems are solved by the following means.

[1] A silicone resin composition containing metal-containing particles, a silicone resin, a solvent A having a boiling point of 210 ° C or higher and 270 ° C or lower at 1 atmosphere and a solvent B having a boiling point lower than 210 ° C at 1 atmosphere, The silicone resin composition contains the above-mentioned metal-containing particles in a solid content of 40% by mass or more and 80% by mass or less.

[2] The siloxane resin composition according to [1], wherein the metal-containing particles contain at least one selected from the group consisting of Ti, Ta, W, Y, Ba, Hf, Zr, Sn, Nb, V, and Si Element as its constituent metal element.

[3] The siloxane resin composition according to [1] or [2], wherein the metal-containing particles contain Ti and Zr as constituent metal elements.

[4] The siloxane resin composition according to any one of [1] to [3], wherein the refractive index of the metal-containing particles is 1.75 to 2.70.

[5] The siloxane resin composition according to any one of [1] to [4], It contains Ti and Zr as elements constituting the above metal-containing particles, where Ti / Zr is 1 to 30.

[6] The siloxane resin composition according to any one of [1] to [5], which is a UV-curable resin composition.

[7] The siloxane resin composition according to any one of [1] to [6], further containing a polymerizable initiator.

[8] The siloxane resin composition according to any one of [1] to [7], wherein the siloxane resin is a hydrolysis-condensation reaction product of an alkoxysilane compound.

[9] The siloxane resin composition according to any one of [3] to [8], which contains 5 to 50 parts by mass based on 100 parts by mass of the metal element-containing Ti element and based on the Si element. Of the above-mentioned siloxane resin.

[10] The siloxane resin composition according to any one of [1] to [9], wherein the solvent A is selected from an ether compound solvent, an alcohol compound solvent, and an ester compound solvent.

[11] The siloxane resin composition according to any one of [1] to [10], wherein the solvent A is selected from a compound represented by any one of the following formulae (V1) to (V4) .

R ^V1 (CO) O- (L ^V1 -L ^V2 ) _mv -R ^V2 (V1)

R ^V3 (CO) O- (L ^V3 )-(O (CO) R ^V4 ) _nv (V2)

R ^V6 O- (L ^V4 -L ^V5 ) _pv -R ^V5 (V3)

[Chemical Formula 1]

R ^V1 is alkyl, alkenyl, alkynyl, aryl, or aralkyl; L ^V1 is a hydrocarbon linking group; L ^V2 is a heteroatom-containing linking group; R ^V2 is a hydrogen atom, a halogen atom, a fluorenyl group, or R ^V1 The meaning is the same; mv is an integer from 0 to 8; R ^V3 and R ^V4 are independently the same as R ^V1 ; L ^V3 is an alkane linking group, an olefin linking group, an alkyne linking group, an aromatic linking group or a combination of these Nv is an integer of 1 to 3; L ^V4 is a hydrocarbon linking group; L ^V5 is a heteroatom-containing linking group; R ^V5 has the same meaning as R ^V2 ; pv is an integer of 1 to 8; R ^V6 is a hydrogen atom or is the same as R ^V1 has the same meaning; a is a ring structure of 4-membered ring to 7-membered ring.

[12] The silicone resin composition according to any one of [1] to [11], wherein the solvent B is diacetone alcohol, dipropylene glycol monomethyl ether, or propylene glycol monomethyl ether acetate.

[13] The siloxane resin composition according to any one of [1] to [12], wherein the SP value of the solvent A is 8.7 or more and 10 or less.

[14] The siloxane resin composition according to any one of [1] to [13], wherein a boiling point of the solvent A is 230 ° C or higher.

[15] The silicone resin composition according to any one of [1] to [14], wherein the silicone resin composition further contains a polymerizable compound, and the polymerizable compound has an epoxy group selected , Oxetanyl, and at least one Polymerizable group of ethylenically unsaturated double bonds.

[16] The siloxane resin composition according to any one of [1] to [15], wherein the siloxane resin is obtained by performing a hydrolysis condensation reaction in the presence of the metal-containing particles.

[17] The siloxane resin composition according to any one of [1] to [16], wherein the refractive index of the cured film is 1.60 or more and 2.0 or less.

[18] A transparent hardened material obtained by curing the siloxane resin composition according to any one of [1] to [17].

[19] A transparent pixel including the transparent hardened body according to [18].

[20] A microlens including the transparent hardened body according to [18].

[21] A solid-state imaging device including the transparent pixel according to [19] and / or the microlens according to [20].

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

The "radiation" in this specification refers to, for example, a bright line spectrum of a mercury lamp, an extreme ultraviolet (EUV light), an X-ray, an electron beam, and the like represented by an excimer laser. In the present invention, light means active light or radiation. Unless otherwise specified, the "exposure" in this specification includes not only exposure through far-ultraviolet rays, X-rays, and EUV light represented by a bright line spectrum of an mercury lamp, excimer laser, or the like, and electron beam or ion beam Isobeam rendering is also included in exposure.

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

In addition, in this specification, a "single body" and a "monomer" have the same meaning. The singular body 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 refers to a compound having a polymerizable group, and may be a singular body or a polymer. Polymerizability refers to the group participating in the polymerization reaction.

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

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

The siloxane resin composition of the present invention is suitable as a material for transparent members such as lenses and transparent pixels. The above-mentioned siloxane resin composition is not limited to a positive type, and can also be applied to a heat-curable resin or a negative photosensitive resin, and can also appropriately respond to micro-processing of microlenses and transparent pixels. Furthermore, the characteristics (crack resistance, gel defect resistance, and surface unevenness prevention) of the cured film can be optimized as required. In addition, it is possible to provide a transparent hardened material, a transparent pixel, a microlens, and a solid-state imaging element with excellent quality using the above-mentioned siloxane resin composition.

1‧‧‧lens material

1a‧‧‧Micro lens

2‧‧‧leveling film

3‧‧‧ substrate

4‧‧‧ photo resist

4a‧‧‧ patterned photosensitive material

4b‧‧‧ hemispherical photosensitive material

10‧‧‧Microlens Array

FIG. 1 is an explanatory diagram schematically showing the manufacturing steps of the lens array, in which (1) refers to a coating and curing step, and (2) refers to a coating step of an i-ray photosensitive material (i- (line photo resist coating), (3) refers to a patterning and photolithography step (Patterning by Litho.), (4) refers to a thermal flow step, and (5) refers to dry etching.

FIG. 2 is a schematic diagram showing differences in pattern shapes evaluated in Examples.

The silicone resin composition of the present invention contains metal-containing particles, a silicone resin, and a specific solvent. Thereby, although the content is not clear, the reason for exerting the above-mentioned effects can be considered as follows. It is considered that when metal-containing particles coexist in the siloxane resin, the metal-containing particles function as a catalyst and react in the system. This may affect the generation of cracks and the like. On the other hand, it is inferred that the above-mentioned specific high-boiling-point solvent is used in the invention of the present application and, for example, remains in the system even after film formation, thereby exhibiting the stress-relieving effect of suppressing the reaction and exerting its unique effect. Furthermore, it is presumed that by using this combination together with a low-boiling-point solvent, the drying performance can be improved while maintaining the above-mentioned performance-improving effect, thereby contributing to the improvement of manufacturing adaptability such as coatability.

Hereinafter, preferred embodiments will be described in detail.

<Metal-containing particles>

The metal-containing particles widely include particles containing a metal as a constituent element. Here, the word "metal" should be interpreted in the broadest sense, and it is assumed that metals such as boron, silicon, and arsenic are also included here. When a metal-containing particle is comprised by including an oxygen atom, it may be especially called a metal oxide particle.

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

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

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

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

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

~ Measurement of refractive index of particles ~

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

~ Measurement of average particle size ~

The number average particle diameter of the metal-containing particles (indicating the average particle diameter among the primary particle diameters) can be obtained from a photograph obtained by observing the particles with a transmission electron microscope. The projected area of the particles was calculated, the equivalent circle diameter was calculated, and the number average particle diameter was calculated. In addition, in order to obtain the average particle diameter, the particle diameter was measured for 100 particles. An average value of the measured particle diameters, excluding the maximum 10 and the minimum 10, was taken as the average particle diameter. In this specification, the average particle diameter means a number average particle diameter unless otherwise specified.

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

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

As the content ratio (elemental composition) of the metal element in the metal-containing particles, Contains Ti and Zr, and its ratio is based on Ti / Zr ratio, 1 or more is preferred, 3 or more is preferred, 4 or more is preferred, and the upper limit is preferably 40 or less, 30 or more is preferred, and 20 or less is further It is better, especially below 12. When such a numerical range is satisfied, it is preferable because the storage property of the composition can be improved while maintaining the refractive index. In addition, by setting the Ti / Zr ratio to this range, the light resistance of the cured product of the siloxane resin composition can be optimized, which is preferable. In particular, in the present invention, the interaction with a specific solvent is further improved, and the desired light resistance can be exhibited at a high level while maintaining the high refractive index of the cured product of the siloxane resin composition, which is preferable.

In addition, Ti and Si are contained in a ratio of Ti / Si, preferably 1 or more. The upper limit is preferably 40 or less, more preferably 30 or less, and even more preferably 10 or less.

The Ti / Sn ratio is preferably 10 or more, 13 or more is more preferable, 15 or more is further preferable, 17 or more is further preferable, 19 or more is further preferable, and 20 or more is more preferable. As the upper limit, 1,000 or less is preferred, 500 or less is preferred, 300 or less is further preferred, 100 or less is further preferred, 60 or less is further preferred, 50 or less is further preferred, and 40 or less is more preferred.

By setting the Ti / Sn ratio to be in this range, the effect of improving the affinity of the organic component used with the metal-containing particles can be expected, and therefore it is preferable.

~ Measurement of Metal Element Content ~

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

The surface treatment of the metal-containing particles may be in an arbitrary state, for example, a state of being treated with a surfactant described later, a state of being treated with a treating agent containing another metal, and the like. For example, a state in which a specific metal-containing particle is formed, and another film such as a metal-containing substance is formed on the surface thereof is mentioned. Alternatively, another film such as a metal-containing substance may be made thicker as the core-shell type metal-containing particles. The ratio of the core to the shell is not particularly limited. When the entire particle is 100 parts by mass, the ratio of the core is preferably 85 parts by mass or more, more preferably 87 parts by mass or more, and even more preferably 90 parts by mass or more. The upper limit is actually 97 parts by mass or less. The combination of the material constituting the core and the shell is not particularly limited, and examples include a core composed of particles containing Ti, Sn, etc., and a shell composed of a film containing Zr, a film containing Si, or a film containing Zr and Si. In order to increase the refractive index of the particles, the material constituting the shell is particularly preferably a high refractive index material. In addition, when titanium oxide is contained as the metal-containing particle component used in the core, the shell system is more preferable than a light-stable material (for example, zirconium) for the purpose of suppressing the photocatalytic activity of the titanium oxide component present on the particle surface. .

The content of the metal-containing particles in the solid content of the composition (silicone resin composition) is 40% by mass or more, 50% by mass or more is preferable, and 55% by mass or more is particularly preferable. The upper limit is 80% by mass or less, and more preferably 70% by mass or less. By using more metal-containing particles, the refractive index of the cured film can be increased. On the other hand, in a composition in which a large amount of metal-containing particles are blended, a gel is easily generated in the system, and it is easy to cause surface unevenness and cracking of the hardened material. The effect of this phenomenon on gold The concentration index of the metal particles became functionally significant. On the other hand, in the present invention, by applying two or more solvents having different boiling points, even if the metal particles are blended at a high concentration, it is possible to suppress the derivation effect and exhibit good optical characteristics.

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

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

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

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

Examples of the solvent for forming the sol include alkaline aqueous solutions such as ammonia, potassium hydroxide, and sodium hydroxide; acidic aqueous solutions such as hydrochloric acid, nitric acid, and sulfuric acid. Alternatively, a sol-gel method using water or various organic media to dissolve a metal alkoxide can be mentioned. Wait.

As a method for producing metal-containing particles that can be used in the present invention, for example, the methods described in paragraphs [0015] to [0043] of Japanese Patent Application Laid-Open No. 2008-69193 can be referred to. In addition, as the specific metal-containing particles, those described in paragraphs [0015] to [0043] of Japanese Patent Application Laid-Open No. 2008-69193 can be used and incorporated into the present application by reference.

<Silicone resin>

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

(R1) aSi (OR2) 4-a (1)

R1 and R2 each independently represent a hydrogen atom or a hydrocarbon group. The hydrocarbon group is an alkyl group (1 to 12 carbon atoms is preferred, 1 to 6 is more preferred, 1 to 3 is more preferred), an alkenyl group (2 to 12 carbon atoms is preferred, 2 to 6 is more preferred), Alkynyl (carbon number 2-12 is preferred, 2-6 is more preferred), aryl (carbon number 6-22 is preferred, 6-14 is more preferred, 6-10 is more preferred), arane A group (carbon number 7 to 23 is more preferable, 7 to 15 is more preferable, and 7 to 11 is more preferable), and an alkyl group, an aryl group, or an alkenyl group is more preferable.

a is 0, 1, or 2.

R3Si (R4) C (OR5) 3-C (2)

R3 is a functional group-containing group. The functional group is preferably a group containing a hetero atom (S, O, N, P, Si, etc.) in the structure. Alternatively, it is preferable to contain a polymerizable group, an acidic group, or a basic group. (Meth) acrylic acid group, thiol group (Sulfanyl group), epoxy group, oxetanyl group, shrink group, glycidyloxy group, hydroxyl group, phenolic hydroxyl group, carboxyl group, Phosphate group, sulfonic acid group, phosphonic acid group, amine group, isocyanate group, urea group or a group having these substituents. When R3 is bonded to Si via a linking group, examples of the linking group L described below can be cited, and among them, a hydrocarbon linking group is preferred. The carboxyl group, sulfonic acid group, phosphate group, and phosphonic acid group may form a salt or an ester, and an acid anhydride thereof. Amine groups can also form salts. In addition, in this specification, when it is called "acrylic acid" or "acrylfluorene", it generally refers to those which include not only an acrylfluorene group but a derivative structure thereof, and a structure having a specific substituent at the α -position of the acrylfluorene group. However, in a narrow sense, the case where the α -position is a hydrogen atom is sometimes referred to as acrylic acid or acrylic fluorene. Those having a methyl group in the α position are referred to as methacrylic acid, and may be referred to as (meth) acrylic acid in the meaning of any one of acrylic acid (the α position is a hydrogen atom) and methacrylic acid (the α position is a methyl group). Wait.

R4 and R5 are each independently a group having the same meaning as R1.

c is 0 or 1.

R63Si-X- (SiR73) d (3)

R6 and R7 are each independently a group having the same meaning as the above-mentioned R1, or are alkoxy groups (the number of carbon atoms is preferably from 1 to 12, more preferably from 1 to 6, especially from 1 to 3), alkenyloxy (2 to 12 carbon atoms is preferred, 2 to 6 is more preferred), alkynyloxy (2 to 12 carbon atoms are preferred, 2 to 6 is more preferred), aryloxy (6 to 22 carbons is preferred, 6 to 14 is more preferred, 6 to 10 is more preferred) or aralkyloxy Group (carbon atoms 7 to 23 are preferred, 7 to 15 are more preferred, 7 to 11 are particularly preferred). One to four of R6 and R7 may be a group of R3.

X is a divalent or more linking group. When X is a divalent linking group, examples of the linking group L described below can be cited. Specific examples thereof include S, O, CO, NRN, and polythio groups (2 to 6 of S). When X is a trivalent linking group, an isocyanuric acid skeleton is mentioned, for example. d is an integer from 1 to 4, and 1 or 2 is preferred.

R1 to R7 each independently have an arbitrary substituent T. In addition, it can be bonded to the silicon atom together with the linking group L within a range where the effects of the present invention are exhibited. Or the neighbors may be bonded or condensed with each other to form a ring.

Examples of the silane compound represented by the formula (1): Examples of the trifunctional silane compound include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, and methyltriisocyanate. Propoxysilane, methyltri-n-butoxysilane, methyltri-n-butoxysilane, methyltri-second-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propane Trimethoxysilane, butyltrimethoxysilane, pentyltrimethoxysilane, cyclopentyltrimethoxysilane, hexyltrimethoxysilane, cyclohexyltrimethoxysilane, octadecyltrimethoxysilane, Octadecyl triethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriisopropoxy, 1-naphthyltrimethoxysilane, 2-naphthyltrimethoxysilane , Heptafluorodecyltrimethoxysilane, heptafluorodecyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, p-styryl Trimethoxysilane, allyltrimethoxysilane, etc.

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

Examples of the tetrafunctional silane compound include tetramethoxysilane and tetraethoxysilane.

Examples of the silane compound represented by the formula (2): Examples of the trifunctional silane compound include 3-glycidyletherpropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methylallyloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, glycidyl ether methyltrimethoxy Silane, glycidyl ether methyltriethoxysilane, α-glycidyl ether ethyltrimethoxysilane, α-glycidyl ether ethyltriethoxysilane, β-glycidyl ether ethyltrimethoxysilane, β-glycidyl ether ethyltriethoxysilane, α-glycidyl ether propyltrimethoxysilane, α-glycidyl ether propyl triethoxysilane, β-glycidyl ether propyl trimethoxysilane, β-glycidyl ether propyl triethoxysilane, γ-glycidyl ether propyl trimethoxy silane, γ-glycidyl ether propyl triethoxy silane, γ-glycidyl ether propyl tripropoxy silane , Γ-glycidyl ether propyl triisopropoxysilane, γ-glycidyl ether propyl tri-n-butoxysilane, -Glycidyl ether propyl tri-tert-butoxysilane, γ-glycidyl ether propyl tri-second butoxy silane, γ-glycidyl ether propyl trimethoxy silane, α-glycidyl ether butyl trimethoxy Silyl, α-glycidyl ether, tert-butyltriethoxy Silane, β-glycidyl ether butyl trimethoxysilane, β-glycidyl ether butyl triethoxysilane, γ-glycidyl ether butyl trimethoxysilane, γ-glycidyl ether butyl triethoxy Silane, δ-glycidyl ether butyltrimethoxysilane, δ-glycidyl ether butyltriethoxysilane, (3,4-epoxycyclohexyl) methyltrimethoxysilane, (3,4-cyclo Oxycyclohexyl) methyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane , 2- (3,4-epoxycyclohexyl) ethyltripropoxysilane, 2- (3,4-epoxycyclohexyl) ethyltri-third-butoxysilane, 2- (3,4- Epoxycyclohexyl) ethyltri-n-butoxysilane, 2- (3,4-epoxycyclohexyl) ethyltri-second-butoxysilane, 3- (3,4-epoxycyclohexyl) propyl Trimethoxysilane, 3- (3,4-epoxycyclohexyl) propyltriethoxysilane, 4- (3,4-epoxycyclohexyl) butyltrimethoxysilane, 4- (3,4 -Epoxycyclohexyl) butyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethylsilane Oxysilane 3-isocyanate propyl triethoxysilane Silane, 3-trimethoxysilyl propyl group silicon succinic anhydride, 3-aminopropyl triethoxy silane-urea and the like.

Examples of the bifunctional silane compound include γ-glycidyl ether propylmethyldimethoxysilane, γ-acrylic methoxypropylmethyldimethoxysilane, and γ-propylene methoxypropyl Methyldiethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, glycidyl ether methyldisiloxane Methoxysilane, glycidyl ether methylmethyldiethoxysilane, α-glycidyl ether ethylmethyldimethoxysilane, α-glycidyl ether ethylmethyldiethoxysilane, β- Glycidyl ether ethylmethyldimethoxysilane, β-glycidyl ether ethylmethyldiethoxysilane, α-glycidyl ether propylmethyldimethoxysilane, α-glycidyl Glyceryl ether propyl methyl diethoxy silane, β-glycidyl ether propyl methyl dimethoxy silane, β-glycidyl ether propyl methyl diethoxy silane, γ-glycidyl ether propyl methyl Dimethoxysilane, γ-glycidyl ether propyl methyl diethoxy silane, γ-glycidyl ether propyl methyl dipropoxy silane, β-glycidyl ether propyl methyl dibutoxy Silane, γ-glycidyl ether propylmethyldimethoxyethoxysilane, γ-glycidyl ether propylethyldimethoxysilane, γ-glycidyl ether propylethyldiethoxysilane, γ-glycidyl ether propyl vinyldimethoxysilane, γ-glycidyl ether propyl vinyl diethoxysilane, 3-methacryloxypropyl dimethoxysilane, and the like.

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

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

In the reaction system of the hydrolysis condensation reaction, a solvent (a solvent for preparation) may be added as necessary. The solvent is not particularly limited as long as it is capable of carrying out a hydrolysis-condensation reaction, and examples of the solvent are mentioned below. Among them, for example, alcohol compounds such as water, methanol, ethanol, propanol, diacetone alcohol (DAA), and tetrahydrofurfuryl alcohol; Ether compounds such as methyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, dipropylene glycol monomethyl ether (DPM); methyl acetate, ethyl acetate, butyl acetate, γ-butyrolactone, propylene glycol monomethyl ether Ester compounds such as acetate; ketone compounds such as acetone, methyl ethyl ketone, and methyl isoamyl ketone.

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

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

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

(Condition 1)

Column: Columns connected to TOSOH TSKgel Super HZM-H, TOSOH TSKgel Super HZ4000, TOSOH TSKgel Super HZ2000

Carrier: Tetrahydrofuran

Measurement temperature: 40 ° C

Carrier flow: 1.0ml / min

Sample concentration: 0.1% by mass

Detector: RI (refractive index) detector

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

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

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

The hydrolysate condensation reaction product of a siloxy resin type and a bifunctional or trifunctional alkoxysilane compound is preferable. Examples of the alkoxysilane compound constituting the siloxane resin include dimethoxydimethylsilane, diethoxydimethylsilane, dimethoxydiphenylsilane, and diethoxydiphenyl. Silyl, dihydroxydiphenylsilane, dimethoxy (methyl) (phenyl) silane, diethoxy (methyl) (phenyl) silane, dimethoxy (methyl) (phenethyl) ) Silane, dicyclopentyldimethoxysilane or cyclohexyldimethoxy (meth) silane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-propenyloxypropyltrimethoxysilane, or 3-propenyloxypropyltriethoxysilane, 3-trimethoxysilane Propyl succinic anhydride, 3-triethoxysilylpropyl succinic anhydride, 3-trimethoxysilylethyl succinic anhydride, 3-trimethoxysilylbutyl succinic anhydride, 3-glycidyl Oxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane, 3- (3,4-cyclo (Oxycyclohexyl) propyltriethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, phenyltrimethoxysilane, phenethyltrimethoxysilane, naphthyltrimethoxysilane, methyl Triethoxysilane, ethyltriethoxysilane, phenyltriethoxysilane, phenethyltriethoxysilane, naphthyltriethoxysilane, tetramethoxysilane or tetraethoxysilane .

The content of the siloxane resin is preferably less when it contains an alkali-soluble resin to be described later, and more when it does not contain the alkali-soluble resin. That is, when an alkali-soluble resin is contained, the content of the siloxane resin in the solid content of the composition is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 3% by mass or more. The upper limit is preferably 40% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less.

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

With respect to 100 parts by mass of the Ti element in the metal-containing particles, the siloxane resin The content is preferably 10 parts by mass or more, and more preferably 20 parts by mass or more. The upper limit is preferably 70 parts by mass or less, more preferably 60 parts by mass or less, and even more preferably 50 parts by mass or less.

The content of the siloxane resin can be changed depending on the progress of the hydrolysis reaction and the like. Taking this into consideration, and based on the mass ratio of the Si element in the siloxane resin (based on the Si element), the Si element is preferably 5 parts by mass or more relative to 100 parts by mass of the Ti element containing the metal particles. 8 mass parts or more is more preferable, and 10 mass parts or more is more preferable. The upper limit is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and even more preferably 25 parts by mass or less.

From the viewpoint of film-forming properties and film durability, it is preferable to use the amount of the siloxane resin at the above lower limit value or more. On the other hand, it is preferable from the viewpoint that a high refractive index can be maintained by being suppressed to the above-mentioned upper limit value or less.

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

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

<Solvent>

． Solvent A

One of the solvents used in the siloxane resin composition of the present invention has a boiling point of 210 ° C. or higher and 270 ° C. or lower at 1 atmosphere (the solvent satisfying this condition is sometimes referred to as “specific high boiling point solvent” or “solvent A "). The upper limit of the boiling point is more preferably below 265 ° C, and even more preferably below 260 ° C. The lower limit of the boiling point of the specific high boiling point solvent is preferably 220 ° C or higher, and more preferably 230 ° C or higher. In the present invention, the advantages of using a high-boiling-point solvent are as described at the beginning, and it is particularly preferable to select one having a good compatibility with the combined low-boiling-point solvent.

The SP value of the solvent is preferably 8 or more, more preferably 8.5 or more, and even more preferably 8.7 or more. The upper limit is preferably 11 or less, more preferably 10.5 or less, and even more preferably 10 or less. In the present invention, the reason why an excellent effect is obtained by setting the SP value of the solvent to the above range is estimated as follows. Metal-containing particles are typically interpreted as being dispersed in a solvent. From the viewpoint of optimizing the dispersibility, the polarity of the siloxane resin and the metal-containing particles is also considered, and it can be understood that it is effective to set the solvent to the range of the above-mentioned SP value. In addition, it is thought that even after being hardened, a small amount of a specific high-boiling-point solvent is uniformly dispersed in the system, which also helps to suppress the occurrence of cracks and gel defects.

The boiling points and SP values of the respective solvents are summarized in the following table.

Es: ester solvent

E: Ether-based solvent

A: Ether-based solvent (with OH)

K: Ketone solvent

In this specification, unless otherwise specified, the SP value is obtained by the Fedors method (R.F. Fedors Polym. Eng. Sci., 14 [2], 147-154 (1974)).

Specific high-boiling solvents (solvent A) include ether compound solvents (solvents formed from compounds with ether groups in the molecule), alcohol compound solvents (solvents formed from compounds with hydroxyl groups in the molecule), and ester compound solvents (made from molecules with The solvent is preferably selected from the group consisting of ester-based compounds. Among them, the specific high-boiling-point solvent is preferably formed of a compound represented by any one of the following formulae (V1) to (V4).

RV1 (CO) O- (LV1-LV2) mv-RV2 (V1)

RV3 (CO) O- (LV3)-(O (CO) RV4) nv (V2)

RV6O- (LV4-LV5) pv-RV5 (V3)

In formula (V1), RV1 represents an alkyl group (carbon number 1 to 12 is preferred, 1 to 6 is more preferred, 1 to 3 is particularly preferred), an alkenyl group (2 to 12 carbon atoms is preferred, 2 to 2 6 is more preferred), alkynyl (2 to 12 carbon atoms is preferred, 2 to 6 is more preferred), aryl (6 to 22 carbons is preferred, 6 to 14 is more preferred, 6 to 10) Especially preferred), aralkyl (7 to 23 carbon atoms is preferred, 7 to 15 is more preferred, 7 to 11 is particularly preferred).

LV 1 is a hydrocarbon linking group of a linking group L described later. The meaning of the preferred range is the same. Among them, an alkylene group is preferred.

LV 2 is a heteroatom-containing linking group of the linking group L described later. The meaning of the preferable range is the same, and an oxygen atom (ether group) is more preferable.

RV2 is a hydrogen atom, a halogen atom, or a fluorenyl group (2 to 12 carbon atoms is preferred, 2 to 6 is more preferred, 2 or 3 is particularly preferred) or has the same meaning as RV1. Among them, a hydrogen atom, an alkyl group or a fluorenyl group is more preferable, and an alkyl group or a fluorenyl group is more preferable.

mv is an integer from 0 to 8, an integer from 1 to 8 is preferred, an integer from 1 to 6 is more Preferably, an integer of 1 to 3 is particularly preferred.

In formula (V2), RV3 and RV4 each independently have the same meaning as RV1.

LV3 is an alkane linking group (1 to 12 carbon atoms is preferred, 1 to 6 is more preferred, 1 to 3 is particularly preferred), an olefin linking group (2 to 12 carbon atoms is preferred, 2 to 6 is more preferred) ), Alkyne linking group (2 to 12 carbon atoms is preferred, 2 to 6 is more preferred), aromatic linking group (6 to 22 carbon atoms is preferred, 6 to 14 is more preferred, 6 to 10 is particularly preferred) Good) or a combination of these. A structure having an oxygen atom in the middle of the linking group is also preferred. Among them, the above-mentioned alkane linking group or a linking group having a structure in which an oxygen atom is interposed in the alkane linking group is preferred. The number of bonding bonds of the linking group is determined by nv + 1.

nv is an integer from 1 to 3, and 1 or 2 is preferred.

In the formula (V3), LV4 is a hydrocarbon linking group of a linking group L described later. The meaning of the preferred range is the same. Among them, an alkylene group is preferred.

LV5 is a heteroatom-containing linking group of the linking group L described later. The meaning of the preferred range is also the same, and an oxygen atom is further preferred.

RV5 and RV2 have the same meaning. Among them, a hydrogen atom or an alkyl group is preferable, and an alkyl group is more preferable.

RV6 is a hydrogen atom or a group having the same meaning as RV1.

pv is an integer from 1 to 8, an integer from 1 to 6 is preferred, and an integer from 1 to 3 is more preferred.

When RV1 to RV6 are alkyl or the like, they may be branched or straight. or Alternatively, it may be looped. These may form a ring with each other or form a ring together with LV1 to LV5.

In formula (V4), the ring structure α is preferably a 4-member ring to a 7-member ring, and a 5-member ring to a 6-member ring is more preferable. The 6-membered ring is preferably a substituted or unsubstituted cyclohexane ring. As the 5-membered ring, a substituted or unsubstituted tetrahydrofuran ring, a substituted or unsubstituted dioxolane ring, or a substituted or unsubstituted cyclopentane ring is preferred. In addition, in the case of a 5-membered ring, it may have a substituent. As a preferred embodiment, a substituted or unsubstituted lactone ring such as γ-butyrolactone may be mentioned.

In consideration of the effects described above, the specific high-boiling-point solvent (solvent A) is more preferably contained in all compositions in an amount of more than 1% by mass, and more preferably in an amount of 5% by mass or more. Although there is no particular upper limit, considering the use of a specific low boiling point solvent (solvent B), 95% by mass or less is preferred, 50% by mass or less is more preferred, and 30% by mass or less is more preferred.

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

In addition, in the invention of the present application, a combination of solvents that occasionally becomes the above-mentioned range is of course also included in the technical scope thereof. For example, a solvent used in the preparation of the siloxane resin may be used as one of the solvents, and a solvent added afterwards may be used as the other solvent, thereby exhibiting a desired effect.

． Solvent B

In the siloxane resin composition of the present invention, in addition to the specific high boiling point solvent (solvent A) described above, a solvent having a boiling point lower than 210 ° C. (at 1 atmosphere) (referred to as a “specific low boiling point solvent” or “solvent”) is used. B "). By doing so, we get Solvent effect is preferred. The boiling point of the solvent B is more preferably 200 ° C or lower, more preferably 190 ° C or lower, 180 ° C or lower, and 170 ° C or lower. The lower limit of the boiling point of the solvent B is preferably 120 ° C or higher, and more preferably 125 ° C or higher. The difference (ΔBp) between the boiling point of solvent A and the boiling point of solvent B (ΔBp) is preferably 5 ° C or higher, more preferably 10 ° C or higher, more preferably 15 ° C or higher, 30 ° C or higher, or 40 ° C or higher, Above 50 ° C is particularly preferred. There is no particular upper limit for the difference in boiling points (ΔBp), but it is actually 120 ° C or lower. The lower limit of the boiling point of the specific low-boiling-point solvent (solvent B) is not particularly limited, and is actually 60 ° C. (under 1 atmosphere) or higher.

The ratio of the specific low boiling point solvent (solvent B) in all compositions is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 5% by mass or more. The upper limit is preferably 75% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less.

The solvent B is preferably selected from a compound-former represented by any one of the formulae (V1) to (V4). Alternatively, it is preferably diacetone alcohol (DAA), propylene glycol monomethyl ether acetate (PGMEA), or dipropylene glycol monomethyl ether (DPM). Among these, diacetone alcohol is preferably used as the solvent B. In particular, DAA may be structurally well placed on the surface of Ti to exert its effect, and therefore, a high effect can be expected when used as a low-boiling solvent (sub-solvent).

The solvent B is preferably 5 parts by mass or more relative to 100 parts by mass of the solvent A, more preferably 10 parts by mass or more, and even more preferably 20 parts by mass or more. The upper limit is preferably 1000 parts by mass or less, more preferably 500 parts by mass or less, more preferably 300 parts by mass or less, and still more preferably 200 parts by mass or less. 150 parts by mass or less is more preferable.

． Solvent C

The solvent in the siloxane resin composition typically represents a component other than the solid content described above. In addition, in the present invention, a solvent (solvent C) may be used in addition to the above-mentioned specific high-boiling-point solvent and the specific low-boiling-point solvent. As the solvent C, an ether compound solvent, an alcohol compound solvent, a ketone solvent, or an ester compound solvent is preferable, and a compound formed by any one of the formulae (V1) to (V4) is preferably selected.

The siloxane resin composition of the present invention may contain a solvent when synthesizing the siloxane resin. Or replace it with a different solvent or add a different solvent.

Solvent C may be used individually by 1 type, and may use 2 or more types together.

In addition, the molecular weights of the solvents A to C are not particularly limited, and low molecular weight compounds are preferred, molecular weights of 1,000 or less are preferred, and 500 or less is more preferred. There is no particular lower limit, but it is actually above 40. The molecular weight of the low-molecular compound can be confirmed by, for example, mass spectrometry.

． Preparation solvent

The siloxane resin composition of the present invention may directly contain a solvent used in preparing a hydrolyzed condensate. Examples of such a production solvent include examples of the production solvent described in the above [Silane resin]. The preparation solvent may remain in the siloxane resin composition together with the solvent A described above. As an example, an example in which a solvent for preparation accounts for more than half of the solvent, and solvents A and B or even C may be added here. The amount of the preparation solvent can be arbitrarily adjusted, and it can be appropriately set according to conditions and the like in the hydrolysis reaction. It's OK.

<Polymerization initiator>

The silicone resin composition of the present invention may contain a polymerization initiator. The polymerization initiator may be a thermal polymerization initiator or a photopolymerization initiator, but a photopolymerization initiator is preferred. Examples include organic halogenated compounds, oxadiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxides, azo compounds, coumarin compounds, azide compounds, metallocene compounds, six Arylbisimidazole compounds, organoboric acid compounds, disulfonic acid compounds, oxime compounds, onium salt compounds, hydroxyacetophenone compounds, aminoacetophenone compounds, fluorenylphosphine oxide compounds, trihalomethyltriazine compounds, benzyl Dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, fluorenyl phosphine compounds, phosphine oxide compounds, metallocene compounds, triarylimidazole dimers, onium compounds, benzothiazole compounds, Benzophenone compound, cyclopentadiene-benzene-iron complex, halomethyloxadiazole compound, 3-aryl substituted coumarin compound, α-amino alkylphenyl ketone compound, benzoic acid Ester compound.

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

Specifically, for example, an acetophenone-based initiator described in Japanese Patent Laid-Open No. 10-291969 and a fluorenylphosphine oxide-based initiator described in Japanese Patent No. 4225898.

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

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

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

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

In the present invention, it is preferable to use an oxime compound. The oxime compound effectively functions as a polymerization initiator for initiating and promoting polymerization in the siloxane resin composition of the present invention. In addition, the oxime compound has less coloring in post-heating, and also has good hardenability. In particular, in the present invention, it is preferable that the pattern deformation of the cured product can be suppressed. Although the details of this reason are not clear, it is presumed to be related to the compatibility between the specific high-boiling-point solvent and the oxime compound. Among them, commercially available products such as IRGACURE OXE01 and IRGACURE OXE02 (all manufactured by BASF SE) can be suitably used.

[Chemical Formula 3]

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

． A1

-A-C or an alkyl group of the A1 formula (OX-1) is preferred. The alkyl-based carbon number is preferably 1 to 12, and more preferably 1 to 6. The alkyl group may have a substituent T described later. The substituent T may be substituted via a linking group L described later.

． C

C represents Ar, -SAr, or -COAr.

． R

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

． B

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

． A

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

． Ar

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

As the oxime initiator, paragraphs 0513 of Japanese Patent Application Laid-Open No. 2012-208494 (corresponding US Patent Application Publication No. 2012/235099 [0632]) and the following formulae (OX-1), ( OX-2) or (OX-3), which are incorporated into the specification of this application.

The polymerization initiator preferably has a maximum absorption wavelength in a wavelength region of 350 nm to 500 nm, and it is more preferable to have an absorption wavelength in a wavelength region of 360 nm to 480 nm, and it is more preferable to have a higher absorbance at 365 nm and 455 nm. From the point of sensitivity, the Mohr absorption coefficient at 365nm or 405nm is preferably 1,000 ~ 300,000. 2,000 to 300,000 is more preferable, and 5,000 to 200,000 is more preferable.

The content of the polymerization initiator (the rhenium content in the case of two or more types) is preferably 0.1 mass% to 10 mass% with respect to the total solid content of the composition, more preferably 0.3 mass% to 8 mass%, and more preferably 0.5 mass. More preferably, it is more than% and less than 5 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.

<Ultraviolet absorbent>

An ultraviolet absorber may also be used in the silicone resin composition of the present invention.

As the ultraviolet absorber, a salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, triazine-based, or conjugated diene-based compound can be used. As specific examples of these, compounds in the columns of paragraphs 0144 to 0164 of Japanese Patent Laid-Open No. 2010-78729, and columns of paragraphs 0137 to 0142 of Japanese Patent Laid-Open No. 2012-068418 (corresponding to paragraphs of US2012 / 0068292) Compounds in the columns (0251 ~ 0254) can refer to these contents and introduce them into the specification of this application.

In addition, a diethylamino-phenylsulfonyl-based ultraviolet absorber (manufactured by DAITO CHEMICAL CO., LTD., Trade name: UV-503) and the like are also suitably used.

Examples of the benzotriazole-based compound include 2- (2Hbenzotriazol-2-yl) phenol and 2- (2H-benzotriazol-2-yl) -4,6-tertiary-pentyl Phenol, 2- (2Hbenzotriazol-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 the benzophenone-based compound include 2-hydroxy-4-methoxybenzophenone.

Examples of the ultraviolet absorber of the triazine-based compound include 2- (4,6-diphenyl-1,3,5triazin-2-yl) -5-[(hexyl) oxy] -phenol.

Regarding the blending amount of the ultraviolet absorber with respect to the metal-containing particles, it is preferable to use one or more ultraviolet absorbers relative to 100 parts by mass of the total solid content, it is more preferable to use two or more, and it is more preferable to use three or more. The upper limit is preferably 20 parts or less, more preferably 15 parts or less, and even more preferably 10 parts or less.

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

<Polymerizable compound>

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

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

[Chemical Formula 6]

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

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

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

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

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

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

In the above formula, E represents-((CH2) yCH2O)-or-((CH2) yCH (CH3) O)-, and-((CH2) yCH2O)-is more preferred.

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

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

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

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

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

The polymerizable compound may be a compound having an epoxy group or an oxetanyl group. Specific examples of the compound having an epoxy group or an oxetanyl group include a polymer having an epoxy group in a side chain and a polymerizable monomer or oligomer having two or more epoxy groups in a molecule. Examples include bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, Aliphatic epoxy resin, etc.

These compounds can be obtained by using a commercially available product or by introducing an epoxy group into the side chain of the polymer.

As a commercial product, for example, you can refer to the description of the paragraph 0191 of Unexamined-Japanese-Patent No. 2012-155288, and these contents are incorporated in this specification.

Examples of commercially available products include polyfunctional aliphatic glycidyl ether compounds such as Denacol EX-212L, EX-214L, EX-216L, EX-321L, and EX-850L (above, manufactured by Nagase ChemteX Corporation). These are low-chlorine products, but EX-212, EX-214, EX-216, EX-321, EX-850, etc. which are not low-chlorine products can also be used.

In addition, ADEKA RESIN EP-4000S, ADEKA RESIN EP-4003S, ADEKA RESIN EP-4010S, ADEKA RESIN EP-4011S (above, manufactured by ADEKA CORPORATION), NC-2000, NC-3000, NC-7300, XD -1000, EPPN-501, EPPN-502 (above, manufactured by ADEKA CORPORATION), JER1031S, etc.

Examples of commercially available products of the phenol novolak epoxy resin include JER-157S65, JER-152, JER-154, and JER-157S70 (above, manufactured by Mitsubishi Chemical Corporation).

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

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

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

<Alkali-soluble resin>

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

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

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

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

R11 represents a hydrogen atom or a methyl group. R12 represents an alkylene group having 2 or 3 carbon atoms, of which 2 is preferred. R13 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. n1 represents an integer from 1 to 15, preferably from 1 to 12. The repeating unit represented by the above formula (A1) has good adsorption and / or orientation on the particle surface due to the effect of the π electrons of the benzene ring existing in the side chain. In particular, when the side chain portion adopts an ethylene oxide or propylene oxide structure of p-cumylphenol, the stereoscopic effect is also increased, and a better adsorption and / or orientation plane can be formed. Therefore, the effect is higher, so it is better.

R13 is preferably an alkyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 1 to 10 carbon atoms. This is because when the number of carbon atoms in R13 is large, the group becomes an obstacle to inhibit the resins from approaching each other and promotes adsorption and / or orientation. However, if it is too large, the effect may be hindered. As the alkyl group represented by R13, an unsubstituted alkyl group or an alkyl group substituted with a phenyl group is preferred.

As the silicone resin composition of the present invention, an alkali-soluble polyester resin can be used. 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 realize effective development.

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

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

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

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

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

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

<Polymerization inhibitor>

The silicone resin composition of the present invention may contain a polymerization inhibitor. Examples of the polymerization inhibitor include phenolic hydroxy compounds, N-oxides, piperidine 1-oxy radical compounds, pyrrolidine 1-oxy radical compounds, and N-nitrosophenylammonium , Diazo compounds and cationic dyes, thioether-containing compounds, nitro-containing compounds, FeCl3, CuCl2 and other transition metal compounds. As a polymerization inhibitor, the paragraph of Japanese Patent Application Laid-Open No. 2010-106268 can be specifically referred to. 0260 ~ 0280 (the corresponding [0284] to [0296] of the specification of US Patent Application Publication No. 2011/0124824), which are incorporated into the specification of this application.

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

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

<Dispersant>

The silicone resin composition of the present invention may contain a dispersant. Examples of the dispersant include polymer dispersants (for example, polyamidoamine and its salts, polycarboxylic acids and their salts, high molecular weight unsaturated esters, modified polyurethanes, modified polyesters, Modified poly (meth) acrylate, (meth) acrylic copolymer, formalin naphthalenesulfonic acid) and polyoxyethylene alkyl phosphate, polyoxyethylene alkylamine, alkanolamine, pigment derivative Wait.

Polymer dispersants can be further classified into linear polymers, terminal modified polymers, graft polymers, and block polymers from their structure.

Specific examples of the dispersant include "Disperbyk-101 (polyamidophosphate), 107 (carboxylic acid ester), 110 (copolymers containing acidic groups), and 130 (polyfluorene) manufactured by BYK Chemie GmbH. Amine), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer) "," BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid), BYK2001 ";" EFKA4047, 4050, 4010, 4165 (polyurethane), EFKA4330, 4340 (block copolymer), 4400, 4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative ");" AJISPER PB821, PB822 "manufactured by Ajinomoto Fine-Techno Co., Inc .;" FLOWLEN TG-710 (urethane oligomer) "," POLYFLOW "manufactured by KYOEISHA CHEMICAL CO., LTD. No. 50E, No. 300 (acrylic copolymer) ";" DISPARLON KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyether ester), "manufactured by Kusumoto Chemicals, Ltd., DA-703-50, DA-705, DA-725 ";" Demol RN, N (formalin naphthalenesulfonate polycondensate), MS, C, SN-B (formalin polysulfonate aromatic sulfonate) manufactured by Kao Corporation. Material) "," HOMOGENOL L-18 (polymer polycarboxylic acid) "," EMULGEN920, 930, 935, 985 (polyoxyethylene nonylphenyl ether) "," ACETAMIN86 (stearylamine acetate )) ";" SOLSPERSE5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyester amine), 3000, 17000, 27000 (a functional part at the end portion) manufactured by Lubrizol Corporation Molecule), 24000, 28000, 32000, 38500 (graft polymers) ";" NIKKOL T106 (polyoxyethylene sorbitan monooleate) ", MYS-IEX (polyoxygen) manufactured by Nikko Chemicals Co., Ltd. Ethylene monostearate) "and the like.

The dispersant is also preferably a polymer compound containing at least one repeating unit selected from the repeating units represented by any one of the following formulae (I) and (II).

[Chemical Formula 9]

R11 to R16 each independently represent a hydrogen atom or a monovalent organic group. As the monovalent organic group, a substituted or unsubstituted alkyl group is preferred. As the alkyl group, an alkyl group having 1 to 12 carbon atoms is preferred, an alkyl group having 1 to 8 carbon atoms is more preferred, and an alkyl group having 1 to 4 carbon atoms is particularly preferred. The alkyl group may have a substituent T.

X11 and X12 each independently represent a linking group L described later, and -CO-, -C (= O) O-, -CONH-, -OC (= O)-, or phenylene is preferred. Among them, -C (= O) O-, -CONH-, and phenylene are more preferable, and -C (= O) O- is particularly preferable.

L1 and L2 each independently represent a single bond or a linking group L described later. Specifically, a hydrocarbon linking group (of which an alkylene group is preferred) or a combination of a hydrocarbon linking group and a heteroatom-containing linking group is preferred. Furthermore, a linking group of a combination of an alkylene group or an alkylene group and a heteroatom-containing linking group selected from the group consisting of -C (= O)-, -OC (= O)-, and -NHC (= O)-is preferred. The number of constituent atoms and the number of linking atoms of the preferred linking group have the same meanings as those for the linking group L.

Among them, a linking group made of -La-Lb- is preferred. La represents an alkylene group having 2 to 10 carbon atoms. Lb represents -C (= O)-or -NHC (= O)-.

As A1 and A2, a group selected from the group consisting of a straight chain having 1 to 20 carbon atoms, a branched chain having 3 to 20 carbon atoms, and a cyclic alkyl group having 5 to 20 carbon atoms is preferred, and is selected from carbon The linear group with 4 to 15 atoms, the branched chain with 4 to 15 carbon atoms, and the cyclic alkyl group with 6 to 10 carbon atoms are more preferred, and are selected from carbon The linear group having 6 to 10 carbon atoms and the branched alkyl group having 6 to 12 carbon atoms are more preferred.

m and n each independently represent an integer of 2 to 8, 4 to 6 is preferable, and 5 is more preferable.

p and q each independently represent an integer from 1 to 100. It is also possible to mix two or more of p different and q different. p and q are preferably 5 to 60, more preferably 5 to 40, and further more preferably 5 to 20.

Examples of the monomer constituting the repeating unit represented by the formula (I) include, for example, paragraphs [0090] to [0093] of Japanese Patent Application Laid-Open No. 2011-089109, which are incorporated herein.

As the dispersant, a polymer compound represented by the general formula (1) in the first patent application scope of Japanese Patent Application Laid-Open No. 2007-277514 (corresponding to the first patent application scope of US2010 / 0233595) is represented. See Japanese Patent Application Laid-Open No. 2007-277514 (corresponding to US2010 / 0233595), which is incorporated into the specification of the present application.

The polymer compound that can be used as a dispersant is not particularly limited, and can be synthesized according to the synthesis methods described in paragraphs 0114 to 0140 and 0266 to 0348 of Japanese Patent Application Laid-Open No. 2007-277514.

The content of the dispersant is preferably 10 to 1000 parts by mass, more preferably 30 to 1000 parts by mass, and even more preferably 50 to 800 parts by mass, relative to 100 parts by mass of the metal-containing particles. Moreover, it is more preferable that it is 10-30 mass% with respect to the total solid content of a composition. These dispersants may be used alone or in combination of two or more.

<Surfactant>

The siloxane resin composition of the present invention may contain a surfactant. Examples of the surfactant include a silicone-based surfactant, a silicone-based surfactant such as an organopolysiloxane, a fluorine-based surfactant, a polyoxyethylene dodecyl ether, and a polyoxyethylene oleyl ether. , Non-ionic surfactants such as polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol laurate or polyethylene glycol distearate, polyalkylene oxide interface An active agent, a poly (meth) acrylate-based surfactant, or a surfactant composed of an acrylic or methacrylic polymer. Examples of commercially available surfactants include "Megafac" (registered trademark) F787-F, F781-F, F142D, F172, F173, F183, F445, F470, F475, or F477 (all manufactured by DIC Corporation) Fluorine surfactants such as NBX-15 or FTX-218 (both manufactured by NEOS COMPANYLIMITED), BYK-333, BYK-301, BYK-331, BYK-345, or BYK-307 (both manufactured by BYK Additives & Instruments) Other silicone-based surfactants.

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

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

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

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

<Developer>

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

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

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

Examples of the substituent T include the following substituents.

Examples include alkyl (alkyl having 1 to 20 carbon atoms is preferred, for example, methyl, ethyl, isopropyl, third butyl, pentyl, heptyl, 1-ethylpentyl, benzyl ,2- Ethoxyethyl, 1-carboxymethyl, etc.), alkenyl (alkenyl having 2 to 20 carbon atoms is preferred, for example, vinyl, allyl, olealkenyl, etc.), alkynyl (carbon atom Alkynyl groups of 2 to 20 are preferred, for example, ethynyl, butadiynyl, phenylethynyl, etc.), cycloalkyl (cycloalkyl groups of 3 to 20 carbon atoms are preferred, for example, cyclopropyl Group, cyclopentyl group, cyclohexyl group, 4-methylcyclohexyl group, etc., but when it is recorded as an alkyl group, it usually includes the meaning of cycloalkyl group.), Aryl group (aryl group having 6 to 26 carbon atoms is preferred, For example, phenyl, 1-naphthyl, 4-methoxyphenyl, 2-chlorophenyl, 3-methylphenyl, etc.), heterocyclic groups (heterocyclic groups having 2 to 20 carbon atoms) are preferred Heterocyclic groups having at least one oxygen atom, sulfur atom, and nitrogen atom having a 5 or 6 member ring are preferred, for example, tetrahydropyran, tetrahydrofuran, 2-pyridyl, 4-pyridyl, 2-imidazolyl , 2-benzimidazolyl, 2-thiazolyl, 2-oxazolyl, pyrrolidone, etc.), alkoxy (alkoxy having 1 to 20 carbon atoms is preferred, for example, methoxy, ethoxy Group, isopropyloxy, benzyloxy, etc.), aryloxy (aryloxy having 6 to 26 carbon atoms is preferred, for example Phenoxy, 1-naphthyloxy, 3-methylphenoxy, 4-methoxyphenoxy, etc.), alkoxycarbonyl (alkoxycarbonyl having 2 to 20 carbon atoms are preferred, for example , Ethoxycarbonyl, 2-ethylhexyloxycarbonyl, etc.), aryloxycarbonyl (aryloxycarbonyl having 6 to 26 carbon atoms is preferred, for example, phenoxycarbonyl, 1-naphthyloxy Carbonyl group, 3-methylphenoxycarbonyl group, 4-methoxyphenoxycarbonyl group, etc.), amine group (amino group having 0 to 20 carbon atoms is preferred, and includes alkylamine group, arylamine group, For example, ammonia, N, N-dimethylamino, N, N-diethylamino, N-ethylamino, aniline, etc.), sulfamoyl groups (aminesulfonyl groups having 0 to 20 carbon atoms) For example, N, N-dimethylaminosulfonyl, N-phenylaminesulfonyl and the like are preferred, and fluorenyl (fluorenyl having 1 to 20 carbon atoms is preferred, for example, ethylfluorenyl , Propionyl, butyryl, etc.), arylmethyl (Arylfluorenyl group having 7 to 23 carbon atoms is preferred, for example, benzamidine, etc.), fluorenyloxy group (fluorenyl group having 1 to 20 carbon atoms is preferred, for example, ethenyloxy group, etc.), Aryloxy (preferably arylfluorenyl having 7 to 23 carbon atoms, for example, benzyloxy, etc.), carbamoyl (aminocarbamyl having 1 to 20 carbon atoms is preferred, For example, N, N-dimethylaminocarbamyl, N-phenylaminocarbamyl, etc.), fluorenylamino (fluorenylamine having 1 to 20 carbon atoms are preferred, for example, ethylamidine, Benzamidine, etc.), alkylthio (alkylthio having 1 to 20 carbon atoms is preferred, for example, methylthio, ethylthio, isopropylthio, benzylthio, etc.), arylthio (Arylthio having 6 to 26 carbon atoms is preferred, for example, phenylthio, 1-naphthylthio, 3-methylphenylthio, 4-methoxyphenylthio, etc.), alkylsulfonyl Fluorenyl (alkylsulfonyl having 1 to 20 carbon atoms is preferred, for example, methylsulfonyl, ethylsulfonyl and the like), arylsulfonyl (aryl having 6 to 22 carbon atoms) Sulfonyl is preferred, for example, benzenesulfonyl, etc.), alkylsilyl (alkylsilyl having 1 to 20 carbon atoms is preferred, for example, monomethylsilyl, Dimethylsilyl, trimethylsilyl, triethylsilyl, etc.), arylsilyl (aryl silyl having 6 to 42 carbon atoms is preferred, for example, triphenyl Silyl, etc.), phosphino (phosphonos with 0 to 20 carbon atoms are preferred, for example, -OP (= O) (RP) 2), phosphino (phosphine with 0 to 20 carbon atoms) The fluorenyl group is preferable, for example, -P (= O) (RP) 2), the phosphine group (the phosphine group having 0 to 20 carbon atoms is preferable, for example, -P (RP) 2), (formaldehyde) (Meth) acrylfluorenyl, (meth) acrylfluorenyloxy, (meth) acrylfluorinimide ((meth) acrylfluorinyl), hydroxyl, thiol, carboxyl, phosphate, phosphonic acid, Sulfonic acid group, cyano group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom, etc.).

In each of the groups exemplified in these substituents T, the above-mentioned substituent T Substitution may be performed further.

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

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

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

As the linking group L, a hydrocarbon linking group (an alkylene group having 1 to 10 carbon atoms (more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms), and an alkenylene group having 2 to 10 carbon atoms (carbon 2 to 6 atoms are more preferred, 2 to 4 are more preferred), alkynylene groups with 2 to 10 carbon atoms (2 to 6 carbon atoms are more preferred, 2 to 4 are more preferred), and 6 carbon atoms ~ 22 arylene (more preferably 6 to 10 carbon atoms), or a combination of these], heteroatom-containing linking group [carbonyl (-CO-), thiocarbonyl (-CS-), ether (- O-), thioether group (-S-), imide group (-NRN-), polythio group (the number of S is 1 to 8), imine linking group (RN-N = C <, -N = C (RN)-), sulfofluorenyl (-SO2-), sulfinamilide (-SO-), phosphate linker (-OP (OH) (O) -O-), phosphonic linker (- P (OH) (O) -O-), or a combination of these], or a combination of these linking groups is preferred. In addition, when condensing to form a ring, the above-mentioned hydrocarbon linking group may be connected by suitably forming a double bond or a triple bond. The formed ring is preferably a 5-membered ring or a 6-membered ring. As the 5-membered ring, a nitrogen-containing 5-membered ring is preferable, and if it is exemplified as a compound constituting the ring, Pyrrole, imidazole, pyrazole, indazole, indole, benzimidazole, piperidine, imidazolidine, pyrazolidine, indolin, carbazole or derivatives thereof are shown. Examples of the 6-membered ring include piperidine, morpholine, piperazine, and derivatives thereof. When aryl groups, heterocyclic groups, and the like are included, they may be a fluorene ring or a condensed ring, and may be substituted or unsubstituted in the same manner.

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

RP is a hydrogen atom, a hydroxyl group, or a substituent. As substituents, alkyl groups (1 to 24 carbon atoms are preferred, 1 to 12 are more preferred, 1 to 6 are further preferred, and 1 to 3 are particularly preferred), alkenyl (2 to 24 carbon atoms are preferred) Better, 2 ~ 12 is even better, 2 ~ 6 is even better, 2 ~ 3 is even better), alkynyl (carbon number 2 ~ 24 is better, 2 ~ 12 is better, 2 ~ 6 is further better Good, especially 2 to 3), aralkyl (7 to 22 carbon atoms is preferred, 7 to 14 is more preferred, 7 to 10 is more preferred), aryl (6 to 22 carbon atoms is more preferred) 6 to 14 is more preferred, 6 to 10 is particularly preferred), alkoxy (carbon number of 1 to 24 is preferred, 1 to 12 is more preferred, 1 to 6 is further preferred, 1 to 3 is particularly preferred), Alkenyloxy (2 to 24 carbon atoms is preferred, 2 to 12 is more preferred, 2 to 6 is more preferred, 2 to 3 is particularly preferred), alkynyloxy (2 to 24 carbon atoms is preferred) , 2 ~ 12 More preferably, 2 to 6 are further preferred, 2 to 3 are particularly preferred), aralkyloxy (carbon number 7 to 22 is preferred, 7 to 14 is more preferred, 7 to 10 is particularly preferred), aryl oxygen The group (carbon number 6 to 22 is more preferable, 6 to 14 is more preferable, and 6 to 10 is more preferable) is more preferable.

The number of atoms constituting the linking group L is preferably from 1 to 36, more preferably from 1 to 24, even more preferably from 1 to 12, and even more preferably from 1 to 6. The number of connecting atoms of the linking group is preferably 10 or less, and more preferably 8 or less. The lower limit is 1 or more. The above-mentioned number of connected atoms refers to the minimum number of atoms that are connected to a path between predetermined structural parts and participate in the connection. For example, in the case of -CH2-C (= O) -O-, the number of atoms constituting the linking group is 6, but the number of linking atoms is 3.

Specifically, as a combination of a linking group, the following are mentioned. Oxycarbonyl (-OCO-), Carbonate (-OCOO-), Amido (-CONH-), Carbamate (-NHCOO-), Urea (-NHCONH-), (Poly) Alkyleneoxy (-(Lr-O) x-), carbonyl (poly) oxyalkylene (-CO- (O-Lr) x-, carbonyl (poly) alkyleneoxy (-CO- (Lr -O) x-), carbonyloxy (poly) alkyleneoxy (-COO- (Lr-O) x-), (poly) alkyleneimine (-(Lr-NRN) x), Alkyl (poly) iminoalkylene (-Lr- (NRN-Lr) x-), carbonyl (poly) iminoalkylene (-CO- (NRN-Lr) x-), carbonyl (poly ) Alkyleneimine (-CO- (Lr-NRN) x-), (poly) ester (-(CO-O-Lr) x-,-(O-CO-Lr) x-,-( O-Lr-CO) x-,-(Lr-CO-O) x-,-(Lr-O-CO) x-), (poly) amido (-(CO-NRN-Lr) x-, -(NRN-CO-Lr) x-,-(NRN-Lr-CO) x-,-(Lr-CO-NRN) x-,-(Lr-NRN-CO) x-), etc. x is 1 or more An integer of 1 to 500 is preferable, and 1 to 100 is more preferable.

Lr is preferably an alkylene group, an alkenylene group, or a hydrocarbylene group. The carbon number of Lr is 1 ~ 12 is better, 1 ~ 6 is better, 1 ~ 3 is better. The plurality of Lr and RN, RP, x, etc. need not be the same. The orientation of the linking group is not limited to the above description, and can be understood as an orientation in which a predetermined chemical formula is appropriately combined.

<Container>

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

<Filter out>

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

The pore size of the filter is preferably about 0.1 to 7.0 μm and about 0.2 to 2.5 μm To be more preferable, about 0.2 to 1.5 μm is more preferable, and 0.3 to 0.7 μm is more preferable. By setting it as this range, it is possible to reliably remove fine foreign matters such as impurities or aggregates contained in the composition while suppressing clogging of the filter.

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

The second filter can be formed from the same material as the first filter described above. The pore diameter of the second filter is suitable for about 0.2 to 10.0 μm, more preferably about 0.2 to 7.0 μm, and more preferably about 0.3 to 6.0 μm. By setting it as this range, the foreign material can be removed in the state where the component particles contained in the mixed liquid remain.

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

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

<Metal concentration>

The metal (Na, K, Ca, Fe, The concentration of Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn) is preferably 5 ppm or less. Regarding the decrease in the concentration of such metals, the same applies to the preferred embodiment of the resist material described later.

<Formation of transparent hardened matter>

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

After pre-baking, for example, a stepper, mirror projection exposure machine (MPA), or parallel light lithography machine (hereinafter, PLA) is used to irradiate 10 ~ 4000J / m2 with or without a desired mask. Left and right (equivalent to 365nm wavelength exposure) light. The exposure light source (radiation) is not limited, and ultraviolet rays such as i-rays (wavelength 365nm), g-rays (wavelength 436nm) or h-rays (wavelength 405nm), KrF (wavelength 248nm) laser, or ArF (wavelength 193nm) laser, etc. can be used. . After that, the film can also be subjected to post-exposure baking by heating the film at 150 to 450 ° C for about an hour by using a heating device such as a hot plate or an oven. In the present invention, it is preferable to use ultraviolet rays having a wavelength of 300 to 400 nm as the active radiation, and it is more preferable to use i rays. That is, the siloxane resin composition of the present invention is preferably an ultraviolet curable resin composition.

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

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

The thickness of the obtained cured film is preferably 0.1 to 10 μm. The leakage current is preferably 10-6 A / cm2 or less, and the dielectric constant is preferably 6.0 or more.

The refractive index of the cured film of the siloxane resin composition of the present invention is preferably 1.60 or more, more preferably 1.70 or more, and even more preferably 1.80 or more. There is no particular upper limit, but it is actually below 2.0. Regarding the refractive index, unless otherwise specified, it is based on the conditions measured in the examples described later.

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

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

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

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

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

In addition, as the above-mentioned resist material, those that can be suitably used for such processing can be used. Examples include positive, negative, and both positive and negative photoresists. Specific examples of the positive resist include various photosensitive resin compositions such as vinyl cinnamate, cyclized polyisobutylene, azo-phenol resin, and diazolone-phenol resin. Specific examples of the negative resist include an azide-cyclized polyisoprene-based resin and an azide-phenol resin. System, chloromethyl polystyrene system, etc. Specific examples of the positive-negative dual-purpose resist include various photosensitive resin compositions such as poly (p-butoxycarbonyloxystyrene). Among them, those disclosed in paragraph [Example 4] of Japanese Patent Laid-Open No. 0-142548 can be suitably used. Specifically, it is a photosensitive resin composition which contains a cresol novolak resin and naphthoquinonediazidesulfonate as a main component. More specifically, an esterification reaction product of 2,3,4,4'-tetrahydroxybenzophenone and naphthoquinone-1,2-diazide-5-sulfofluorene chloride (triester) can be exemplified. Content is 85 mol%).

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

In the formula, R13 to R16 each independently represent a hydrogen atom or an alkyl group (1 to 12 carbon atoms are preferred, 1 to 6 are more preferred, and 1 to 3 are particularly preferred). s represents an integer from 1 to 3. The molecular weight of the above resin is not particularly limited, but the weight average molecular weight in terms of polystyrene is usually 10 to 1 million, more preferably 2,000 to 100,000, and more preferably 3,000 to 50,000.

<Solid-state image sensor>

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

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

[Example]

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

<Combination of metal oxide fine particle siloxane resin (dispersed sol) A-1 Examples>

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

7.60 kg of a titanium tetrachloride aqueous solution containing 7.8% by mass of titanium tetrachloride based on TiO2 conversion basis and 3.0 kg of ammonia water containing 15% by mass of ammonia were mixed to prepare a white slurry having a pH of 9.5. Next, the white slurry was filtered, and then washed with ion-exchanged water to obtain 6.2 kg of a water-containing titanate filter cake having a solid content of 10% by mass.

Next, 7.1 kg of a hydrogen peroxide aqueous solution containing 35% by mass of hydrogen peroxide and 20.0 kg of ion-exchanged water were added to the filter cake, and then stirred and heated at a temperature of 80 ° C. for 1 hour, and then 28.9 kg of ion-exchanged water was added. Thus, 62.2 kg of a peroxytitanic acid aqueous solution containing 1% by mass of peroxytitanic acid in terms of TiO2 conversion was obtained. This aqueous solution of peroxytitanic acid was transparent yellow-brown and had a pH of 8.5.

Next, 3.0 kg of a cation exchange resin was mixed with 62.2 kg of the above-mentioned titanium peroxy acid aqueous solution, and 7.8 kg of a potassium stannate aqueous solution containing 1% by mass of potassium stannate based on SnO2 conversion was slowly added thereto under stirring. Next, after the cation exchange resin introduced with potassium ions and the like was separated, the mixed aqueous solution was heated in an autoclave at a temperature of 165 ° C. for 18 hours.

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

Water-dispersed sol containing metal oxide fine particles (AA-1) thus obtained It is transparent milky white. When the content of the metal component contained in the metal oxide fine particles was measured, based on the oxide conversion of each metal component, TiO2 was 87.5% by mass, SnO2 was 10.6% by mass, and K2O was 1.8% by mass.

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

To 7.0 kg of the water-dispersed sol (AA-1) of the nuclear fine particles obtained above, slowly adjust the pH to 7.0 with potassium hydroxide aqueous solution, and slowly add an aqueous solution of 3.6% strength zirconium oxyzirconium chloride in terms of ZrO2 mass conversion to 1.5 kg, 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% based on the oxide conversion basis with respect to the metal element contained in the core fine particles.

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

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

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

When measuring the content of the metal components contained in the surface-treated metal oxide fine particles, based on the oxide conversion of each metal component, TiO2 was 82.6 mass%, SnO2 was 10.3 mass%, ZrO2 was 4.9 mass%, and K2O was 2.2 quality%. The Ti / Zr ratio is 26.00. The average particle diameter of the obtained metal oxide fine particles is about 5-20 nm.

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

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

<Preparation of Disperse Sol A-1>

10.9 g (0.08 mol) of methyltrimethoxysilane, 63.5 g (0.32 mol) of phenyltrimethoxysilane, and methanol-dispersed sol (AC-1) (solid content concentration 30% by mass, methanol 70% by mass) 1050.0g 44.1 g of γ-butyrolactone was put into a reaction container, and 32.0 g of water and 1.0 g of phosphoric acid were dropped into the solution while stirring so that the reaction temperature did not exceed 40 ° C. After the dropping, the flask was equipped with a distillation device, and the obtained solution was stirred and heated at a bath temperature of 105 ° C. for 2.5 hours. The methanol produced by the hydrolysis was distilled and reacted at the same time. Thereafter, the solution was further heated and stirred at a bath temperature of 130 ° C for 2 hours, and then cooled to room temperature to obtain a dispersed sol A-1.

<Synthesis example of Siloxane resin (dispersed sol) A-2 containing metal oxide fine particles>

<Preparation of Water-dispersed Sol (AD-1) of Core-shell Inorganic Oxide Particles>

Preparation of zirconium peroxide aqueous solution

To 13.2 kg of an aqueous zirconium oxychloride solution containing 2.0% by mass of zirconium oxychloride on a ZrO2 conversion basis, slowly adding 15.0% by mass of ammonia water containing ammonia under stirring to obtain a pH of 8.5 containing zirconium hydrate Of slurry. Next, filter this After the slurry was washed with pure water, 2.5 kg of a cake having a zirconium content of 10.0% by mass in terms of ZrO2 conversion was obtained.

Next, 0.7 kg of pure water was added to 72.0 g of the cake, and 43.2 g of a potassium hydroxide aqueous solution containing 10.0% by mass of potassium hydroxide was further added to make it alkaline, followed by addition of 35.0% by mass of hydrogen peroxide. 144.0 g of an aqueous hydrogen oxide solution was heated to a temperature of 50 ° C. to dissolve the filter cake. Furthermore, 0.5 kg of pure water was added to obtain 1.4 kg of a zirconium oxide aqueous solution containing 0.5% by mass of zirconium peroxide in terms of ZrO2 conversion. The pH of the zirconium peroxide aqueous solution was 12.

Preparation of silicic acid solution

On the other hand, after diluting 0.3 kg of commercially available water glass with pure water, debasing was performed using a cation exchange resin (manufactured by Mitsubishi Chemical Corporation) to obtain a silicic acid aqueous solution 3.0 containing 2.0% by mass of silicic acid on a SiO2 conversion basis. kg. The pH of the aqueous silicic acid solution was 2.3.

Preparation of Core-shell Inorganic Oxide Microparticles in Water-dispersed Sol (AD-1)

3.3 kg of pure water was added to 1.8 kg of the water-dispersed sol (AB-1) (solid content: 2.0% by mass) of the surface-treated metal oxide fine particles prepared in the above, and the mixture was stirred and heated to a temperature of 90 ° C. To this, 1.4 kg of the zirconium peroxide aqueous solution and 1.1 kg of the silicic acid aqueous solution were slowly added, and after the addition was completed, the mixture was aged for 1 hour while maintaining the temperature at 90 ° C. At this time, the amount of the composite oxide coated with the surface-treated metal oxide fine particles was 25 parts by mass relative to 100 parts by mass of the surface-treated metal oxide fine particles. Next, this mixed solution was put into an autoclave, and heat-treated at a temperature of 165 ° C for 18 hours.

Next, the obtained mixed solution was cooled to room temperature, and then concentrated using an ultrafiltration membrane (manufactured by Asahi Kasei Corporation., SIP-1013) to prepare a water-dispersed sol having a solid content of 10.0% by mass. Thereby, 0.6 kg of a water-dispersed sol (AD-1) containing metal oxide fine particles obtained by coating the surface of the surface-treated metal oxide fine particles with a composite oxide containing silicon and zirconium was obtained.

The water-dispersed sol (AD-1) of the core-shell type inorganic oxide fine particles thus obtained was transparent milky white. When measuring the content of metal components contained in the metal oxide fine particles, based on the oxide conversion of each metal component, TiO2 was 63.8% by mass, SnO2 was 8.0% by mass, SiO2 was 13.9% by mass, and ZrO2 was 11.0 The mass% and K2O were 3.3 mass%. The Ti / Zr ratio is 8.94. The average particle diameter of the obtained metal oxide fine particles is about 5 to 20 nm.

<Preparation of a methanol-dispersed sol (AE-1) of core-shell type inorganic oxide fine particles>

To 0.6 kg of the water-dispersed sol (AD-1) of the core-shell inorganic oxide fine particles (core-shell composite oxide fine particles) prepared in the above, 9.6 g of a cation exchange resin was added under stirring, and the resin was separated to prepare Aqueous dispersion of deionized core-shell composite oxide particles. Next, the aqueous dispersion of the deionized core-shell type composite oxide fine particles was concentrated by replacing the dispersion medium from water with methanol using an ultrafiltration membrane device (filtration membrane manufactured by Asahi Kasei Corporation., SIP-1013). 0.32 kg of a methanol-dispersed sol (AE-1) of core-shell inorganic oxide fine particles was obtained. As a result, the solid content concentration in the obtained methanol-dispersed sol (AE-1) was 30% by mass, and the water content was about 0.3% by mass.

<Preparation of Disperse Sol (A-2)>

10.9 g (0.08 mol) of methyltrimethoxysilane, 63.5 g (0.32 mol) of phenyltrimethoxysilane, and methanol dispersed sol (AE-1) (solid content concentration: 30% by mass, methanol: 70% by mass): 1050.0 g 44.1 g of γ-butyrolactone was put into a reaction container, and 32.0 g of water and 1.0 g of phosphoric acid were dropped into the solution while stirring so that the reaction temperature did not exceed 40 ° C. After the dropping, a distillation device was installed in the flask, and the obtained solution was heated and stirred at a bath temperature of 105 ° C. for 2.5 hours, and the methanol produced by the hydrolysis was distilled and reacted at the same time. Thereafter, the solution was further heated and stirred at a bath temperature of 130 ° C for 2 hours, and then cooled to room temperature to obtain a dispersed sol (A-2).

<Synthesis example of metal oxide fine particle dispersion (dispersion sol) A-3>

About the mixed liquid of the following composition, as a circulation type dispersion apparatus (bead mill), NPM manufactured by SHINMARU ENTERPRISES CORPORATION was used, and the dispersion process was performed as follows, and the titanium dioxide dispersion liquid was obtained as a dispersion sol (A-3).

~ Composition ~

． Titanium dioxide (TTO-51 (C) manufactured by ISHIHARA SANGYO KAISHA, LTD.): 150.0 parts

(Crystalline form: rutile, purity of TiO2 (%): 79 ~ 85%, surface treatment with Al2O3 and stearic acid, specific surface area 50 ~ 60m2 / g, primary particle size 10 ~ 30nm, oil absorption 24 ~ 30g / 100g )

． The following specific dispersion resin (1) (solid content 20% PGMEA solution): 165.0 parts

． Propylene glycol monomethyl ether acetate (PGMEA): 200 parts

In the specific dispersant (1), n is 14, the polystyrene equivalent mass average molecular weight of the dispersant is 6,400, and the acid value is 80 mgKOH / g.

In addition, the dispersion apparatus is operated under the following conditions.

． Bead diameter: φ 0.05mm

． Bead filling rate: 60% by volume

． Peripheral speed: 10m / s

． Pump supply: 30kg / hour

． Cooling water: tap water

． Bead mill ring passage internal volume: 1.0L

． Amount of mixed liquid for dispersion treatment: 10kg

<Synthesis example of metal oxide fine particle dispersion (dispersion sol) A-4>

A dispersion sol (A-4) was synthesized by the same method as the synthesis example of the dispersion sol (A-3), except that only the following components were changed.

~ Composition ~

． Titanium dioxide (TTO-51 (C) manufactured by ISHIHARA SANGYO KAISHA, LTD.): 212.5

(Crystalline form: rutile, purity of TiO2 (%): 79 ~ 85%, Surface treatment with Al2O3 and stearic acid, specific surface area 50 ~ 60m2 / g, primary particle size 10 ~ 30nm, oil absorption 24 ~ 30g / 100g)

． The following specific dispersion resins (20% solid PGMEA solution): 286.9 parts

． Propylene glycol monomethyl ether acetate (PGMEA): 350.6 parts

The above specific dispersion resin: acid value: 50mg / KOH, mass average molecular weight is 10,000

(Example 1, Comparative Example 1)

Using the dispersed sols A-1 to A-3 obtained above, the components were mixed so as to have the composition shown in Table 1 below to obtain thermosetting resin compositions of Examples and Comparative Examples. The following evaluations were performed using each thermosetting composition of the examples and comparative examples obtained in the above.

<Evaluation of cracks under high temperature and high humidity [1-1]>

Each of the thermosetting compositions of the Examples and Comparative Examples obtained in the above was coated on a 8-inch Si wafer (substrate) by a spin coating method so that the film thickness after forming the layer became 1.2 μm. . The spin coating conditions at this time were set to be the same as those of the following test [1-3]. The substrate on which the thermosetting composition was applied was heated on a hot plate at 100 ° C for 2 minutes. Furthermore, the substrate was heated on a hot plate at 230 ° C for 10 minutes. Minutes to form a thermosetting composition layer. The substrate on which the thermosetting composition layer was formed was exposed to a constant temperature and humidity layer (IW222; manufactured by Yamato Scientific Co., Ltd.) at 85 ° C / 95% for 500 hours. After that, the number of crack defects (number of the entire 8-inch Si wafer) generated on the substrate was measured with a defect inspection device ComPlus (manufactured by Applied Materials, Inc.). It was measured 5 times and the average value was used. The results are shown in Table 1 below.

<The number of gel defects after the resist solution was passed at 45 ° C for 3 days [1-2]>

Each of the thermosetting compositions of the examples and comparative examples obtained above was forcibly degraded over time at 45 ° C for 3 days, and the film thickness after the formation of the layer was 1.2 μm on an 8 inch Si wafer ( The substrate) was coated by a spin coating method. The spin coating conditions at this time were set to be the same as those of the following test [1-3]. The substrate coated with the thermosetting composition was heated on a hot plate at 100 ° C for 2 minutes. Furthermore, the substrate was heated at 230 ° C. for 10 minutes on a hot plate to form a thermosetting composition layer. The number of occurrences of gel-like defects with a size of 1 μm or more was measured with a defect inspection device ComPlus (manufactured by Applied Materials, Inc.) on a substrate on which the thermosetting composition layer was formed (each of the entire 8-inch Si wafer). number). It was measured 5 times and the average value was used. The results are shown in Table 1 below.

<Surface unevenness 7 days after coating [1-3]>

Each of the thermosetting compositions of the Examples and Comparative Examples obtained in the above was coated by a spin coating method on an 8-inch Si wafer so that the film thickness after forming the layer became 1.2 μm, and then On a hot plate, heat at 100 ° C for 2 minutes. A thermosetting composition layer is formed. For spin coating, a device of 1H-D7 (trade name) manufactured by MIKASA CO., LTD was used. As a device condition, the rotation speed was set to 900 rpm, and the ambient temperature was set to room temperature (25 ° C). The substrate on which the thermosetting composition layer was formed was allowed to stand at room temperature for 7 days, and the surface condition was observed with a light microscope (optical microscope) to evaluate unevenness. The results are shown in Table 1 below.

A: No unevenness

B: In light observation, unevenness (foreign matter) of 10 μm or more was observed in an area of 0.1% or more and less than 1% of the observation area.

C: In light observation, unevenness (foreign matter) of 10 μm or more was observed in an area of 1% or more and less than 3% of the observation area

D: In light observation, unevenness (foreign matter) of 10 μm or more was observed in an area of 3% or more of the observation area

In addition, the observation area is a total of 1 square area of 1 mm selected at five arbitrary points, and the average value is used in the evaluation of unevenness.

In addition to the components in Table 1, the following components were blended in all samples.

Epoxy compound: JER-157S65 (trade name) manufactured by Mitsubishi Chemical Corporation 5 parts by mass

Blending: content rate (mass parts) in the composition

B-1: SR-13 (Polysilsesquioxane, weight-average molecular weight 6,000) manufactured by KONISHI CHEMICAL IND.CO., LTD.

DAA: Diacetone alcohol

DPM: Dipropylene glycol monomethyl ether

Refer to Table A for the abbreviations of the first solvent and the second solvent

80 parts by mass of each dispersed sol contained the following amount of a preparation solvent. The balance of each dispersed sol is a solid content.

A-1 contains 49 parts by mass of methanol and 2.9 parts by mass of γ-butyrolactone

A-2 contains 49 parts by mass of methanol and 2.9 parts by mass of γ-butyrolactone

A-3 contains 52 parts by mass of PGMEA

A-4 contains 55 parts by mass of PGMEA

Mass ratio of Ti element to Si element in metal oxide fine particles

A-1: 16.79 parts by mass

A-2: 16.79 parts by mass

The content of the metal-containing particles in each dispersed sol is as follows.

A-1: 28.1% by mass

A-2: 28.1% by mass

A-3: 23.0% by mass

A-4: 22.0% by mass

As a result of confirming the optical characteristics of the transparent cured film of Test 101, it showed a refractive index of 1.9 and a light transmittance of 90% or more. The optical properties of the other test films were also checked in the same manner, and it was confirmed that the films of the examples all exhibited the desired high refractive index and high light transmittance. In addition, the refractive index and light transmittance were measured as described below.

~ Measurement of refractive index and visible light transmittance ~

The composition was applied to a high refractive index glass (SFLD-6 manufactured by SUMITA OPTICAL GLASS, Inc.) with a spin coater (Act8 manufactured by Tokyo Electron Limited) to a thickness of 0.6 μm. A hot plate (Act8 manufactured by Tokyo Electron Limited) was pre-baked at 90 ° C for 2 minutes to obtain a coating film. This coating film was heated at 200 ° C for 8 minutes on a hot plate (Act8 manufactured by Tokyo Electron Limited) in an air atmosphere to obtain a cured film. With respect to the obtained cured film, the refractive index at a wavelength of 550 nm at a room temperature of 25 ° C. was measured with an ellipsimeter (manufactured by Otsuka Electronics Co., Ltd.). At this time, the transmittance of the test transparent film was measured within 400 nm to 700 nm. For the transmittance, the lowest transmittance value from 400 to 700 nm is used. The test was performed 5 times for each sample, and the average of the 3 times of results obtained by excluding the maximum value and the minimum value was used.

From the above results, it is found that when the specific high-boiling point solvent and the specific low-boiling point solvent are used in combination, when the siloxane resin composition of the present invention is used as a cured film thereof, good crack resistance and gel defect resistance can be exhibited. Furthermore, it turns out that the unevenness of the film surface is also small, and it becomes a favorable one.

(Example 2 and Comparative Example 2)

Using the dispersed sols A-1 to A-4 obtained in the above, the components were mixed so as to have the following composition, thereby obtaining curable resin compositions of Examples and Comparative Examples. The following evaluations were performed using each hardenable composition of the Examples and Comparative Examples obtained in the above.

<Evaluation of cracks under constant temperature and humidity [2-1]>

Each of the curable compositions of the Examples and Comparative Examples obtained in the above was coated on a 8-inch Si wafer (substrate) by a spin coating method so that the film thickness after forming the layer became 0.8 μm. The spin coating conditions at this time were set to be the same as the above-mentioned test [1-3]. The substrate coated with the curable composition was heated on a hot plate at 100 ° C for 2 minutes. Further, the substrate was heated at 200 ° C. for 10 minutes on a hot plate to form a curable composition layer. The substrate on which the hardenable composition layer was formed was exposed to a constant temperature and humidity layer (IW 222; manufactured by Yamato Scientific Co., Ltd.) at 85 ° C / 95% for 500 hours. Thereafter, the number of crack defects (the number of the entire 8-inch Si wafer) generated on the substrate was measured using a defect inspection device ComPlus (manufactured by Applied Materials, Inc.) on the substrate. It was measured 5 times and the average value was used. The results are shown in Table 2 below.

<The number of gel defects after the resist solution was advanced at 45 ° C for 3 days [2-2]>

Each hardenable composition obtained in the above was forced to pass 45 days at 45 ° C for 3 days, and the film thickness after the formation of the layer was 0.8 μm so that a 8-inch Si wafer (substrate) was spin-coated. Perform coating. The spin coating conditions at this time are set to The above tests [1-3] are the same. The substrate coated with the curable composition was heated on a hot plate at 100 ° C for 2 minutes. Further, the substrate was heated at 200 ° C. for 10 minutes on a hot plate to form a curable composition layer. A defect inspection device ComPlus (manufactured by Applied Materials, Inc.) was used to measure the number of occurrences of gel-like defects having a size of 1 μm or more (the number of the entire 8-inch Si wafer) on the substrate on which the curable composition layer was formed. ). It was measured 5 times and the average value was used. The results are shown in Table 2 below.

<Surface unevenness after 7 days after coating [2-3]>

Each curable composition obtained in the above was coated on a 8-inch Si wafer by a spin coating method so that the film thickness after forming the layer became 0.8 μm. The spin coating conditions at this time were set to be the same as the above-mentioned test [1-3]. The substrate coated with the curable composition was heated on a hot plate at 100 ° C. for 2 minutes to form a curable composition layer. The substrate on which the curable composition layer was formed was left to stand at room temperature for 7 days, and unevenness was evaluated by observing the surface state with a light display. The results are shown in Table 2 below.

A: No unevenness

B: In light observation, unevenness (foreign matter) of 10 μm or more was observed in an area of 0.1% or more and less than 1% of the observation area.

C: In light observation, unevenness (foreign matter) of 10 μm or more was observed in an area of 1% or more and less than 3% of the observation area

D: In light observation, unevenness (foreign matter) of 10 μm or more was observed in an area of 3% or more of the observation area

In addition, the observation area is the total area of a 1 mm square area selected at five arbitrary locations. The average value is used in the evaluation of unevenness.

<Evaluation of pattern distortion [2-4]>

Each hardenable composition obtained in the above was coated on a 8-inch Si wafer with an undercoat layer by a spin coating method so that the film thickness after forming the layer was 0.6 μm. The spin coating conditions at this time were set to be the same as the above-mentioned test [1-3]. The substrate coated with the curable composition was heated on a hot plate at 90 ° C. for 2 minutes to obtain a curable composition layer.

Next, the obtained hardenable composition layer was exposed to a 0.9 μm square Bayer pattern with an i-ray stepper exposure device FPA-3000i5 + (manufactured by Canon Inc.) through a mask. cm2). The time (PCD (post coating delay)) after the formation of the hardenable composition layer using the hardenable composition and the time before the exposure of the hardenable composition layer was set to 24 hours.

Next, the developability of the curable composition layer after exposure was evaluated using a developing device (Act8 manufactured by Tokyo Electron Limited). As the developing solution, a 0.3% aqueous solution of tetramethylammonium hydroxide (TMAH) was used, and spray development was performed at 23 ° C. for 60 seconds. Thereafter, the pattern was obtained by washing with pure water in a rotary shower. The deformation of the obtained pattern was evaluated by observation (magnification: 20000 times) with a scanning electron micromirror (SEM) (S-4800H, manufactured by Hitachi High-Technologies Corporation.). The results are shown in Table 2 below. In addition, the results are displayed by dividing them into the following four by taking the average of five times.

A: Pattern (a) in Figure 2 without distortion

B: More than 1 and less than 10 are observed in 100 patterns Figure 2 (b) (c) (d)

C: 10 or more and less than 20 of 100 patterns were observed as the pattern deformation of Fig. 2 (b) (c) (d)

D: 20 or more patterns out of 100 patterns were observed as in (b) (c) (d) of Fig. 2

In addition, it is considered that such a distortion occurs because a phase separation occurs due to the resist being left until exposure (PCD), and a difference in development speed is locally generated in the pattern.

Except for the components in Table 2, the subordinate components were blended in all samples.

7 parts by mass of compound KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) having an unsaturated double bond

Polymer A

1.0 part by mass of benzyl methacrylate / methacrylic acid copolymer (copolymerization ratio: 80/20 (mass%), weight average molecular weight: 12,000)

1.0 part by mass of the ultraviolet absorber (A) having the following structure

0.5 parts by mass of a surfactant with the following structure (1% PGMEA solution)

Polymerization inhibitor (p-methoxyphenol) 0.01 parts by mass

The ratio of the preparation solvent in each dispersed sol and the mass ratio of the Si element to the metal-containing particles are the same as those of Example 1 and Comparative Example 1.

B-1: SR-13 (Polysilsesquioxane, weight average molecular weight 6,000)

B-2: SR-20 (Polysilsesquioxane, weight average molecular weight 6,000)

B-3: SR-33 (Polysilsesquioxane, weight average molecular weight 7,500)

Manufactured by KONISHI Chemical IND CO., LTD.

F1: IRGACURE OXE 02

F2: IRGACURE OXE 01

F3: IRGACURE 369

F4: IRGACURE 379

Made by BASF SE

[Chemical Formula 13]

Ultraviolet absorbent (A): Ultraviolet absorbent with butadiene skeleton (manufactured by DAITO Chemical Co., Ltd.)

Surfactant: Megafac F-781F, manufactured by DIC Corporation (mixture of (F1) and (F2))

l, m, n are integers

Refer to Table A for the abbreviations of the first solvent and the second solvent

Based on the above results, it can be seen that the silicone resin composition according to the present invention exhibits excellent performance not only as a thermosetting resin, but also as a negative photocuring material.

(Example 3)

Using the siloxane resin composition (photosensitivity) of the above-mentioned tests 201 and 202, a Si wafer sample similar to the crack evaluation test [2-1] was prepared. The sample was exposed with a moisture resistance tester (manufactured by ESPEC CORP., EHS-221M) (135 ° C / 95%). The light was irradiated for 300 hours to perform a moisture resistance test. After the moisture resistance test, the moisture resistance was evaluated by measuring the transmittance of the cured film. As a result, the sample of the test 201 (solvent B = DAA) showed a good result of a change in transmittance of 5% or less. On the other hand, the transmittance change of the sample (solvent B = DPM) of Test 202 was more than 5% and 8% or less. From this result, it was found that by using DAA as the solvent B, the moisture resistance was further improved. This is presumably because the coordination of DAA with Ti inhibits the coordination of water to Ti, which reduces the hygroscopicity of the film and suppresses the surface roughness.

(Example 4)

In the preparation of the above-mentioned dispersed sols (AB-1) and (A-1), the amount of each raw material was adjusted so that its component composition (composition ratio of Ti and Zr) became the following Table 3 to prepare each sample. . For each sample, each test [2-1] to [2-4] was performed in the same manner as in Example 2. Furthermore, the pattern distortion was evaluated under more severe conditions [2-4a]. Specifically, as a developing solution, a tetramethylammonium hydroxide (TMAH) 0.15% aqueous solution was used, and spray development was performed at 23 ° C. for 60 seconds. Thereafter, the pattern is obtained by rinsing with a spin spray using pure water.

As a result, regarding the evaluation of cracks [2-1], the number of gel defects [2-2], the surface unevenness [2-3], and the pattern deformation test [2-4], all the samples were good. On the other hand, in the severe pattern deformation test [2-4a], it was confirmed that a significant difference occurred as described below.

From the above results, it is understood that, in a preferred embodiment of the present invention, by setting the Ti / Zr ratio of the metal particles to an appropriate range, particularly high performance can be achieved when manufactured under severe environments.

The content of the metal-containing particles in each dispersed sol is as follows.

A-1a: 28.1% by mass

A-1b: 28.1% by mass

A-1c: 28.1% by mass

(Example 5)

For the above-mentioned dispersed sol (A-2), samples were prepared in which the content of the metal-containing particles in the solid content was changed to 40% by mass, 50% by mass, and 55% by mass, respectively. The refractive indices of the cured films of each sample were 1.70, 1.76, and 1.79. The same tests [2-1] to [2-4] were performed with each sample, and it was confirmed that good performance was exhibited in each item.

A sample was prepared in which the content of the metal-containing particles in the solid content was 10% by mass. As a result, the refractive index of the cured film fell significantly below 1.6. Under the concentration of such a metal oxide (very low concentration conditions), even if only solvent A or solvent B is used, problems such as reduced crack resistance, gel defect, surface unevenness, and pattern distortion will hardly occur. . From this result, it can be seen that the selection of the solvent of the present invention The equivalent will exert its usefulness when it contains metal-containing particles.

(Example 6)

For test 201, the amounts of BDGAC and DAA were changed to the following tests and the same tests [2-1] to [2-4] were performed. As a result, as described below, it can be seen that by changing this amount, it is possible to adjust each performance item while maintaining good performance in any item.

(Example 7)

Each of the siloxane resin composition samples prepared in the above-mentioned tests 101, 103, and 114 was coated on a silicon wafer. Thereafter, pre-baking (2 minutes at 100 ° C) and post-baking (10 minutes at 230 ° C) were performed to form a coating film having a film thickness of 1.1 µm ((1) in Fig. 1). Further, FH i-4750 ([trade name] a resist solution manufactured by FUJIFILM Electronic Materials Co., Ltd.) was applied so that the dry film thickness became 1.5 μm, and was heated at 90 ° C. on a hot plate. Heat for 1 minute ((2) in Figure 1). This coating film was passed through a mask having a square lattice pattern having a side length of 1.4 μm and a gap between the patterns of 0.35 μm, and was performed at 300 mJ / cm2 using an i-ray stepper (product name: FPA-3000i5 +, manufactured by Canon Inc.). exposure.

Use alkaline developer H PRD-429E (FUJIFILM Electronic (Made by Materials CO., LTD.), And after the aforesaid coating film was subjected to agitation development at room temperature for 60 seconds, it was further rinsed with pure water in a spin spray for 20 seconds. After that, the substrate is further washed with pure water, and then the substrate is dried by high-speed rotation to form a resist pattern ((3) in FIG. 1). When patterned, the separation width was 238.7 nm. In the order of 120 seconds at 145 ° C, 120 seconds at 160 ° C, and 120 seconds at 175 ° C, post-baking treatment is performed on a hot plate to shape the resist into a lens shape (hemispherical shape) (Figure 1) (4)).

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

． RF power: 800W

． Antenna Bias: 400W

． Wafer Bias: 400W

． Chamber pressure: 2Pa

． Substrate temperature: 50 ° C

． Type and flow of mixed gas: CF4 / C4F6 / Ar = 350/25 / 800ml / min

． Photoresist etching rate: 140 nm / minute.

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

Next, examples using B1, C-1, D-1, and E-1 of a siloxane resin (dispersed sol) containing metal oxide fine particles will be described.

<Synthesis Example of Siloxane Resin (Disperse Sol) B-1 Containing Metal Oxide Fine Particles>

(Preparation of Water-dispersed Sol (BA-1) of Nuclear Microparticles)

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

Next, 7.1 kg of a hydrogen peroxide aqueous solution containing 35% by mass of hydrogen peroxide and 20.0 kg of ion-exchanged water were added to the filter cake, and then stirred and heated at a temperature of 80 ° C. for 1 hour, and 28.90 kg of ion-exchanged water was further added. Thus, 61.39 kg of a titanium peroxyzirconate aqueous solution containing 1% by mass of titanium peroxyzirconate based on TiO2 conversion was obtained. This titanium peroxyzirconic acid aqueous solution was transparent yellow-brown and had a pH of 8.9.

Next, 4.00 kg of a cation exchange resin (manufactured by Mitsubishi Chemical Corporation) was mixed with 60.78 kg of the above-mentioned titanium peroxide zirconate aqueous solution, and potassium stannate containing 1% by mass of potassium stannate based on SnO2 conversion was slowly added thereto with stirring. Aqueous solution 8.01kg. Next, after the cation exchange resin introduced with potassium ions and the like was separated, the mixed aqueous solution was heated at a temperature of 168 ° C for 20 hours in an autoclave.

Next, the obtained mixed aqueous solution was cooled to room temperature, and then concentrated using an ultrafiltration membrane device to obtain nuclear fine particles having a solid content of 10% by mass. Of water-dispersed sol (BA-1) 6.89kg.

The water-dispersed sol (BA-1) containing the metal oxide fine particles thus obtained was transparent milky white.

When measuring the content of the metal components contained in the metal oxide fine particles, based on the oxide conversion of each metal component, TiO2 was 90.0% by mass, SnO2 was 4.2% by mass, K2O was 0.5% by mass, and ZrO2 was 5.3% by mass .

(Preparation of water-dispersed sol (BB-1) of metal oxide fine particles)

A spray dryer (NIRO ATOMIZER, manufactured by NIRO Corporation) was used to spray-dry 7.51 kg of the above-mentioned metal oxide fine particle aqueous dispersion (AB-1). Thereby, 0.90 kg of dry powder composed of metal oxide fine particles having an average particle diameter of about 2 μm was obtained.

Next, 0.90 kg of the dry powder of the metal oxide fine particles obtained in the above was fired at 500 ° C. for 2 hours in an air atmosphere to obtain 0.90 kg of a fired powder of the metal oxide fine particles. 0.20 kg of the calcined powder of the metal oxide fine particles obtained above was dispersed in 0.18 kg of pure water, and 0.13 kg of an aqueous tartaric acid solution at a concentration of 28.6% and 0.06 kg of an KOH aqueous solution at a concentration of 50% by mass were added to the mixture. Stir. Next, alumina beads (high-purity alumina beads manufactured by TAIMEI Chemicals Co., Ltd.) having a particle diameter of 0.1 mm were added, and this was supplied to a wet grinder (a batch type bench sander manufactured by Men`s Collection Hayashi). ), And pulverizing and dispersing the fired powder of the metal oxide fine particles for 180 minutes. Thereafter, alumina beads were separated and removed by a stainless steel filter having a pore diameter of 44 μm, and then 1.39 kg of pure water was further added and stirred to obtain a solid product. An aqueous dispersion of metal oxide fine particles having a content of 11.0% by mass was 1.70 kg.

Next, this aqueous dispersion was washed with ion-exchanged water with an ultrafiltration membrane, and then 0.09 kg of an anion-exchange resin (manufactured by Mitsubishi Chemical Corporation: SANUPC) was added to perform deionization treatment. Next, it was supplied to a centrifugal separator (CR-21G manufactured by Hitachi Koki Co., Ltd.) and treated at 11,000 rpm for 1 hour, and then ion-exchanged water was added to prepare a metal oxide having a solid content concentration of 10% by mass. Microparticles of water-dispersed sol (BB-1) 1.86 kg.

Furthermore, when the content of the metal component contained in the metal oxide fine particles was measured, each metal component was calculated on an oxide conversion basis, TiO2 was 88.9 mass%, SnO2 was 5.3 mass%, ZrO2 was 5.3 mass%, and K2O was 0.5 mass % (TiO2 is 79.87 g / mol, ZrO2 is 123.2 g / mol, and the Ti / Zr (molar ratio) in the above blend is 26).

(Preparation of metal oxide fine particles in methanol-dispersed sol (BC-1))

Next, after the water-dispersed sol (BB-1) was cooled, the dispersion medium was replaced with water by using an ultrafiltration membrane device (a membrane filter manufactured by Asahi Kasei Corporation, SIP-1013) to obtain methanol dispersion of metal oxide fine particles. Sol (BC-1) 0.32kg. 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.

(Preparation of Disperse Sol (B-1))

In the preparation of the dispersed sol (A-1), a methanol dispersed sol (BC-1) (solid content concentration: 30% by mass and methanol: 70% by mass) was used instead of the methanol-dispersed sol (AC-1). In the same manner, a dispersed sol (siloxane resin group Adults) (B-1).

<Synthesis example of Siloxane resin (dispersed sol) C-1 containing metal oxide fine particles>

(Preparation of Silicic Acid Solution)

0.31 kg of commercially available water glass (manufactured by AGC Si-Tech. Co., Ltd.) was diluted with pure water, and then alkali-removed with a cation exchange resin (manufactured by Mitsubishi Chemical Corporation) to obtain 2.0 mass in terms of SiO2 conversion. % Silicic acid in silicic acid aqueous solution 3.00kg. The pH of the aqueous silicic acid solution was 2.3.

(Preparation of methanol-dispersed sol (CC-1) of core (Ti and Zr) shell (Si) type inorganic oxide particles)

12.3 kg of pure water was added to 1.80 kg of the metal oxide fine particles in a methanol-dispersed sol (BC-1), and the mixture was stirred and heated to a temperature of 90 ° C. Then, 2.39 kg of the aforementioned silicic acid aqueous solution was slowly added thereto. The mixture solution was aged for 10 hours with stirring while maintaining the temperature at 90 ° C. At this time, the amount of the silicon-containing compound coated with the metal oxide fine particles was 12 parts by mass based on 100 parts by mass of the metal oxide fine particles.

Next, this mixed solution was put into an autoclave (manufactured by Taiatsu Techno), and heat-treated at a temperature of 165 ° C for 18 hours.

Next, the obtained mixed solution was cooled to room temperature, and then concentrated using an ultrafiltration device to obtain a water-dispersed sol (CB-1). For this water-dispersed sol (CB-1), an ultrafiltration membrane (manufactured by Asahi Kasei Corporation., SIP-1013) was used. 0.31 kg of a methanol-dispersed sol (CC-1) of inorganic oxide fine particles was obtained by replacing the dispersion medium with water to methanol. Thereby, 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 are obtained. As a result of measuring the content of the metal component contained in the obtained core-shell type metal oxide fine particles, based on the oxide conversion of each metal component, TiO2 was 86.3% by mass, SnO2 was 5.1% by mass, and ZrO2 was 5.1% by mass. And K2O was 0.5% by mass (TiO2 was 79.87 g / mol, ZrO2 was 123.2 g / mol, and the Ti / Zr (molar ratio) in the above blend was 26). The concentration of solid components contained in the obtained methanol dispersion was about 30% by mass, and the moisture content was 0.25% by mass.

(Preparation of Disperse Sol (C-1))

In the preparation of the dispersed sol (A-1), a methanol-dispersed sol (CC-1) was used instead of the methanol-dispersed sol (AC-1) (solid content concentration: 30% by mass, methanol: 70% by mass). In the same manner, a dispersed sol (siloxane resin composition) (C-1) was obtained.

<Synthesis Example of Silane Resin (Disperse Sol) D-1 Containing Metal Oxide Fine Particles>

(Preparation of Disperse Sol (D-1))

In the preparation of the methanol-dispersed sol (BC-1), the heat treatment in an autoclave when preparing the water-dispersed sol (BA-1) used in the preparation of the methanol-dispersed sol (BC-1) was set to 175 ° C, except Otherwise, a methanol-dispersed sol (DC-1) was obtained in the same manner.

Next, in the preparation of the dispersed sol (A-1), instead of the methanol dispersed sol, (AC-1) A methanol-dispersed sol (DC-1) (solid content concentration: 30% by mass, methanol: 70% by mass) was used, and a dispersion sol (siloxane resin composition) was obtained in the same manner (D -1).

<Synthesis Example of Silane Resin (Disperse Sol) E-1 Containing Metal Oxide Fine Particles>

(Preparation of Disperse Sol (E-1))

In the preparation of the methanol-dispersed sol (CC-1), the heat treatment in an autoclave at the time of preparing the water-dispersed sol (CB-1) used in the preparation of the methanol-dispersed sol (CC-1) was set to 175 ° C, except that Otherwise, a methanol-dispersed sol (EC-1) was obtained in the same manner.

Next, in the preparation of the dispersed sol (A-1), a methanol-dispersed sol (EC-1) was used instead of the methanol-dispersed sol (AC-1) (solid content concentration: 30% by mass, methanol: 70% by mass) In the same manner, a dispersed sol (siloxane resin composition) (E-1) was obtained.

Table 4 shows the number average particle diameter (Mn) of the particles contained in each dispersed sol. The measurement method is as described above. Correspondingly, the Ti / Zr ratio of each dispersed sol is shown.

80 parts by mass of each of the dispersed sols contained a preparation solvent contained in the following amount. The balance of each dispersed sol is a solid content.

B-1 contains 49 parts by mass of methanol and 2.9 parts by mass of γ-butyrolactone

C-1 contains 49 parts by mass of methanol and 2.9 parts by mass of γ-butyrolactone

D-1 contains 49 parts by mass of methanol and 2.9 parts by mass of γ-butyrolactone

E-1 contains 49 parts by mass of methanol and 2.9 parts by mass of γ-butyrolactone

The content of the metal-containing particles in each dispersed sol is as follows.

B-1: 28.1% by mass

C-1: 28.1% by mass

D-1: 28.1% by mass

E-1: 28.1% by mass

(Example 8)

Using the dispersed sols (B-1) and (C-1) obtained above, the components were mixed into the composition shown in Table 5 below to obtain a thermosetting resin composition of the example. With respect to each sample, each test [1-1] to [1-3] was performed in the same manner as in Example 1. The results are shown in Table 5 below.

In addition to the components in Table 5, the following components were blended in all samples.

Epoxy compound: JER-157 S 65 (trade name) manufactured by Mitsubishi Chemical Corporation 5 parts by mass

Blending: content rate (mass parts) in the composition

The content of γ-butyrolactone contained in the resin sample in the composition was 2.9 parts by mass.

(Example 9)

Using the dispersion sols (B-1) and (C-1) obtained in the above, each component was mixed into the composition of Table 6 below to obtain a curable resin composition of the example. For each sample, each test [2-1] to [2-4] was performed in the same manner as in Example 2. The results are shown in Table 6 below.

In addition to the components in Table 6, the following components were blended in all samples.

7 parts by mass of compound KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) having an unsaturated double bond

Polymer A

Benzyl methacrylate / methacrylic acid copolymer (copolymerization ratio: 80/20 (mass%), weight average molecular weight: 12,000) 1.0 part by mass

1.0 part by mass of the ultraviolet absorber (A) having the following structure

0.5 parts by mass of a surfactant with the following structure (1% PGMEA solution)

Polymerization inhibitor (p-methoxyphenol) 0.01 parts by mass

The content ratio of γ-butyrolactone to the composition in the resin sample was 2.5 parts by mass.

(Example 10)

Using the dispersed sols (D-1) and (E-1) obtained in the above, each component was mixed into the composition shown in Table 7 below to obtain a thermosetting resin composition of the example. With respect to each sample, each test [1-1] to [1-3] was performed in the same manner as in Example 1. The results are shown in Table 7 below.

In addition to the components in Table 7, the following components were blended in all samples.

Epoxy compound: JER-157 S 65 (trade name) 5 parts by mass manufactured by Mitsubishi Chemical Corporation

Blending: content rate (mass parts) in the composition

The content of γ-butyrolactone contained in the resin sample in the composition was 2.9 parts by mass.

(Example 11)

Using the dispersion sols (D-1) and (E-1) obtained in the above, each component was mixed into the composition shown in Table 8 below to obtain a curable resin composition of the example. For each sample, each test [2-1] to [2-4] was performed in the same manner as in Example 2. The results are shown in Table 8 below.

In addition to the components in Table 8, the following components were blended in all samples.

7 parts by mass of compound KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) having an unsaturated double bond

Polymer A

Benzyl methacrylate / methacrylic acid copolymer (copolymerization ratio: 80/20 (mass%), weight average molecular weight: 12,000) 1.0 part by mass

1.0 part by mass of the ultraviolet absorber (A) having the following structure

0.5 parts by mass of a surfactant with the following structure (1% PGMEA solution)

Polymerization inhibitor (p-methoxyphenol) 0.01 parts by mass

The content ratio of γ-butyrolactone contained in the resin sample to the composition was 2.9 parts by mass.

(Production of a methanol dispersion with a changed ZrO ₂ ratio)

In the preparation of the water-dispersed sol (BA-1), except that the addition amount of the zirconyl oxychloride octahydrate aqueous solution was changed, it was prepared in the same manner as the water-dispersed sol (BA-1), and the value of Ti / Zr was changed to Silane resin (dispersed sol) containing metal oxide fine particles in the range of 1 to 40 degrees. Each of the dispersed sols that changed the value of Ti / Zr to about 1 to 40 was used as the sample resin 1 in Tables 1 and 2 to prepare a curable composition. The results of evaluation of each curable composition were good.

Claims (21)

A siloxane resin composition containing metal particles, a siloxane resin, a solvent A having a boiling point of 210 ° C or higher and 270 ° C or lower at 1 atmosphere, and a solvent B having a boiling point lower than 210 ° C at 1 atmosphere. Siloxane The resin composition contains the above-mentioned metal-containing particles in a solid content of 40% by mass or more and 80% by mass or less. The siloxane resin composition according to item 1 of the patent application scope, wherein the metal-containing particles contain at least one selected from the group consisting of Ti, Ta, W, Y, Ba, Hf, Zr, Sn, Nb, V, and Si Element as its constituent metal element. The siloxane resin composition according to item 1 of the scope of the patent application, wherein the metal-containing particles contain Ti and Zr as elements constituting the metal. The siloxane resin composition according to any one of claims 1 to 3, wherein the refractive index of the metal-containing particles is 1.75 to 2.70. The siloxane resin composition according to any one of claims 1 to 3 of the scope of patent application, which contains Ti and Zr as elements constituting the metal-containing particles, wherein Ti / Zr is 1 to 30. The siloxane resin composition according to any one of claims 1 to 3 of the scope of patent application, which is a UV-curable resin composition. The siloxane resin composition according to any one of claims 1 to 3 of the scope of patent application, further comprising a polymerization initiator. 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 item 3 of the scope of application for a patent, wherein the siloxane resin composition contains 5 to 50 parts by mass of the above-mentioned siloxane resin based on Si element based on 100 parts by mass of the Ti element containing metal particles. The siloxane resin composition according to any one of claims 1 to 3, wherein the solvent A is selected from an ether compound solvent, an alcohol compound solvent, and an ester compound solvent. The siloxane resin composition according to any one of claims 1 to 3, wherein the solvent A is selected from a compound represented by any one of the following formulae (V1) to (V4), and R ^V1 (CO) O- (L ^V1 -L ^V2 ) _mv -R ^V2 (V1) R ^V3 (CO) O- (L ^V3 )-(O (CO) R ^V4 ) _nv (V2) R ^V6 O- (L ^V4 -L ^V5 ) _pv -R ^V5 (V3) [Chemical Formula 1] R ^V1 is alkyl, alkenyl, alkynyl, aryl, or aralkyl; L ^V1 is a hydrocarbon linking group; L ^V2 is a heteroatom-containing linking group; R ^V2 is a hydrogen atom, a halogen atom, a fluorenyl group, or R ^V1 The meaning is the same; mv is an integer from 0 to 8; R ^V3 and R ^V4 are each independently the same as R ^V1 ; L ^V3 is an alkane linking group, an olefin linking group, an alkyne linking group, an aromatic linking group, or a combination of these Nv is an integer of 1 to 3; L ^V4 is a hydrocarbon linking group; L ^V5 is a heteroatom-containing linking group; R ^V5 has the same meaning as R ^V2 ; pv is an integer of 1 to 8; R ^V6 is a hydrogen atom or R ^V1 has the same meaning; a is a ring structure of 4-membered ring to 7-membered ring. The siloxane resin composition according to any one of claims 1 to 3, wherein the solvent B is diacetone alcohol, dipropylene glycol monomethyl ether, or propylene glycol monomethyl ether acetate. The siloxane resin composition according to any one of claims 1 to 3, wherein the SP of the solvent A is 8.7 or more and 10 or less. The siloxane resin composition according to any one of claims 1 to 3, wherein the boiling point of the solvent A is 230 ° C or higher. The siloxane resin composition according to any one of claims 1 to 3, wherein the siloxane resin composition further contains a polymerizable compound, and the polymerizable compound has a member selected from an epoxy group and an oxygen group. A polymerizable group of a heterocycloalkyl group and at least one ethylenically unsaturated double bond. The siloxane resin composition according to any one of claims 1 to 3, wherein the siloxane resin is obtained by performing a hydrolysis condensation reaction in the presence of the metal-containing particles. The siloxane resin composition according to any one of claims 1 to 3, wherein the refractive index of the cured film is 1.60 or more and 2.0 or less. A transparent hardened product, which is hardened from the siloxane resin composition described in any one of claims 1 to 17 of the scope of patent application. A transparent pixel includes the transparent hardened body described in item 18 of the scope of patent application. A microlens comprising the transparent hardened body described in item 18 of the scope of patent application. A solid-state imaging element includes the transparent pixels described in item 19 of the scope of patent application.