JP6795572B2 - Composition for forming an optical functional layer, solid-state image sensor and camera module using the composition - Google Patents

Description

The present invention relates to a composition for forming an optical functional layer, a solid-state image sensor using the same, and a camera module.

An optical functional layer such as a low refractive index film is applied to the surface of a transparent substrate, for example, in order to prevent reflection of incident light. Its application fields are wide, and it is applied to products in various fields such as optical instruments, building materials, observation instruments, and window glass. Particularly in recent years, the development of materials applied to optical instruments has been actively promoted. Specifically, in display panels such as liquid crystals and organic EL, optical lenses, and image sensors, the search for materials having physical properties and processability suitable for the products is underway.

As a material for the optical functional layer, various materials, organic or inorganic, are used and are targeted for development. Among them, there is one that proposes the use of silica fine particles having a low refractive index and internal voids (see Patent Documents 1 to 6). There, the silica fine particles are dispersed in an organic material which is a matrix material, and the silica fine particles are coated, dried and cured to form a transparent film having a low refractive index.

Japanese Unexamined Patent Publication No. 2002-79616 Japanese Unexamined Patent Publication No. 2004-83307 Japanese Unexamined Patent Publication No. 2004-258267 Japanese Unexamined Patent Publication No. 2005-283872 Japanese Unexamined Patent Publication No. 2007-182511 Japanese Unexamined Patent Publication No. 2013-014680

The usage patterns of optical instruments and the like provided with an optical functional layer such as an antireflection film are diversifying more and more. With the spread of equipment used, it is desired to improve performance such as durability in addition to optical characteristics.
The present invention provides a composition for forming an optical functional layer, which can realize good transparency and a low refractive index, and has excellent moisture resistance of the formed film, and a solid-state image sensor and a camera module using the same. The purpose.

式（Ｘ１）において、Ｒ^Ｘ１は炭素数３〜１２のフッ素を有する有機基を表す。Ｒ^Ｘ２は炭素数１〜４の炭化水素基を表す。Ｘは加水分解性基を表す。ａは０または１である。
式（Ｘ２）において、Ｒ^Ｘ３およびＲ^Ｘ４は各々、エポキシ基またはグリシドキシ基を有する基を表す。ＹはＸと同義の基である。ｂおよびｃは０または１であり、(ｂ＋ｃ)は１または２である。
〔２〕粒子凝集体が、平均粒子径５〜５０ｎｍの複数の球状粒子とこの複数の球状粒子を互いに接合する接合部と、からなる〔１〕に記載の光学機能層形成用組成物。
〔３〕シロキサン樹脂１００質量部に対してシリカ微粒子を５０質量部以上含有する〔１〕または〔２〕に記載の光学機能層形成用組成物。
〔４〕シロキサン樹脂１００質量部に対してシリカ微粒子を１００質量部以上含有する〔１〕〜〔３〕のいずれか１つに記載の光学機能層形成用組成物。
〔５〕シロキサン樹脂１００質量部に対してシリカ微粒子を２００質量部以上含有する〔１〕〜〔４〕のいずれか１つに記載の光学機能層形成用組成物。
〔６〕シリカ微粒子の含有量が６０〜９０質量％である〔１〕〜〔５〕のいずれか１つに記載の光学機能層形成用組成物。
〔７〕粒子凝集体が下記の諸元（ａ）および（ｂ）を有する〔１〕〜〔６〕のいずれか１つに記載の光学機能層形成用組成物。
（ａ）動的光散乱法により測定された平均粒子径Ｄ１が３０〜３００ｎｍである。
（ｂ）比表面積より求めた平均粒子径Ｄ２と上記Ｄ１との比率、Ｄ１／Ｄ２が３以上である。
〔８〕有機溶媒をさらに含有する〔１〕〜〔７〕のいずれか１つに記載の光学機能層形成用組成物。
〔９〕有機溶媒が、プロピレングリコールモノ−ｎ−ブチルエーテル、ジアセトンアルコール、プロピレングリコールモノエチルアセテート、γ−ブチロラクトン、エチレングリコールモノ−ｔ−ブチルエーテル、プロピレングリコールモノ−ｔ−ブチルエーテルからなる群から選ばれる少なくとも1つを含む〔８〕に記載の光学機能層形成用組成物。
〔１０〕界面活性剤をさらに含有する〔１〕〜〔９〕のいずれか１つに記載の光学機能層形成用組成物。
〔１１〕低屈折率膜形成用である〔１〕〜〔１０〕のいずれか１つに記載の光学機能層形成用組成物。
〔１２〕カラーフィルタのグリッド形成用である〔１〕〜〔１１〕のいずれか１つに記載の光学機能層形成用組成物。
〔１３〕光学機能層の厚さが５０ｎｍ以上５μｍ以下である〔１〕〜〔１２〕のいずれか１つに記載の光学機能層形成用組成物。
〔１４〕〔１〕〜〔１３〕のいずれか１つに記載の光学機能層形成用組成物を用いる光学機能層の製造方法。
〔１５〕支持体上に塗布された光学機能層形成用組成物層を、５０℃〜２００℃でプリベークする〔１４〕に記載の光学機能層の製造方法。
〔１６〕支持体上に塗布された光学機能層形成用組成物層を、プリベークしたのち、形成した塗布膜を２５０℃以下でポストベークする〔１４〕または〔１５〕に記載の光学機能層の製造方法。
〔１７〕〔１〕〜〔１３〕のいずれか１つに記載の光学機能層形成用組成物の硬化膜を備える固体撮像素子。
〔１８〕〔１〕に記載の光学機能層形成用組成物の硬化膜を備える固体撮像素子であって、屈折率１．３以下の光学機能層を備える固体撮像素子。
〔１９〕〔１７〕または〔１８〕に記載の固体撮像素子を備えるカメラモジュール。 The above problems have been solved by the following means.
[1] It contains a siloxane resin and silica fine particles, and has a refractive index of 1.3 or less when formed into a cured film.
The siloxane resin is a hydrolyzed condensate of a siloxane compound containing a compound represented by the following formula (X1) and a compound represented by the following formula (X2).
A composition for forming an optical functional layer, wherein the silica fine particles are particle aggregates in which a plurality of particles are connected in a chain.

In formula ^{(X1), R} X1 represents an organic group having a fluorine having 3 to 12 carbon atoms. ^RX2 represents a hydrocarbon group having 1 to 4 carbon atoms. X represents a hydrolyzable group. a is 0 or 1.
In formula ^{(X2), R X3} and ^{R X4} each represent a group having an epoxy group or glycidoxy group. Y is a synonym for X. b and c are 0 or 1, and (b + c) is 1 or 2.
[2] The composition for forming an optical functional layer according to [1], wherein the particle aggregate comprises a plurality of spherical particles having an average particle diameter of 5 to 50 nm and a joint portion for joining the plurality of spherical particles to each other.
[3] The composition for forming an optical functional layer according to [1] or [2], which contains 50 parts by mass or more of silica fine particles with respect to 100 parts by mass of a siloxane resin.
[4] The composition for forming an optical functional layer according to any one of [1] to [3], which contains 100 parts by mass or more of silica fine particles with respect to 100 parts by mass of a siloxane resin.
[5] The composition for forming an optical functional layer according to any one of [1] to [4], which contains 200 parts by mass or more of silica fine particles with respect to 100 parts by mass of a siloxane resin.
[6] The composition for forming an optical functional layer according to any one of [1] to [5], wherein the content of silica fine particles is 60 to 90% by mass.
[7] The composition for forming an optical functional layer according to any one of [1] to [6], wherein the particle aggregate has the following specifications (a) and (b).
(A) The average particle diameter D1 measured by the dynamic light scattering method is 30 to 300 nm.
(B) The ratio of the average particle diameter D2 obtained from the specific surface area to the above D1 and D1 / D2 are 3 or more.
[8] The composition for forming an optical functional layer according to any one of [1] to [7], which further contains an organic solvent.
[9] The organic solvent is selected from the group consisting of propylene glycol mono-n-butyl ether, diacetone alcohol, propylene glycol monoethyl acetate, γ-butyrolactone, ethylene glycol mono-t-butyl ether, and propylene glycol mono-t-butyl ether. The composition for forming an optical functional layer according to [8], which comprises at least one.
[ 10 ] The composition for forming an optical functional layer according to any one of [1] to [ 9 ], which further contains a surfactant.
[ 11 ] The composition for forming an optical functional layer according to any one of [1] to [ 10 ] for forming a low refractive index film.
[ 12 ] The composition for forming an optical functional layer according to any one of [1] to [ 11 ], which is used for forming a grid of a color filter.
[13] The composition for forming an optical functional layer according to any one of [1] to [12], wherein the thickness of the optical functional layer is 50 nm or more and 5 μm or less.
[ 14 ] A method for producing an optical functional layer using the composition for forming an optical functional layer according to any one of [1] to [ 13 ].
[ 15 ] The method for producing an optical functional layer according to [ 14 ], wherein the composition layer for forming an optical functional layer coated on the support is prebaked at 50 ° C. to 200 ° C.
[ 16 ] The composition layer for forming an optical functional layer coated on a support is prebaked, and then the formed coating film is post-baked at 250 ° C. or lower. [ 14 ] or [ 15 ]. Production method.
[ 17 ] A solid-state image sensor comprising a cured film of the composition for forming an optical functional layer according to any one of [1] to [ 13 ].
[ 18 ] A solid-state image sensor including the cured film of the composition for forming an optical functional layer according to [1], which includes an optical functional layer having a refractive index of 1.3 or less.
[ 19 ] A camera module including the solid-state image sensor according to [ 17 ] or [ 18 ].

In the notation of a group (atomic group) in the present specification, the notation not describing substitution and non-substituent includes those having no substituent and those having a substituent to the extent that the effect of the present invention is not impaired. To do. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). This is synonymous with each compound.
Further, in the present specification, "(meth) acrylate" represents both acrylate and methacrylate, or either, and "(meth) acrylic" represents both acrylic and methacrylic, or "(meth). ) Acryloyl "represents both acryloyl and / or methacryloyl.
Further, in the present specification, "monomer" and "monomer" are synonymous. The monomer in the present 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 unless otherwise specified. In the present specification, the polymerizable compound means a compound having a polymerizable functional group, and may be a monomer or a polymer. A polymerizable functional group is a group involved in a polymerization reaction.
The weight average molecular weight and the number average molecular weight can be determined by gel permeation chromatography (GPC).
In the present specification, Me in the chemical formula represents a methyl group, Et represents an ethyl group, Pr represents a propyl group, Bu represents a butyl group, and Ph represents a phenyl group.

The composition for forming an optical functional layer of the present invention can realize good transparency and a low refractive index when a cured film is formed, and is excellent in moisture resistance of the formed film.
The optical functional layer formed by using the above-mentioned optical functional layer forming composition exhibits good optical characteristics, and the solid-state image sensor and the camera module provided with the optical functional layer exhibit excellent performance.

It is an enlarged view which shows typically the shape of the particle aggregate which connected a plurality of particles in a chain.

The composition for forming an optical functional layer of the present invention contains a siloxane resin and silica fine particles. The cured film realizes an extremely low refractive index of 1.3 or less. Hereinafter, each configuration of the present invention will be described in detail.

[Silica fine particles]
The silica fine particles that can be used in the present invention are not particularly limited, and may be any of "hollow particles", "porous particles", "non-hollow particles", and "particle agglomerates in which a plurality of particles are connected in a chain". Of these, "non-hollow particles" or "particle agglomerates in which a plurality of particles are connected in a chain" are preferable, and "particle agglomerates in which a plurality of particles are connected in a chain" are particularly preferable.

(Non-hollow particles)
Specific examples of the non-hollow silica fine particles include the following (both are trade names).
-Nissan Chemical Industries, Ltd. ST-30 with a number average particle size of 12 nm using water as a dispersant
IPA-ST with an average particle size of 12 nm using isopropanol as a dispersant
MIBK-ST with a number average particle size of 12 nm using methyl isobutyl ketone as a dispersant
IPA-STL with a number average particle size of 45 nm using isopropanol as a dispersant
IPA-ST-ZL with a number average particle size of 100 nm using isopropanol as a dispersant
PGM-ST with a number average particle size of 15 nm using propylene glycol monomethyl ether as a dispersant,
"Oscar (registered trademark)" 101 with a number average particle size of 12 nm using γ-butyrolactone manufactured by Catalytic Chemical Industry Co., Ltd. as a dispersant.
"Oscar" 105 with a number average particle diameter of 60 nm using γ-butyrolactone as a dispersant
"Oscar" 106 with a number average particle size of 120 nm using diacetone alcohol as a dispersant
"Cataroid®" -S with a number average particle diameter of 5 to 80 nm in which the dispersion solution is water
-"Quatron (registered trademark)" PL-2LP with a number average particle diameter of 16 nm using propylene glycol monomethyl ether manufactured by Fuso Chemical Industry Co., Ltd. as a dispersant.
GME
"Quatron" PL-1-PGME with a number average particle diameter of 12 nm
"Quatron" PL-2L-BL with a number average particle size of 17 nm using γ-butyrolactone as a dispersant
"Quatron" PL-1-BL with a number average particle diameter of 13 nm
"Quatron" PL-2L-DAA with a number average particle diameter of 17 nm using diacetone alcohol as a dispersant
"Quatron" PL-1-DAA with a number average particle diameter of 13 nm
"Quatron" PL-2L-IPA with a number average particle size of 17 nm using isopropyl alcohol as a dispersant
The dispersion solution is water "Quatron" PL-2L, GP-2L with a number average particle diameter of 18 to 20 nm.
"Quatron" PL-1 with a number average particle diameter of 13 to 15 nm
-Manufactured by KCM Corporation Silica (SiO ₂ ) SG-SO100 with a number average particle size of 100 nm
-Made by Tokuyama Corporation "Leoloseal (registered trademark)" with a number average particle size of 5 to 50 nm
In addition, those used in the examples can be exemplified as appropriate.

Non-hollow particles (silica fine particles that are not porous inside and do not have hollow) usually have a refractive index of 1.45 to 1.5. On the other hand, silica fine particles having a porous and / or hollow inside usually have a refractive index of 1.2 to 1.4.

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

(Hollow particles / Porous particles)
The "hollow particles" are preferably silica fine particles having a hollow portion and surrounded by an outer shell. The "porous particles" are preferably silica fine particles having a large number of cavities on the surface or inside of the particles. Of these, silica fine particles having a hollow shape and high strength of the particles themselves are preferable in consideration of the hardness of the transparent film. The refractive index of these silica fine particles themselves is preferably 1.2 to 1.4, and more preferably 1.2 to 1.35. These silica fine particles can be produced by the methods disclosed in Japanese Patent No. 3272111 and Japanese Patent Application Laid-Open No. 2001-233611. Further, examples of such silica fine particles include those disclosed in Japanese Patent Application Laid-Open No. 2001-233611 and those generally commercially available as shown in Japanese Patent No. 3272111. Specific examples of commercially available products include the Sururia series manufactured by JGC Catalysts and Chemicals Co., Ltd. and Sirinax manufactured by Nittetsu Mining Co., Ltd. Further, as a method for producing porous particles, for example, the methods described in JP-A-2003-327424, 2003-335515, 2003-226516, 2003-238140 and the like can be applied. The presence or absence of hollowness can be confirmed by a cross-sectional image of particles using a TEM (scanning electron microscope) photograph.

The porosity of the hollow particles and the porous particles is preferably 10 to 80% by volume, more preferably 20 to 60% by volume, and particularly preferably 30 to 60% by volume. It is preferable to set the porosity of the particles in the above range from the viewpoint of lowering the refractive index and maintaining the durability of the particles.

The average particle size of the non-hollow particles, hollow particles, and porous particles is preferably 1 nm or more, more preferably 3 nm or more, and particularly preferably 5 nm or more. The upper limit is preferably 1 μm or less, more preferably 500 nm or less, further preferably 100 nm or less, and particularly preferably 50 nm or less.
The average particle size of non-hollow particles, hollow particles, and porous particles is measured using a dynamic light scattering type particle size distribution measuring device (LB-500 [trade name] manufactured by Horiba Seisakusho Co., Ltd.). The procedure is as follows. The inorganic solid electrolyte particle dispersion is separated into a 20 ml sample bottle, and diluted with toluene so that the solid component concentration becomes 0.2% by mass. Data are captured 50 times at a temperature of 25 ° C. using a 2 ml quartz cell for measurement, and the obtained "number average" is used as the average particle size. For other detailed conditions, etc., refer to the description of JISZ8825: 2013 “Particle size analysis laser diffraction / scattering method” as necessary. Five samples are prepared for each level and the average value is adopted.

(Particle agglomerates [beaded particles])
In the "particle agglomerate in which a plurality of particles are connected in a chain" (hereinafter, may be simply referred to as "particle agglomerate" or also referred to as "beaded particle") according to the present embodiment, dynamic light is applied. The ratio D1 / D2 of the average particle size (D1) measured by the scattering method and the average particle size (D2) obtained from the specific surface area is preferably 3 or more. The upper limit of D1 / D2 is not particularly limited, but is preferably 20 or less, and more preferably 10 or less. By setting D1 / D2 in such a range, good optical characteristics can be exhibited.

The silica fine particles contained in the composition for forming an optical functional layer of the present invention are preferably particle aggregates from the viewpoint of low refractive index and excellent moisture resistance. Specifically, the particle agglomerates are preferably those in which a plurality of spherical silica particles are bonded by a bonding portion such as metal oxide-containing silica (see FIG. 1). It is preferable to use such a particle agglomerate because the refractive index of the film after formation can be sufficiently lowered. As for the silica particles, it is preferable that the spherical silica particles are connected in one plane.

The average particle size (D2) determined from the specific surface area Sm ² / g of the particle aggregate can be evaluated as an average particle size close to the primary particles of spherical silica. The average particle size (D2) is preferably 2 nm or more, and more preferably 5 nm or more. The upper limit is preferably 100 nm or less, more preferably 50 nm or less, and particularly preferably 30 nm or less. The average particle size (D2) means the average particle size measured by the BET method. Specifically, the average particle size (D2) is the average particle size obtained by the formula D2 = 2720 / S from the specific surface area Sm ² / g measured by the nitrogen adsorption method.
The average particle size (D1) measured by the dynamic light scattering method of the silica particles (for example, using the above device) is the average particle size of the secondary particles in which a plurality of spherical silica particles are formed into a chain. It can be evaluated as (number average particle size). Therefore, the relationship D1> D2 usually holds. The average particle size (D1) is preferably 25 nm or more, more preferably 30 nm or more, and particularly preferably 35 nm or more. The upper limit is preferably 1000 nm or less, more preferably 700 nm or less, further preferably 500 nm or less, and particularly preferably 300 nm or less.
As used herein, the term "spherical" means that it may be substantially spherical and may be deformed as long as the effect of the present invention is exhibited. For example, it is meant to include a shape having irregularities on the surface and a flat shape having a length in a predetermined direction. "Beaded" can be rephrased as "necklace-like" and typically means a structure in which a plurality of spherical particles are connected in a chain at a joint having a smaller outer diameter. The outer diameter of the joint can be defined by the diameter of the cross section orthogonal to the connecting direction. Examples of the metal oxide-containing silica forming the joint include amorphous silica and amorphous alumina.

As the silica particle liquid (sol) in which a particle aggregate in which a plurality of particles are linked in a chain is dispersed, for example, the silica sol described in Japanese Patent No. 4328935 can be used. Further, the description in JP2013-253145A can be referred to.

As the particle liquid of the particle aggregate, a commercially available liquid sol can be used. For example, "Snowtex OUP", "Snowtex UP", "IPA-ST-UP", "Snowtex PS-M", "Snowtex PS-MO", "Snowtex PS-S", manufactured by Nissan Chemical Industries, Ltd. "Snowtex PS-SO", "Fine Cataloid F-120" manufactured by Catalytic Chemical Industry Co., Ltd., "Quatron PL" manufactured by Fuso Chemical Industry Co., Ltd., HDK (hydrophilic HDK @ V15) manufactured by Asahi Kasei Wacker, HDK @ N20, HDK @ T30, HDK @ T40, hydrophobic HDK @ H15, HDK @ H18, HDK @ H20, HDK @ H30) and the like. It is preferable that these particle aggregates have a structure in which a large number of primary particles made of silicon oxide are bonded and are curved two-dimensionally or three-dimensionally.

In the composition for forming an optical functional layer of the present invention, the content of silica fine particles is preferably 40% by mass or more, more preferably 50% by mass or more, and 60% by mass or more in the total solid components. It is particularly preferable to have. The upper limit is preferably 99% by mass or less, more preferably 95% by mass or less, and particularly preferably 90% by mass or less.
In relation to the following siloxane resin, silica fine particles are preferably used in an amount of 50 parts by mass or more, more preferably 100 parts by mass or more, and particularly preferably 200 parts by mass or more with respect to 100 parts by mass of the siloxane resin. preferable.
By setting the amount of silica fine particles in the above range, it is possible to effectively form a film having a low refractive index and high moisture resistance.
In the present specification, the solid component (solid content) means a component that does not volatilize or evaporate and disappear when it is dried at 100 ° C. Typically, it refers to components other than solvents and dispersion media.

[resin]
In the present invention, it is preferable to use a compound having a fluoro group. Fluoro group is a general term for substituents having a fluorine atom, for example, a fluoroalkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 3 carbon atoms), a fluoroaryl group (6 carbon atoms). ~ 22, preferably 6-14, more preferably 6-10), fluoroalkenyl group (preferably 2-12 carbon atoms, more preferably 2-6 carbon atoms), fluoroalkynyl group (2-12 carbon atoms are preferred). Preferably, 2 to 6 are more preferable), a fluoroalkoxy group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1-3), a fluoroaryloxy group (preferably 6 to 22 carbon atoms). Examples thereof include 6 to 14 more preferably, 6 to 10 being particularly preferable), a fluoroether group (2 to 12 carbon atoms are preferable, and 2 to 6 are more preferable) and the like. Of these, a fluoroalkyl group is preferable. In the present invention, the fluorogroup is preferably a perfluorogroup. The perfluoro group means a group in which at least one carbon atom of the target substituent is filled with fluorine atoms at all the substitutable positions. For example, a trifluoromethyl group or a heptafluorophenyl group corresponds to this.

Various compounds having a perfluoro group can be applied, for example, acrylic resin, melamine resin, silicone resin, urethane resin, urea resin, epoxy resin, allyl resin, maleimide resin, phosphazene resin, fluororesin, and the like. Butyral resin, phenol resin, vinyl chloride resin and the like can be mentioned. It is also preferable to use a photopolymerizable composition in combination.
The matrix resin used as the thermosetting low refractive index layer preferably has the property of effectively three-dimensionally cross-linking by heating. When photopolymerization is performed after the low refractive index layer is provided, a material having a light transmittance of 10% or more required for photopolymerization is preferably used. As the three-dimensional cross-linking, various bonding modes such as covalent bond, ionic bond, and hydrogen bond can be taken. Among them, it is preferable that the cross-linking is performed by covalent bond from the viewpoint of environmental stability such as water and oxygen. .. Examples of the crosslink by covalent bond include (thio) urethane crosslink, melamine crosslink, (meth) acrylic crosslink, and polysiloxane crosslink from the viewpoint of thermal stability.
Among them, polysiloxane cross-linking is particularly preferable from the viewpoint of improving surface hardness and antireflection. In particular, in polysiloxane cross-linking, a 2-3 functional organic silane compound is preferably used from the viewpoint of surface hardness, flexibility and the like. As the organic group, it has an aliphatic organic group from the viewpoint that it is easy to impart a low refractive index, and from the viewpoint of improving the surface hardness, a reactive organic such as an epoxy group or a (meth) acryloyl group. Examples thereof include an alkyl group having 1 to 3 carbon atoms such as a group, a methyl group and an ethyl group, and a vinyl group as an organic group having low reactivity but capable of imparting a low refractive index. Further, it is more preferable that at least a part of the polysiloxane component is a fluorine-containing organic polysiloxane from the viewpoint of enabling a lower refractive index. As a starting material for polysiloxane formation, each compound such as an organic alkoxysilane, an organic acyloxysilane, and an organic halogensilane may be used as it is, but in order to achieve cross-linking at a lower temperature, each compound is hydrolyzed. It is preferable to use it.

[First Embodiment]
Examples of the siloxane resin include a siloxane resin having a fluorine atom, which is a compound represented by the following formula (X1), a compound represented by (X2), a hydrolyzate thereof, a condensate thereof, or a combination thereof. Is preferable. Of these, a hydrolyzed condensate of a siloxane compound containing a compound represented by the following formula (X1) and a compound represented by the following formula (X2) is preferable.

^RX1- Si ( ^RX2 ) _a X _3-a ... (X1)

R ^X1 represents an organic group having a fluorine atom having 1 to 12 carbon atoms (preferably 3-12). The organic group having fluorine is preferably a hydrocarbon group, has an alkyl group having a fluorine atom (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 3 carbon atoms), and having a fluorine atom. Alkyl group having an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 14 carbon atoms, particularly preferably 6 to 10 carbon atoms) and a fluorine atom (preferably 7 to 23 carbon atoms, more preferably 7 to 15 carbon atoms, 7 to 15 carbon atoms). 11 is particularly preferable).
^RX2 represents a hydrocarbon group (preferably an alkyl group or an alkenyl group) having 1 to 12 carbon atoms (preferably 1 to 8, more preferably 1 to 4).
X is a hydrolyzable group. The hydrolyzable group represented by X is an alkoxy group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 3 carbon atoms), an aryloxy group (preferably 6 to 22 carbon atoms, 6 carbon atoms). ~ 14 is more preferable, 6 to 10 is particularly preferable), and an aryloxy group (7 to 23 carbon atoms is preferable, 7 to 15 is more preferable, and 7 to 11 is particularly preferable).
a is 0 or 1.

^RX3 _b- SiR ^X4 _c Y _{4- (b + c)} ... (X2)

R ^X3, R ^X4 are each an alkyl group, an alkenyl group, an aryl group, an epoxy group, glycidoxy group, an amino group, a group having a methacryloxy group or a cyano group. R ^{X3, R X4} is preferably 1 to 24 carbon atoms, more preferably 1 to 12, 1 to 8 especially preferred. However, the minimum carbon number may be set according to each of the above substituents, and the minimum carbon number of the glycidoxy group is 3.
b and c are 0 or 1, and (b + c) is 1 or 2.
Y is a synonym for X.

The compound represented by the formula (X1) is, for example, trifluoroethyltrimethoxysilane, trifluoroethyltriethoxysilane, trifluoroethyltripropoxysilane, trifluoroethyltriisopropoxysilane, trifluoroethyltributoxysilane, tri. Fluoroethyltriacetoxysilane, trifluoropropyltrichlorosilane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, trifluoropropyltripropoxysilane, trifluoropropyltriisopropoxysilane, trifluoropropyltriacetoxysilane, trifluoro Propyltrimethoxyethoxysilane, trifluoropropylmethyldimethoxysilane, trifluoropropylmethyldiethoxysilane, trifluoropropylethyldimethoxysilane, trifluoropropylethyldiethoxysilane, nonafluorobutylethyltrichlorosilane, nonafluorobutylethyltrimethoxysilane , Nonafluorobutylethyltriethoxysilane, nonafluorobutylethyltripropoxysilane, nonafluorobutylethyltriisopropoxysilane, nonafluorobutylethyltriacetoxysilane, nonafluorobutylethyltrimethoxyethoxysilane, nonafluorobutylethylmethyldimethoxysilane , Nonafluorobutylethylmethyldiethoxysilane, nonafluorobutylethylethyldimethoxysilane, nonafluorobutylethylethyldiethoxysilane, tridecafluorooctyltrichlorosilane, tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriethoxysilane, Tridecafluorooctyllipopoxysilane, tridecafluorooctylriisopropoxysilane, tridecafluorooctylriacetoxysilane, tridecafluorooctyltrimethoxyethoxysilane, tridecafluorooctylmethyldimethoxysilane, tridecafluorooctylmethyldiethoxysilane , Tridecafluorooctylethyldimethoxysilane, tridecafluorooctylethyldiethoxysilane, heptadecafluorodecyltrichlorosilane, heptadecafluorodecyltrimethoxysilane, heptadecafluorodecyltriethoxysilane, heptadecafluorodecyltripropoxysilane, hepta Decafluorodecyltriisopropoxysi Orchid, heptadecafluorodecyltributoxysilane, heptadecafluorodecyltriacetoxysilane, heptadecafluorodecyltrimethoxyethoxysilane, heptadecafluorodecylmethyldimethoxysilane, heptadecafluorodecylmethyldiethoxysilane, heptadecafluorodecylethyldimethoxy Examples thereof include bifunctional and trifunctional silane compounds such as silane and heptadecafluorodecylethyldiethoxysilane.

Examples of the compound represented by the formula (X2) include methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, methyltriacetoxysilane, methyltripropoxysilane, methyltributoxysilane, and ethyltrimethoxy. Silane, ethyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octadecyltrichlorosilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, phenyltrichlorosilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, Vinyl trichlorosilane, vinyl trimethoxysilane, vinyl triethoxysilane, vinyl triacetoxysilane, vinyl trimethoxyethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltriacetoxysilane, γ -Methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, N -(Β-Aminoethyl) -γ-aminopropyltrimethoxysilane, β-cyanoethyltriethoxysilane, methyltriphenoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycid Xymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, α-glycid Xipropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycid Xipropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyltrimethoxyethoxysilane, γ-glycidoxypropyltriphenoxysilane, α-gly Sidoxybutyltrimethoxysilane, α-glycidoxybutyl Triethoxysilane, β-glycidoxybutyltrimethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, δ-glycidoxybutyl Trimethoxysilane, δ-glycidoxybutyltriethoxysilane, (3,4-epylcyclohexyl) methyltrimethoxysilane, (3,4-epylcyclohexyl) methyltriethoxysilane, β- (3,4-epylcyclohexyl) Ethyltrimethoxysilane, β- (3,4-epylcyclohexyl) ethyltriethoxysilane, β- (3,4-epylcyclohexyl) ethyltripropoxysilane, β- (3,4-epylcyclohexyl) ethyltributoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxyethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriphenyloxysilane, γ- (3,4-epylcyclohexyl) propyltrimethoxysilane, γ- (3) , 4-epylcyclohexyl) propyltriethoxysilane, δ- (3,4-epoxycyclohexyl) butyltrimethoxysilane, δ- (3,4-epylcyclohexyl) butyltriethoxysilane, 3- (N, N-diglycidyl) Aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, cyanoethyltrichlorosilane, cyanopropyltrichlorosilane, cyanopropyltrimethoxysilane, dimethyldichlorosilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiacetoxysilane, phenyl Methyldimethoxysilane, phenylmethyldiethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-aminopropyl Methyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, glycidoxymethylmethyldimethoxysilane, grease Sidoxymethylmethyldiethoxysilane, α-glycidoxyethylmethyldimethoxysilane, α-glycidoxyethylmethyldier Toxisilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylmethyldiethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyldiethoxysilane, β-glycidoxypropyl Methyldimethoxysilane, β-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-gly Sidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldimethoxyethoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropylmethyldiacetoxysilane, γ-glycidoxypropylethyldimethoxysilane , Γ-Glysidoxypropyl ethyldiethoxysilane, γ-Glysidoxypropylvinyldimethoxysilane, γ-Glysidoxypropylvinyldiethoxysilane, γ-Glysidoxypropylphenyldimethoxysilane, γ-Glysidoxypropylphenyl Diethoxysilane, diethyldichlorosilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldichlorosilane, diphenyldimethoxysilane, diphenyldiethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, cyclohexylmethyldimethoxy Examples thereof include silane, octadecylmethyldimethoxysilane, and octadecylmethyldiethoxysilane.

As for the compound represented by the formula (X1) or (X2), it is not a problem to use not only one kind but also two or more kinds in combination. Further, in such polysiloxane cross-linking, tetrafunctional silane, specifically tetramethoxysilane, tetraethoxysilane, and tetrapropoxy, can be easily increased in surface hardness by being used in combination with other silane compounds. Silane, tetrabutoxysilane, tetraacetoxysilane and the like are also preferably used.

Further, in the present invention, it is desirable that the compound having a perfluoro group and the silica fine particles have a reactive group for reacting with each other. Thereby, the dispersion stability of the silica fine particles can be further improved.

Examples of the acid catalyst used for the hydrolysis reaction of these silane compounds include formic acid, oxalic acid, hydrochloric acid, sulfuric acid, acetic acid, trifluoroacetic acid, phosphoric acid, polyphosphoric acid, polyvalent carboxylic acid or its anhydride, ion exchange resin and the like. Acid catalyst of.

The amount of the acid catalyst added is preferably 0.05 parts by mass to 10 parts by mass, and more preferably 0.1 parts by mass to 5 parts by mass with respect to 100 parts by mass of the total silane compound used. If the amount of acid catalyst is too small, the hydrolysis reaction may not proceed sufficiently. On the contrary, if this is too much, the hydrolysis reaction may proceed excessively.

As the solvent used in the hydrolysis and polycondensation reactions, an organic solvent is preferable, and those described in the section [Solvent] described later can be preferably used.

As the siloxane resin according to the first embodiment, the resin and the preparation method described in JP-A-2007-182511 can be referred to.

[Second Embodiment]
The siloxane resin is preferably a siloxane resin obtained by hydrolyzing and condensing a siloxane compound containing a compound represented by the following formula (1). Further, it is preferable that the compound represented by the formula (1) is hydrolyzed and condensed with the compound represented by the formula (2) or the siloxane compound containing the compound represented by the formula (3). In particular, it is a product obtained by hydrolyzing and condensing a siloxane compound containing a compound represented by the formula (1), a compound represented by the formula (2), and a compound represented by the formula (3). preferable.

(R ¹ ) Si (R ² ) _a (OR ⁶ ) _3-a (1)

R ¹ represents a fluoroalkyl group having 3 to 13 fluorines (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 3 carbon atoms).
R ² represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. As the hydrocarbon group, a C _1-12 alkyl group, a C _2-12 alkenyl group, a C _2-12 alkynyl group, a C _6-10 aryl group and a C _7-11 aralkyl group are preferable, and an alkyl group or an alkenyl group is more preferable.
R ⁶ represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and the hydrocarbon group is a C _1-10 alkyl group, a C _2-10 alkenyl group, a C _2-10 alkynyl group, or a C _6-10 aryl group. , C _7-10 aralkyl group is preferred, and alkyl or alkenyl group is more preferred.
The plurality of R ¹ , R ² , and R ⁶ may be the same or different.
a is 0 or 1.

(R ³ ) _b Si (OR ⁷ ) _4-b (2)

R ³ represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. As the hydrocarbon group, a C _1-12 alkyl group, a C _2-12 alkenyl group, a C _2-12 alkynyl group, a C _6-10 aryl group and a C _7-11 aralkyl group are preferable, and an alkyl group or an alkenyl group is more preferable.
R ⁷ represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. As the hydrocarbon group, a C _1-10 alkyl group, a C _2-10 alkenyl group, a C _2-10 alkynyl group, a C _6-10 aryl group and a C _7-10 aralkyl group are preferable, and an alkyl group or an alkenyl group is more preferable.
The plurality of R ³ and R ⁷ may be the same or different from each other.
b is 0, 1 or 2.

R ⁴ Si (R ⁵ ) _c (OR ⁸ ) _3-c (3)

R ⁴ is an organic group having a (meth) acryloyloxy group, a mercapto group (sulfanyl group), an epoxy group, an oxetane group, a glycidoxy group, a carboxyl anhydride group, an amino group, an isocyanate group, a urea group or a substituent thereof. .. The organic group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms. However, the minimum carbon number may be set according to each of the above substituents, and the minimum carbon number of the glycidoxy group is 3.
R ⁵ represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. As the hydrocarbon group, a C _1-10 alkyl group, a C _2-10 alkenyl group, a C _2-10 alkynyl group, a C _6-10 aryl group and a C _7-10 aralkyl group are preferable, and an alkyl group or an alkenyl group is more preferable.
R ⁸ represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. As the hydrocarbon group, a C _1-10 alkyl group, a C _2-10 alkenyl group, a C _2-10 alkynyl group, a C _6-10 aryl group and a C _7-10 aralkyl group are preferable, and an alkyl group or an alkenyl group is more preferable.
The plurality of R ⁴ , R ⁵ , and R ⁸ may be the same or different, and c is 0 or 1.

Examples of the trifunctional silane compound represented by the formula (1) include trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, and perfluoropropyltri. Methoxysilane, perfluoropropyltriethoxysilane, perfluoropentyltrimethoxysilane, perfluoropentyltriethoxysilane, tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriethoxysilane, tridecafluorooctyl lipoxysilane, trideca Fluorooctyl lysopropoxysilane and the like can be mentioned.

Examples of the bifunctional silane compound represented by the formula (1) include trifluoropropylmethyldimethoxysilane, trifluoropropylmethyldiethoxysilane, trifluoropropylmethyldipropoxysilane, and trifluoropropylmethyldiisopropoxysilane. Trifluoropropylethyldimethoxysilane, trifluoropropylethyldiethoxysilane, trifluoropropylvinyldimethoxysilane, trifluoropropylvinyldiethoxysilane, heptadecafluorodecylmethyldimethoxysilane, tridecafluorooctylmethyldimethoxysilane, tridecafluorooctyl Examples thereof include methyldiethoxysilane, tridecafluorooctylmethyldipropoxysilane, and tridecafluorooctylmethyldiisopropoxysilane.

Examples of the trifunctional silane compound represented by the formula (2) include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, methyltri-n-butoxysilane, and methyltri-t-. Butoxysilane, methyltri-sec-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, butyltrimethoxysilane, pentyltrimethoxysilane, cyclopentyltrimethoxysilane, hexyltrimethoxysilane, cyclohexyltrimethoxysilane, Octadecyltrimethoxysilane, octadecyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriisopropoxysilane, 1-naphthyltrimethoxysilane, 2-naphthyltrimethoxysilane, heptadecafluorodecyltrimethoxysilane, heptadeca Examples thereof include fluorodecyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, p-styryltrimethoxysilane, and allyltrimethoxysilane.

Examples of the bifunctional silane compound represented by the formula (2) include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, methylvinyldimethoxysilane, and methylvinyldiethoxy. Examples thereof include silane and cyclohexylmethyldimethoxysilane. Of these, dimethyldialkoxysilane is preferably used for the purpose of imparting flexibility to the obtained coating film.

Examples of the tetrafunctional silane compound represented by the formula (2) include tetramethoxysilane and tetraethoxysilane.

Examples of the trifunctional silane compound represented by the formula (3) include 3-glycidoxypropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, and γ-acryloyloxy. Trimethoxysilane, γ-acryloyloxypropyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β -Glysidoxyethyl trimethoxysilane, β-glycidoxyethyl triethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β -Glysidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltriisopropoxysilane, γ-glycidoxypropyltri-n-butoxysilane, γ-glycidoxypropyltri-t-butoxysilane, γ-glycidoxypropyltri-sec-butoxysilane, γ-glycidoxypropyltrimethoxysilane, α -Glysidoxybutyltrimethoxysilane, α-glycidoxy-t-butyltriethoxysilane, α-glycidoxy-t-butyltriethoxysilane, α-glycidoxy-t-butyltriethoxysilane, β-glycidoxybutyltrimethoxy Silane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, δ-glycidoxybutyltrimethoxysilane, δ-glycidoxybutyltriethoxysilane Silane, (3,4-epylcyclohexyl) methyltrimethoxysilane, (3,4-epylcyclohexyl) methyltriethoxysilane, 2- (3,4-epylcyclohexyl) ethyltrimethoxysilane, 2- (3,4-) Epoxycyclohexyl) ethyltriethoxysilane, 2- (3,4-epylcyclohexyl) ethyltripropoxysilane, 2- (3,4-epylcyclohexyl) ethyltri-t-butoxysilane, 2- (3,4-epylcyclohexyl) Ethyltri-n-butoxysilane, 2- (3,4- Epoxycyclohexyl) ethyltri-sec-butoxysilane, 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane, 3- (3,4-epoxycyclohexyl) propyltriethoxysilane, 4- (3,4-epoxycyclohexyl) Butyltrimethoxysilane, 4- (3,4-epylcyclohexyl) butyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-mercaptopropyltri Examples thereof include methoxysilane, 3-isopropylpropyltriethoxysilane, 3-trimethoxysilylpropylsuccinate anhydride, 3-ureidopropyltriethoxysilane, and the like.

Examples of the bifunctional silane compound represented by the formula (3) include γ-glycidoxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyldiethoxysilane, and γ-methacryloxy. Propylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, glycidoxymethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, α-glycidoxyethylmethyldimethoxysilane, α-glycidoxyethylmethyldiethoxy Silane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylmethyldiethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyldiethoxysilane, β-glycidoxypropyl Methyldimethoxysilane, β-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, β-gly Sidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldimethoxyethoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylvinyldimethoxysilane, Examples thereof include γ-glycidoxypropyl vinyldiethoxysilane and 3-methacryloxypropyldimethoxysilane.

The conditions such as the catalyst and the solvent for synthesizing the siloxane resin are the same as those in the first embodiment.

The amount of the solvent used in the synthesis of the siloxane resin is preferably added in the range of 50 parts by mass to 500 parts by mass, particularly preferably 80 parts by mass to 200 parts by mass, based on 100 parts by mass of the total of all silane compounds. It is in the range of parts by mass. The water used for hydrolysis is preferably purified water such as distilled water. The amount of water can be arbitrarily selected, but it is preferably used in the range of 1.0 to 4.0 mol per 1 mol of the silane compound.
For the siloxane resin of the second embodiment, the description in JP2013-014680 can be referred to.

[Surfactant]
It is preferable that a surfactant is applied to the composition for forming an optical functional layer of the present invention. As the surfactant, any of a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant may be used. Among these, nonionic surfactants are preferable, and fluorine-based surfactants are particularly preferable.

In the present invention, it is preferable to contain a surfactant having a polyoxyalkylene structure. The polyoxyalkylene structure refers to a structure in which an alkylene group and a divalent oxygen atom are present adjacent to each other, and specific examples thereof include an ethylene oxide (EO) structure and a propylene oxide (PO) structure. .. The polyoxyalkylene structure may constitute a graft chain of an acrylic polymer.

When the surfactant is a polymer compound, the molecular weight is preferably 2000 or more, more preferably 7500 or more, and particularly preferably 12500 or more. The upper limit is preferably 50,000 or less, more preferably 25,000 or less, and particularly preferably 17,500 or less.

In the present invention, the molecular weight of the polymer compound (polymer) refers to the weight average molecular weight unless otherwise specified, and the value measured by gel permeation chromatography (GPC) in terms of standard polystyrene is adopted. The measuring device and measuring conditions are basically based on the following condition 1, and it is allowed to be set to condition 2 depending on the solubility of the sample and the like. However, depending on the polymer species, an appropriate carrier (eluent) and a column suitable for the carrier may be selected and used as appropriate.
(Condition 1)
Column: TOSOH TSKgel Super HZM-H,
TOSOH TSKgel Super HZ4000,
TOSOH TSKgel Super HZ2000
Carrier using a column connected to: tetrahydrofuran Measurement temperature: 40 ° C
Carrier flow rate: 1.0 ml / min
Sample concentration: 0.1% by mass
Detector: RI (refractive index) detector (condition 2)
Column: Tosoh TSKgel Super AWM-H Connecting two carriers: 10 mM LiBr / N-methylpyrrolidone Measurement temperature: 40 ° C.
Carrier flow rate: 1.0 ml / min
Sample concentration: 0.1% by mass
Detector: RI (refractive index) detector

The fluorine-based surfactant is preferably a polymer surfactant having a polyethylene main chain. Of these, a polymer surfactant having a poly (meth) clearing structure is preferable. In addition, poly (meth) clearate is a general term for polyacrylate and polymethacrylate. Among them, in the present invention, a copolymer of the (meth) acrylate structural unit having the polyoxyalkylene structure and the fluoroalkyl acrylate structural unit is preferable.

Alternatively, as the fluorine-based surfactant, a compound having a fluoroalkyl group or a fluoroalkylene group (preferably 1 to 24 carbon atoms, more preferably 2 to 12 carbon atoms) at any site can be preferably used. Preferably, a polymer compound having the above fluoroalkyl group or fluoroalkylene group in the side chain can be used. The fluorine-based surfactant preferably has the above-mentioned polyoxyalkylene structure, and more preferably has a polyoxyalkylene structure in the side chain.

Examples of the fluorine-based surfactant include Megafuck F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F479, and F482. F554, F780 (above, DIC Co., Ltd.), Florard FC430, FC431, FC171 (above, Sumitomo 3M Ltd.), Surfron S-382, S-141, S-145, same SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, KH-40 (all manufactured by Asahi Glass Co., Ltd.), F. Top EF301, EF303, EF351, EF352 (all manufactured by Gemco Co., Ltd.), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA) and the like can be mentioned.
Further, the compound represented by the following formula is also exemplified as a suitable fluorine-based surfactant. The weight average molecular weight of the compound represented by the following formula is not limited to this, and for example, 14000 can be used.

Specifically, as the nonionic surfactant, glycerol, trimethylolpropane, ethoxylate and propoxylate of trimethylolethane (for example, glycerolpropoxylate, glycerin ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, etc. Polyoxyethylene oleyl ether (Emargen 404 manufactured by Kao Co., Ltd.), polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, ELEBASE manufactured by Aoki Oil & Fat Industry Co., Ltd. BUB-3 and the like can be mentioned.

Specifically, as anionic surfactants, W004, W005, W017 (manufactured by Yusho Co., Ltd.), EMULSOGEN COL-020 manufactured by Clariant Japan Co., Ltd., EMULSOGEN COA-070, EMULSOGEN COL-080, Dai-ichi Kogyo Seiyaku Co., Ltd. Examples thereof include Clariant A208B manufactured by Co., Ltd.

A cationic surfactant generally has a plurality of cationic groups and hydrophobic portions which are hydrophilic portions in the same molecule. Examples of the cationic group in the hydrophilic part include an amino group or a salt thereof, a quaternary ammonium group or salt, a hydroxyammonium group or salt, an etherammonium group or salt, a pyridinium group or salt, an imidazolium group or salt, an imidazoline group or a salt. , Phosphonium groups or salts and the like. Examples of the cationic surfactant include a quaternary ammonium salt-based surfactant, an alkylpyridium-based surfactant, and a polyallylamine-based surfactant.

Examples of the silicone-based surfactant include "Torre Silicone DC3PA", "Torre Silicone SH7PA", "Torre Silicone DC11PA", "Torre Silicone SH21PA", "Torre Silicone SH28PA" and "Torre Silicone SH28PA" manufactured by Toray Dow Corning Co., Ltd. Silicone SH29PA "," Torre Silicone SH30PA "," Torre Silicone SH8400 "," TSF-4440 "," TSF-4300 "," TSF-4445 "," TSF-4460 "," TSF "manufactured by Momentive Performance Materials. -4452 ", Shinetsu Silicone Co., Ltd." KP341 "," KF6001 "," KF6002 ", Big Chemie", "BYK307", "BYK323", "BYK330", GELEST "DBE-224", "DBE-621", etc. Can be mentioned.

The lower limit of the amount of the surfactant added is preferably 0.1 part by mass or more with respect to 100 parts by mass of SiO ₂ minutes containing the silica fine particles described above, and is 1 part by mass or more. More preferably, 2 parts by mass or more is particularly preferable. The upper limit is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and particularly preferably 10 parts by mass or less.
The content of the surfactant in the composition for forming an optical functional layer of the present invention is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, based on the solid content in the composition. 1% by mass or more is particularly preferable. The upper limit is preferably 1% by mass or less, more preferably 0.75% by mass or less, and particularly preferably 0.5% by mass or less.
Only one type of surfactant may be used, or two or more types may be combined.

[Dispersant]
In the present invention, it is also preferable to use a dispersant in the composition for forming an optical functional layer.
As the dispersant, a polymer dispersant (for example, polyamide amine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth) acrylic) Copolymers, naphthalene sulfonic acid formarin condensates), polyoxyethylene alkyl phosphates, polyoxyethylene alkyl amines, alkanolamines, pigment derivatives and the like.
Polymer dispersants can be further classified into linear polymers, terminally modified polymers, graft-type polymers, and block-type polymers based on their structures.

The polymer dispersant adsorbs to the surface of the particles and acts to prevent reaggregation. Therefore, a terminal-modified polymer, a graft polymer, and a block polymer having an anchor site on the particle surface are preferable structures. On the other hand, the pigment derivative has the effect of promoting the adsorption of the polymer dispersant by modifying the particle surface.

Specific examples of the dispersant that can be used in the present embodiment include "Disperbyk-101 (polyamide amine phosphate), 107 (carboxylic acid ester), 110 (copolymer containing an acid group), 130 (polypolymer) manufactured by BYK Chemie. ), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer) "," BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid), BYK2001 "," EFKA4047, 4050, manufactured by EFKA. , 4010, 4165 (polyurethane type), EFKA4330, 4340 (block copolymer), 4400, 4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylic acid salt), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative) ", Ajinomoto Fan Techno Co., Ltd." Azisper PB821, PB822 ", Kyoeisha Chemical Co., Ltd." Floren TG-710 (urethane oligomer) "," Polyflow No. 50E, No. 300 (Acrylic copolymer) ”, Kusumoto Kasei Co., Ltd.“ Disparon KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyether ester), DA-703-50, DA- 705, DA-725 ", Kao" Demor RN, N (naphthalene sulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate) "," Homogenol L-18 ( "High molecular weight polycarboxylic acid)", "Emargen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether)", "Acetamine 86 (stearylamine acetate)", "Solsperse 5000 (phthalocyanine derivative)" manufactured by Lubrizol, 22000 (Azo pigment derivative), 13240 (polyesteramine), 3000, 17000, 27000 (polymer having a functional part at the end), 24000, 28000, 32000, 38500 (graft type polymer) ", Nikko Chemical Co., Ltd." Nikkor Examples thereof include T106 (polyoxyethylene sorbitan monoolate) and MYS-IEX (polyoxyethylene monostearate).

The concentration of the dispersant is preferably 1 to 100 parts by mass, more preferably 3 to 100 parts by mass, and even more preferably 5 to 80 parts by mass with respect to 100 parts by mass of SiO 2 containing silica fine particles. Further, it is preferably 1 to 30% by mass with respect to the total solid content of the composition.
These dispersants may be used alone or in combination of two or more.

[solvent]
The composition for forming an optical functional layer of the present invention may contain the solvent used as the preparation solvent for the siloxane resin, or may further contain other solvents. Examples of the solvent contained in the composition include organic solvents (aliphatic compounds, halogenated hydrocarbon compounds, alcohol compounds, ether compounds, ester compounds, ketone compounds, nitrile compounds, amide compounds, sulfoxide compounds, aromatic compounds) or Water is mentioned. Each example is listed below.
・ Aliper compounds hexane, heptane, cyclohexane, methylcyclohexane, octane, pentane, cyclopentane, etc. ・ Halogenated hydrocarbon compounds Methylene chloride, chloroform, dichloromethane, ethane dichloride, carbon tetrachloride, trichloroethylene, tetrachlorethylene, epichlorohydrin, Monochlorobenzene, orthodichlorobenzene, allyl chloride, HCFC, methyl monochloroacetate, ethyl monochloroacetate, trichloroacetic acid monochloroacetate, methyl bromide, methyl iodide, tri (tetra) chloroethylene, etc.-Alcohol compounds Methyl alcohol, ethyl alcohol, 1- Propyl alcohol, 2-propyl alcohol, 2-butanol, ethylene glycol, propylene glycol, glycerin, 1,6-hexanediol, cyclohexanediol, sorbitol, xylitol, 2-methyl-2,4-pentanediol, 1,3-butane Diore, 1,4-butanediol, diacetone alcohol, etc. ・ Ether compounds (including hydroxyl group-containing ether compounds)
Dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, t-butyl methyl ether, cyclohexyl methyl ether, anisole, tetrahydrofuran, alkylene glycol alkyl ether (ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol, dipropylene glycol, propylene glycol monomethyl ether) , Diethylene glycol monomethyl ether, triethylene glycol, polyethylene glycol, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether, etc.)-Ester compounds Ethyl acetate, ethyl lactate, 2- (1-methoxy) propyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl acetate, ethyl 3-ethoxypropionate, γ-butyrolactone, etc.-Ketone compounds Acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, etc.-nitrile Compounds acetonitrile, etc. Amide compounds N, N-dimethylformamide, 1-methyl-2-pyrrolidone, 2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, 2-pyrrolidinone, ε-caprolactam, formamide, N-methyl Formamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropanamide, hexamethylphosphoric triamide, etc.-Sulfoxide compound, dimethylsulfoxide, etc.-Aromatic compound benzene, toluene, etc. Among the preferred solvents. Examples thereof include methyl alcohol, ethyl alcohol, 2-propyl alcohol, propylene glycol monomethyl ether, ethyl lactate, propylene glycol-1-monomethyl ether-2-acetate, ethyl 3-ethoxypropionate and cyclohexanone.

The amount of the solvent used is not particularly limited, but is preferably 0.1 times (v / w) or more, and 0.5 times (v / w) or more, based on the total amount of the SiO ₂ minutes containing the silica fine particles. ) Or more, preferably 1 time amount (v / w) or more, and more preferably 2 times amount (v / w) or more. The upper limit is preferably 30 times the amount (v / w) or less, and more preferably 10 times the amount (v / w) or less.

[Adhesion improver]
The composition for forming an optical functional layer of the present invention may further contain an adhesion improver. As the adhesion improver, for example, the adhesion improvers described in JP-A-5-11439, JP-A-5-341532, JP-A-6-43638 and the like are preferable. Specifically, benzimidazole, benzoxazole, benzthiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzthiazole, 3-morpholinomethyl-1-phenyl-triazole-2-thione, 3-morpholino Methyl-5-phenyl-oxadiazole-2-thione, 5-amino-3-morpholinomethyl-thiadiazole-2-thione, and 2-mercapto-5-methylthio-thiadiazole, triazole, tetrazole, benzotriazole, carboxybenzotriazole , Amino group-containing benzotriazole, silane coupling agent and the like. As the adhesion improver, a silane coupling agent is preferable.

The silane coupling agent preferably has an alkoxysilyl group as a hydrolyzable group that can be chemically bonded to the inorganic material. Further, it is preferable to have a group that exhibits affinity by interacting or forming a bond with an organic resin, and such a group has a (meth) acryloyl group, a phenyl group, a mercapto group, a glycidyl group, and an oxetanyl group. Those having a (meth) acryloyl group or a glycidyl group are preferable.

The silane coupling agent is preferably a silane compound having at least two different reactive functional groups in one molecule, and particularly preferably one having an amino group and an alkoxy group as functional groups. Examples of such a silane coupling agent include N-β-aminoethyl-γ-aminopropyl-methyldimethoxysilane (trade name KBM-602 manufactured by Shin-Etsu Chemical Industry Co., Ltd.) and N-β-aminoethyl-γ-amino. Propyl-trimethoxysilane (trade name KBM-603 manufactured by Shin-Etsu Chemical Industry Co., Ltd.), N-β-aminoethyl-γ-aminopropyl-triethoxysilane (trade name KBE-602 manufactured by Shin-Etsu Chemical Industry Co., Ltd.), γ-aminopropyl -Trimethoxysilane (trade name KBM-903 manufactured by Shin-Etsu Chemical Industry Co., Ltd.), γ-aminopropyl-triethoxysilane (trade name KBE-903 manufactured by Shin-Etsu Chemical Industry Co., Ltd.), 3-methacryloyloxypropyltrimethoxysilane (Shin-Etsu Chemical Industry Co., Ltd.) Company-made product name KBM-503), etc.

Specific examples of the silane coupling agent include, but are not limited to, the following compounds.

Ｅｔ：エチル基

Et: Ethyl group

The content of the adhesion improver is preferably 0.001% by mass to 20% by mass, more preferably 0.01 to 10% by mass, and 0.1% by mass to 5% by mass with respect to the solid content of the composition of the present invention. % Is particularly preferable.

In the present specification, the indication of a compound (for example, when referred to as a compound at the end) is used to mean that the compound itself, its salt, and its ion are included. In addition, it is meant to include a derivative in which a part is changed such as introducing a substituent within a range in which a desired effect is obtained.
Substituents (same for linking groups) for which substitution / non-substitution is not specified in the present specification means that the group may have any substituent. This is also synonymous with compounds that do not specify substitution / non-substitution. Preferred substituents include the following substituent T.
Examples of the substituent T include the following.
Alkyl groups (preferably alkyl groups having 1 to 20 carbon atoms, such as methyl, ethyl, isopropyl, t-butyl, pentyl, heptyl, 1-ethylpentyl, benzyl, 2-ethoxyethyl, 1-carboxymethyl, etc.), alkenyl Groups (preferably alkoxy groups having 2 to 20 carbon atoms, such as vinyl, allyl, oleyl, etc.), alkynyl groups (preferably, alkynyl groups having 2 to 20 carbon atoms, such as ethynyl, butadynyl, phenylethynyl, etc.), Cycloalkyl groups (preferably cycloalkyl groups having 3 to 20 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, etc.), aryl groups (preferably aryl groups having 6 to 26 carbon atoms, for example, Phenyl, 1-naphthyl, 4-methoxyphenyl, 2-chlorophenyl, 3-methylphenyl, etc.), heterocyclic group (preferably heterocyclic group having 2 to 20 carbon atoms, preferably at least one oxygen atom, sulfur atom , A 5- or 6-membered heterocyclic group having a nitrogen atom is preferred, for example, tetrahydropyran, tetrahydrofuran, 2-pyridyl, 4-pyridyl, 2-imidazolyl, 2-benzoimidazolyl, 2-thiazolyl, 2-oxazolyl, etc.), Alkoxy groups (preferably alkoxy groups having 1 to 20 carbon atoms, such as methoxy, ethoxy, isopropyloxy, benzyloxy, etc.), aryloxy groups (preferably aryloxy groups having 6 to 26 carbon atoms, such as phenoxy, 1-naphthyloxy, 3-methylphenoxy, 4-methoxyphenoxy, etc.), alkoxycarbonyl group (preferably alkoxycarbonyl group having 2 to 20 carbon atoms, such as ethoxycarbonyl, 2-ethylhexyloxycarbonyl, etc.), aryloxycarbonyl Groups (preferably aryloxycarbonyl groups with 6 to 26 carbon atoms, such as phenoxycarbonyl, 1-naphthyloxycarbonyl, 3-methylphenoxycarbonyl, 4-methoxyphenoxycarbonyl, etc.), amino groups (preferably 0 carbon atoms). It contains ~ 20 amino groups, alkylamino groups, arylamino groups, for example, amino, N, N-dimethylamino, N, N-diethylamino, N-ethylamino, anilino, etc.), sulfamoyl group (preferably number of carbon atoms). 0 to 20 sulfamoyl groups, such as N, N-dimethylsulfamoyl, N-phenylsulfamoyl, etc.), acyl groups (Preferably an acyl group having 1 to 20 carbon atoms, such as acetyl, propionyl, butyryl, etc.), an aryloyl group (preferably an aryloyl group having 7 to 23 carbon atoms, such as benzoyl), an acyloxy group (preferably carbon). Acyloxy groups having 1 to 20 atoms, such as acetyloxy, allyloyloxy groups (preferably allyloxy groups having 7 to 23 carbon atoms, such as benzoyloxy), carbamoyl groups (preferably having carbon atoms). 1 to 20 carbamoyl groups, such as N, N-dimethylcarbamoyl, N-phenylcarbamoyl, etc.), acylamino groups (preferably acylamino groups having 1 to 20 carbon atoms, such as acetylamino, benzoylamino, etc.), alkylthio groups. (Preferably an alkylthio group having 1 to 20 carbon atoms, for example, methylthio, ethylthio, isopropylthio, benzylthio, etc.), an arylthio group (preferably an arylthio group having 6 to 26 carbon atoms, for example, phenylthio, 1-naphthylthio, 3 -Methylphenylthio, 4-methoxyphenylthio, etc.), alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 20 carbon atoms, for example, methylsulfonyl, ethylsulfonyl, etc.), arylsulfonyl group (preferably 6 carbon atoms). ~ 22 arylsulfonyl groups (eg, benzenesulfonyl, etc.), alkylsilyl groups (preferably alkylsilyl groups with 1 to 20 carbon atoms, such as monomethylsilyl, dimethylsilyl, trimethylsilyl, triethylsilyl, etc.), arylsilyl groups (preferably preferably an aryl silyl group 6-42 carbon atoms, for example, triphenylsilyl, etc.), a phosphoryl group (preferably a phosphate group 0-20 carbon atoms, for ^{example, -OP (= O) (R} P) 2 ), a phosphonyl group (preferably a phosphonyl group having 0-20 carbon atoms, for ^{example, -P (= O) (R} P) 2), a phosphinyl group (preferably a phosphinyl group having 0 to 20 carbon atoms, e.g., - Examples thereof include P ( ^RP ) ₂ ), (meth) acryloyl group, (meth) acryloyloxy group, hydroxyl group, cyano group and halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom and the like).
Further, each group listed in these substituents T may be further substituted with the above-mentioned substituent T.
When the compound, substituent, linking group, etc. contains an alkyl group / alkylene group, an alkenyl group / alkenylene group, an alkynyl group / an alkynylene group, etc., these may be cyclic or chain-like, or may be linear or branched. , It may be substituted or not substituted as described above.
Each substituent specified in the present specification may be substituted via the following linking group L as long as the effect of the present invention is exhibited. For example, the alkyl group / alkylene group, the alkenyl group / alkenylene group and the like may further have the following heterolinking group interposed in the structure.
Examples of the linking group L include a hydrocarbon linking group [alkylene group having 1 to 10 carbon atoms (more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms) and alkenylene group having 2 to 10 carbon atoms (more preferably carbon). Alquinylene group having 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms (more preferably 2 to 6 carbon atoms, further preferably 2 to 4 carbon atoms), and an arylene group having 6 to 22 carbon atoms (more preferable). Has 6 to 10 carbon atoms], heterolinking group [carbonyl group (-CO-), thiocarbonyl group (-CS-), ether group (-O-), thioether group (-S-), imino group (-) NR ^N -), imine linking group ^{(R N -N = C <,} - N = C (R N) -) ], or a linking group is preferably a combination thereof. In the case of condensation to form a ring, the above-mentioned hydrocarbon linking group may be linked by appropriately forming a double bond or a triple bond. As the ring to be formed, a 5-membered ring or a 6-membered ring is preferable. As the 5-membered ring, a nitrogen-containing 5-membered ring is preferable, and examples of the compounds forming the ring include pyrrole, imidazole, pyrazole, indazole, indole, benzimidazole, pyrrolidine, imidazolidine, pyrazole, indolin, carbazole, or these. Derivatives of. Examples of the 6-membered ring include piperidine, morpholine, piperazine, and derivatives thereof. When an aryl group, a heterocyclic group and the like are contained, they may be monocyclic or condensed, and may be similarly substituted or unsubstituted.
^RN is a hydrogen atom or a substituent. As the substituent, an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 1 to 6 carbon atoms, particularly preferably 1 to 3 carbon atoms), an alkenyl group (preferably 2 to 24 carbon atoms, 2). ~ 12 is more preferable, 2 to 6 is further preferable, 2 to 3 is particularly preferable), an alkynyl group (2 to 24 carbon atoms is preferable, 2 to 12 is more preferable, 2 to 6 is further preferable, and 2 to 3 is preferable. (Preferably), aralkyl group (preferably 7 to 22 carbon atoms, more preferably 7 to 14 carbon atoms, particularly preferably 7 to 10), aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 14 carbon atoms, 6 to 14 carbon atoms). 10 is particularly preferable).
^RP is a hydrogen atom, a hydroxyl group, or a substituent. As the substituent, an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 1 to 6 and particularly preferably 1 to 3 carbon atoms), an alkenyl group (preferably 2 to 24 carbon atoms, 2). ~ 12 is more preferable, 2 to 6 is more preferable, 2 to 3 is particularly preferable), an alkynyl group (2 to 24 carbon atoms is preferable, 2 to 12 is more preferable, 2 to 6 is further preferable, and 2 to 3 is preferable. 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 preferable), an alkoxy group (1 to 24 carbon atoms is preferable, 1 to 12 is more preferable, 1 to 6 is more preferable, 1 to 3 is particularly preferable), and an alkenyloxy group (2 to 24 carbon atoms is preferable). , 2-12 are more preferred, 2-6 are even more preferred, 2-3 are particularly preferred), alkynyloxy groups (2-24 carbon atoms are preferred, 2-12 are more preferred, 2-6 are even more preferred, 2 ~ 3 is particularly preferable), an aralkyloxy group (7 to 22 carbon atoms is preferable, 7 to 14 is more preferable, 7 to 10 is particularly preferable), an aryloxy group (6 to 22 carbon atoms is preferable, 6 to 14 is preferable). More preferably, 6 to 10 is particularly preferable).
In the present specification, the number of atoms constituting the linking group is preferably 1 to 36, more preferably 1 to 24, further preferably 1 to 12, and 1 to 6. Is particularly preferable. The number of connecting atoms of the linking group is preferably 10 or less, and more preferably 8 or less. The lower limit is 1 or more. The number of connected atoms is the minimum number of atoms that are located in a path connecting predetermined structural parts and are involved in the connection. For _example, -CH 2 -C (= O) For -O-, number of atoms constituting the linking group is a 6, the number of connecting atoms is three.
Specific examples of the combination of linking groups include the following. Oxycarbonyl group (-OCO-), carbonate group (-OCOO-), amide group (-CONH-), urethane group (-NHCOO-), urea group (-NHCONH-), (poly) alkyleneoxy group (-(poly) Lr-O) _x- ), carbonyl (poly) oxyalkylene group (-CO- (O-Lr) _x- , carbonyl (poly) alkyleneoxy group (-CO- (Lr-O) _x- ), carbonyloxy ( Poly) alkyleneoxy group (-COO- (Lr-O) _x- ), (poly) alkyleneimino group (-(Lr-NR ^N ) _x ), alkylene (poly) iminoalkylene group (-Lr- (NR ^N- ) Lr) _x- ), carbonyl (poly) iminoalkylene group (-CO- (NR ^N- Lr) _x- ), carbonyl (poly) alkyleneimino group (-CO- (Lr-NR ^N ) _x- ), (poly) ) Ester group (-(COO-Lr) _x -,-(O-CO-Lr) _x -,-(O-Lr-CO) _x -,-(Lr-CO-O) _x -,-(Lr-) _{O-CO) x -),} ( poly) amide group _{^{(- (CO-NR N -Lr}} ) x -, - (NR N -CO-Lr) x -, - (NR N -Lr-CO) x -, -(Lr-CO-NR ^N ) _x -,-(Lr-NR ^N CO) _x- ), etc. x is an integer of 1 or more, preferably 1 to 500, and more preferably 1 to 100.
Lr is preferably an alkylene group, an alkenylene group, or an alkynylene group. The carbon number of Lr is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3. A plurality of Lr and ^{R N, R P,} x, etc. need not be the same. The orientation of the linking group is not limited by the above description, and the orientation may be appropriately understood according to a predetermined chemical formula.

[Filter filtration]
The composition for forming an optical functional layer of the present invention is preferably filtered with a filter for the purpose of removing foreign substances and reducing defects. Anything that has been conventionally used for filtration or the like can be used without particular limitation. Examples thereof include a filter made of a fluororesin such as PTFE (polytetrafluoroethylene), a polyamide resin such as nylon, and a polyolefin resin (including high density and ultrahigh molecular weight) such as polyethylene and polypropylene (PP). Among these materials, polypropylene (including high-density polypropylene) and nylon are preferable.
The pore size of the filter is preferably about 0.1 to 7 μm, preferably about 0.2 to 2.5 μm, more preferably about 0.2 to 1.5 μm, and further preferably about 0.3 to 0.7 μm. is there. Within this range, it is possible to more reliably remove fine foreign substances such as impurities and agglomerates while suppressing filtration clogging.
When using filters, different filters may be combined. At that time, the filtering by the first filter may be performed only once or twice or more. When filtering is performed twice or more by combining different filters, it is preferable that the pore diameters of the second and subsequent times are the same or larger than the pore diameter of the first filtering. Further, first filters having different pore diameters within the above-mentioned range may be combined. For the hole diameter here, the nominal value of the filter manufacturer can be referred to. As 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 Nippon Microlith Co., Ltd.), KITZ Micro Filter Co., Ltd., and the like. ..
As the second filter, one formed of the same material as the first filter described above can be used. The pore size of the second filter is preferably about 0.2 to 10.0 μm, preferably about 0.2 to 7.0 μm, and more preferably about 0.3 to 6.0 μm. Within this range, foreign substances mixed in the mixed solution can be removed while the component particles contained in the mixed solution remain.
For example, the filtering with the first filter may be performed only with the dispersion liquid, and after mixing the other components, the filtering with the second filter may be performed.

[Formation of optical functional layer]

The composition for forming an optical functional layer of the present invention preferably uses this to form an optical functional layer applied to optical products and the like. In the present invention, the method for applying the composition for forming an optical functional layer on the support is preferably a coating method. Specifically, various coating methods such as slit coating, inkjet method, rotary coating, cast coating, roll coating, and screen printing method can be applied. The optical functional layer is preferably formed by curing a composition for forming an optical functional layer containing silica fine particles and a specific resin. As the support, for example, a substrate for a solid-state image sensor in which an image sensor (light receiving element) such as a CCD (Charge Coupled Device) or CMOS (Complementary Metal-Oxide Semiconductor) is provided on a substrate (for example, a silicon substrate) is used. be able to. A light-shielding film may be provided between the image pickup devices on the solid-state image sensor substrate or on the back surface of the solid-state image sensor substrate. Further, if necessary, an undercoat layer may be provided on the support for improving adhesion with the upper layer, preventing diffusion of substances, or flattening the surface of the substrate.

-Pre-baking step The composition layer for forming an optical functional layer applied on the support can be dried (pre-baked) in a hot plate, an oven or the like at a temperature of 50 ° C. to 200 ° C. in 10 seconds to 300 seconds.

-Post-baking In the present embodiment, it is preferable to perform heat treatment (post-baking) next. The heating temperature is preferably 350 ° C. or lower, more preferably 300 ° C. or lower, and even more preferably 250 ° C. or lower. There is no particular lower limit, but in consideration of efficient and effective treatment, it is preferable to perform a thermosetting treatment at 50 ° C. or higher, and more preferably 100 ° C. or higher. The post-baking time is preferably 1 to 20 minutes.
This heat treatment can be performed continuously or in batch by using a heating means such as a hot plate, a convection oven (hot air circulation type dryer), or a high frequency heater so that the coating film meets the above conditions. Atmospheric conditions and the like are not particularly limited, and for example, treatment may be performed in the atmosphere.

[Optical functional layer]
The refractive index of the optical functional layer formed by the composition for forming an optical functional layer of the present invention is 1.3 or less, and particularly preferably 1.28 or less. It is practical that the lower limit is 1.1 or more. Unless otherwise specified, the refractive index of the film in the present specification shall be based on the conditions described in Examples described later.

The thickness of the optical functional layer is preferably 5 μm or less, more preferably 3 μm or less, and particularly preferably 1.5 μm or less. There is no particular lower limit, but it is practical that it is 50 nm or more.
In the present invention, the film thickness of the test piece is measured by microscopic observation according to JIS K5600-1-7: 2014 5.4 “Optical method”. Five test pieces are prepared for each level, two points are measured for each, and a total of 10 points are measured, and the average value is adopted.

[Adhesion processing]
In the present invention, it is preferable to apply a surface adhesion treatment to the above optical functional layer. For example, it is preferable that after the optical functional layer is formed, the surface thereof is subjected to an adhesion treatment to obtain a hydrophobic surface. Next, the procedure is to apply a resist.
As the adhesion treatment, for example, the HMDS treatment can be mentioned. HMDS (hexamethyldisilazane) is used for this treatment. When HMDS is applied to, for example, the above-mentioned layer containing SiO ₂ , it is considered that it reacts with the Si—OH bond existing on the surface of the layer to form Si—O—Si (CH ₃ ) ₃ . Thereby, the membrane surface can be made hydrophobic. By making the surface of the optical functional layer hydrophobic in this way, it is possible to prevent the invasion of the developing solution and suppress / prevent damage in the subsequent step of patterning the resist.

[Micro lens unit]
The microlens unit, which is a preferred embodiment of the present invention, has a laminated structure including the above optical functional layer and a microlens coated therein. This microlens unit is incorporated in a solid-state image sensor (optical device).

[Solid image sensor]
In the solid-state image sensor according to the preferred embodiment of the present invention, the optical functional layer formed by the composition for forming the optical functional layer is formed of an antireflection film or an interlayer film on a microlens, a partition wall of a color filter, or a color filter layer. It can be applied to the grid structure arranged in the frame and the color filter layer. The structure of the solid-state image sensor is composed of, for example, a light receiving element (photodiode) provided on a silicon substrate, a lower flattening film, a color filter, an upper flattening film, a microlens, and the like. The color filter is composed of red (R), green (G), and blue (B) color filter pixel portions. The color filter is composed of a plurality of green pixel portions arranged two-dimensionally. Each colored pixel portion is formed at a position above the light receiving element. The green pixel portion is formed in a Bayer pattern (checkerboard pattern), and the blue pixel portion and the red pixel portion are formed between the green pixel portions.
The flattening film is formed so as to cover the upper surface of the color filter, and flattens the surface of the color filter. The microlens is a condensing lens arranged with the convex surface facing up, and is provided above the flattening film and above the light receiving element. That is, the microlens, the color filter pixel portion, and the light receiving element are arranged in series along the incident direction of the light, and the structure is such that the light from the outside is efficiently guided to each light receiving element. Although detailed description of the light receiving element and the microlens will be omitted, those usually applied to this type of product can be appropriately used.
The optical functional layer formed of the composition of the present invention can be suitably applied to the above-mentioned solid-state image sensor.

The composition for forming an optical functional layer of the present invention is suitably used for display panels, solar cells, optical lenses, camera modules, sensor modules and the like. More specifically, in the above-mentioned solar cell or the like, an optical functional layer for preventing reflection of incident light, or an optical functional layer for forming an interlayer film or the like using a difference in refractive index used in a sensor, a camera module, or the like. It is also useful as a forming composition.

[Grid structure]
Examples of the grid structure (partition wall) arranged in the color filter layer include the exemplary structures of JP2012-227478, JP2010-02323537, and JP2009-11125. One embodiment is shown below. In the solid-state image sensor according to the present embodiment, a semiconductor substrate in which a photodiode is formed as a light receiving portion, an insulating film formed on the semiconductor substrate, and a position corresponding to an adjacent photodiode on the insulating film stand. It has a partition wall provided. Further, the solid-state image sensor is formed on a color filter formed on the insulating film between adjacent partition walls, an adhesion layer extending from the upper surface of the partition wall and the side surface of the partition wall onto the insulating film, and a color filter. Equipped with a microlens. Wiring is embedded in the insulating film, and these laminates correspond to the wiring layer. When the partition wall is viewed in a plan view, it has a grid pattern, and a color filter is formed in the square opening of the partition wall. Here, there are three types of color filters, red (R), green (G), and blue (B), and they are arranged in Bayer, for example.

[Picture frame structure]
Examples of the frame structure around the color filter of the present embodiment include an exemplary structure of JP-A-2014-048596. In the present embodiment, a transparent substrate made of a glass substrate is used as a base material, and a colored layer of each color for a color filter and a light-shielding portion for pixel classification are arranged in a display area on one surface side of the base material. Moreover, a light-shielding frame portion is provided as a non-display area outside the display area, and a protective layer is arranged flatly so as to cover the colored layer of the display area and the frame portion.

Next, the present invention will be described with reference to examples, but the present invention is not limited thereto. The amount and ratio specified in the examples are based on mass unless otherwise specified.

Test 101
Silica fine particles (PL-2L-IPA, manufactured by Fuso Chemical Industry Co., Ltd., solid content concentration 24.9% by mass) 200.0 g, methyltrimethoxysilane 34.9 g (0.26 mol), 3,3,3-tri Fluoropropyltrimethoxysilane 37.3 g (0.17 mol), 3,4-epoxycyclohexylethyltrimethoxysilane 5.5 g (0.02 mol), and propylene glycol mono-n-butyl ether (PNB, boiling point at 1 atmospheric pressure: 170 ° C., surface tension: 26.3 mN / m) 350 g was placed in a reaction vessel, and 49.4 g of water and 0.78 g of phosphoric acid were added dropwise to this solution while stirring so that the reaction temperature did not exceed 40 ° C. did. After the dropping, a distillation apparatus was attached to the flask, and the obtained solution was heated and stirred at a bath temperature of 80 ° C. for 1.0 hour to react while distilling off methanol produced by hydrolysis. Then, the solution was heated and stirred at a bath temperature of 120 ° C. for another 2 hours, and the by-produced water was distilled off. Then, this solution was cooled to room temperature to obtain a solution (solid content 23% by weight) of silica-containing fluorinated siloxane resin (I).

Since the silica solid content in the silica fine particles is 24.9% by mass, the mass of the silica fine particle solid content is 200 g × 24.9 / 100 = 49.8 g. The total mass of the siloxane resin component at the time of preparation is 34.9 g + 37.3 g + 5.5 g = 77.7 g, but since water and the like are lost due to dehydration condensation after hydrolysis, etc., the siloxane resin component is derived after the solution is prepared. The solid content of was 46 g. Therefore, the mass ratio of the solid content derived from the silica fine particle component to the solid content derived from the siloxane resin component having a perfluoro group is 52:48 (silica mass ratio (52% by mass)).

9.85 g of propylene glycol mono-n-butyl ether (PNB) was added to 10.07 g of a solution of silica-containing fluorinated siloxane resin (I). Further, 0.069 g of alkylacetate aluminum diisopropylate (AL-D) and 0.014 g of BYK-352 were added to this solution as a curing agent and stirred to obtain a siloxane resin composition. Then, in a class 1000 clean room, this siloxane resin composition was filtered using a 0.2 μmΦ polypropylene syringe filter and bottled in a clean bottle. In this way, a composition for forming an optical functional layer was obtained.

Preparation of Cured Film The composition for forming an optical functional layer was applied to a 4-inch wafer with a speen coater (1H-360S (manufactured by Mikasa Co., Ltd.)) at 700 rpm for 10 seconds and 1100 rpm for 30 seconds. Next, a coating film was obtained by prebaking at 120 ° C. for 3 minutes using a hot plate (SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.). This coating film was heated at 230 ° C. for 5 minutes on a hot plate in an air atmosphere to obtain a cured film having a film thickness of 0.5 μm.

Refractive index The obtained cured film was measured for its refractive index at a wavelength of 633 nm at room temperature of 25 ° C. using an ellipsometer (manufactured by Otsuka Electronics Co., Ltd.). At this time, the film thickness was also measured.

<Moisture resistance evaluation>
The obtained film was exposed to an environment of a temperature of 85 ° C. and a humidity of 95% RH for 20 hours with an advanced accelerated life test apparatus EHS-221 (M) manufactured by Espec, and the refractive index was measured.
The results were classified into the following and judged.
5: Refractive index difference before and after moisture resistance evaluation is less than 0.003 4: Refractive index difference before and after moisture resistance evaluation is 0.003 or more and less than 0.005 3: Refractive index difference before and after moisture resistance evaluation is 0.005 or more and less than 0.075 2: Refractive index difference before and after moisture resistance evaluation is 0.075 or more and less than 0.01 1: Refractive index difference before and after moisture resistance evaluation is 0.01 or more

Other compositions for forming an optical functional layer were obtained in the same manner as in Test 101 except that the types of silica fine particles, the compounding ratio of the silica fine particles and the siloxane resin, and the types of the solvent were as shown in the table. The results of measurement in the same manner as in Test 101 using the obtained composition for forming an optical functional layer are shown in the table. The siloxane resin (II) of Test 203 was prepared as follows.

(Table note)
PNB: Propylene glycol mono-n-butyl ether DAA: Diacetone alcohol PGMEA: Propylene glycol monoethyl acetate γ-BL: γ-Butyrolactone ETB: Ethylene glycol mono-t-butyl ether PTB: Propylene glycol mono-t-butyl ether PL-2L- IPA Fuso Chemical Industry Co., Ltd. Number average particle size 17 nm Quattron solvent Isopropanol PL-2L-DAA Fuso Chemical Industry Co., Ltd. Number average particle size 17 nm Quattron solvent Diacetone alcohol PL-1-DAA Fuso Chemical Industry Co., Ltd. Number Average particle size 13nm Quattron Solvent Diacetone alcohol Oscar 106 Catalytic Chemicals Co., Ltd.
Number average particle size 120 nm Solvent: Diacetone alcohol Oscar 105 Made by Catalytic Chemical Industry Co., Ltd.
Number average particle size 60 nm Solvent: γ-butyrolactone Oscar 101 Made by Catalytic Chemical Industry Co., Ltd.
Number average particle size 12 nm Solvent: γ-butyrolactone SG-SO100 Number average particle size 100 nm Kyoritsu Material Co., Ltd. Sururia 4110 Nikki Catalyst Kasei Co., Ltd.
Number average particle diameter 80 nm
ST-OUP: Nissan Chemical "Snowtex OUP"
ST-PS-SO: Nissan Chemical "Snowtex PS-SO"
ST-PS-MO: Nissan Chemical "Snowtex PS-MO"
F-120: "Fine Cataloid F-120" manufactured by Catalytic Chemical Industry Co., Ltd.
Quattron PL: "Quatron PL" manufactured by Fuso Chemical Industry Co., Ltd.
HDK @ N20: Made by Asahi Kasei Wacker HDK @ H20: Made by Asahi Kasei Wacker

Siloxane resin (II)
Tetraethoxysilane (TEOS) was prepared as the silicon alkoxide (A), and trifluoropropyltrimethoxysilane (TFPTMS) was prepared as the fluoroalkyl group-containing silicon alkoxide (B). Weighed so that the ratio (mass ratio) of the fluoroalkyl group-containing silicon alkoxide (B) when the mass of the silicon alkoxide (A) was 1, and put these into a separable flask. The mixture was obtained by mixing. 1.0 part by mass of propylene glycol monomethyl ether (PGME) was added as an organic solvent (E) to 1 part by mass of this mixture, and the mixture was stirred at a temperature of 30 ° C. for 15 minutes to prepare a first liquid.
In addition to this first liquid, 1.0 part by mass of ion-exchanged water (C) and 0.01 part by mass of formic acid (D) were put into a beaker and mixed with respect to 1 part by mass of the mixture. A second solution was prepared by stirring at a temperature of 30 ° C. for 15 minutes. Next, the first liquid prepared above was kept at a temperature of 55 ° C. in a water bath, then the second liquid was added to the first liquid, and the mixture was stirred for 60 minutes while maintaining the above temperature. As a result, a hydrolyzate (F) of the silicon alkoxide (A) and the fluoroalkyl group-containing silicon alkoxide (B) was obtained.

In the above 101 to 104, instead of the silica fine particles, Examples 1-2 to 1-3, 2-1 to 2-2, 3-1 and 3-4-3 to paragraphs 0043 and subsequent paragraphs of JP-A-2014-201598 A composition for forming an optical functional layer was obtained in the same manner except that the silica particle composition described in 5, 4-2, and 5-5 was used. As a result of measurement using the obtained composition for forming an optical functional layer in the same manner as in Test 101, the refractive index was 1.3 or less and the moisture resistance was good.

Claims (19)

It contains siloxane resin and silica fine particles, and has a refractive index of 1.3 or less when formed into a cured film.
The siloxane resin is a hydrolysis condensate of a siloxane compound containing a compound represented by the following formula (X1) and a compound represented by the following formula (X2).
A composition for forming an optical functional layer, wherein the silica fine particles are particle aggregates in which a plurality of particles are connected in a chain.

In formula ^{(X1), R} X1 represents an organic group having a fluorine having 3 to 12 carbon atoms. ^RX2 represents a hydrocarbon group having 1 to 4 carbon atoms. X represents a hydrolyzable group. a is 0 or 1.
In formula ^{(X2), R X3} and ^{R X4} each represent a group having an epoxy group or glycidoxy group. Y is a synonym for X. b and c are 0 or 1, and (b + c) is 1 or 2. The composition for forming an optical functional layer according to claim 1, wherein the particle aggregate comprises a plurality of spherical particles having an average particle diameter of 5 to 50 nm and a bonding portion for joining the plurality of spherical particles to each other. The composition for forming an optical functional layer according to claim 1 or 2, which contains 50 parts by mass or more of the silica fine particles with respect to 100 parts by mass of the siloxane resin. The composition for forming an optical functional layer according to any one of claims 1 to 3, which contains 100 parts by mass or more of the silica fine particles with respect to 100 parts by mass of the siloxane resin. The composition for forming an optical functional layer according to any one of claims 1 to 4, which contains 200 parts by mass or more of the silica fine particles with respect to 100 parts by mass of the siloxane resin. The composition for forming an optical functional layer according to any one of claims 1 to 5, wherein the content of the silica fine particles in the total solid content is 60 to 90% by mass. The composition for forming an optical functional layer according to any one of claims 1 to 6, wherein the particle aggregate has the following specifications (a) and (b).
(A) The average particle diameter D1 measured by the dynamic light scattering method is 30 to 300 nm.
(B) The ratio of the average particle diameter D2 obtained from the specific surface area to the above D1 and D1 / D2 are 3 or more. The composition for forming an optical functional layer according to any one of claims 1 to 7, further comprising an organic solvent. The organic solvent is at least one selected from the group consisting of propylene glycol mono-n-butyl ether, diacetone alcohol, propylene glycol monoethyl acetate, γ-butyrolactone, ethylene glycol mono-t-butyl ether, and propylene glycol mono-t-butyl ether. The composition for forming an optical functional layer according to claim 8, which comprises one. The composition for forming an optical functional layer according to any one of claims 1 to 9 , further comprising a surfactant. The composition for forming an optical functional layer according to any one of claims 1 to 10 , which is used for forming a low refractive index film. The composition for forming an optical functional layer according to any one of claims 1 to 11 , which is used for forming a grid of a color filter. The composition for forming an optical functional layer according to any one of claims 1 to 12 , wherein the thickness of the optical functional layer is 50 nm or more and 5 μm or less. A method for producing an optical functional layer using the composition for forming an optical functional layer according to any one of claims 1 to 13. The method for producing an optical functional layer according to claim 14, wherein the composition layer for forming an optical functional layer coated on the support is prebaked at 50 ° C. to 200 ° C. The method for producing an optical functional layer according to claim 14 or 15, wherein the composition layer for forming an optical functional layer coated on the support is prebaked, and then the formed coating film is post-baked at 250 ° C. or lower. A solid-state image sensor comprising a cured film of the composition for forming an optical functional layer according to any one of claims 1 to 13. A solid-state image sensor including the cured film of the composition for forming an optical functional layer according to claim 1, wherein the solid-state image sensor includes an optical functional layer having a refractive index of 1.3 or less. A camera module comprising the solid-state image sensor according to claim 17 or 18.

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