WO2016052658A1 - シロキサン樹脂組成物、これを用いた透明硬化物、透明画素、マイクロレンズ、固体撮像素子 - Google Patents

シロキサン樹脂組成物、これを用いた透明硬化物、透明画素、マイクロレンズ、固体撮像素子 Download PDF

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WO2016052658A1
WO2016052658A1 PCT/JP2015/077825 JP2015077825W WO2016052658A1 WO 2016052658 A1 WO2016052658 A1 WO 2016052658A1 JP 2015077825 W JP2015077825 W JP 2015077825W WO 2016052658 A1 WO2016052658 A1 WO 2016052658A1
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group
siloxane resin
mass
resin composition
solvent
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PCT/JP2015/077825
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English (en)
French (fr)
Japanese (ja)
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貴規 田口
祐継 室
久保田　誠
高桑　英希
上村　哲也
翔一 中村
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富士フイルム株式会社
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Priority to KR1020177006948A priority Critical patent/KR101787492B1/ko
Publication of WO2016052658A1 publication Critical patent/WO2016052658A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G02B1/041—Lenses
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B3/00—Simple or compound lenses
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
    • H01L27/144—Devices controlled by radiation
    • H01L27/146—Imager structures
    • H01L27/14601—Structural or functional details thereof
    • H01L27/14625—Optical elements or arrangements associated with the device
    • H01L27/14627—Microlenses
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • C08G77/58—Metal-containing linkages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/66—Substances characterised by their function in the composition
    • C08L2666/68—Plasticizers; Solvents

Definitions

  • the present invention relates to a siloxane resin composition, a transparent cured product using the siloxane resin composition, a transparent pixel, a microlens, and a solid-state imaging device.
  • Patent Document 1 proposes a positive photosensitive resin composition in which particles such as titanium oxide are contained in polyimide.
  • An object of the present invention is to provide a siloxane resin composition suitable as a material for transparent members such as lenses and transparent pixels. It can be used not only as positive type but also as thermosetting resin or negative type photosensitive resin, and can also be suitably applied to micro-processing of micro lenses and transparent pixels, and is cured as necessary.
  • An object of the present invention is to provide a siloxane resin composition capable of improving the characteristics of a film.
  • Another object of the present invention is to provide a transparent cured product, a transparent pixel, a microlens, and a solid-state imaging device using the siloxane resin composition.
  • 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 of less than 210 ° C. at 1 atmosphere.
  • the metal-containing particles contain at least one element selected from Ti, Ta, W, Y, Ba, Hf, Zr, Sn, Nb, V, and Si as constituent metal elements in [1].
  • 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.
  • the solvent A is selected from an ether compound solvent, an alcohol compound solvent, and an ester compound solvent.
  • L V2 is a hetero linking group.
  • R V2 has the same meaning as a hydrogen atom, a halogen atom, an acyl group, or R V1 .
  • mv is an integer of 0-8.
  • R V3 and R V4 are independently the same as R V1 .
  • L V3 is an alkane linking group, an alkene linking group, an alkyne linking group, an aryl linking group, or a linking group obtained by combining them.
  • nv is an integer of 1 to 3.
  • L V4 is a hydrocarbon linking group.
  • L V5 is a hetero 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 a group having the same meaning as R V1 .
  • ⁇ is a 4- to 7-membered ring structure.
  • a polymerizable compound is further contained, and the polymerizable compound has a polymerizable group selected from an epoxy group, an oxetanyl group, and at least one ethylenically unsaturated double bond.
  • the siloxane resin composition as described in any one of.
  • a transparent cured product obtained by curing the siloxane resin composition according to any one of [1] to [17].
  • a transparent pixel comprising the transparent cured product according to [18].
  • a microlens comprising the transparent cured product according to [18].
  • a solid-state imaging device comprising the transparent pixel according to [19] and / or the microlens according to [20].
  • the notation which does not describe substitution and unsubstituted includes what has a substituent with what does not have a substituent.
  • the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • “radiation” in the present specification means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams, and the like. In the present invention, light means actinic rays or radiation.
  • exposure in this specification is not limited to exposure with an emission line spectrum of a mercury lamp, far ultraviolet rays typified by excimer laser, X-rays, EUV light, etc., but also particles such as electron beams and ion beams. Line drawing is also included in the exposure.
  • (meth) acrylate represents both and / or acrylate and methacrylate
  • (meth) acryl represents both and / or acryl and “(meth) acrylic”
  • Acryloyl represents both and / or acryloyl and methacryloyl.
  • “monomer” and “monomer” are synonymous.
  • the monomer in this specification is distinguished from an oligomer and a polymer, and refers to a compound having a weight average molecular weight of 2,000 or less.
  • the polymerizable compound refers to a compound having a polymerizable group, and may be a monomer or a polymer.
  • the polymerizable group refers to a group that participates in a polymerization reaction.
  • the weight average molecular weight and the number average molecular weight can be determined by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • Me in the chemical formula represents a methyl group
  • Et represents an ethyl group
  • Pr represents a propyl group
  • Bu represents a butyl group
  • Ph represents a phenyl group.
  • the siloxane resin composition of the present invention is suitable as a material for transparent members such as lenses and transparent pixels. Not only the positive type but also a thermosetting resin or a negative photosensitive resin can be used, and it can also be suitably applied to micro-processing of micro lenses and transparent pixels. Furthermore, the characteristics (crack resistance, gel defect resistance, surface unevenness prevention) of the cured film can be improved as required. In addition, a high-quality transparent cured product, a transparent pixel, a microlens, and a solid-state imaging device using the siloxane resin composition can be provided.
  • the siloxane resin composition of the present invention contains metal-containing particles, a siloxane resin, and a specific solvent.
  • the reason for the above-mentioned effect includes the unclear point, but is presumed as follows.
  • the metal-containing particles coexist with the siloxane resin, it is considered that this acts catalytically and the reaction proceeds in the system. This may affect the occurrence of cracks.
  • the specific high boiling point solvent described above is employed, and, for example, remains in the system even after film formation, thereby exhibiting stress relaxation and reaction inhibiting action, and exhibiting its unique effects. It is guessed.
  • the metal-containing particles widely include particles containing a metal as a constituent element.
  • the term “metal” is to be interpreted in the broadest sense, and includes semimetals such as boron, silicon, and arsenic.
  • the metal-containing particles When the metal-containing particles are configured to include oxygen atoms, they may be particularly referred to as metal oxide particles.
  • the metal-containing particles preferably contain a metal selected from Ti, Ta, W, Y, Ba, Hf, Zr, Sn, Nb, V, and Si. Especially, it is preferable that it is the oxide particle of the composite metal containing 2 or more types of them.
  • a combination of Ti and Zr (more Si if necessary), Ti and Sn (more Si if necessary), Ti, Zr and Sn (more Si if necessary) is preferable, and a combination having Ti, Zr, Sn and Si is preferable. Further preferred.
  • constituent material of the metal-containing particles examples include titanium oxide, zirconium oxide, silicon oxide, barium titanate, barium sulfate, barium oxide, hafnium oxide, tantalum oxide, tungsten oxide, and yttrium oxide. These constituent materials may contain two or more kinds, preferably contain at least titanium oxide and zirconium oxide, and more preferably contain titanium oxide, zirconium oxide, tin oxide and silicon oxide. In the case of containing titanium oxide as a constituent material, it is preferable to contain rutile type titanium oxide. Furthermore, it is preferable to contain 80% by mass or more of rutile type titanium oxide with respect to the total amount of titanium oxide, more preferably 90% by mass or more, and particularly preferably 95% by mass or more. The upper limit is 100% by mass.
  • the refractive index of the metal-containing particles is preferably 1.75 or more and particularly preferably 1.90 or more from the viewpoint of obtaining a high refractive index.
  • the upper limit is preferably 2.90 or less, and particularly preferably 2.70 or less.
  • the average particle size of the metal-containing particles is preferably 500 nm or less, more preferably 200 nm or less, further preferably 100 nm or less, more preferably 50 nm or less, and particularly preferably 30 nm or less.
  • As a lower limit 1 nm or more is preferable and 3 nm or more is more preferable.
  • the metal-containing particles can be pulverized or dispersed using a dispersing machine such as a bead mill by procuring appropriate particle powder.
  • the refractive index of metal-containing particles can be measured by the following method.
  • the content rate of the metal-containing particles is adjusted to 0% by mass, 20% by mass, 30% by mass, 40% by mass, and 50% by mass to prepare a mixed solution sample in which the metal-containing particles and the matrix resin are mixed.
  • the solid content concentration of each mixed solution sample is 10%.
  • Each mixed solution sample was applied on a silicon wafer so as to have a thickness of 0.3 to 1.0 ⁇ m using a spin coater, and then heated and dried on a 200 ° C. hot plate for 5 minutes, A coating film is obtained.
  • the refractive index at a wavelength of 633 nm (25 ° C.) is obtained using an ellipsometer (manufactured by Otsuka Electronics Co., Ltd.), and the value of 100% by mass of the metal-containing particles can be extrapolated.
  • the number average particle size of the metal-containing particles (meaning the average particle size in the primary particle size) can be determined from the photograph obtained by observing the particles with a transmission electron microscope. The projected area of the particles is obtained, the equivalent circle diameter is obtained therefrom, and the number average particle diameter is calculated. In order to determine the average particle size, the particle size was measured for 100 particles, and the average value of 80 particles excluding the maximum 10 particles and the minimum 10 particles among the measured particle sizes was defined as the average particle size. . In this specification, the average particle diameter means the number average particle diameter unless otherwise specified.
  • metal-containing particles examples include T-BTO-020RF (barium titanate; manufactured by Toda Kogyo Co., Ltd.), UEP-100 (zirconium oxide; manufactured by Daiichi Rare Element Chemical Co., Ltd.), or STR-100N.
  • STR-100W, STR-100WLPT titanium oxide; both manufactured by Sakai Chemical Industry Co., Ltd.
  • the metal-containing particles can also be obtained as a dispersion dispersed in a liquid.
  • silicon oxide-titanium oxide particles examples include “OPTRAIK” (registered trademark) TR-502, “OPTRAIK” TR-503, “OPTRAIK” TR-504, “OPTRAIK” TR-513, “OPTRAIK” “TR-520", “Optlake” TR-527, “Optlake” TR-528, “Optlake” TR-529, “Optlake” TR-544 or “Optlake” TR-550 Kogyo Co., Ltd.).
  • the content ratio (element composition) of the metal element in the metal-containing particles contains Ti and Zr, and the ratio is preferably 1 or more, more preferably 3 or more, and particularly preferably 4 or more in terms of Ti / Zr ratio.
  • As an upper limit 40 or less are preferable, 30 or less are more preferable, 20 or less are further more preferable, and 12 or less are especially preferable.
  • the Ti / Zr ratio be in this range because the light resistance of the cured product of the siloxane resin composition can be improved.
  • the interaction with a specific solvent is further increased, 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.
  • Ti and Si are contained, and the ratio is preferably 1 or more in terms of Ti / Si ratio. As an upper limit, 40 or less are preferable, 30 or less are more preferable, and 10 or less are especially preferable.
  • the Ti / Sn ratio is preferably 10 or more, more preferably 13 or more, further preferably 15 or more, further preferably 17 or more, further preferably 19 or more, and particularly preferably 20 or more.
  • the Ti / Sn ratio within this range, it is preferable that the compatibility with the organic component used together with the metal-containing particles can be expected.
  • grain is evaluated by the element composition (atomic%) quantified by the fluorescent X ray analysis (Rigaku's PrimusII type
  • the ratio of a plurality of elements is determined by obtaining each element composition (atomic%) and evaluating the ratio of each elemental composition (atomic%).
  • the elemental composition ratio is synonymous even if it is obtained as a mole ratio.
  • the surface treatment of the metal-containing particles may be in any form, for example, an aspect of treatment with a surfactant described later, an aspect of treatment with a treatment agent containing another metal, or the like.
  • a treatment agent containing another metal for example, the aspect which forms a specific metal containing particle
  • a coating of another type of metal-containing material or the like may be thick and core-shell type metal-containing particles may be used.
  • the ratio of the core to the shell is not particularly limited, but when the total particle is 100 parts by mass, the ratio of the core is preferably 85 parts by mass or more, more preferably 87 parts by mass or more, and particularly preferably 90 parts by mass or more.
  • the upper limit is practically 97 parts by mass or less.
  • the combination of materials constituting the core and the shell is not particularly limited, but the core is composed of particles containing Ti, Sn, etc., and the shell is coated with Zr, coated with Si, or contains Zr and Si. An example comprising a coating is given.
  • the material constituting the shell is a high refractive index material.
  • the shell is a material that is stable to light (for example, zirconium) for the purpose of suppressing the photocatalytic activity of the titanium oxide component present on the particle surface. ) Is desirable.
  • a metal containing particle is 40 mass% or more in the solid component of a composition (siloxane resin composition), It is preferable that it is 50 mass% or more, It is especially preferable that it is 55 mass% or more. As an upper limit, it is 80 mass% or less, and it is especially preferable that it is 70 mass% or less.
  • a metal containing particle may be used individually by 1 type, or may be used in combination of 2 or more type.
  • a solid component means a component which does not lose
  • 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 metal salt as a constituent element is added to a medium for forming a sol, and an alkali or an acid is further added as necessary to obtain a dispersed sol (cake). In addition, when a medium is an acid or an alkali, it is not necessary to add these additionally. The example which solidifies and pulverizes by heating this is given. At this time, composite metal particles can be obtained by adding a metal element salt to be mixed to the sol. Alternatively, once the core particles are formed, a sol containing the desired metal salt is formed in the same manner as described above. By heating this and pulverizing the solidified material, core-shell type particles can be obtained.
  • the salt of each metal illustrated above is mentioned.
  • Specific examples include titanium tetrachloride, potassium stannate, zirconium oxychloride, aluminum oxychloride, and aluminum chloride.
  • various organic metal compounds and metal alkoxides can also be used.
  • the solvent that forms the sol include aqueous alkaline solutions such as aqueous ammonia, potassium hydroxide, and sodium hydroxide, and acidic aqueous solutions such as hydrochloric acid, nitric acid, and sulfuric acid.
  • a sol-gel method in which metal alkoxide is dissolved using water or various organic media can be used.
  • metal-containing particles for example, the method described in paragraphs [0015] to [0043] of JP-A-2008-69193 can be referred to. Moreover, as the specific metal-containing particles, those described in paragraphs [0015] to [0043] of JP-A-2008-69193 can be used, and are incorporated herein by reference.
  • the siloxane resin is preferably a resin obtained by hydrolytic condensation reaction of an alkoxysilane compound represented by any of the following formulas (1) to (3). Furthermore, it is also preferable that the compound represented by the formula (1) and the compound represented by the formula (2) are both subjected to a hydrolytic condensation reaction. Alternatively, both the compound of formula (1) and the compound of formula (3) may be subjected to a hydrolytic condensation reaction. The compound of formula (2) and the compound of formula (3), or the compound of formula (1) and the formula The compound of (2) and the compound of formula (3) may be subjected to a hydrolytic condensation reaction. In addition, 1 type of compounds of each formula may be used, or 2 or more types may be used.
  • R 1 and R 2 each independently represents a hydrogen atom or a hydrocarbon group.
  • the hydrocarbon group is an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms), alkynyl A group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 14 carbon atoms, particularly preferably 6 to 10 carbon atoms), an aralkyl group (7 carbon atoms).
  • a is 0, 1 or 2.
  • R 3 is a functional group-containing group.
  • the functional group is preferably a group containing a hetero atom (S, O, N, P, Si, etc.) in the structure. Or it is preferable that a polymeric group, an acidic group, or a basic group is included.
  • the carboxyl group, sulfonic acid group, phosphoric acid group, and phosphonic acid group may form a salt, ester, or anhydride thereof.
  • the amino group may also form a salt.
  • the term “acryl” or “acryloyl” broadly refers to not only an acryloyl group but also a derivative structure thereof, and includes a structure having a specific substituent at the ⁇ -position of the acryloyl group. However, in a narrow sense, the case where the ⁇ -position is a hydrogen atom may be referred to as acryl or acryloyl.
  • methacryl which means either acryl (the ⁇ -position is a hydrogen atom) or methacryl (the ⁇ -position is a methyl group), and is sometimes referred to as (meth) acryl.
  • R 4 and R 5 are each independently a group having the same meaning as R 1 . c is 0 or 1;
  • R 6 and R 7 are each independently a group having the same meaning as R 1 above, or an alkoxy group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 3 carbon atoms), an alkenyloxy group.
  • R 6 and R 7 may be R 3 groups.
  • X is a divalent or higher linking group. When X is a divalent linking group, examples of the linking group L described below are given.
  • X is a trivalent linking group
  • X is a trivalent linking group
  • d is an integer of 1 to 4, preferably 1 or 2.
  • R 1 to R 7 may each independently have an arbitrary substituent T.
  • adjacent ones may be bonded to each other or condensed to form a ring.
  • Examples of the bifunctional silane compound include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, cyclohexylmethyldimethoxysilane, and the like. Can be mentioned.
  • Examples of the tetrafunctional silane compound include tetramethoxysilane and tetraethoxysilane.
  • Examples of silane compounds represented by formula (2) Examples of the trifunctional silane compound include 3-glycidoxypropyltrimethoxysilane, ⁇ -methacryloyloxypropyltrimethoxysilane, ⁇ -methacryloxypropyltriethoxysilane, ⁇ -acryloyloxytrimethoxysilane, and ⁇ -acryloyloxy.
  • bifunctional silane compound examples include ⁇ -glycidoxypropylmethyldimethoxysilane, ⁇ -acryloyloxypropylmethyldimethoxysilane, ⁇ -acryloyloxypropylmethyldiethoxysilane, ⁇ -methacryloxypropylmethyldimethoxysilane, and ⁇ -methacrylic.
  • Examples of the silane compound represented by the formula (3) include 1,3-bis (3-aminopropyl) tetramethyldisiloxane, 1,3-bis (3-aminoethyl) tetramethyldisiloxane, 1,3 -Bis (3-aminopropyl) tetraethyldisiloxane and the like.
  • the siloxane resin can be obtained through the hydrolysis reaction and the condensation reaction using the above-described alkoxysilane compound.
  • a known method can be used as the hydrolysis-condensation reaction, and a catalyst such as an acid or a base may be used as necessary.
  • the catalyst is not particularly limited as long as the pH is changed.
  • examples of the acid (organic acid, inorganic acid) include nitric acid, phosphoric acid, oxalic acid, acetic acid, formic acid, hydrochloric acid and the like.
  • examples of the alkali include ammonia, triethylamine, ethylenediamine, and the like.
  • the amount to be used is not particularly limited as long as the siloxane resin satisfies a predetermined molecular weight.
  • a solvent preparation solvent
  • the solvent is not particularly limited as long as the hydrolysis-condensation reaction can be carried out, and examples of the solvent described below can be given.
  • alcohol compounds such as water, methanol, ethanol, propanol, diacetone alcohol (DAA), tetrahydrofurfuryl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, dipropylene glycol monomethyl
  • ether compounds such as ether (DPM), ester compounds such as methyl acetate, ethyl acetate, butyl acetate, ⁇ -butyrolactone, and propylene glycol monomethyl ether acetate
  • ketone compounds such as acetone, methyl ethyl ketone, and methyl isoamyl ketone.
  • the conditions (temperature, time, amount of solvent) for the hydrolysis-condensation reaction may be appropriately selected according to the type of material used.
  • the weight average molecular weight of the siloxane resin used in this embodiment is preferably 2,000 or more, and more preferably 3,000 or more.
  • the upper limit is preferably 500,000 or less, more preferably 450,000 or less, and particularly preferably 250,000 or less.
  • the molecular weight of the polymer means a weight average molecular weight unless otherwise specified, and is measured in terms of standard polystyrene by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • a measuring device manufactured by Tosoh Corporation is used. As conditions, it shall be based on the following condition 1. However, depending on the polymer type, an appropriate carrier (eluent) and a column suitable for it may be selected and used. (Condition 1) Column: TOSOH TSKgel Super HZM-H, TOSOH TSKgel Super HZ4000, TOSOH TSKgel A column connected with Super HZ2000 is used
  • Carrier Tetrahydrofuran Measurement temperature: 40 ° C.
  • the siloxane resin is adjusted with dimethylformamide so that the sample concentration is 0.3% by mass, and measurement is performed. However, depending on the type and molecular weight, measurement may be performed under the above condition 1.
  • preferred siloxane resins include the following.
  • alkoxysilane having four or more alkoxy groups include tetramethoxysilane, tetraethoxysilane, tetraacetoxysilane, tetraphenoxysilane, tetramethoxydisiloxane, tetraethoxydisiloxane, and bis (triethoxysilylpropyl) tetrasulfide.
  • Tris- (3-trimethoxysilylpropyl) isocyanurate
  • tris- (3-triethoxysilylpropyl) isocyanurate Tris- (3-triethoxysilylpropyl) isocyanurate.
  • a mixture of tetrafunctional silane and 9 functional silane is used in order to allow bulky 9 functional silane and tetrafunctional silane with less steric hindrance to react with each other. Is preferred.
  • the siloxane resin is also preferably a hydrolyzate condensation reaction product with a bifunctional or trifunctional alkoxysilane compound.
  • alkoxysilane compound constituting the siloxane resin include dimethoxydimethylsilane, diethoxydimethylsilane, dimethoxydiphenylsilane, diethoxydiphenylsilane, dihydroxydiphenylsilane, dimethoxy (methyl) (phenyl) silane, and diethoxy (methyl) (phenyl).
  • Silane dimethoxy (methyl) (phenethyl) silane, dicyclopentyldimethoxysilane or cyclohexyldimethoxy (methyl) silane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane Or 3-acryloxypropyltriethoxysilane, 3-trimethoxysilylpropyl succinic anhydride, 3-triethoxysilylpropyl anhydride Acid, 3-trimethoxysilylethyl succinic anhydride, 3-trimethoxysilylbutyl succinic anhydride, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3- (3,4-epoxy (Cyclohexyl) propyltrimethoxysilane, 3- (3,4-epoxy (C
  • the content of the siloxane resin is small when the alkali-soluble resin described later is contained, and is preferably increased when the alkali-soluble resin is not contained. That is, when the alkali-soluble resin is contained, the content of the siloxane resin is preferably 1% by mass or more, more preferably 2% by mass or more in the solid component of the composition, and 3% by mass.
  • the above is particularly preferable. As an upper limit, it is preferable that it is 40 mass% or less, it is more preferable that it is 30 mass% or less, and it is especially preferable that it is 20 mass% or less.
  • the content of the siloxane resin is preferably 10% by mass or more, more preferably 15% by mass or more, and more preferably 20% by mass or more in the solid component of the composition. It is particularly preferred that As an upper limit, it is preferable that it is 40 mass% or less, and it is more preferable that it is 35 mass% or less.
  • the amount is preferably 10 parts by mass or more and more preferably 20 parts by mass or more with respect to 100 parts by mass of the Ti element in the metal-containing particles. As an upper limit, it is preferable that it is 70 mass parts or less, It is more preferable that it is 60 mass parts or less, It is especially preferable that it is 50 mass parts or less.
  • the content of the siloxane resin can vary depending on the degree of progress of the hydrolysis reaction.
  • the Si element may be 5 parts by mass or more with respect to 100 parts by mass of the Ti element of the metal-containing particles.
  • it is more preferably 8 parts by mass or more, and particularly preferably 10 parts by mass or more.
  • the upper limit is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and particularly preferably 25 parts by mass or less.
  • the amount of the siloxane resin is preferably used in the above lower limit or more from the viewpoint of film forming property and film durability. On the other hand, it is preferable from the viewpoint that a high refractive index can be maintained by suppressing it to the upper limit value or less.
  • a siloxane resin may be used individually by 1 type, or may be used in combination of 2 or more type.
  • siloxane resin basically means a polymer obtained through a hydrolytic condensation reaction of an alkoxysilane compound.
  • a polymer obtained by other reaction and a silane compound itself as a raw material are also included.
  • the siloxane resin is preferably a hydrolytic condensation reaction product of a silane compound.
  • the hydrolysis condensation reaction of the silane compound may be performed in the presence of metal-containing particles.
  • a particle-resin matrix in which a silane compound reacts with metal-containing particles and the surface thereof, or a core-shell structure in which a core is a metal-containing particle and a shell is a silane compound may be formed.
  • 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 atm (a solvent satisfying this condition is referred to as “specific high-boiling solvent” or “solvent A”. Sometimes called).
  • the upper limit of the boiling point is further preferably 265 ° C. or lower, and more preferably 260 ° C. or lower.
  • the lower limit of the boiling point of the specific high boiling point solvent is preferably 220 ° C or higher, more preferably 230 ° C or higher.
  • the SP value of the solvent is preferably 8 or more, more preferably 8.5 or more, and particularly preferably 8.7 or more.
  • the upper limit is preferably 11 or less, more preferably 10.5 or less, and particularly preferably 10 or less.
  • the reason why an excellent effect is obtained by setting the SP value of the solvent in the above range is estimated as follows. It is understood that the metal-containing particles are typically dispersed in a solvent. From the viewpoint of improving the dispersibility, it is understood that it was effective to set the solvent in the above SP value range in consideration of the polarity of the siloxane resin and metal-containing particles. And after hardening, it is thought that it contributed also to generation
  • the SP value is determined by the Fedors method (R.F.Fedors Polym. Eng.Sci., 14 [2], 147-154 (1974)).
  • Specific high boiling point solvents are ether compound solvents (solvents composed of compounds having an ether group in the molecule), alcohol compound solvents (solvents composed of compounds having a hydroxyl group in the molecule), ester compound solvents (intramolecular It is preferable to select from a solvent comprising a compound having an ester group.
  • the specific high boiling point solvent is preferably composed of a compound represented by any of the following formulas (V1) to (V4).
  • R V1 represents an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms), alkynyl A group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 14 carbon atoms, particularly preferably 6 to 10 carbon atoms), an aralkyl group (7 carbon atoms).
  • L V1 is a hydrocarbon linking group of the linking group L described later.
  • L V2 is a hetero linking group of the linking group L described later.
  • a preferable range is also synonymous, and an oxygen atom (ether group) is more preferable.
  • R V2 is a hydrogen atom, a halogen atom, an acyl group (preferably having a carbon number of 2 to 12, more preferably 2 to 6, and particularly preferably 2 or 3), or the same meaning as R V1 .
  • a hydrogen atom, an alkyl group, or an acyl group is preferable, and an alkyl group or an acyl group is more preferable.
  • mv is an integer of 0 to 8, preferably an integer of 1 to 8, more preferably an integer of 1 to 6, and particularly preferably an integer of 1 to 3.
  • R V3 and R V4 are independently the same as R V1 .
  • LV3 is an alkane linking group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 3 carbon atoms), an alkene linking group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms).
  • An alkyne linking group preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms
  • an aryl linking group preferably having 6 to 22 carbon atoms, more preferably 6 to 14 carbon atoms, and particularly preferably 6 to 10 carbon atoms
  • a structure in which an oxygen atom is interposed in the middle of the linking group is also preferable. Especially, it is preferable that it is the said alkane coupling group or a coupling group of the structure where the oxygen atom intervened there.
  • the number of bonds of the linking group is determined by nv + 1.
  • nv is an integer of 1 to 3, preferably 1 or 2.
  • L V4 is a hydrocarbon linking group of the linking group L described later.
  • the preferred range is also synonymous.
  • an alkylene group is preferable.
  • L V5 is a hetero linking group of the linking group L described later.
  • a preferable range is also synonymous, and an oxygen atom is more preferable.
  • R V5 has the same meaning as R V2 .
  • a hydrogen atom or an alkyl group is preferable, and an alkyl group is more preferable.
  • R V6 is a hydrogen atom or a group having the same meaning as R V1 .
  • pv is an integer of 1 to 8, preferably an integer of 1 to 6, and more preferably an integer of 1 to 3.
  • R V1 to R V6 may be branched or linear when they are alkyl groups or the like. Or it may be annular. These may form a ring with each other or with L V1 to L V5 .
  • the ring structure ⁇ is preferably a 4-membered ring to a 7-membered ring, and more preferably a 5-membered ring to a 6-membered ring.
  • the 6-membered ring is preferably a substituted or unsubstituted cyclohexane ring.
  • a substituted or unsubstituted tetrahydrofuran ring, a substituted or unsubstituted dioxolane ring, or a substituted or unsubstituted cyclopentane ring is preferable.
  • a 5-membered ring may have a substituent, and a substituted or unsubstituted lactone ring such as ⁇ -butyrolactone is also a preferred embodiment.
  • the specific high boiling point solvent (solvent A) is preferably contained in an amount of more than 1% by mass, more preferably 5% by mass or more, in the entire composition. Although there is no particular upper limit, it is preferably 95% by mass or less, more preferably 50% by mass or less, and even more preferably 30% by mass or less in consideration of using the specific low boiling point solvent (solvent B). Solvent A may be used individually by 1 type, or may be used in combination of 2 or more type. In addition, in this invention, what became the combination of the solvent which becomes the said range accidentally is also included in the technical scope naturally. For example, the solvent used in the preparation of the siloxane resin may serve as one solvent, and the solvent added thereafter may serve as the other solvent to exhibit a desired effect.
  • a solvent having a boiling point of less than 210 ° C. (1 atm) (referred to as “specific low boiling point solvent” or “solvent B”) is used. .
  • the boiling point of the solvent B is further preferably 200 ° C. or lower, more preferably 190 ° C. or lower, further preferably 180 ° C. or lower, and particularly preferably 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 between the boiling point of solvent A and the boiling point of solvent B is preferably 5 ° C. or more, more preferably 10 ° C. or more, further preferably 15 ° C. or more, and more preferably 30 ° C. or more. More preferably, it is more preferably 40 ° C. or more, and particularly preferably 50 ° C. or more.
  • the lower limit of the boiling point of the specific low-boiling solvent (solvent B) is not particularly limited, but is practically 60 ° C. (1 atm) or more.
  • the ratio of the specific low boiling point solvent (solvent B) in the entire composition is preferably 1% by mass or more, more preferably 2% by mass or more, and further preferably 5% by mass or more. As an upper limit, 75 mass% or less is preferable, 70 mass% or less is more preferable, and 60 mass% or less is especially preferable.
  • the solvent B is preferably selected from those consisting of a compound represented by any one of the above formulas (V1) to (V4). Alternatively, diacetone alcohol (DAA), propylene glycol monomethyl ether acetate (PGMEA), or dipropylene glycol monomethyl ether (DPM) is preferable. Among them, diacetone alcohol is preferably used as the solvent B.
  • DAA is structurally well coordinated on the Ti surface and may have an effect, so a high effect can be expected when applied as a low-boiling solvent (sub-solvent).
  • the solvent B is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and particularly preferably 20 parts by mass or more.
  • 1000 mass parts or less are preferable, 500 mass parts or less are more preferable, It is more preferable to be 300 mass parts or less, 200 mass parts or less is further more preferable, It is more preferable to be 150 mass parts or less.
  • the solvent typically means a component other than the solid component.
  • the solvent C is preferably an ether compound solvent, an alcohol compound solvent, a ketone solvent, or an ester compound solvent, and is selected from those consisting of a compound represented by any one of the above formulas (V1) to (V4). It is preferable.
  • the solvent C may be used alone or in combination of two or more.
  • the molecular weight of the solvents A to C is not particularly limited, but is preferably a low molecular weight compound, preferably a molecular weight of 1000 or less, and more preferably 500 or less. Although there is no lower limit in particular, it is practical that it is 40 or more.
  • the molecular weight of the low molecular weight compound can be identified, for example, by mass spectrum measurement.
  • the siloxane resin composition of this invention may contain the solvent used at the time of preparation of a hydrolysis-condensation product as it is.
  • a preparation solvent include the preparation solvents described in the above section [Siloxane resin].
  • the solvent for preparation may remain together with the solvent A in the siloxane resin composition.
  • the solvent for preparation occupies a majority of the solvent and the solvents A and B or C are added thereto.
  • the amount of the solvent for preparation can be arbitrarily adjusted, and may be appropriately set according to the conditions in the hydrolysis reaction.
  • the siloxane resin composition of the present invention may contain a polymerization initiator.
  • the polymerization initiator may be either a thermal polymerization initiator or a photopolymerization initiator, but a photopolymerization initiator is preferred.
  • aminoacetophenone initiators described in JP-A-10-291969 and acylphosphine oxide initiators described in Japanese Patent No. 4225898 examples include aminoacetophenone initiators described in JP-A-10-291969 and acylphosphine oxide initiators described in Japanese Patent No. 4225898.
  • examples of the hydroxyacetophenone-based initiator include IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (trade names: all manufactured by BASF).
  • aminoacetophenone initiators IRGACURE-907, IRGACURE-369, IRGACURE-379 (trade names: all manufactured by BASF) and the like can be used.
  • a compound described in JP-A-2009-191179 in which an absorption wavelength is matched with a long wave light source such as 365 nm or 405 nm can also be used.
  • acylphosphine initiators IRGACURE-819, Darocur 4265, DAROCUR-TPO (trade names: all manufactured by BASF) can be used.
  • the azo compound include 2,2-azobisisobutyronitrile (AIBN), 3-carboxypropionitrile, azobismaleonitrile, dimethyl-2,2′-azobis (2-methylpropionate) [V -601] (manufactured by Wako).
  • an oxime compound In the present invention, it is preferable to use an oxime compound.
  • the oxime compound effectively functions as a polymerization initiator that initiates and accelerates polymerization in the siloxane resin composition of the present invention.
  • the oxime compound is less colored by post-heating and has good curability.
  • the present invention is preferable in that the pattern distortion of the cured product can be suppressed. Although details of this reason are unclear, it is assumed that the compatibility between the specific high boiling point solvent and the oxime compound is involved. Of these, commercially available products such as IRGACURE OXE01 and IRGACURE OXE02 (both manufactured by BASF) can be suitably used.
  • oxime compound serving as a polymerization initiator those represented by the following formula (OX) are preferred, and those represented by the formula (OX-1) are more preferred.
  • ⁇ A 1 A 1 is preferably —AC or an alkyl group of the formula (OX-1).
  • the alkyl group preferably has 1 to 12 carbon atoms, and more preferably 1 to 6 carbon atoms.
  • the alkyl group may have a substituent T described later. Further, the substituent T may be substituted via a linking group L described later.
  • ⁇ C C represents Ar, —SAr, or —COAr.
  • ⁇ R R represents a monovalent substituent, and is preferably a monovalent nonmetallic atomic group.
  • the monovalent nonmetallic atomic group include an alkyl group (preferably having a carbon number of 1 to 12, more preferably 1 to 6, particularly preferably 1 to 3), and an aryl group (preferably having a carbon number of 6 to 14, more preferably 6-10), an acyl group (preferably 2-12 carbon atoms, more preferably 2-6, particularly preferably 2-3), an aryloyl group (preferably 7-15 carbon atoms, more preferably 7-11).
  • An alkoxycarbonyl group (preferably having a carbon number of 2 to 12, more preferably 2 to 6, particularly preferably 2 to 3), an aryloxycarbonyl group (preferably having a carbon number of 7 to 15, more preferably 7 to 11), a complex A cyclic group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms), an alkylthiocarbonyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, particularly preferably 2 to 3 carbon atoms), Over thiocarbonyl group include (preferably having 7 to 15, more preferably from 7 to 11 carbon atoms) and the like. Moreover, these groups may have one or more substituents.
  • substituent T may be further substituted with another substituent T.
  • substituent T a halogen atom, an alkyl group (preferably having a carbon number of 1 to 12, more preferably 1 to 6, particularly preferably 1 to 3), an aryl group (preferably having a carbon number of 6 to 14, more preferably 6).
  • an arylthio group preferably having 6 to 14 carbon atoms, more preferably 6 to 10
  • an aryloyl group preferably having 7 to 15 carbon atoms, more preferably 7 to 11
  • the linking group L is preferably an alkylene group having 1 to 6 carbon atoms, O, S, CO, NR N , or a combination thereof.
  • ⁇ B B represents a monovalent substituent, and is an alkyl group (preferably having 1 to 12 carbon atoms), an aryl group (preferably having 6 to 14 carbon atoms, more preferably having 6 to 10 carbon atoms), a heterocyclic group (preferably having carbon atoms). 2 to 18, more preferably 2 to 12 carbon atoms. These groups may be bonded via a linking group L. In addition, these groups may have one or more substituents T. The substituent T may also be substituted through an arbitrary linking group L.
  • the linking group L is also preferably an alkylene group having 1 to 6 carbon atoms, O, S, CO, NR N , or a combination thereof. Specific examples of B include the following.
  • ⁇ A A is a single bond or a linking group.
  • the linking group include the linking group L or arylene group (preferably having 6 to 14 carbon atoms, more preferably 6 to 10 carbon atoms) or a heterocyclic linking group (preferably an aromatic heterocyclic linking group) (preferably Has 2 to 18 carbon atoms, more preferably 2 to 12 carbon atoms.
  • Ar Ar is an aryl group or heteroaryl (aromatic heterocyclic group).
  • the aryl group preferably has 6 to 14 carbon atoms, more preferably 6 to 10 carbon atoms, and is preferably a phenyl group or a naphthyl group.
  • the heteroaryl group is preferably a carbazolyl group having preferably 2 to 18 carbon atoms, more preferably 2 to 12 carbon atoms, and optionally having a substituent such as an alkyl group at the N-position.
  • the polymerization initiator preferably has a maximum absorption wavelength in a wavelength region of 350 nm to 500 nm, more preferably has an absorption wavelength in a wavelength region of 360 nm to 480 nm, and particularly has a high absorbance at 365 nm and 455 nm. preferable.
  • the molar extinction coefficient at 365 nm or 405 nm is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, and 5,000 to 200,000. It is particularly preferred.
  • the content of the polymerization initiator (total content in the case of two or more) is preferably 0.1% by mass or more and 10% by mass or less, more preferably 0.3% by mass with respect to the total solid content of the composition. % To 8% by mass, more preferably 0.5% to 5% by mass. Within this range, good curability and transparency can be obtained. Moreover, a polymerization initiator can be used individually or in combination of 2 or more types.
  • ⁇ Ultraviolet absorber> You may use a ultraviolet absorber for the siloxane resin composition of this invention.
  • the ultraviolet absorber salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, triazine-based, and conjugated diene-based ultraviolet absorbers can be used. Specific examples thereof include compounds described in paragraphs 0144 to 0164 of JP2010-78729, paragraphs 0137 to 0142 of JP2012-068418 (corresponding to paragraphs 0251 to 0254 of US2012 / 0068292). Compounds can be used and their contents can be incorporated and incorporated herein.
  • a diethylamino-phenylsulfonyl ultraviolet absorber (trade name: UV-503, manufactured by Daito Chemical Co., Ltd.) is also preferably used.
  • the benzotriazole compounds include 2- (2H benzotriazol-2-yl) phenol, 2- (2H-benzotriazol-2-yl) -4,6-tert-pentylphenol, and 2- (2H benzotriazole).
  • the blending amount of the ultraviolet absorber with respect to the metal-containing particles is preferably 1 part or more, more preferably 2 parts or more, particularly preferably 3 parts or more, based on 100 parts by mass of the total solid content. preferable. As an upper limit, 20 parts or less are preferable, 15 parts or less are more preferable, and 10 parts or less are especially preferable.
  • An ultraviolet absorber may be used individually by 1 type, or may be used in combination of 2 or more type.
  • the siloxane resin composition of the present invention may contain a polymerizable compound.
  • the polymerizable compound is preferably an addition polymerizable compound having a polymerizable group such as at least one ethylenically unsaturated double bond, an epoxy group, or an oxetanyl group.
  • it is selected from compounds having at least one polymerizable group, more preferably two or more.
  • it may have a chemical form such as a monomer, a prepolymer (that is, a polymer such as a dimer, a trimer, and an oligomer) or a mixture thereof and a copolymer thereof.
  • Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, and amides.
  • unsaturated carboxylic acids for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.
  • esters thereof and amides.
  • an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used.
  • an addition reaction product of an unsaturated carboxylic acid ester or unsaturated carboxylic acid amide having a nucleophilic substituent such as a hydroxyl group, an amino group or a mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and A dehydration condensation reaction product with a monofunctional or polyfunctional carboxylic acid is also preferably used.
  • a substitution reaction product of an unsaturated carboxylic acid ester or unsaturated carboxylic acid amide having a leaving group such as a halogen group or a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. It is.
  • the compounds described in paragraph numbers 0095 to 0108 of JP-A-2009-288705 can be preferably used in the present invention.
  • the polymerizable compound is preferably further represented by the following formulas (MO-1) to (MO-6).
  • n 0 to 14, respectively, and m is 1 to 8, respectively.
  • a plurality of R, T and Z present in one molecule may be the same or different.
  • T is an oxyalkylene group
  • the terminal on the carbon atom side is bonded to R.
  • At least one of R is a polymerizable group.
  • n is preferably 0 to 5, and more preferably 1 to 3.
  • m is preferably 1 to 5, and more preferably 1 to 3.
  • dipentaerythritol triacrylate (as a commercially available product, KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercially available product, KAYARAD D-320; Nippon Kayaku) as the polymerizable compound, etc.
  • Dipentaerythritol penta (meth) acrylate (commercially available) KAYARAD D-310 (commercially available from Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available KAYARAD DPHA; Nippon Kayaku Co., Ltd.) And a structure in which these (meth) acryloyl groups are mediated by ethylene glycol and propylene glycol residues, diglycerin EO (ethylene oxide) -modified (meth) acrylate (commercially available product is M-460; Made sub-synthesis) is preferable. These oligomer types can also be used.
  • polymerizable compound a compound represented by the following formula (i) or (ii) can also be used.
  • E represents — ((CH 2 ) y CH 2 O) — or — ((CH 2 ) y CH (CH 3 ) O) —, and — ((CH 2 ) y CH 2 O)-is preferred.
  • Each y represents an integer of 1 to 10, preferably an integer of 1 to 5, and more preferably an integer of 1 to 3.
  • X represents a hydrogen atom, an acryloyl group, a methacryloyl group, or a carboxyl group, respectively.
  • the total number of acryloyl groups and methacryloyl groups is preferably 3 or 4, more preferably 4.
  • the total number of acryloyl groups and methacryloyl groups is 5 or 6, with 6 being preferred.
  • m represents an integer of 0 to 10 and is preferably an integer of 1 to 5.
  • n represents an integer of 0 to 10, and an integer of 1 to 5 is preferable.
  • the ethylenic compound may have an unreacted carboxyl group as in the case of a mixture, and this can be used as it is.
  • an acidic group may be introduced by reacting a hydroxyl group of the ethylenic compound with a non-aromatic carboxylic acid anhydride.
  • non-aromatic carboxylic acid anhydride examples include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, alkylated hexahydrophthalic anhydride, succinic anhydride, anhydrous Maleic acid is mentioned.
  • a compound having an epoxy group or an oxetanyl group may be used as the polymerizable compound.
  • the compound having an epoxy group or oxetanyl group include a polymer having an epoxy group in the side chain, and a polymerizable monomer or oligomer having two or more epoxy groups in the molecule, and a bisphenol A type epoxy resin, Bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, aliphatic epoxy resin and the like can be mentioned. These compounds may be used as commercial products or can be obtained by introducing an epoxy group into the side chain of the polymer.
  • JP 2012-155288 A paragraph 0191 can be referred to, and the contents thereof are incorporated in the present specification.
  • commercially available products include polyfunctional aliphatic glycidyl ether compounds such as Denacol EX-212L, EX-214L, EX-216L, EX-321L, and EX-850L (manufactured by Nagase ChemteX Corporation). . These are low-chlorine products but are not low-chlorine products, and EX-212, EX-214, EX-216, EX-321, EX-850, and the like can be used as well.
  • ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4010S, EP-4011S (above, manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above, manufactured by ADEKA Co., Ltd.), JER1031S, and the like are also included.
  • commercially available phenol novolac type epoxy resins include JER-157S65, JER-152, JER-154, JER-157S70 (manufactured by Mitsubishi Chemical Corporation) and the like.
  • the molecular weight of the polymerizable compound is not particularly limited, but is preferably 300 or more and 1500 or less, and more preferably 400 or more and 700 or less.
  • the content of the polymerizable compound with respect to the total solid content in the composition is preferably in the range of 1% by mass to 50% by mass, more preferably in the range of 3% by mass to 40% by mass, The range of 5% by mass to 30% by mass is more preferable. Within this range, the curability is good and preferable without excessively reducing the refractive index and transparency.
  • a polymeric compound may be used individually by 1 type, or may be used in combination of 2 or more type.
  • the siloxane resin composition of the present invention may contain an alkali-soluble resin.
  • the alkali-soluble resin is a linear organic polymer, and promotes at least one alkali-solubility in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be suitably selected from alkali-soluble resins having a group. From the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferred.
  • acrylic resins acrylamide resins, and acrylic / acrylamide copolymer resins are preferred.
  • examples of the group that promotes alkali solubility include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group. Those which are soluble in a solvent and can be developed with a weak alkaline aqueous solution are preferred, and (meth) acrylic acid is particularly preferred.
  • These acidic groups may be only one type or two or more types.
  • a polymer having a carboxylic acid in the side chain is preferable, such as a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, and a crotonic acid copolymer.
  • a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is suitable as the alkali-soluble resin.
  • examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds.
  • alkyl (meth) acrylate and aryl (meth) acrylate examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and (iso) pentyl (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) ) Acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, and other vinyl compounds include styrene, ⁇ -methylstyrene, vinyltoluene, glycid
  • the other monomer copolymerizable with (meth) acrylic acid is preferably a repeating unit represented by the following formula (A1).
  • R 11 represents a hydrogen atom or a methyl group.
  • R 12 represents an alkylene group having 2 or 3 carbon atoms, and among them, 2 carbon atoms are preferable.
  • R 13 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
  • n1 represents an integer of 1 to 15, and preferably 1 to 12.
  • the repeating unit represented by the above formula (A1) has good adsorption and / or orientation on the particle surface due to the effect of ⁇ electrons of the benzene ring present in the side chain. In particular, when this side chain portion has an ethylene oxide or propylene oxide structure of paracumylphenol, its steric effect is added, and a better adsorption and / or orientation plane can be formed.
  • R 13 is preferably an alkyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 1 to 10 carbon atoms. This is because when R 13 has a large number of carbon atoms, this group becomes an obstacle to suppress the approach between the resins and promote adsorption and / or orientation, but if it is too large, the effect may be hindered. Because.
  • the alkyl group represented by R 13 is preferably an unsubstituted alkyl group or an alkyl group substituted with a phenyl group.
  • An alkali-soluble polyester resin may be used for the siloxane resin composition of the present invention. Although the action mechanism of the effect obtained by containing an alkali-soluble polyester resin is not clear, it is thought that those having an aromatic ring reduce the decomposability of the ester group and enable effective development.
  • a method for synthesizing the alkali-soluble polyester resin a method of undergoing a polyaddition reaction between a polyfunctional epoxy compound and a polycarboxylic acid compound or a polyaddition reaction between a polyol compound and a dianhydride is preferable.
  • a polyol compound what was obtained by reaction of a polyfunctional epoxy compound and a radically polymerizable group containing monobasic acid compound is preferable.
  • Examples of the catalyst used in the polyaddition reaction and the addition reaction include ammonium catalysts such as tetrabutylammonium acetate; amino catalysts such as 2,4,6-tris (dimethylaminomethyl) phenol or dimethylbenzylamine; triphenylphosphine And a phosphorus catalyst such as acetylacetonate chromium or chromium chloride.
  • ammonium catalysts such as tetrabutylammonium acetate
  • amino catalysts such as 2,4,6-tris (dimethylaminomethyl) phenol or dimethylbenzylamine
  • triphenylphosphine triphenylphosphine
  • a phosphorus catalyst such as acetylacetonate chromium or chromium chloride.
  • the alkali-soluble resin is preferably soluble in a tetramethylammonium hydroxide (TMAH) aqueous solution at a concentration of 0.1% by mass or more at 23 ° C. Further, it is preferably soluble in 1% by mass or more of TMAH aqueous solution, and more preferably soluble in 2% or more of TMAH aqueous solution.
  • TMAH tetramethylammonium hydroxide
  • the acid value of the alkali-soluble resin is preferably 30 to 200 mgKOH / g, more preferably 50 to 150 mgKOH / g, still more preferably 70 to 120 mgKOH / g. By setting it as such a range, the image development residue of an unexposed part can be reduced effectively.
  • the weight average molecular weight (Mw) of the alkali-soluble resin is preferably 2,000 to 50,000, more preferably 5,000 to 30,000, and particularly preferably 7,000 to 20,000.
  • the content of the alkali-soluble resin is preferably 10 to 50% by mass, more preferably 15 to 40% by mass, and particularly preferably 20 to 35% by mass with respect to the total solid content of the composition.
  • An alkali-soluble resin may be used individually by 1 type, or may be used in combination of 2 or more type.
  • the siloxane resin composition of the present invention may contain a polymerization inhibitor.
  • Polymerization inhibitors include phenolic hydroxyl group-containing compounds, N-oxide compounds, piperidine 1-oxyl free radical compounds, pyrrolidine 1-oxyl free radical compounds, N-nitrosophenylhydroxylamines, diazonium compounds, and cations Examples include dyes, sulfide group-containing compounds, nitro group-containing compounds, transition metal compounds such as FeCl 3 and CuCl 2 .
  • the description of JP 2010-106268 A paragraphs 0260 to 0280 (corresponding to [0284] to [0296] of the corresponding US Patent Application Publication No. 2011/0124824) can be referred to. The contents of which are incorporated herein by reference.
  • a preferable addition amount of the polymerization inhibitor is preferably 0.01 parts by mass or more and 10 parts by mass or less, and more preferably 0.01 parts by mass or more and 8 parts by mass or less with respect to 100 parts by mass of the polymerization initiator. It is most preferable that it exists in the range of 0.05 mass part or more and 5 mass parts or less.
  • a polymerization inhibitor may be used individually by 1 type, or may be used in combination of 2 or more type.
  • the siloxane resin composition of the present invention may contain a dispersant.
  • a dispersant for example, polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth) acrylic type) Copolymer, naphthalenesulfonic acid formalin condensate), polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl amine, alkanol amine, pigment derivative and the like.
  • the polymer dispersant can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer from the structure thereof.
  • dispersant examples include “Disperbyk-101 (polyamideamine phosphate), 107 (carboxylic acid ester), 110 (copolymer containing an acidic group), 130 (polyamide), 161, 162, manufactured by BYK Chemie.
  • the dispersant is also preferably a polymer compound containing at least one repeating unit selected from repeating units represented by any of the following formulas (I) and (II).
  • R 11 to R 16 each independently represents a hydrogen atom or a monovalent organic group.
  • a substituted or unsubstituted alkyl group is preferable.
  • an alkyl group having 1 to 12 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, and an alkyl group having 1 to 4 carbon atoms is particularly preferable.
  • the alkyl group may have a substituent T.
  • X 11 and X 12 each independently represent a linking group L described later, and are preferably —CO—, —C ( ⁇ O) O—, —CONH—, —OC ( ⁇ O) —, or a phenylene group.
  • —C ( ⁇ O) O—, —CONH—, and a phenylene group are preferable, and —C ( ⁇ O) O— is particularly preferable.
  • L 1 and L 2 each independently represents a single bond or a linking group L described later. Specifically, a hydrocarbon linking group among them (in particular, an alkylene group is preferred) or a combination of this with a hetero linking group is preferred. Furthermore, an alkylene group or a linking group relating to a combination of an alkylene group and a hetero-linking group selected from —C ( ⁇ O) —, —OC ( ⁇ O) —, and —NHC ( ⁇ O) — is preferable. The number of constituent atoms of the preferred linking group and the number of linking atoms are as defined for the linking group L. Of these, a linking group represented by -La-Lb- is preferable. La represents an alkylene group having 2 to 10 carbon atoms. Lb represents —C ( ⁇ O) — or —NHC ( ⁇ O) —.
  • a 1 and A 2 are preferably groups selected from linear alkyl groups having 1 to 20 carbon atoms, branched alkyl groups having 3 to 20 carbon atoms, and cyclic alkyl groups having 5 to 20 carbon atoms.
  • a group selected from a linear alkyl group having 4 to 15 carbon atoms, a branched chain having 4 to 15 carbon atoms, and a cyclic alkyl group having 6 to 10 carbon atoms is more preferable.
  • a group selected from branched alkyl groups having 6 to 12 carbon atoms is more preferable.
  • M and n each independently represents an integer of 2 to 8, preferably 4 to 6, and particularly preferably 5.
  • P and q each independently represents an integer of 1 to 100. Two or more different p and different q may be mixed. p and q are preferably 5 to 60, more preferably 5 to 40, and still more preferably 5 to 20.
  • Examples of the monomer constituting the repeating unit represented by the above formula (I) include the examples of paragraphs [0090] to [0093] of JP2011-089109A, which are incorporated herein.
  • a polymer compound represented by the general formula (1) of claim 1 (corresponding claim 1 of US2010 / 0233595) of JP-A-2007-277514 is preferable.
  • the description in Japanese Patent Application Laid-Open No. 2007-277514 (corresponding US2010 / 0233595) can be referred to, and the contents thereof are incorporated in the present specification.
  • the polymer compound that can be used as the dispersant is not particularly limited, but can be synthesized according to the synthesis methods described in paragraphs 0114 to 0140 and 0266 to 0348 of JP-A-2007-277514.
  • the content of the dispersing agent is preferably 10 to 1000 parts by mass, more preferably 30 to 1000 parts by mass, and further preferably 50 to 800 parts by mass with respect to 100 parts by mass of the metal-containing particles.
  • the total solid content of the composition is preferably 10 to 30% by mass.
  • the siloxane resin composition of the present invention may contain a surfactant.
  • the surfactant include silicone surfactants, silicon surfactants such as organopolysiloxanes, fluorine surfactants, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, and polyoxyethylene octylphenyl ether.
  • Nonionic surfactants such as polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate or polyethylene glycol distearate, polyalkylene oxide surfactants, poly (meth) acrylate surfactants, acrylic or methacrylic surfactants
  • a surfactant made of a polymer is exemplified.
  • surfactants examples include “Megafac” (registered trademark) F787-F, F781-F, F142D, F172, F173, F183, F445, F470, F475 or F477 (all manufactured by DIC) or Fluorosurfactants such as NBX-15 or FTX-218 (both manufactured by Neos), BYK-333, BYK-301, BYK-331, BYK-345 or BYK-307 (all of which are Big Chemie Japan ( And silicone surfactants such as those manufactured by the same company).
  • surfactant is not specifically limited, 1 mass% or more is preferable in a solid component of a composition, 1.5 mass% or more is more preferable, and 5 mass% or more is especially preferable. Although an upper limit is not specifically limited, 30 mass% or less is preferable and 15 mass% or less is more preferable.
  • Surfactant may be used individually by 1 type, or may be used in combination of 2 or more type. One developer may be used alone, or two or more developers may be used in combination.
  • the siloxane resin composition of the present invention may contain other additives such as a dissolution inhibitor, a stabilizer, or an antifoaming agent, if necessary.
  • an alkaline solution is preferably used.
  • the concentration of the alkaline compound is preferably 0.001 to 10% by mass, and more preferably 0.01 to 5% by mass.
  • Alkaline compounds include, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxy , Tetrabutylammonium hydroxy, benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene and the like.
  • an organic alkali is preferable.
  • a washing treatment with water is generally performed after development.
  • quaternary ammonium salts are preferable, and tetramethylammonium hydroxide (TMAH) or choline is more preferable.
  • alkyl group preferably an alkyl group having 1 to 20 carbon atoms, such as methyl, ethyl, isopropyl, t-butyl, pentyl, heptyl, 1-ethylpentyl, benzyl, 2-ethoxyethyl, 1-carboxymethyl, etc.
  • alkenyl A group preferably an alkenyl group having 2 to 20 carbon atoms such as vinyl, allyl, oleyl and the like
  • an alkynyl group preferably an alkynyl group having 2 to 20 carbon atoms such as ethynyl, butadiynyl, phenylethynyl and the like
  • a cycloalkyl group preferably a cycloalkyl group having 3 to 20 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, etc., but the alkyl
  • Aryloxy groups such as phenoxy, 1-naphthylo Si, 3-methylphenoxy, 4-methoxyphenoxy, etc.
  • alkoxycarbonyl groups preferably alkoxycarbonyl groups having 2 to 20 carbon atoms, such as ethoxycarbonyl, 2-ethylhexyloxycarbonyl, etc.
  • aryloxycarbonyl groups preferably Is an aryloxycarbonyl group having 6 to 26 carbon atoms, such as phenoxycarbonyl, 1-naphthyloxycarbonyl, 3-methylphenoxycarbonyl, 4-methoxyphenoxycarbonyl, etc., an amino group (preferably having 0 to 20 carbon atoms)
  • alkylamino group, arylamino group for example, amino, N, N-dimethylamino, N, N-diethylamino, N-ethylamino, anilino, etc.
  • sulfamoyl group preferably having 0 to 20
  • phosphinyl group for example, -P (R P) 2), (meth) acryloyl group, (meth) acryloyloxy group, (meth) acryloyl Louis amino group ((meth) acrylamide group), a hydroxyl group, a thiol group, a carboxyl group , Phosphoric acid group, phosphonic acid group, sulfonic acid group, cyano group, halogen atom (eg fluorine atom, chlorine atom, bromine atom, iodine atom, etc.) ).
  • substituent T may be further substituted with the substituent T described above.
  • the salt may be formed.
  • a compound or a substituent / linking group includes an alkyl group / alkylene group, an alkenyl group / alkenylene group, an alkynyl group / alkynylene group, etc., these may be cyclic or linear, and may be linear or branched These may be substituted as described above or may be unsubstituted.
  • Each substituent defined in the present specification may be substituted through the following linking group L within the scope of the effects of the present invention, or the linking group L may be present in the structure thereof.
  • the alkyl group / alkylene group, alkenyl group / alkenylene group and the like may further have the following hetero-linking group interposed in the structure.
  • the linking group L includes a hydrocarbon linking group [an alkylene group having 1 to 10 carbon atoms (more preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms), an alkenylene group having 2 to 10 carbon atoms (more preferably carbon atoms).
  • the said hydrocarbon coupling group may form the double bond and the triple bond suitably, and may connect.
  • the ring to be formed is preferably a 5-membered ring or a 6-membered ring.
  • a nitrogen-containing five-membered ring is preferable, and examples of the compound forming the ring include pyrrole, imidazole, pyrazole, indazole, indole, benzimidazole, pyrrolidine, imidazolidine, pyrazolidine, indoline, carbazole, or these And derivatives thereof.
  • 6-membered ring examples include piperidine, morpholine, piperazine, and derivatives thereof. Moreover, when an aryl group, a heterocyclic group, etc. are included, they may be monocyclic or condensed and may be similarly substituted or unsubstituted.
  • RN is a hydrogen atom or a substituent. Examples of the substituent include an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms), and an alkenyl group (preferably having 2 to 24 carbon atoms and 2 carbon atoms).
  • To 12 is more preferable, 2 to 6 is more preferable, and 2 to 3 is particularly preferable, and an alkynyl group (2 to 24 carbon atoms is preferable, 2 to 12 is more preferable, 2 to 6 is more preferable, and 2 to 3 is Particularly preferred), an aralkyl group (preferably 7 to 22 carbon atoms, more preferably 7 to 14 carbon atoms, particularly preferably 7 to 10 carbon atoms), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 14 carbon atoms, 6 to 14 carbon atoms). 10 is particularly preferred).
  • RP is a hydrogen atom, a hydroxyl group, or a substituent.
  • substituents examples include an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms), and an alkenyl group (preferably having 2 to 24 carbon atoms and 2 carbon atoms).
  • To 12 is more preferable, 2 to 6 is more preferable, and 2 to 3 is particularly preferable, and an alkynyl group (2 to 24 carbon atoms is preferable, 2 to 12 is more preferable, 2 to 6 is more preferable, and 2 to 3 is Particularly preferred), an aralkyl group (preferably 7 to 22 carbon atoms, more preferably 7 to 14 carbon atoms, particularly preferably 7 to 10 carbon atoms), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 14 carbon atoms, 6 to 14 carbon atoms).
  • an alkoxy group preferably having 1 to 24 carbon atoms, more preferably 1 to 12, more preferably 1 to 6 and particularly preferably 1 to 3
  • an alkenyloxy group having carbon number
  • More preferably 2 to 12, more preferably 2 to 6, particularly preferably 2 to 3, and an alkynyloxy group preferably having 2 to 24 carbon atoms, more preferably 2 to 12 and more preferably 2 to 6.
  • More preferably, 2 to 3 are particularly preferred
  • an aralkyloxy group preferably 7 to 22 carbon atoms, more preferably 7 to 14 carbon atoms, particularly preferably 7 to 10 carbon atoms
  • an aryloxy group preferably 6 to 22 carbon atoms, 6 to 14 are more preferable, and 6 to 10 are particularly preferable.
  • the number of atoms constituting the linking group L is preferably 1 to 36, more preferably 1 to 24, still more preferably 1 to 12, and particularly preferably 1 to 6.
  • the number of linking atoms in the linking group is preferably 10 or less, and more preferably 8 or less.
  • the lower limit is 1 or more.
  • the number of connected atoms refers to the minimum number of atoms that are located in a path connecting predetermined structural portions and are involved in the connection. For example, in the case of —CH 2 —C ( ⁇ O) —O—, the number of atoms constituting the linking group is 6, but the number of linking atoms is 3. Specific examples of combinations of linking groups include the following.
  • x is an integer of 1 or more, preferably 1 to 500, and more preferably 1 to 100.
  • Lr is preferably an alkylene group, an alkenylene group or an alkynylene group.
  • the carbon number of Lr is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3.
  • a plurality of Lr, R N , R P , x, etc. need not be the same.
  • the direction of the linking group is not limited by the above description, and may be understood as appropriate according to a predetermined chemical formula.
  • the siloxane resin composition of the present invention can be stored, transported and used in any container as long as corrosion resistance or the like does not matter (whether or not it is a kit).
  • a container having a high cleanliness and a low impurity elution is preferable.
  • the containers that can be used include, but are not limited to, “Clean Bottle” series manufactured by Aicero Chemical Co., Ltd., “Pure Bottle” manufactured by Kodama Resin Co., Ltd., and the like.
  • the container or the inner wall of the container is subjected to a resin different from one or more resins selected from the group consisting of polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin, or subjected to rust prevention and metal elution prevention treatment.
  • a resin different from one or more resins selected from the group consisting of polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin, or subjected to rust prevention and metal elution prevention treatment.
  • it is formed from a finished metal.
  • Such container storage is the same for the resist storage described below for the preferred embodiment.
  • the siloxane resin composition of the present invention is preferably filtered with a filter for the purpose of removing foreign substances and reducing defects. If it is conventionally used for the filtration use etc., it can use without being specifically limited.
  • a filter made of fluorine resin such as PTFE (polytetrafluoroethylene), polyamide resin such as nylon, polyolefin resin (including high density and ultra high molecular weight) such as polyethylene and polypropylene (PP), and the like can be given.
  • PTFE polytetrafluoroethylene
  • polyamide resin such as nylon
  • polyolefin resin including high density and ultra high molecular weight
  • polyethylene and polypropylene (PP) polypropylene
  • nylon are preferable.
  • the pore size of the filter is suitably about 0.1 to 7.0 ⁇ m, preferably about 0.2 to 2.5 ⁇ m, more preferably about 0.2 to 1.5 ⁇ m, and still more preferably 0.3 to 0.0 ⁇ m. 7 ⁇ m. By setting it within this range, it becomes possible to reliably remove fine foreign matters such as impurities and aggregates contained in the composition while suppressing filtration clogging.
  • different filters may be combined. At that time, the filtering by the first filter may be performed only once or may be performed twice or more. When filtering two or more times by combining different filters, it is preferable that the second and subsequent hole diameters are the same or larger than the first filtering hole diameter.
  • the pore diameter here can refer to the nominal value of the filter manufacturer.
  • a commercially available filter for example, it can be selected from various filters provided by Nippon Pole Co., Ltd., Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd. (formerly Japan Microlith Co., Ltd.) or KITZ Micro Filter Co., Ltd. .
  • the second filter a filter formed of the same material as the first filter described above can be used.
  • the pore size of the second filter is suitably about 0.2 to 10.0 ⁇ m, preferably about 0.2 to 7.0 ⁇ m, more preferably about 0.3 to 6.0 ⁇ m.
  • the filtering by the first filter may be performed only with the dispersion, and the second filtering may be performed after mixing other components. Such filtering is the same for the preferred embodiment of the resist filtering described below.
  • ⁇ Formation of transparent cured product> An example is given and demonstrated about the formation method of transparent hardened
  • the siloxane resin composition When the siloxane resin composition is used as a coating solution, it can be applied on a base substrate by a known method such as microgravure coating, spin coating, dip coating, curtain flow coating, roll coating, spray coating or slit coating. . Then, it can pre-bake with heating apparatuses, such as a hot plate or oven, and a film
  • ⁇ 365 nm exposure amount conversion ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇
  • post-exposure baking may be performed by heating the film at 150 to 450 ° C. for about 1 hour using a heating device such as a hot plate or an oven.
  • a heating device such as a hot plate or an oven.
  • ultraviolet rays having a wavelength of 300 to 400 nm are preferably used as active radiation, and i-rays are more preferably used. That is, the siloxane resin composition of the present invention is preferably an ultraviolet curable resin composition.
  • the unexposed portion is dissolved by development, and a negative pattern can be obtained.
  • a developing method a method of immersing in a developing solution for 5 seconds to 10 minutes by a method such as shower, dipping or paddle is preferable. Examples of the developer include those exemplified above.
  • the film is preferably rinsed with water. Subsequently, dry baking may be performed at 50 to 150 ° C. Thereafter, the film is thermally cured at 120 to 280 ° C. for about 1 hour using a heating device such as a hot plate or an oven to obtain a cured product (film).
  • Transparent pixels and the like incorporated in the solid-state imaging device can be formed on the substrate in such a procedure.
  • the thickness of the resulting cured film is preferably 0.1 to 10 ⁇ m.
  • the leakage current is preferably 10 ⁇ 6 A / cm 2 or less, and the relative dielectric constant is preferably 6.0 or more.
  • the refractive index of the cured film of the siloxane resin composition of the present invention is preferably 1.60 or more, more preferably 1.70 or more, and particularly preferably 1.80 or more. Although there is no upper limit in particular, it is practical that it is 2.0 or less. Unless otherwise specified, the refractive index is based on the conditions measured in Examples described later.
  • the cured film of the siloxane resin composition of the present invention preferably has high transparency.
  • the visible light transmittance is preferably 80% or more, more preferably 88% or more, and particularly preferably 90% or more. There is no particular upper limit, but it is practical that it is 99% or less. Unless otherwise specified, the visible light transmittance is based on the conditions measured in the examples described later.
  • the cured film obtained by curing the siloxane resin composition of the present invention can be particularly suitably used as a microlens or a transparent pixel of a solid-state imaging device.
  • microlens array 10 An example of the formation process of the microlens array 10 will be described as one form of the microlens formation method.
  • the surface (base material) 3 of the uneven element is embedded and flattened by spin coating with a transparent resin (flattening film) 2 if necessary.
  • the lens material 1 is uniformly applied to the surface of the flattened substrate 3 (step 1).
  • the siloxane resin composition described above can be used as the lens material.
  • a photoresist (photosensitive material) 4 is uniformly applied on the lens material 1 (step 2). As this photosensitive material, those commonly used for this type of processing can be used.
  • the stepper device irradiates ultraviolet rays using the reticle as a mask to expose the space between the lenses.
  • the part exposed by the developer is decomposed and removed to form a pattern (step 3).
  • a hemispherical pattern (photosensitive material 4b) is heated from the patterned photosensitive material 4a (step 4).
  • the resist (photosensitive material) melts into a liquid phase, becomes a hemispherical state, and then changes to a solid phase.
  • the lens material layer is etched by dry etching (step 5).
  • the lens array 10 in which hemispherical lenses (microlenses 1a) are arranged can be formed.
  • Another embodiment of the lens array includes a method in which the use of the resist is omitted and the lens material is patterned by exposure. In this embodiment, the patterned lens material is melted as it is to obtain a hemispherical lens.
  • the resist material a material that can be appropriately used for this kind of processing can be adopted.
  • a positive type, a negative type, and a positive / negative type photoresist can be mentioned.
  • the positive resist include photosensitive resin compositions such as vinyl cinnamate, cyclized polyisobutylene, azo-novolak resin, and diazoketone-novolak resin.
  • the negative resist include azide-cyclized polyisoprene, azido-phenol resin, and chloromethyl polystyrene.
  • specific examples of the positive / negative resist include poly (p-butoxycarbonyloxystyrene) -based photosensitive resin compositions.
  • JP-A-1-142548 can be preferably used.
  • it is a photosensitive resin composition containing cresol novolac resin and naphthoquinone diazide sulfonic acid ester as main components. More specifically, an esterification reaction product of 2,3,4,4′-tetrahydroxybenzophenone and naphthoquinone-1,2-diazide-5-sulfonyl chloride (the content of triester is 85 mol%) is exemplified. can do.
  • the resist material is preferably a positive resist containing a novolac resin. More specifically, a positive resist containing a resin having a repeating unit represented by the following formula (R-1) can be given.
  • R 13 to R 16 each independently represent a hydrogen atom or an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms).
  • s represents an integer of 1 to 3.
  • the molecular weight of the resin is not particularly limited, but is usually 1,000 to 1,000,000, preferably 2,000 to 100,000, more preferably 3,000 to 50,000 in terms of polystyrene-equivalent weight average molecular weight.
  • a solid-state imaging device includes a transparent pixel and / or a microlens made of a cured product of the siloxane resin composition of the present invention.
  • a lens unit is provided on the semiconductor light receiving unit, and the lens array member and the color filter are incorporated so as to be adjacent to each other.
  • the light receiving element receives light passing through the transparent resin film, the lens, and the color filter in this order, and functions as an image sensor.
  • the transparent resin film functions as an antireflection film, improves the light collection efficiency of the lens, and the light efficiently collected by the lens is detected by the light receiving element via the color filter. These function over the whole element which detects the light corresponding to RGB.
  • the cured product of the siloxane resin composition of the present invention can be suitably used as a transparent pixel interposed in the lens or RGB pixel array.
  • Examples of solid-state imaging devices to which a lens array is applied include those described in Japanese Patent Application Laid-Open No. 2007-119744. Specifically, a transfer electrode is provided between a CCD region and a photoelectric conversion unit formed on the surface of the semiconductor substrate, and a light shielding film is formed thereon via an interlayer film. On the light shielding film, an interlayer insulating film made of BPSG (Boro-Phospho-Silicate Glass), a passivation film, a transparent planarizing film having a low refractive index made of acrylic resin, and the like are laminated. G. B. Are combined to form a color filter. Further, a large number of microlenses are arranged so as to be positioned above the photoelectric conversion portion which is a light receiving region via a protective film.
  • BPSG Bo-Phospho-Silicate Glass
  • aqueous dispersion sol (AA-1) of nuclear fine particles A white slurry liquid having a pH of 9.5 was prepared by mixing 7.60 kg of titanium tetrachloride aqueous solution containing 7.8% by mass of titanium tetrachloride on a TiO 2 basis and 3.0 kg of aqueous ammonia containing 15% by mass of ammonia. . Subsequently, this white slurry was filtered and then washed with ion-exchanged water to obtain 6.2 kg of a hydrous titanate cake having a solid content of 10% by mass.
  • the obtained mixed aqueous solution is cooled to room temperature and then concentrated with an ultrafiltration membrane device (ACV-3010, manufactured by Asahi Kasei Co., Ltd.) to disperse water in the form of core fine particles having a solid content of 10% by mass.
  • 7.0 kg of sol (AA-1) was obtained.
  • the aqueous dispersion sol (AA-1) containing the metal oxide fine particles thus obtained was transparent and milky white. Furthermore, when the content of the metal component contained in the metal oxide fine particles was measured, 87.5% by mass of TiO 2 , 10.6% by mass of SnO 2 , and K 2 O based on the oxide conversion standard of each metal component. It was 1.8% by mass.
  • 0.2 kg of the fired powder of the surface-treated metal oxide fine particles obtained above was dispersed in 0.2 kg of pure water, and 0.1 kg of a tartaric acid aqueous solution having a concentration of 28.6% and a KOH aqueous solution having a concentration of 50 mass% were added thereto. 0.06 kg was added and sufficiently stirred.
  • alumina beads having a particle diameter of 0.1 mm (Daimei Chemical Co., Ltd., high-purity alumina beads) were added, and this was subjected to a wet crusher (Batch type tabletop sand mill manufactured by Campe Co., Ltd.) for 180 minutes.
  • the fired powder of the treated metal oxide fine particles was pulverized and dispersed.
  • alumina beads were separated and removed using a stainless steel filter having an aperture of 44 ⁇ m, and then 1.4 kg of pure water was further added and stirred, so that the surface-treated metal oxide fine particles having a solid content of 11% by mass were obtained. 1.7 kg of an aqueous dispersion was obtained.
  • anion exchange resin manufactured by Mitsubishi Chemical Corporation: SANUPC
  • a centrifuge Hitachi Machine (CR-21G manufactured by Kikai Co., Ltd.) and treated for 1 hour at a speed of 12,000 rpm, and then water-dispersed sol (AB) of surface-treated metal oxide fine particles having a solid content concentration of 10 mass% by adding ion exchange water -1) 1.9 kg was prepared.
  • the content of the metal component contained in the surface-treated metal oxide fine particles was measured, 82.6% by mass of TiO 2 , 10.3% by mass of SnO 2 , and ZrO 2 4 in terms of oxide conversion of each metal component. And 9% by mass and 2.2% by mass of K 2 O, respectively.
  • the Ti / Zr ratio was 26.00.
  • the obtained metal oxide fine particles had an average particle size of about 5 to 20 nm.
  • an ultrafiltration membrane device a filtration membrane manufactured by Asahi Kasei Corporation, SIP-1013
  • the slurry was filtered and washed with pure water to obtain 2.5 kg of a cake having a zirconium component of 10.0% by mass in terms of ZrO 2 .
  • hydrogen peroxide was added at 35.0 g. 144.0 g of hydrogen peroxide containing mass% was added and heated to a temperature of 50 ° C. to dissolve this cake.
  • aqueous zirconate peroxide solution containing 0.5% by mass of zirconate peroxide in terms of ZrO 2 .
  • the pH of the aqueous zirconate peroxide solution was 12.
  • Water-dispersed sol (AD-1) of core-shell type inorganic oxide fine particles Water-dispersed sol (AB-1) of surface-treated metal oxide fine particles prepared above (solid content is 2.0 mass%) 1 After adding 3.3 kg of pure water to 8 kg and stirring and heating to 90 ° C., 1.4 kg of the above-mentioned zirconic acid aqueous solution and 1.1 kg of silicic acid aqueous solution were gradually added thereto, and the addition was completed. Thereafter, the mixture was aged with stirring for 1 hour while maintaining the temperature at 90 ° C. At this time, the amount of the composite oxide covering the surface-treated metal oxide fine particles was 25 parts by mass with respect to 100 parts by mass of the surface-treated metal oxide fine particles.
  • this mixed solution was put in an autoclave and subjected to heat treatment at a temperature of 165 ° C. for 18 hours.
  • the obtained mixed solution is cooled to room temperature, and then concentrated using an ultrafiltration membrane (SIP-1013, manufactured by Asahi Kasei Co., Ltd.) to disperse in water with a solid content of 10.0% by mass.
  • a sol was prepared.
  • 0.6 kg of an aqueous dispersion 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.
  • the content of the metal component contained in the metal oxide fine particles was measured, 63.8% by mass of TiO 2 , 8.0% by mass of SnO 2 , and SiO 2 13 based on the oxide conversion standard of each metal component. It was 0.9 mass%, ZrO 2 11.0 mass%, and K 2 O 3.3 mass%. The Ti / Zr ratio was 8.94.
  • the obtained metal oxide fine particles had an average particle size of about 5 to 20 nm.
  • methanol-dispersed sol (AE-1) of core-shell type inorganic oxide fine particles 0.32 kg of methanol-dispersed sol (AE-1) of core-shell type inorganic oxide fine particles was obtained.
  • the solid content concentration contained in the obtained methanol dispersion sol (AE-1) was 30% by mass, and the water content was about 0.3% by mass.
  • AE-1 solid content concentration 30% by mass, methanol 70% by mass
  • n 14
  • the polystyrene-reduced mass average molecular weight of this dispersant is 6400
  • the acid value is 80 mgKOH / g.
  • the dispersing device was operated under the following conditions. ⁇ Bead diameter: ⁇ 0.05mm ⁇ Bead filling rate: 60% by volume ⁇ Peripheral speed: 10 m / sec ⁇ Pump supply: 30 kg / hour ⁇ Cooling water: Tap water ⁇ Bead mill annular passage volume: 1.0 L ⁇ Amount of liquid mixture to be dispersed: 10kg
  • a dispersion sol (A-4) was synthesized using the same method as in the synthesis example of the dispersion sol (A-3) except that only the following compositional part was changed.
  • Titanium dioxide (TTO-51 (C) manufactured by Ishihara Sangyo Co., Ltd.): 212.5 parts (crystal form: rutile, TiO 2 purity (%): 79-85%, Surface treatment with Al 2 O 3 and stearic acid, Specific surface area of 50-60 m 2 / g, (Primary particle size 10-30nm, oil absorption 24-30g / 100g) -The following specific dispersion resin (solid content 20% PGMEA solution): 286.9 parts-Propylene glycol monomethyl ether acetate (PGMEA): 350.6 parts
  • Example 1 and Comparative Example 1 Using the dispersion sols A-1 to A-3 obtained above, each component was mixed so as to have the composition shown in Table 1 below to obtain thermosetting resin compositions of Examples and Comparative Examples. The evaluation shown below was performed using the thermosetting compositions of Examples and Comparative Examples obtained above.
  • thermosetting compositions of Examples and Comparative Examples obtained above were applied on an 8-inch Si wafer (substrate) by spin coating so that the film thickness after layer formation was 1.2 ⁇ m.
  • the spin coating conditions at this time were the same as those in the following test [1-3].
  • the substrate coated with the thermosetting composition was heated on a hot plate at 100 ° C. for 2 minutes. Further, this substrate was heated on a hot plate at 230 ° C. for 10 minutes to form a thermosetting composition layer.
  • the substrate on which the thermosetting composition layer was formed was exposed to an 85 ° C./95% constant temperature and humidity layer (IW222; manufactured by Yamato Kagaku) for 500 hours.
  • IW222 constant temperature and humidity layer
  • the number of crack defects having a size of 1 ⁇ m or more was measured on the substrate using a defect inspection apparatus ComPlus (manufactured by Applied Materials). The measurement was performed 5 times and the average value was adopted. The results are shown in Table 1 below.
  • thermosetting compositions of Examples and Comparative Examples obtained above were forcibly aged for 3 days at 45 ° C., and then 8 inch Si so that the film thickness after layer formation was 1.2 ⁇ m. It apply
  • the substrate coated with the thermosetting composition was heated on a hot plate at 100 ° C. for 2 minutes. Further, this substrate was heated on a hot plate at 230 ° C. for 10 minutes to form a thermosetting composition layer.
  • thermosetting compositions of Examples and Comparative Examples obtained above were applied on an 8-inch Si wafer by spin coating so that the film thickness after layer formation was 1.2 ⁇ m, and then hot plate Above, it heated at 100 degreeC for 2 minute (s), and formed the thermosetting composition layer.
  • an apparatus of 1H-D7 (trade name) manufactured by Mikasa Co., Ltd. was used for spin coating.
  • the rotation speed was 900 rpm
  • the environmental 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 state was observed with a light microscope (optical microscope) to evaluate unevenness.
  • Epoxy compounds JER-157S65 (trade name) manufactured by Mitsubishi Chemical Co., Ltd. 5 parts by mass Formulation: Content in composition (parts by mass)
  • B-1 SR-13 (polysilsesquioxane, weight average molecular weight 6,000) Made by Konishi Chemical Industry Co., Ltd.
  • DAA Diacetone alcohol
  • DPM Dipropylene glycol monomethyl ether See Table A for abbreviations of the first and second solvents
  • each dispersed sol In 80 parts by mass of each dispersed sol, the preparation solvent is contained in the following amounts. The balance of each dispersed sol is a solid component.
  • A-1 49 parts by weight of methanol and 2.9 parts by weight of ⁇ -butyrolactone
  • A-2 49 parts by weight of methanol and 2.9 parts by weight of ⁇ -butyrolactone
  • A-3 52 parts by weight of PGMEA
  • A-4 55 parts by weight of PGMEA including
  • Mass ratio of Ti element in metal oxide fine particles / mass ratio of Si element in siloxane resin A-1: 16.79 parts by mass A-2: 16.79 parts by mass
  • the content of metal-containing particles in each dispersed sol is as follows. It is as follows. A-1: 28.1% by mass A-2: 28.1% by mass A-3: 23.0 mass%
  • the refractive index was 1.9 and the light transmittance was 90% or more.
  • the optical characteristics of other test films were confirmed in the same manner, and it was confirmed that all of the films of the examples exhibited a desired high refractive index and high light transmittance.
  • the refractive index and light transmittance were measured as follows.
  • the composition was applied to a high refractive index glass (SFLD-6 manufactured by Sumita Optical Glass Co., Ltd.) with a spine coater (Act 8 manufactured by Tokyo Electron) to a thickness of 0.6 ⁇ m.
  • SFLD-6 high refractive index glass
  • a spine coater Act 8 manufactured by Tokyo Electron
  • pre-baking was performed 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 (Act 8 manufactured by Tokyo Electron) in an air atmosphere to obtain a cured film.
  • the refractive index in wavelength 550nm at room temperature 25 degreeC was measured using the ellipsometer (made by Otsuka Electronics Co., Ltd.). At this time, the light transmittance of the test transparent film was measured at 400 nm to 700 nm. As the transmittance, a minimum transmittance value of 400 to 700 nm was adopted. The test was performed 5 times for each sample, and the average value of 3 results excluding the maximum and minimum values was adopted.
  • the siloxane resin composition of the present invention exhibits good crack resistance and gel defect resistance when used as its cured film. I found out that Furthermore, it was found that the film surface unevenness was small and good.
  • Example 2 and Comparative Example 2 Using the dispersion sols A-1 to A-4 obtained above, the components were mixed so as to have the following compositions to obtain curable resin compositions of Examples and Comparative Examples. The evaluation shown below was performed using each of the curable compositions of Examples and Comparative Examples obtained above.
  • the number of crack defects having a size of 1 ⁇ m or more was measured on the substrate using a defect inspection apparatus ComPlus (manufactured by Applied Materials). The measurement was performed 5 times and the average value was adopted. The results are shown in Table 2 below.
  • the time for which the curable composition layer was allowed to stand before exposure was 24 hours.
  • developability was evaluated with respect to the curable composition layer after exposure using a developing device (Act 8 manufactured by Tokyo Electron).
  • a developing device Act 8 manufactured by Tokyo Electron.
  • TMAH tetramethylammonium hydroxide
  • shower development was performed at 23 ° C. for 60 seconds.
  • it rinsed with the spin shower using a pure water and the pattern was obtained.
  • the distortion of the obtained pattern was evaluated by observation with a scanning electron microscope (SEM) (S-4800H, manufactured by Hitachi High-Technologies Corporation) (magnification: 20000 times).
  • 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) All are manufactured by Konishi Chemical Industry Co., Ltd.
  • the siloxane resin composition of the present invention exhibits its excellent performance not only as a thermosetting resin but also as a negative photocurable material.
  • EHS-221M manufactured by Espec Corp.
  • Example 4 In the preparation of the dispersion sols (AB-1) and (A-1), the amount of each raw material was adjusted so that the component composition (composition ratio of Ti and Zr) was as shown in Table 3 below. Was prepared. Each test [2-1] to [2-4] was performed on each sample in the same manner as in Example 2. Further, pattern distortion was evaluated [2-4a] under more severe conditions. Specifically, using a 0.15% aqueous solution of tetramethylammonium hydroxide (TMAH) as a developer, shower development was performed at 23 ° C. for 60 seconds. Then, it rinsed with the spin shower using a pure water, and the pattern was obtained.
  • TMAH tetramethylammonium hydroxide
  • Example 5 Samples were prepared by changing the content of the metal-containing particles in the solid component to 40% by mass, 50% by mass, and 55% by mass with respect to the dispersion sol (A-2).
  • the refractive index of the cured film of each sample was 1.70, 1.76, and 1.79, respectively.
  • the same tests [2-1] to [2-4] were performed on each sample, and it was also confirmed that good performance was exhibited in each item.
  • the sample which made content in the solid component of a metal containing particle 10 mass% was prepared. As a result, the refractive index of the cured film greatly fell below 1.6.
  • Example 7 Each of the siloxane resin composition samples prepared in tests 101, 103, and 114 was applied onto a silicon wafer. Thereafter, pre-baking (100 ° C. for 2 min) and post-baking (230 ° C. for 10 min) were performed to form a coating film having a film thickness of 1.1 ⁇ m (FIG. 1 (1)). Further, FHi-4750 ([trade name] Fujifilm Electronics Materials Co., Ltd., FFEM resist solution) is applied on this to a dry film thickness of 1.5 ⁇ m, and heated on a hot plate at 90 ° C. for 1 minute. (FIG. 1 (2)).
  • This coated film was 300 mJ / cm 2 by an i-line stepper (product name: FPA-3000i5 +, manufactured by Canon Inc.) through a mask having a square lattice pattern with a side of 1.4 ⁇ m and a gap between patterns of 0.35 ⁇ m. And exposed.
  • the separation width when patterning was 238.7 nm.
  • Post-baking was performed with a hot plate in the order of 145 ° C. for 120 seconds, 160 ° C. for 120 seconds, and 175 ° C. for 120 seconds, and the resist was shaped into a lens shape (hemisphere) (FIG. 1 (4)).
  • the substrate obtained as described above was dry-etched using a dry etching apparatus (manufactured by Hitachi High-Technologies: U-621) under the following conditions to form a lens array (FIG. 1 (5)). ).
  • the height of the lens body was 380 nm.
  • RF power 800W ⁇
  • Antenna bias 400W ⁇
  • Wafer bias 400W ⁇
  • Photoresist etching rate 140 nm / min
  • microlens array specimen exhibited excellent performance suitable for use in a solid-state imaging device.
  • this mixed aqueous solution was heated in the autoclave at the temperature of 168 degreeC for 20 hours.
  • the obtained mixed aqueous solution was cooled to room temperature and then concentrated with an ultrafiltration membrane device to obtain 6.89 kg of an aqueous dispersion sol (BA-1) of core fine particles having a solid content of 10% by mass. It was.
  • the water-dispersed sol (BA-1) containing the metal oxide fine particles thus obtained was transparent and milky white.
  • the content of the metal component contained in the metal oxide fine particles was measured, it was 90.0% by mass of TiO 2 , 4.2% by mass of SnO 2 , 0.2% by mass of K 2 O, based on the oxide conversion standard of each metal component. 5 wt%, and was ZrO 2 5.3% by mass.
  • alumina beads having a particle diameter of 0.1 mm (high-purity alumina beads manufactured by Daimei Chemical Industry Co., Ltd.) are added, and this is subjected to a metal oxidizer for 180 minutes using a wet pulverizer (batch-type tabletop sand mill manufactured by Hayashi Shoten). The fired powder of the product fine particles was pulverized and dispersed. Thereafter, the alumina beads were separated and removed using a stainless steel filter having an opening of 44 ⁇ m, and further 1.39 kg of pure water was added and stirred to obtain metal oxide fine particles having a solid content of 11.0% by mass. 1.70 kg of aqueous dispersion was obtained.
  • this aqueous dispersion was washed with ion exchanged water using an ultrafiltration membrane, and then 0.09 kg of an anion exchange resin (manufactured by Mitsubishi Chemical Corporation: SANUPC) was added for deionization treatment.
  • the resultant was subjected to a centrifuge (CR-21G manufactured by Hitachi Koki Co., Ltd.) for 1 hour at a speed of 11,000 rpm, and then ion-exchanged water was added to form metal oxide fine particles having a solid content concentration of 10% by mass. 1.86 kg of an aqueous dispersion sol (BB-1) was prepared.
  • TiO 2 88.9% by mass
  • ZrO 2 5 based on the oxide conversion standard of each metal component.
  • 0.3 wt% and K 2 O 0.5 wt% TiO 2 was 79.87 g / mol
  • ZrO 2 was 123.2 g / mol
  • Ti / Zr (molar ratio) in the above composition was 26 Becomes).
  • aqueous dispersion sol (CB-1).
  • This water-dispersed sol (CB-1) was replaced with methanol from water by using an ultrafiltration membrane (Asahi Kasei Co., Ltd., SIP-1013), and methanol-dispersed sol (CC- 1) 0.31 kg was obtained.
  • core (Ti and Zr) shell (Si) type metal oxide fine particles obtained by coating the surface of the metal oxide fine particles with an oxide containing silicon were obtained.
  • TiO 2 was 86.3% by mass, SnO 2 5.1% by mass, ZrO based on the oxide conversion standard of each metal component. 2 5.1% by mass and K 2 O 0.5% by mass (TiO 2 was 79.87 g / mol, ZrO 2 was 123.2 g / mol, Ti / Zr (molar ratio) in the above formulation) Becomes 26).
  • the solid content concentration contained in the obtained methanol dispersion was about 30% by mass, and the water content was 0.25% by mass.
  • Table 4 shows the number average particle size (Mn) of the particles contained in each dispersed sol. The measuring method is as described above. In addition, the Ti / Zr ratio of each dispersed sol is shown.
  • each dispersed sol In 80 parts by mass of each dispersed sol, the preparation solvent is contained in the following amounts. The balance of each dispersed sol is a solid component.
  • B-1 49 parts by weight of methanol and 2.9 parts by weight of ⁇ -butyrolactone
  • C-1 49 parts by weight of methanol and 2.9 parts by weight of ⁇ -butyrolactone
  • D-1 49 parts by weight of methanol and 2.9 parts of ⁇ -butyrolactone Including parts by weight
  • E-1 Including 49 parts by weight of methanol and 2.9 parts by weight of ⁇ -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 dispersion sols (B-1) and (C-1) obtained above, each component was mixed so as to have the composition shown in Table 5 below to obtain the thermosetting resin compositions of the examples. Each test [1-1] to [1-3] was performed on each sample in the same manner as in Example 1. The results are shown in Table 5 below.
  • Epoxy compounds JER-157S65 (trade name) manufactured by Mitsubishi Chemical Co., Ltd. 5 parts by mass Formulation: Content in composition (parts by mass) The content of ⁇ -butyrolactone contained in the resin sample in the composition is 2.9 parts by mass.
  • Example 9 Using the dispersion sols (B-1) and (C-1) obtained above, each component was mixed so as to have the composition shown in Table 6 below to obtain the curable resin compositions of the examples. Each test [2-1] to [2-4] was performed on each sample in the same manner as in Example 2. The results are shown in Table 6 below.
  • Example 10 Using the dispersion sols (D-1) and (E-1) obtained above, each component was mixed so as to have the composition shown in Table 7 below to obtain the thermosetting resin compositions of Examples. Each test [1-1] to [1-3] was performed on each sample in the same manner as in Example 1. The results are shown in Table 7 below.
  • Epoxy compounds JER-157S65 (trade name) manufactured by Mitsubishi Chemical Co., Ltd. 5 parts by mass
  • Formulation Content in composition (parts by mass) The content of ⁇ -butyrolactone contained in the resin sample in the composition is 2.9 parts by mass.
  • Example 11 Using the dispersion sols (D-1) and (E-1) obtained above, each component was mixed so as to have the composition shown in Table 8 below to obtain curable resin compositions of Examples. Each test [2-1] to [2-4] was performed on each sample in the same manner as in Example 2. The results are shown in Table 8 below.

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