WO2016052113A1 - Composition de résine de siloxane, objet durci transparent obtenu à partir de cette dernière, pixel transparent, microlentille et élément d'imagerie solide - Google Patents

Composition de résine de siloxane, objet durci transparent obtenu à partir de cette dernière, pixel transparent, microlentille et élément d'imagerie solide Download PDF

Info

Publication number
WO2016052113A1
WO2016052113A1 PCT/JP2015/075604 JP2015075604W WO2016052113A1 WO 2016052113 A1 WO2016052113 A1 WO 2016052113A1 JP 2015075604 W JP2015075604 W JP 2015075604W WO 2016052113 A1 WO2016052113 A1 WO 2016052113A1
Authority
WO
WIPO (PCT)
Prior art keywords
compound
group
siloxane resin
resin composition
mass
Prior art date
Application number
PCT/JP2015/075604
Other languages
English (en)
Japanese (ja)
Inventor
翔一 中村
貴規 田口
祐継 室
久保田　誠
上村　哲也
高桑　英希
Original Assignee
富士フイルム株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2014248286A external-priority patent/JP6001041B2/ja
Application filed by 富士フイルム株式会社 filed Critical 富士フイルム株式会社
Priority to KR1020177008874A priority Critical patent/KR101913604B1/ko
Publication of WO2016052113A1 publication Critical patent/WO2016052113A1/fr

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic 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
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B3/00—Simple or compound lenses
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds

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 is not limited to the positive type, and can be applied as a thermosetting resin or a negative type photosensitive resin, and can be suitably applied to micro-processing of micro lenses and transparent pixels, and if necessary, An object is to provide a siloxane resin composition capable of improving manufacturing suitability and properties of a cured 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 having a molar extinction coefficient at 365 nm of 5000 mol ⁇ 1 ⁇ L ⁇ cm ⁇ 1 or more and a molar extinction coefficient at 400 nm of 3500 mol ⁇ 1 ⁇ L ⁇ cm ⁇ 1 or less.
  • Composition. [3] The siloxane resin composition according to [1] or [2], wherein the metal-containing particles have a refractive index of 1.75 or more and 2.90 or less.
  • the siloxane resin composition according to any one of [1] to [6] which is an ultraviolet curable resin composition.
  • the polymerization initiator is an organic halogenated compound, oxydiazole compound, carbonyl compound, ketal compound, benzoin compound, acridine compound, organic peroxide compound, azo compound, coumarin compound, azide compound, metallocene compound, hexaary Rubiimidazole compound, organic boric acid compound, disulfonic acid compound, oxime compound, onium salt compound, hydroxyacetophenone compound, aminoacetophenone compound, acylphosphine oxide compound, trihalomethyltriazine compound, benzyldimethyl ketal compound, ⁇ -hydroxyketone compound, ⁇ -Aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, triallylimidazole dimers, onium compounds, benzothiazo Selected from the group consisting of a phenolic compound, a benzophenone compound, a cyclopentadiene-benzene-iron complex
  • siloxane resin composition according to any one of [1] to [10], wherein the siloxane resin is a hydrolysis condensation reaction product of an alkoxysilane compound.
  • the ultraviolet absorber is contained in a solid component in an amount of 0.01% by mass to 20% by mass.
  • siloxane resin composition according to any one of [1] to [13], wherein the siloxane resin is obtained by a hydrolytic condensation reaction in the presence of the metal-containing particles.
  • a transparent cured product obtained by curing the siloxane resin composition according to any one of [1] to [14].
  • a transparent pixel comprising the transparent cured product according to [15].
  • a microlens comprising the transparent cured product according to [15].
  • a solid-state imaging device comprising the transparent pixel according to [16], the microlens according to [17], or both.
  • the description which does not describe substitution and non-substitution includes what does not have a substituent and what has 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 only exposure with far-ultraviolet rays such as mercury lamps and excimer lasers, X-rays, EUV light, but also drawing with particle beams such as electron beams and ion beams. Are 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.
  • 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.
  • 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 a specific amount of metal-containing particles, a siloxane resin, a polymerization initiator, and a specific ultraviolet absorber.
  • 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 metalloids such as boron, silicon and arsenic are also included here.
  • 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 containing Ti and Zr (further Si if necessary), Ti and Sn (further Si if necessary), Ti, Zr and Sn (further Si if necessary) is preferable, and a combination containing 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, and preferably contain at least titanium oxide and zirconium oxide.
  • titanium oxide is contained as a constituent material, it is preferable to contain rutile titanium oxide.
  • 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 metal-containing particles preferably have a refractive index of 1.75 or higher, more preferably 1.90 or higher.
  • the upper limit is preferably 2.90 or less, and more 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.
  • 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.
  • a mixed solution sample of a matrix resin having a solid content concentration of 10%, prepared so that the content of the metal-containing particles is 0% by mass, 20% by mass, 30% by mass, 40% by mass, and 50% by mass, and metal-containing particles is prepared.
  • Each is coated on a silicon wafer using a spin coater so as to have a thickness of 0.3 to 1.0 ⁇ m, and then heated and dried on a hot plate at 200 ° C. for 5 minutes to obtain a coating film.
  • 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 diameter of the metal-containing particles (meaning the average particle diameter in the primary particle diameter) can be determined from the photograph obtained by observing the particles with a transmission electron microscope. The projected area of the particles is obtained, and the equivalent circle diameter is obtained from this to obtain the average particle diameter. In addition, in order to obtain
  • the average particle diameter is determined as an average value of 80 particles excluding the maximum 10 and the minimum 10. 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 (oxidized oxide). Titanium, 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
  • STR-100W and STR-100WLPT both manufactured by Sakai Chemical Industry Co., Ltd.
  • the content ratio (element composition) of the metal element in the metal-containing particles includes Ti and Zr, and the ratio is preferably 1 to 40, more preferably 1 to 30, more preferably 3 to 20 in terms of Ti / Zr ratio. 4 to 12 is more preferable, and 4 to 9 is most preferable. When satisfying such a numerical range, it is preferable because the storage stability of the composition can be enhanced while maintaining a high refractive index. Moreover, by making Ti / Zr into this range, the light resistance of the cured product of the siloxane resin composition can be improved, which is preferable.
  • the interaction with a specific ultraviolet absorber is further enhanced, 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 thereof is preferably 1 to 40, more preferably 1 to 30, and further preferably 1 to 10 in terms of Ti / Si ratio. In other words, Ti and Si are contained, and the ratio is preferably 1 or more in terms of Ti / Si ratio.
  • 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 compatibility (affinity) 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 mode, and examples include a mode in which the surface is treated with a surfactant described later and a mode in which the surface is treated with a processing agent containing another metal.
  • a mode in which the surface is treated with a surfactant described later and a mode in which the surface is treated with a processing agent containing another metal.
  • grain and forms a film, such as another kind of metal containing material, on the surface is mentioned.
  • a coating of another type of gold-containing material or the like may be thick and core-shell type metal-containing particles may be used.
  • the ratio of the core to the shell is not particularly limited, but when the total particle is 100 parts by mass, the ratio of the core is preferably 85 parts by mass or more, more preferably 87 parts by mass or more, and particularly preferably 90 parts by mass or more.
  • the upper limit is practically 97 parts by mass or less.
  • the combination of the materials constituting the core and the shell is not particularly limited, but examples include that the core is composed of particles containing Ti, Sn, etc., and the shell is composed of a coating containing Zr or Si. In view of increasing the refractive index of the particles, it is particularly desirable that 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.
  • the content of the metal-containing particles is 40% by mass or more in the solid component of the composition, preferably 45% by mass or more, more preferably 50% by mass or more, and 55% by mass or more. Is particularly preferred.
  • As an upper limit it is preferable that it is 80 mass% or less, It is more preferable that it is 75 mass% or less, It is especially preferable that it is 70 mass% or less.
  • the refractive index of the cured film can be increased.
  • it is thought that such a high concentration of metal-containing particles contributes to the deterioration of the cured film through the above-described photocatalytic action.
  • a metal containing particle may be used individually by 1 type, or may be used in combination of 2 or more type.
  • the solid component refers to a component that does not volatilize or evaporate when subjected to a drying treatment at 170 ° C. Typically, it refers to components other than solvents and dispersion media.
  • 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) (hereinafter also simply referred to as “silane compound”). Furthermore, it is also preferable that the silane compound represented by the formula (1) and the silane compound represented by the formula (2) are both subjected to a hydrolytic condensation reaction. Alternatively, both of the silane compound of formula (1) and the silane compound of formula (3) may be subjected to a hydrolytic condensation reaction. The silane compound of formula (2) and the silane compound of formula (3), or A silane compound of formula (2) and a silane compound of formula (3) may be subjected to a hydrolytic condensation reaction. One silane compound of each formula may be used, or two or more silane compounds 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.
  • a is preferably 0 or 1, and more preferably 1.
  • 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.
  • 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, for example, an isocyanuric skeleton is exemplified.
  • d is an integer of 1 to 4, preferably 1 or 2.
  • R 1 to R 7 may each independently have an arbitrary substituent T. Moreover, you may couple
  • 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 may be added as necessary.
  • the solvent is not particularly limited as long as the hydrolysis-condensation reaction can be carried out, and examples of the solvent described below can be given. Among them, for example, alcohol compounds such as water, methanol, ethanol, propanol, diacetone alcohol, tetrahydrofurfuryl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, dipropylene glycol methyl ether, etc.
  • Examples include ether compounds, ester compounds such as methyl acetate, ethyl acetate, butyl acetate, ⁇ -butyrolactone, and propylene glycol monomethyl ether acetate, and ketone compounds such as acetone, methyl ethyl ketone, and methyl isoamyl ketone.
  • the conditions (temperature, time, amount of solvent) for the hydrolysis-condensation reaction may be appropriately selected according to the type of material used.
  • the weight average molecular weight of the siloxane resin used in this embodiment is preferably 2,000 or more, particularly preferably 3,000 or more.
  • the upper limit is preferably 500,000 or less, more preferably 450,000 or less, and particularly preferably 250,000 or less.
  • 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.
  • 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 preferably reduced when the composition contains an alkali-soluble resin to be described later, and is preferably increased when the composition does not contain an alkali-soluble resin. That is, when the composition contains an alkali-soluble resin, 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, It is particularly preferably 3% by mass or more. As an upper limit, it is preferable that it is 30 mass% or less, and it is more preferable that it is 20 mass% or less.
  • the content of the siloxane resin is preferably 10% by mass or more, more preferably 15% by mass or more in the solid component of the composition, It is particularly preferable that the content is at least mass%. 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 content of the siloxane resin with respect to 100 parts by mass of the metal-containing particles is preferably 1 part by mass or more, more preferably 10 parts by mass or more, and particularly preferably 15 parts by mass or more.
  • the upper limit is preferably 60 parts by mass or less, more preferably 50 parts by mass or less, and particularly preferably 45 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.
  • siloxane resin basically means a polymer obtained through a hydrolytic condensation reaction of an alkoxysilane compound. However, a polymer obtained by other reaction and a silane compound itself as a raw material are also included. Including meaning.
  • the siloxane resin is preferably a hydrolytic condensation reaction product of a silane compound. The hydrolysis condensation reaction of the silane compound may be performed in the presence of metal-containing particles. At this time, a particle-resin matrix or a core-shell structure that reacts with the metal-containing particles on the surface thereof may be formed.
  • the ultraviolet absorber employed in the present invention has a molar extinction coefficient (unit: mol ⁇ 1 ⁇ L ⁇ cm ⁇ 1 ) at a wavelength of 365 nm of 5000 or more, preferably 6500 or more, and preferably 8000 or more. Is more preferably 10,000 or more.
  • the molar extinction coefficient at a wavelength of 400 nm is 3500 or less, preferably 2500 or less, and more preferably 1500 or less.
  • the molar extinction coefficient is based on the conditions measured in Examples described below unless otherwise specified.
  • the effect of the ultraviolet absorber in this invention is described. This effect is estimated as follows.
  • the siloxane resin composition of the present invention is used as a negative photosensitive resin composition (ultraviolet curable), an example in which the siloxane resin composition is applied on a substrate is used. At this time, actinic radiation (for example, i-line) is irradiated through a photomask. Then, this exposed portion is exposed and cured. The pattern of the hardened
  • the siloxane resin composition is highly transparent, particularly when it is affected by the particles in the composition, light may be scattered in the resin and the resin around the side may be exposed.
  • the resin of the side periphery will also harden
  • the siloxane resin composition of the present invention employs an ultraviolet absorbent having specific absorption characteristics, exposure blur can be suppressed and a sharp cured product can be obtained.
  • ultraviolet rays i-rays
  • the matrix of the siloxane resin and the metal-containing particles tends to cause the above-described light scattering. Therefore, it is understood that the effect of the specific ultraviolet absorber adopted in the present invention is remarkable.
  • the siloxane resin composition of the present invention can also realize excellent light resistance in the cured product.
  • the reason for this includes estimation, but it is possible that the ultraviolet absorbent having the specific absorption characteristics is adsorbed on the surface of the metal-containing particles in a specific state. As a result, it is understood that the scattering of ultraviolet rays on the particle surface is effectively suppressed, and the deterioration of the composition and the cured product are suppressed. And this effect
  • the ultraviolet absorber can be widely selected and used as long as it has the above optical characteristics. Specifically, (benzo) triazole compound, benzophenone compound, diene compound, avobenzone compound, (benzo) dithiazole compound, (Benzo) dithiol compound, coumarin compound, triazine compound, etc. are mentioned.
  • () means that it may or may not be a benzo-substituted product.
  • a diene compound, an avobenzone compound, a benzodithiol compound, a triazole, or a triazine compound is preferable.
  • the ultraviolet absorber employed in the present invention may have one or more CO groups (carbonyl groups), CONH groups (amide groups), COO groups (ester groups), and CN groups (cyano groups) in the molecule.
  • Preferred hereinafter these groups are referred to as specific adsorbing groups). It is more preferable that there are two or more specific adsorption groups in the molecule. Although there is no upper limit in particular, it is practical that it is eight or less. Although its action includes unknown points, it is understood that it effectively adsorbs or disperses on the surface of the metal-containing particles as described above, and alleviates the influence of light scattering by the above-mentioned particles.
  • the ultraviolet absorber used in the present invention is preferably composed of a compound having a skeleton of any one of the following formulas (a) to (g), and particularly from a compound having a skeleton of the formulas (d) to (g). More preferably, it is particularly preferably made of a compound having a skeleton of formulas (d) to (f).
  • a compound having an arbitrary substituent in a predetermined range in these skeletons can be used.
  • the example of the postscript substituent T is mentioned.
  • an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 3 carbon atoms), a hydroxyl group, an alkoxy group (preferably having 1 to 24 carbon atoms, 1 to 12 is more preferable, 1 to 6 is more preferable, and 1 to 3 is particularly preferable.)
  • the heterocyclic group preferably contains any of N, O, and S, and particularly preferably contains N.
  • the heterocyclic group is preferably a 5- to 7-membered ring, more preferably a 5- or 6-membered ring.
  • the benzene rings of the formulas (a) to (f) have one or more of the above substituents. When there are a plurality of optional substituents on the benzene ring, they may form a ring.
  • R U1 and R U2 are each independently a substituent T, and among them, a cyano group or an acyl group (preferably having 1 to 24 carbon atoms, more preferably 4 to 18 carbon atoms) is preferable.
  • R U1 and R U2 may be the same or different.
  • R U3 and R U4 each independently represent a substituent T, and among them, an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms). To 3 are particularly preferable, and an alkyl group having a cyano group or a carboxyl group is preferable.
  • R U5 and R U6 are preferably groups having the same meanings as R U1 and R U2 , respectively.
  • R U1 and R U2 , R U3 and R U4 , R U5 and R U6 may be combined or condensed to form a ring.
  • an ultraviolet absorber for example, Uvinul A, 3000, 3008, 3049, 3050 (manufactured by BASF), Sumsorb 130, 140, 200, 250, 320, 340, 350 (manufactured by Sumitomo Chemical Co., Ltd.), EVERSORB10, EVERSORB11, EVERSORB12 (manufactured by Yongkou Chemical Industry Co., Ltd.), Tomissorb 800 (manufactured by API Corporation), SEESORB100, 101, 101S, 102, 103, 105, 106, Benzophenone compounds such as 107, 151 (Cipro Kasei), and Dysizer M (Sankyo Kasei); Sumisorb 200, 250, 300, 320, 340, 350 (Sumitomo Chemical), JF77, JF78, JF79, JF80, JF83 (Johoku Chemical), TINUVIN PS, 99-2, 109, 171, 328, 384-2, 4
  • the ultraviolet absorber is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and particularly preferably 1% by mass or more.
  • 20 mass% or less is preferable, 15 mass% or less is more preferable, and 10 mass% or less is especially preferable.
  • 100 parts by mass of the metal-containing particles 0.1 part by mass or more is preferable, 0.5 part by mass or more is more preferable, and 1 part by mass or more is particularly preferable.
  • 20 mass parts or less are preferable, 10 mass parts or less are more preferable, and 5 mass parts or less are especially preferable.
  • the ultraviolet absorber it is preferable to apply the ultraviolet absorber at the above lower limit value or more because the above-described developability and light resistance can be effectively improved. By setting it to the upper limit value or less, it is possible to suppress an excessive influence on optical properties such as transparency, and to suppress bloom and contribute to manufacturing aptitude, which is 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 contains 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 resolution of the pattern and the light resistance of the cured product can be improved.
  • commercially available products such as IRGACURE OXE01 (lower formula) and IRGACURE OXE02 (lower formula) 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 method for measuring the molar extinction coefficient is the same as that of the ultraviolet absorber, and unless otherwise specified, is based on the conditions measured in Examples described later.
  • 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.
  • the siloxane resin composition of the present invention may contain a solvent.
  • the solvent used in the hydrolysis condensation reaction of the silane compound may be used as it is as the solvent of the composition, or the following solvent may be used in addition to or in place of the solvent.
  • the solvent include water, aliphatic compounds, halogenated hydrocarbon compounds, alcohol compounds, ether compounds, ester compounds, ketone compounds, nitrile compounds, amide compounds, sulfoxide compounds, and aromatic compounds. These solvents may be used as a mixture. Examples of each are listed below.
  • Ketone compounds Acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, cyclopentanone, etc.
  • Nitrile compounds Acetonitrile, etc.
  • Amide compounds N, N-dimethylformamide, 1-methyl-2-pyrrolidone, 2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, 2-pyrrolidinone, ⁇ -caprolactam, formamide, N-methylformamide, acetamide N-methylacetamide, N, N-dimethylacetamide, N-methylpropanamide, hexamethylphosphoric triamide, etc.
  • ⁇ Sulphoxide compound Dimethylsulfoxy Etc.
  • Aromatic compounds as benzene, toluene, etc.
  • an alcohol compound, an ester compound, or an ether compound is preferable because each component of the composition is uniformly dissolved.
  • the amount of the solvent used is not particularly limited, but when it is a coating solution, the solid component is preferably 5% by mass or more, more preferably 8% by mass or more, It is particularly preferable that the content be 10% by mass or more.
  • the upper limit is preferably 50% by mass or less, more preferably 40% by mass or less, and particularly preferably 35% by mass or less.
  • the solvent may be used alone or in combination of two or more.
  • 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 multimer 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 end of the oxyalkylene group 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.
  • 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 in which a polyaddition reaction between a polyfunctional epoxy compound and a polyvalent carboxylic 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> in the corresponding US Patent Application Publication No. 2011/0124824) can be referred to. The contents of which are incorporated herein.
  • 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.
  • a polymer compound represented by the general formula (1) of claim 1 (corresponding claim 1 of US2010 / 0233595) of JP-A-2007-277514 is preferable.
  • the description of JP 2007-277514 A (corresponding US 2010/0233595) can be referred to, and the contents thereof are incorporated in the present specification.
  • the polymer compound represented by the general formula (1) is not particularly limited, but can be synthesized according to the synthesis methods described in paragraphs 0114 to 0140 and 0266 to 0348 of JP-A-2007-277514.
  • the content of the dispersing agent is preferably 10 to 1000 parts by mass, more preferably 30 to 1000 parts by mass, and further preferably 50 to 800 parts by mass with respect to 100 parts by mass of the metal-containing particles.
  • the total solid content of the composition is preferably 10 to 30% by mass.
  • 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.
  • Examples of commercially available surfactants include “Megafac” (registered trademark) F142D, F172, F173, F183, F445, F470, F475 or F477 (all manufactured by Dainippon Ink & Chemicals, Inc.) or NBX- 15 or FTX-218 (both manufactured by Neos Co., Ltd.) and other fluorine-based surfactants, BYK-333, BYK-301, BYK-331, BYK-345 or BYK-307 (all of which are Big Chemie Japan Co., Ltd.) And the like.
  • surfactant is not specifically limited, 1 mass% or more is preferable in a solid component of a composition, 1.5 mass% or more is more preferable, and 5 mass% or more is especially preferable. Although an upper limit is not specifically limited, 30 mass% or less is preferable and 15 mass% or less is more preferable.
  • Surfactant may be used individually by 1 type, or may be used in combination of 2 or more type.
  • the siloxane resin composition of the present invention may contain other additives such as a dissolution inhibitor, a stabilizer, or an antifoaming agent, if necessary.
  • 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.
  • TMAH tetramethylammonium hydroxide
  • One developer may be used alone, or two or more developers may be used in combination.
  • 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, 1 to 100 is more preferable.
  • Lr is preferably an alkylene group, an alkenylene group or an alkynylene group.
  • the carbon number of Lr is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3.
  • a plurality of Lr, R N , R P , x, etc. need not be the same.
  • the direction of the linking group is not limited by the above description, and may be understood as appropriate according to a predetermined chemical formula.
  • 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.
  • 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.
  • a transparent cured product (preferably an ultraviolet curable resin composition)
  • the siloxane resin composition of the present invention preferably an ultraviolet curable resin composition
  • 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. .
  • it can pre-bake with heating apparatuses, such as a hot plate or oven, and a film
  • Prebaking is preferably performed at 50 to 150 ° C. for 30 seconds to 30 minutes.
  • the film thickness after pre-baking is preferably 0.1 to 15 ⁇ m.
  • the exposure light source is not limited, and ultraviolet rays such as i-line (wavelength 365 nm), g-line (wavelength 436 nm), or h-line (wavelength 405 nm), KrF (wavelength 248 nm) laser, ArF (wavelength 193 nm) laser, etc. Can be used.
  • 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.
  • actinic radiation having a wavelength of 300 to 400 nm is preferably used, and i-line is more preferably used.
  • 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 product (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 1.6 or more, and more preferably 1.7 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. If necessary, the unevenness on the surface of the base material (element) 3 is embedded and flattened by spin-coating a transparent resin (flattening film) 2.
  • 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 photoresist 4 is irradiated with ultraviolet rays using a reticle as a mask by a stepper device to expose a portion of the space between the lenses.
  • the exposed portion is decomposed and removed with a developer to form a pattern (step 3).
  • the patterned resist 4a is heated to obtain a hemispherical pattern (semispherical resist 4b) (step 4).
  • the resist 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 microlens 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.
  • the solid-state imaging device has a transparent pixel and / or a microlens made of a cured product of the siloxane resin composition of the present invention.
  • the solid-state imaging element has a microlens array on a semiconductor light receiving element, and is incorporated so that the microlens array and the color filter are adjacent to each other.
  • the light receiving element receives light that passes 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 microlens, and the light efficiently collected by the microlens is detected by the light receiving element via the color filter.
  • 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
  • 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.
  • ACV-3010 ultrafiltration membrane device
  • the water-dispersed sol (AA-1) of 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, 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 high-purity alumina beads manufactured by Daimei Chemical Industry Co., Ltd.
  • the surface-treated metal oxide fine particles were pulverized and dispersed for 180 minutes.
  • 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.
  • a distillation apparatus was attached to the flask, and the resulting solution was heated and stirred at a bath temperature of 105 ° C. for 2.5 hours, and reacted while distilling off methanol produced by hydrolysis. Thereafter, the solution was further heated and stirred at a bath temperature of 130 ° C. for 2 hours and then cooled to room temperature to obtain a dispersion composition A-1.
  • thermosetting compositions thermosetting compositions
  • Metal oxide particles 70 parts by mass Siloxane resin 25 parts by mass PGMEA 135 parts by mass (*) DAA 266 parts by mass (*) KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) 2 parts by weight Photopolymerization initiator 1 part by weight Ultraviolet absorber (A) having the structure shown in the table 2 parts by weight (#) Polymerization inhibitor (p-methoxyphenol) 0.01 parts by mass (*)
  • ⁇ Light resistance test [1-2]> The composition was applied to high refractive index glass (SFLD-6 [trade name] manufactured by Sumita Optical Glass Co., Ltd.) with a spin coater (H-360S [trade name] (Mikasa Corp.)). Using a hot plate, the coating film was obtained by prebaking at 100 ° C. for 2 minutes. Exposure was performed at 1000 mJ / cm 2 using an ultrahigh pressure mercury lamp “USH-500BY” [trade name] manufactured by USHIO INC. This coating film was heated at 200 ° C. for 5 minutes on a hot plate in an air atmosphere to obtain a cured film having a thickness of 0.5 ⁇ m.
  • the obtained cured film was irradiated with light of 5 million lxh for 50 hours using a light resistance tester (Xenon Weather Meter SX75 [trade name] manufactured by Suga Test Instruments Co., Ltd.) to perform a light resistance test.
  • the temperature of the subject (temperature in the test apparatus) was set to 63 ° C.
  • the relative humidity in the test apparatus was 50% RH.
  • the transmittance of the cured film was measured, and the light resistance was evaluated based on the following criteria.
  • the light resistance test was performed five times for each sample (cured films of each example and comparative example), and an average value of three results excluding one each of the maximum value and the minimum value of the evaluation points was adopted.
  • the refractive index at a wavelength of 633 nm at a room temperature of 25 ° C. was measured using an ellipsometer (manufactured by Otsuka Electronics Co., Ltd.) with the same cured film sample.
  • the refractive indexes of the cured films of the examples were all about 1.8, realizing a desired high refractive index.
  • molar extinction coefficient of each ultraviolet absorber was calculated by preparing a 1.00 ⁇ 10 ⁇ 3 mol / L chloroform solution and measuring the absorbance according to the following procedure.
  • the chloroform solution adjusted to the above concentration was placed in a glass cell having an internal space width of 1 cm, and the absorbance was measured using a UV-Vis-NIR spectrum meter (Cary5000) [trade name] manufactured by Agilent Technologies.
  • the measurement temperature was 25 ° C.
  • the absorbance A thus obtained was applied to the following formula to calculate the molar extinction coefficient (mol ⁇ 1 ⁇ L ⁇ cm ⁇ 1 ).
  • ⁇ represents the molar extinction coefficient (mol ⁇ 1 ⁇ L ⁇ cm ⁇ 1 )
  • A represents the absorbance
  • c represents the concentration (mol / L)
  • l represents the optical path length (cm).
  • the concentration c is 1.00 ⁇ 10 ⁇ 3 mol / L.
  • the optical path length l corresponds to the width of the internal space of the glass cell and is therefore 1 cm.
  • the cured film obtained by using the siloxane resin composition of the present invention achieves good optical properties, excellent resolution, and light resistance. It was found that it demonstrated high performance.
  • Example 1-2 Preparation of aqueous dispersion sol of nuclear fine particles (E-1)) 7.60 kg of titanium tetrachloride aqueous solution containing 7.75% by mass of titanium tetrachloride in terms of TiO 2 and 2.91 kg of aqueous ammonia containing 15% by mass of ammonia were mixed, and ZrO 2 was mixed therewith while mixing them. 7.6 kg of 1.23% concentration zirconium oxychloride octahydrate aqueous solution in terms of mass was added dropwise over 24 hours to prepare a white slurry liquid having a pH of 8.8.
  • the slurry was diluted 5 times with ion-exchanged water, filtered, and further washed with ion-exchanged water to obtain 5.2 kg of a hydrous titanium zirconate cake having a solid content of 10% by mass.
  • 7.1 kg of hydrogen peroxide containing 35% by mass of hydrogen peroxide and 20.0 kg of ion-exchanged water were added to the cake, and then heated at 80 ° C. for 1 hour with stirring. Thereto was added 28.90 kg of ion-exchanged water to obtain 61.39 kg of an aqueous titanium zirconate solution containing 1% by mass of titanium zirconate in terms of TiO 2 .
  • This aqueous solution of titanium zirconate acid was transparent yellowish brown and had a pH of 8.9.
  • 4.00 kg of a cation exchange resin (manufactured by Mitsubishi Chemical Corporation) was mixed with 60.78 kg of the above titanium peroxide zirconate aqueous solution, and tin containing 1% by mass of potassium stannate in terms of SnO 2 conversion standard was added thereto. 8.01 kg of potassium acid aqueous solution was gradually added with stirring.
  • it after separating the cation exchange resin which took in potassium ion etc., it heated at the temperature of 168 degreeC for 20 hours in the autoclave.
  • 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. 6.89 kg of sol (water dispersion sol of metal oxide fine particles (E-1)) was obtained.
  • the water-dispersed sol (E-1) of 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 size of 0.1 mm (Daimei Chemical Co., Ltd. high-purity alumina beads) are added to the stirred solution, and this is subjected to a wet crusher (Kampe Co., Ltd. batch type tabletop sand mill). For 180 minutes, the fired powder of the metal oxide fine particles was pulverized and dispersed. Thereafter, the alumina beads were separated and removed using a stainless steel filter having an opening of 44 ⁇ 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 mixed solution was put into an autoclave (manufactured by Pressure Glass Industrial Co., Ltd.) 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.
  • SIP-1013 ultrafiltration membrane
  • a sol was prepared.
  • an aqueous dispersion sol (CST-1) of core-shell type metal oxide fine particles in which the surface of the metal oxide fine particles was coated with an oxide containing silicon was 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. It was 2 5.1 wt% and K 2 O 0.5 wt%. (TiO 2 was 79.87 g / mol, ZrO 2 was 123.2 g / mol, and Ti / Zr (molar ratio) in the above composition was 26).
  • the dispersion medium is replaced with methanol by using an ultrafiltration membrane device (a filtration membrane manufactured by Asahi Kasei Co., Ltd., SIP-1013), and methanol-dispersed sol of core-shell type metal oxide fine particles (CSTM- 1) was obtained.
  • an ultrafiltration membrane device a filtration membrane manufactured by Asahi Kasei Co., Ltd., SIP-1013
  • methanol-dispersed sol of core-shell type metal oxide fine particles (CSTM- 1) was obtained.
  • the solid content concentration contained in the obtained methanol dispersion sol (CSTM-1) was about 30% by mass, and the water content was 0.28% by mass.
  • dispersion composition E-1 10.9 g (0.08 mol) of methyltrimethoxysilane, 63.5 g (0.32 mol) of phenyltrimethoxysilane, methanol dispersion sol EM-1 of metal oxide fine particles (solid content concentration 30 mass%, methanol 70 mass%) 440.0 g and DAA 370.0 g were placed in a reaction vessel, and 32.0 g of water and 1.0 g of phosphoric acid were added dropwise to this solution with stirring so that the reaction temperature did not exceed 40 ° C. After the dropwise addition, a distillation apparatus was attached to the flask, and the resulting solution was heated and stirred at a bath temperature of 105 ° C.
  • dispersion composition C-1 was prepared in the same manner as the preparation of dispersion composition E-1, except that the metal-containing material used was changed to CSTM-1.
  • ⁇ Test 400 range> A siloxane resin composition was obtained in the same manner as in Example 1 except that the dispersion composition and / or ultraviolet absorber used was changed as shown in Table 1-4. Using the obtained siloxane resin composition, the resolution, light resistance, and transparency were evaluated in the same manner as in Example 1.
  • the siloxane resin compositions of Tests 401 to 409 shown in Table 1-4 all show good resolution, light resistance, and transparency with respect to the siloxane resin compositions of Comparative Examples shown in Table 1-2. Accordingly, in the case of Zr-containing titanium oxide (metal oxide fine particles), if Ti / Zr is 1 to 40, the shape is core-shell type (test 101 to 302) or non-core shell type (test 401 to 408). Regardless, all showed good results. The test 409 coated with an oxide containing silicon also showed good results.
  • Example 2 A siloxane resin composition was prepared in the same manner as in Test 101 of Example 1 except that ethyltrimethoxysilane was used instead of methyltrimethoxysilane in the preparation of the dispersion composition A-1.
  • a siloxane resin composition was prepared in the same manner as in Example 1 except that part of methyltrimethoxysilane was changed to tetramethoxysilane (methyltrimethoxysilane and tetramethoxysilane were used in combination). These siloxane resin compositions were used to carry out the above-described tests for resolution, light resistance, and applicability, and all confirmed that good results were obtained.
  • each sample (dispersion composition A-) was prepared in the same manner as the dispersion composition A-1, except that the composition ratio of TiO 2 and ZrO 2 was adjusted to be as shown in Table 2 below. 2 to A-5) were prepared.
  • a siloxane resin composition was prepared in the same manner as in Test 101 of Example 1 except that each of the above dispersion compositions was used, and the same items as in Table 1 were tested.
  • the light resistance test [1-2] the light resistance test [1-2a] under severer conditions was performed. Specifically, for the conditions of the above light resistance test [1-2], the temperature around the subject (internal temperature) was 63 ° C., and the humidity was 90% RH. The light irradiation time was 50 hours.
  • the light resistance is high. Can be realized.
  • Example 4 A similar test was performed on the above dispersion composition A-1 by changing the concentration of the metal oxide fine particles to 40 mass%, 50 mass%, and 55 mass%, respectively.
  • the refractive indexes of the cured films were 1.67, 1.73, and 1.75, respectively. It was also confirmed that each item showed good performance.
  • the concentration of the metal oxide fine particles was set to 10% by mass, the refractive index of the cured film greatly fell below 1.6.
  • this concentration there was no problem of resolution, light resistance, and transparency even when using an ultraviolet absorber whose molar absorption coefficient does not have the molar absorption coefficient defined in the present invention. . From this result, it can be seen that the ultraviolet absorbent used in the present invention exhibits its usefulness only when a considerable amount of metal oxide fine particles is used.
  • Example 5 The siloxane resin compositions prepared in the above tests 101, 123, 124, and 201 were used and applied onto a silicon wafer. Thereafter, pre-baking (100 ° C., 2 min) and post-baking (230 ° C., 10 min) were performed to form a coating film (lens material 1) having a film thickness of 1.1 ⁇ 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. Then, a photoresist film 4 was formed (FIG. 1 (2)).
  • This photoresist film 4 is 300 mJ / 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. It was exposed in cm 2. This was subjected to paddle development for 60 seconds at room temperature using an alkaline developer HPRD-429E (manufactured by FUJIFILM Electronics Materials Co., Ltd.) and then rinsed with pure water for 20 seconds in a spin shower. It was. Thereafter, the substrate was further washed with pure water, and then the substrate was dried at a high speed to form a resist pattern (patterned photoresist 4a) (FIG.
  • i-line stepper product name: FPA-3000i5 +, manufactured by Canon Inc.
  • the separation width when patterning was 238.7 nm.
  • the resist was shaped into a lens shape (hemisphere) by post-baking with a hot plate at 145 ° C. for 120 seconds, then at 160 ° C. for 120 seconds, and further at 175 ° C. for 120 seconds (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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Optics & Photonics (AREA)
  • Inorganic Chemistry (AREA)
  • Silicon Polymers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition de résine de siloxane qui comprend des particules contenant du métal, une résine de siloxane, un initiateur de polymérisation, et un absorbeur d'ultraviolets, les particules contenant du métal étant contenues en une quantité de 40 à 80 % en masse par rapport aux constituants solides de la composition et l'absorbeur d'ultraviolets présentant un coefficient d'absorption molaire à 365 nm de 5 000 mole-1·L·cm-1 ou plus et un coefficient d'absorption molaire à 400 nm de 3 500 mole-1·L·cm-1 ou moins.
PCT/JP2015/075604 2014-10-03 2015-09-09 Composition de résine de siloxane, objet durci transparent obtenu à partir de cette dernière, pixel transparent, microlentille et élément d'imagerie solide WO2016052113A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
KR1020177008874A KR101913604B1 (ko) 2014-10-03 2015-09-09 실록세인 수지 조성물, 이를 이용한 투명 경화물, 투명 화소, 마이크로렌즈, 고체 촬상 소자

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2014-205275 2014-10-03
JP2014205275 2014-10-03
JP2014-248286 2014-12-08
JP2014248286A JP6001041B2 (ja) 2014-10-03 2014-12-08 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

Publications (1)

Publication Number Publication Date
WO2016052113A1 true WO2016052113A1 (fr) 2016-04-07

Family

ID=55630156

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2015/075604 WO2016052113A1 (fr) 2014-10-03 2015-09-09 Composition de résine de siloxane, objet durci transparent obtenu à partir de cette dernière, pixel transparent, microlentille et élément d'imagerie solide

Country Status (1)

Country Link
WO (1) WO2016052113A1 (fr)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006119476A (ja) * 2004-10-22 2006-05-11 Nippon Zeon Co Ltd 反射防止積層体および光学部材
JP2007246877A (ja) * 2005-10-03 2007-09-27 Toray Ind Inc シロキサン系樹脂組成物、光学物品およびシロキサン系樹脂組成物の製造方法
JP2010031272A (ja) * 2008-07-01 2010-02-12 Asahi Kasei E-Materials Corp 感光性樹脂組成物
JP2010047746A (ja) * 2008-07-01 2010-03-04 Asahi Kasei E-Materials Corp 感光性樹脂組成物
JP2010059235A (ja) * 2008-09-01 2010-03-18 Fujifilm Corp 紫外線吸収剤組成物
WO2014157296A1 (fr) * 2013-03-29 2014-10-02 富士フイルム株式会社 Composition de résine photosensible, film durci, procédé de formation d'image, élément d'imagerie à l'état solide, filtre coloré et absorbant ultraviolet

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006119476A (ja) * 2004-10-22 2006-05-11 Nippon Zeon Co Ltd 反射防止積層体および光学部材
JP2007246877A (ja) * 2005-10-03 2007-09-27 Toray Ind Inc シロキサン系樹脂組成物、光学物品およびシロキサン系樹脂組成物の製造方法
JP2010031272A (ja) * 2008-07-01 2010-02-12 Asahi Kasei E-Materials Corp 感光性樹脂組成物
JP2010047746A (ja) * 2008-07-01 2010-03-04 Asahi Kasei E-Materials Corp 感光性樹脂組成物
JP2010059235A (ja) * 2008-09-01 2010-03-18 Fujifilm Corp 紫外線吸収剤組成物
WO2014157296A1 (fr) * 2013-03-29 2014-10-02 富士フイルム株式会社 Composition de résine photosensible, film durci, procédé de formation d'image, élément d'imagerie à l'état solide, filtre coloré et absorbant ultraviolet

Similar Documents

Publication Publication Date Title
JP6476211B2 (ja) 遮光膜、遮光膜付き赤外光カットフィルタ、及び、固体撮像装置
JP6893236B2 (ja) 組成物、膜、光センサおよび分散剤
JP6744921B2 (ja) 分散液、組成物、膜、膜の製造方法および分散剤
JP6387110B2 (ja) 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、およびマイクロレンズの製造方法
JP6701324B2 (ja) 組成物、膜、硬化膜、光学センサおよび膜の製造方法
JP6001041B2 (ja) 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
JP7127194B2 (ja) シロキサン樹脂組成物、これを用いたマイクロレンズ若しくは透明画素、固体撮像素子
TW201609540A (zh) 光學機能層形成用組成物、使用其的固體攝像元件及照相機模組、以及光學機能層的圖案形成方法、固體攝像元件及照相機模組的製造方法
WO2021044988A1 (fr) Composition, film, structure, filtre coloré, élément d'imagerie à semi-conducteurs, et dispositif d'affichage d'image
JP5799182B1 (ja) 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
JP6298175B2 (ja) 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
WO2017158914A1 (fr) Composition, film, film durci, capteur optique et procédé de production de film
JP6013422B2 (ja) 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
WO2016052113A1 (fr) Composition de résine de siloxane, objet durci transparent obtenu à partir de cette dernière, pixel transparent, microlentille et élément d'imagerie solide
WO2021044987A1 (fr) Composition, film, structure, filtre coloré, élément d'imagerie à semi-conducteurs, et dispositif d'affichage d'image

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15846633

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 20177008874

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 15846633

Country of ref document: EP

Kind code of ref document: A1