JP5976575B2 - Curable composition for forming low refractive index film, method for producing optical member set, and method for producing curable composition - Google Patents

Description

The invention, the low refractive index film-forming curable compositions, methods for producing a preparation and curable compositions of the optical engine member set.

  Recently, there are a wide variety of optical devices, many of which have a structure in which an antireflection low refractive index film is formed on the surface of an optical mechanism. The optical mechanism is not limited to a flat surface shape, and examples thereof include a brightness enhancement lens and a diffusion lens of a backlight for liquid crystal, a Fresnel lens, a lenticular lens, and a microlens used for a screen of a video projection television. In such a device, a desired geometrical optical performance is obtained mainly by forming a fine structure with a resin material. In order to provide further antireflection properties in this device, a low refractive index film may be formed in conformity with the surface of these microstructures.

  In particular, research and development relating to the material and structure of the microlens unit used in the solid-state imaging device has been vigorously advanced (see, for example, Patent Documents 1 to 3). As the background, solid-state imaging devices are becoming finer and higher performance is required to achieve efficient light collection. Particularly in recent years, the size of one pixel has become extremely small as the number of pixels increases. In addition, since a larger number of devices are produced in one manufacturing process, the wafer size used is also increased. Against this background, the improvement of the manufacturing quality and product quality of the microlens unit is becoming more important.

JP 2006-186295 A JP 2006-98985 A JP 2007-119744 A

  By the way, the antireflective low-refractive-index film described above has an optical characteristic that the reflection is minimized and the transmittance of the transmitted light of the image sensor portion is maximized because of the function required for the film. Ideal. That is, it is preferable that the low refractive index film has a refractive index distribution equivalent to that of the high refractive index film in the visible light region in consideration of the relationship with the combined high refractive index film. However, the curable composition used for forming a conventional low refractive index film has a smaller difference (distribution) depending on the wavelength of the refractive index than the curable composition used for forming a high refractive index film. It has been found that it is difficult to have an ideal refractive index distribution over the entire visible light region by applying the above.

The present invention is suitable for a high refractive index film applied to an optical member such as a solid-state imaging device, and realizes an optical characteristic of a low refractive index film having a desired optical characteristic widely contributing to an improvement in optical performance. film-forming hardening composition, and an object thereof is to provide a manufacturing method of preparation and curable compositions of the optical member set having a low refractive index film formed thereby.

  In response to the above problems, the present inventor has developed a high refractive index material having specific optical characteristics (Abbe number and refractive index) with respect to a low refractive index material having specific optical characteristics (Abbe number and refractive index). It was found that a low refractive index film having a low refractive index and a high Abbe number can be obtained by mixing. It has been confirmed that the novel low refractive index film having the specific refractive index and Abbe number exhibits good optical performance in combination with the high refractive index film in response to the above-mentioned demand. The present invention has been completed based on this finding, and the above problems have been solved by the following means.

式（１）中、Ｒ^１は、（ｍ＋ｎ）価の連結基を表し、Ｒ^２は単結合又は２価の連結基を表す。Ａ^１は酸基を少なくとも１種有する１価の置換基を表す。ｎ個のＡ^１及びＲ^２は、それぞれ、同一であっても、異なっていてもよい。ｍは８以下の正の数、ｎは１〜９を表し、ｍ＋ｎは３〜１０を満たす。Ｐ^１はポリマー鎖を表す。ｍ個のＰ^１は、同一であっても、異なっていてもよい。
〔６〕グラフト共重合体のグラフト鎖のポリマー構造が、ポリ（メタ）アクリル構造、ポリエステル構造、ポリウレタン構造、ポリウレア構造、ポリアミド構造またはポリエーテル構造である〔５〕に記載の低屈折率膜形成用硬化性組成物。
〔７〕グラフト共重合体が、ポリ（炭素数１〜５のアルキレン鎖を含むアルキレンイミン）系繰り返し単位、ポリアリルアミン系繰り返し単位、ポリジアリルアミン系繰り返し単位、メタキシレンジアミン−エピクロルヒドリン重縮合物系繰り返し単位、及びポリビニルアミン系繰り返し単位から選択される少なくとも１種の、塩基性窒素原子を有する繰り返し単位であって、ｐＫａ１４以下の官能基を有する部分構造を有する繰り返し単位と原子数４０〜１０，０００の側鎖を有する〔５〕に記載の低屈折率膜形成用硬化性組成物。
〔８〕グラフト共重合体が、下記式（Ｉ−１）で表される繰り返し単位及び式（Ｉ−２）で表される繰り返し単位、又は、式（Ｉ−１）で表される繰り返し単位及び式（Ｉ−２ａ）で表される繰り返し単位を含む〔５〕または〔７〕に記載の低屈折率膜形成用硬化性組成物。

式中、Ｒ^１及びＲ^２は、各々独立に、水素原子、ハロゲン原子又はアルキル基を表す。ａは、各々独立に、１〜５の整数を表す。＊は繰り返し単位間の連結部を表す。Ｒ^８及びＲ^９はＲ^１と同義の基である。Ｌは単結合、アルキレン基、アルケニレン基、アリーレン基、ヘテロアリーレン基、イミノ基、エーテル基、チオエーテル基、カルボニル基、またはこれらの組合せに係る連結基を表し、Ｌ ^ａ はＣＲ ^８ ＣＲ ^９ とＮとともに環構造形成する構造部位を表す。ＸはｐＫａ１４以下の官能基を有する基を表し、Ｙは原子数４０〜１０，０００の側鎖を表す。
〔９〕式（１）で表される高分子化合物が、下記式（２）で表される〔５〕に記載の低屈折率膜形成用硬化性組成物。

式（２）中、Ａ^２は、式（１）におけるＡ^１と同義である。Ｒ^４およびＲ^５は各々独立に単結合または２価の連結基を表す。ｎ個のＲ^４は、同一であっても、異なっていてもよい。また、ｍ個のＲ^５は、同一であっても、異なっていてもよい。Ｒ^３は、（ｍ＋ｎ）価の連結基を表す。ｍ＋ｎは３〜１０を満たす。Ｐ^２は、式（１）におけるＰ^１と同義である。ｍ個のＰ^２は、同一であっても、異なっていてもよい。
〔１０〕フッ素系界面活性剤とノニオン系界面活性剤を含有する〔１〕〜〔９〕のいずれか１項に記載の低屈折率膜形成用硬化性組成物。
〔１１〕下記式（ａ）〜（ｆ）のいずれかで表される重合性化合物を含有する〔１〕〜〔１０〕のいずれか１項に記載の低屈折率膜形成用硬化性組成物。

〔１２〕重合開始剤としてオキシム化合物を含有する〔１〕〜〔１１〕のいずれか１項に記載の低屈折率膜形成用硬化性組成物。
〔１３〕第１の光学部材と、これに被覆された第２の光学部材とを有してなる光学部材セットの製造方法であって、
〔１〕〜〔１２〕のいずれか１項に記載の低屈折率膜形成用硬化性組成物を準備する工程、
硬化性組成物を第２の光学部材上に塗布する工程、
硬化性組成物を硬化させて低屈折率膜である第１の光学部材を形成する工程を含む、光学部材セットの製造方法。
〔１４〕第１の組成物と第２の組成物を混合して調製する硬化性組成物の製造方法であって、
硬化性組成物が低屈折率膜を形成するための硬化性組成物であり、
第１の組成物が、アッベ数４０〜８０、屈折率１．２〜１．４を示す低屈折率材料を含み、第２の組成物が、アッベ数５〜４０、屈折率１．６〜２を示す高屈折率材料を含み、かつ、
低屈折率材料が、シロキサン樹脂を含み、硬化性組成物中に、シロキサン樹脂を１５〜４０質量％含有する硬化性組成物の製造方法。
本明細書を通じて屈折率及びアッベ数は特に断らない限り、後記実施例で測定した条件によるものとする。 [ 1 ] Low refractive index film including low refractive index material having Abbe number of 40 to 80 and refractive index of 1.2 to 1.4 and high refractive index material having Abbe number of 5 to 40 and refractive index of 1.6 to 2 A curable composition for forming, wherein the low refractive index material contains a siloxane resin, and the curable composition for forming a low refractive index film contains 15 to 40% by mass of the siloxane resin. Sex composition.
[ 2 ] The curable composition for forming a low refractive index film according to [ 1 ], wherein the low refractive index material contains hollow particles or non-hollow particles.
[ 3 ] The curable composition for forming a low refractive index film according to [ 1 ] or [ 2 ], wherein the high refractive index material contains titania or zirconia.
[ 4 ] The curable composition for forming a low refractive index film according to any one of [ 1 ] to [ 3 ], further comprising at least one of a dispersant, a surfactant, a polymerizable compound and a polymer thereof. object.
[ 5 ] A graft copolymer having a graft chain in which the number of atoms excluding hydrogen atoms is in the range of 40 to 10,000 or a polymer compound dispersant represented by the following formula (1) [ 1 ] to [ 4 ] The curable composition for low-refractive-index film formation of any one of.

In formula (1), R ¹ represents an (m + n) -valent linking group, and R ² represents a single bond or a divalent linking group. A ¹ represents a monovalent substituent having at least one acid group. The n A ¹ and R ² may be the same or different. m represents a positive number of 8 or less, n represents 1 to 9, and m + n satisfies 3 to 10. P ¹ represents a polymer chain. The m P ¹ may be the same or different.
[ 6 ] The low refractive index film formation according to [ 5 ], wherein the polymer structure of the graft chain of the graft copolymer is a poly (meth) acrylic structure, a polyester structure, a polyurethane structure, a polyurea structure, a polyamide structure or a polyether structure Curable composition.
[ 7 ] The graft copolymer is a poly (alkylene imine containing an alkylene chain having 1 to 5 carbon atoms) -based repeating unit, a polyallylamine-based repeating unit, a polydiallylamine-based repeating unit, a metaxylenediamine-epichlorohydrin polycondensate-based repeating unit. A repeating unit having at least one basic nitrogen atom selected from a unit and a polyvinylamine-based repeating unit, having a partial structure having a functional group of pKa14 or less, and an atom number of 40 to 10,000 [ 5 ] The curable composition for forming a low refractive index film according to [ 5 ].
[ 8 ] The graft copolymer is a repeating unit represented by the following formula (I-1) and a repeating unit represented by the formula (I-2), or a repeating unit represented by the formula (I-1). And the curable composition for forming a low refractive index film according to [ 5 ] or [ 7 ], comprising a repeating unit represented by formula (I-2a).

In the formula, R ¹ and R ² each independently represents a hydrogen atom, a halogen atom or an alkyl group. a represents the integer of 1-5 each independently. * Represents a connecting part between repeating units. R ⁸ and R ⁹ are the same groups as R ¹ . L represents a single bond, an alkylene group, an alkenylene group, an arylene group, heteroarylene group, an imino group, an ether group, a thioether group, a carbonyl group or a linking group according to a combination thereof,, L ^a is CR ⁸ CR ⁹ and N And a structural site that forms a ring structure. X represents a group having a functional group having a pKa of 14 or less, and Y represents a side chain having 40 to 10,000 atoms.
[ 9 ] The curable composition for forming a low refractive index film according to [ 5 ], wherein the polymer compound represented by the formula (1) is represented by the following formula (2).

Wherein (2), ^{A 2} has the same meaning as ^{A 1} in formula (1). R ⁴ and R ⁵ each independently represents a single bond or a divalent linking group. The n R ^{4 s} may be the same or different. The m R ^{5 s} may be the same or different. R ³ represents a (m + n) -valent linking group. m + n satisfies 3-10. P ² has the same meaning as ^{P 1} in formula (1). the m P ² can be the same or different.
[ 10 ] The curable composition for forming a low refractive index film according to any one of [ 1 ] to [ 9 ], which contains a fluorine-based surfactant and a nonionic surfactant.
[ 11 ] The curable composition for forming a low refractive index film according to any one of [ 1 ] to [ 10 ], comprising a polymerizable compound represented by any one of the following formulas (a) to (f): .

[ 12 ] The curable composition for forming a low refractive index film according to any one of [ 1 ] to [ 11 ], which contains an oxime compound as a polymerization initiator.
[ 13 ] A method for producing an optical member set comprising a first optical member and a second optical member coated thereon,
The step of preparing the curable composition for forming a low refractive index film according to any one of [ 1 ] to [ 12 ],
Applying the curable composition onto the second optical member;
The manufacturing method of an optical member set including the process of hardening the curable composition and forming the 1st optical member which is a low refractive index film | membrane.
[ 14 ] A method for producing a curable composition prepared by mixing a first composition and a second composition,
The curable composition is a curable composition for forming a low refractive index film,
The first composition includes a low refractive index material having an Abbe number of 40 to 80 and a refractive index of 1.2 to 1.4, and the second composition has an Abbe number of 5 to 40 and a refractive index of 1.6 to A high refractive index material exhibiting 2 and
A method for producing a curable composition, wherein the low refractive index material contains a siloxane resin, and the curable composition contains 15 to 40% by mass of the siloxane resin.
Throughout this specification, the refractive index and the Abbe number are based on the conditions measured in Examples described below unless otherwise specified.

The low refractive index film obtained from the curable composition of the present invention has optical characteristics suitable for a high refractive index film applied to an optical member such as a solid-state imaging device, and contributes widely to improving optical performance in products. .
The curable composition in the present invention realizes a desired refractive index and a wavelength distribution with a good refractive index when it is a low refractive index film, and further has stability and good coating properties. The cured film is light transmissive and exhibits excellent optical performance when incorporated into a product.
The optical member produced using the low refractive index film having the above excellent properties and the solid-state imaging device using the same exhibit excellent optical performance in which reflected light is suitably suppressed and prevented in a wide wavelength region.
Moreover, according to the manufacturing method of this invention, the curable composition which exhibits said outstanding performance, a low refractive index film | membrane, an optical member, and a solid-state image sensor can be manufactured suitably.

A low refractive index film (hereinafter referred to as a low refractive index film of the present invention) obtained from a curable composition for forming a low refractive index film which is a preferred embodiment of the present invention has a specific Abbe number and refractive index. . It is formed from a curable composition for forming a low refractive index film (hereinafter also simply referred to as a curable composition ) using a specific low refractive index material and a high refractive index material, and has an antireflection property in the visible region. Has the advantage of less wavelength dependency. An example of a preferred embodiment of an optical member set using this low refractive index film as an optical member is a microlens unit. This includes a low refractive index film (first optical member) containing a specific low refractive index material and a high refractive index material, and a plurality of microlens bodies (second optical members) coated thereon. It comprises.
In the present invention, the above-mentioned optical characteristics and the like are realized at the same time by adopting the specific low refractive index material and the high refractive index material as materials for forming the low refractive index film.
Hereinafter, the present invention will be described focusing on a specific low refractive index material and high refractive index material in a curable composition and a low refractive index film according to preferred embodiments. The optical member set will be described using a microlens unit as an example, the first optical member will be described using a low refractive index film as an example, and the second optical member will be described using a microlens body as an example.

<Curable composition>
In the present embodiment, the curable composition contains a low refractive index material and a high refractive index material. The content of the low refractive index material and the high refractive index material in the composition is described below together with the description of the individual materials. However, when defined as a whole, the low refractive index material is 40 to 40 It is preferably 99% by mass, and more preferably 50 to 95% by mass. About high refractive index material, it is preferable that it is 1-60 mass%, and it is more preferable that it is 5-55 mass%. In terms of the blending ratio of both, the high refractive index material is preferably 1 to 45 parts by mass and more preferably 5 to 35 parts by mass with respect to 100 parts by mass of the low refractive index material. It is preferable to make both materials have the above-mentioned contents (mixing ratio) because the desired refractive index and its distribution can be adjusted more effectively.
The curable composition of the present invention may be produced by a conventional method, but the first composition containing the low refractive index material and the high refractive index material are suitably prepared by mixing the second composition. Can do.
In the present invention, the low refractive index material contains a siloxane resin, and the curable resin for forming a low refractive index film contains 15 to 40% by mass of the siloxane resin.

<Low refractive index material>
The refractive index of the low refractive index material is preferably 1.45 or less, more preferably 1.43 or less, further preferably 1.41 or less, and further preferably 1.40 or less. , 1.39 or less, more preferably 1.37 or less, and particularly preferably 1.35 or less. Although there is no particular lower limit, it is practical that it is 1.2 or more. By selecting a specific resin as a constituent component of the low refractive index material, it is preferable to realize desired optical characteristics and further reduce variation between pixels. Or it is preferable to use a hollow particle or a non-hollow particle as a component contained in a composition. The low refractive index material refers to a constituent component (usually solid content) for forming a low refractive index film. Unless otherwise specified, the identification is evaluated by the refractive index measured by the solvent and measurement method employed in the examples described later. However, the solvent may be changed to a commonly used solvent in consideration of the solubility / dispersibility of the raw material liquid. The same applies to the high refractive index material. In addition, the low refractive index material may satisfy | fill the said refractive index with one component, and may combine the 2 or more component and may satisfy | fill the said refractive index. The same applies to the Abbe number described below, and the same applies to the high refractive index material.

The Abbe number of the low refractive index material is preferably 40 or more, more preferably 45 or more, further preferably 50 or more, further preferably 53 or more, and particularly preferably 55 or more. preferable. The upper limit is preferably 90 or less, more preferably 85 or less, further preferably 80 or less, and particularly preferably 75 or less. By setting the Abbe number of the low refractive index material in this range, when the film is combined with the high refractive index material described later, good optical characteristics can be exhibited.
Unless otherwise specified, the Abbe number is evaluated by the refractive index measured by the solvent and measurement method employed in Examples below.
However, in the present invention, the refractive index of the low refractive index material is 1.2 to 1.4, and the Abbe number is 40 to 80.

<Siloxane resin composition>
The siloxane resin can be obtained through the hydrolysis reaction and the condensation reaction using the alkoxysilane raw material described later. More specifically, in the compound, a part or all of alkoxy groups of the alkyltrialkoxysilane are hydrolyzed to be converted into silanol groups, and at least a part of the generated silanol groups is condensed to form Si-O-Si. It can be said that a bond is formed. The siloxane resin may be a siloxane resin having any silsesquioxane structure such as a cage type, a ladder type, or a random type. The “cage type”, “ladder type”, and “random type” can refer to structures described in, for example, the chemistry and application development of silsesquioxane materials (CMC Publishing).

(Silsesquioxane structure)
The siloxane resin of this embodiment preferably has a silsesquioxane structure represented by the following formula (1).
^{_{- (R 1 SiO 3/2) n}} - Formula (1)
(In the above formula (1), .n ^{R 1} is represents an alkyl group having 1 to 3 carbon atoms is an integer of 20 to 1,000.)
The alkyl group represented by R ¹ is not particularly limited as long as the carbon number is within the above range, and examples thereof include a methyl group, an ethyl group, a propyl group, and an isopropyl group. Of these, a methyl group and an ethyl group are preferable, and a methyl group is most preferable. The alkyl group represented by R ¹ may be an alkyl group having no substituent or an alkyl group having a substituent, but is preferably an alkyl group having no substituent.

The substituent which the alkyl group represented by R ¹ may have is preferably not a halogen atom or a group having an ethylenically unsaturated bond, and an amino group (preferably an amino group having 0 to 20 carbon atoms, For example, amino, N, N-dimethylamino, N, N-diethylamino, N-ethylamino, anilino, etc.), a sulfonamide group (preferably a sulfonamide group having 0 to 20 carbon atoms, for example, N, N-dimethyl Sulfonamide, N-phenylsulfonamide and the like), acyloxy group (preferably an acyloxy group having 1 to 20 carbon atoms, such as acetyloxy, benzoyloxy, etc.), carbamoyl group (preferably a carbamoyl group having 1 to 20 carbon atoms) , For example, N, N-dimethylcarbamoyl, N-phenylcarbamoyl, etc.), acylamino group (preferably Or an acylamino group having 1 to 20 carbon atoms (for example, acetylamino, benzoylamino, etc.).

  In the present invention, unless otherwise specified, a silicon-containing polymer whose main chain is composed of siloxane bonds is called a polysiloxane or a siloxane resin. Since silicon has four bonds, the basic structural unit of polysiloxane is classified according to the number of organic groups typified by methyl and phenyl groups per silicon atom. It can be divided into two. In the following formula, R is an organic group.

In the present invention, silsesquioxane means a general term for polysiloxanes whose basic structural units are T units unless otherwise specified. Since silicon in silsesquioxane is bonded to three oxygens and oxygen is bonded to two silicons, the theoretical composition is RSiO _3/2 (the Latin word for three-half is "Sesquix (SESQUI) "). In the present embodiment, it is preferable that R in the formula of the T unit is the R ¹ and the silsesquioxane structure site is included at the specific content.

  The siloxane resin of the present embodiment is 65% by mass or more and 100% by mass or less of the entire siloxane resin contained in the cured film, that is, 65 of the entire siloxane resin contained in the low refractive index film-forming resin composition (curable composition). More than mass% and less than 100 mass% are comprised by said silsesquioxane structure. This proportion is preferably 80% by mass or more and 100% by mass or less, more preferably 95% by mass or more and 100% by mass or less, and most preferably 100% by mass (however, 100% by mass). Even in this case, other components such as inevitable impurities may be contained within a range that does not impair the desired effect. In addition, the siloxane resin of this embodiment may contain the specific polysilsesquioxane structure individually by 1 type, or may contain 2 or more types.

  The siloxane resin of this embodiment is preferably a hydrolysis condensate obtained by hydrolytic condensation of alkyltrialkoxysilane.

(Alkyl trialkoxysilane)
In order to produce the hydrolysis condensate in the present embodiment, an alkoxysilane raw material containing an alkyltrialkoxysilane can be used as a starting raw material. In addition, the alkoxysilane raw material intends the starting raw material comprised from alkoxysilane (silicon compound which has an alkoxy group). By using alkyltrialkoxysilane as a raw material, the structure of the obtained hydrolysis condensate becomes more flexible, and the wettability to the substrate can be enhanced by the presence of the organic component.

An alkyltrialkoxysilane is an organosilicon compound in which one alkyl group and three alkoxy groups are bonded to a silicon atom, and can be represented by the following formula (2).
Formula (2): R ² Si (OR ³ ) ₃
(R ² represents an alkyl group having 1 to 3 carbon atoms, and R ³ represents an alkyl group.)

The alkyl group of alkyltrialkoxysilane (R ² in formula (2)) is not particularly limited as long as it has a carbon number of 1 to 3, but is preferably a methyl group or an ethyl group, and most preferably a methyl group.

The alkoxy group of the alkyltrialkoxysilane is not particularly limited, and examples thereof include a methoxy group and an ethoxy group. More specifically, R ³ in the formula (2) is preferably a linear or branched alkyl group having 1 to 20 carbon atoms. Especially, C1-C10 is preferable and C1-C4 is more preferable. In particular, an ethoxy group in which R ³ in the formula (2) is an ethyl group is preferable because the hydrolysis rate can be easily controlled.

  Examples of the alkyltrialkoxysilane include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, and the like. Of these, methyltriethoxysilane and ethyltriethoxysilane are preferably used, and methyltriethoxysilane is most preferably used. In addition, as alkyl trialkoxysilane, only 1 type may be used and 2 or more types may be used together.

  65% by mass or more of the alkoxysilane raw material is preferably alkyltrialkoxysilane, more preferably 80% by mass or more and 100% by mass or less, and more preferably 95% by mass or more and 100% by mass or less. When the content is within the range, the flexibility of the structure of the obtained hydrolysis condensate and the wettability to the workpiece are ensured, which is preferable.

(Tetraalkoxysilane)
As the alkoxysilane raw material, in addition to the trialkoxysilane, other alkoxysilanes can be used, and tetraalkoxysilane is particularly preferable. By containing tetraalkoxysilane, the crosslink density in the hydrolyzed condensate is increased, which is preferable in terms of further improving the electrical insulation, development resistance, and heat resistance of the film obtained by hardening.

Tetraalkoxysilane is an organosilicon compound in which four alkoxy groups are bonded to a silicon atom, and can be represented by the following formula (3).
Formula (3): Si (OR ⁴ ) ₄
(R ⁴ each independently represents an alkyl group.)

The alkoxy group of tetraalkoxysilane is not particularly limited, and examples thereof include a methoxy group and an ethoxy group. More specifically, as R ⁴ in formula (3), the number of carbon atoms is 1 to 1.
Twenty linear or branched alkyl groups are preferred. Especially, C1-C10 is preferable and C1-C4 is more preferable. In particular, an ethoxy group in which R ⁴ in the formula (3) is an ethyl group is preferable because the hydrolysis rate can be easily controlled.

Examples of the tetraalkoxysilane include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, and tetra-tert-butoxysilane. . Of these, tetramethoxysilane and tetraethoxysilane are preferably used.
In addition, as tetraalkoxysilane, only 1 type may be used and 2 or more types may be used together.

  The content of tetraalkoxysilane in the alkoxysilane raw material is not particularly limited, but is preferably 35% by mass or less, and more preferably 20% by mass or less. Although there is no lower limit in particular, in order to obtain the effect of adding tetraalkoxysilane, it is preferably 0.01% by mass or more, and more preferably 0.1% by mass or more.

  In addition, in this specification, it uses for the meaning containing the salt, a complex, and its ion besides the said compound itself about the display of a compound. Moreover, it is the meaning including the derivative modified with the predetermined form in the range with the desired effect. Further, in the present specification, a substituent (including a linking group) for which substitution / non-substitution is not specified means that the group may have an arbitrary substituent. This is also synonymous for compounds that do not specify substitution / non-substitution. Preferred substituents include the following substituent T.

Examples of the substituent T include the following.
An alkyl group (preferably an alkyl group having 1 to 20 carbon atoms, such as methyl, ethyl, isopropyl, t-butyl, pentyl, heptyl, 1-ethylpentyl, benzyl, 2-ethoxyethyl, 1-carboxymethyl, etc.), alkenyl A group (preferably an alkenyl group having 2 to 20 carbon atoms, such as vinyl, allyl, oleyl, etc.), an alkynyl group (preferably an alkynyl group having 2 to 20 carbon atoms, such as ethynyl, butadiynyl, phenylethynyl, etc.), A cycloalkyl group (preferably a cycloalkyl group having 3 to 20 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, etc.), an aryl group (preferably an aryl group having 6 to 26 carbon atoms, for example, Phenyl, 1-naphthyl, 4-methoxyphenyl, -Chlorophenyl, 3-methylphenyl, etc.), heterocyclic groups (preferably heterocyclic groups having 2 to 20 carbon atoms, such as 2-pyridyl, 4-pyridyl, 2-imidazolyl, 2-benzimidazolyl, 2-thiazolyl, 2 -Oxazolyl etc.), an alkoxy group (preferably an alkoxy group having 1 to 20 carbon atoms, such as methoxy, ethoxy, isopropyloxy, benzyloxy etc.), an aryloxy group (preferably an aryloxy group having 6 to 26 carbon atoms) , For example, phenoxy, 1-naphthyloxy, 3-methylphenoxy, 4-methoxyphenoxy, etc.), alkoxycarbonyl groups (preferably C2-C20 alkoxycarbonyl groups such as ethoxycarbonyl, 2-ethylhexyloxycarbonyl, etc.) ), Amino group (preferably carbon Amino group having 0 to 20 children, such as amino, N, N-dimethylamino, N, N-diethylamino, N-ethylamino, anilino, etc.), sulfonamide group (preferably sulfonamide having 0 to 20 carbon atoms) A group such as N, N-dimethylsulfonamide, N-phenylsulfonamide, etc., an acyloxy group (preferably an acyloxy group having 1 to 20 carbon atoms such as acetyloxy, benzoyloxy, etc.), a carbamoyl group (preferably A carbamoyl group having 1 to 20 carbon atoms, such as N, N-dimethylcarbamoyl, N-phenylcarbamoyl, etc.), an acylamino group (preferably an acylamino group having 1 to 20 carbon atoms, such as acetylamino, benzoylamino, etc.) , A cyano group, or a halogen atom (eg, fluorine atom, chlorine atom, bromine atom) Child, iodine atom, etc.).

  When a compound or a substituent includes an alkyl group, an alkenyl group, etc., these may be linear or branched, and may be substituted or unsubstituted. When an aryl group, a heterocyclic group, or the like is included, they may be monocyclic or condensed, and may be substituted or unsubstituted.

(Manufacture of siloxane resin)
The siloxane resin contained in the resin composition for forming a low refractive index film (curable composition) of the present embodiment can be obtained through the hydrolysis reaction and the condensation reaction using the above-described alkoxysilane raw material.
As the hydrolysis reaction and the condensation reaction, known methods can be used, and a catalyst such as an acid or a base may be used as necessary. The catalyst is not particularly limited as long as the pH is changed. Specifically, as the acid (organic acid, inorganic acid), for example, nitric acid, oxalic acid, acetic acid, formic acid, hydrochloric acid, etc., as the alkali, for example, Ammonia, triethylamine, ethylenediamine and the like can be mentioned. The amount to be used is not particularly limited as long as the siloxane resin satisfies a predetermined molecular weight.

  You may add a solvent to the reaction system of a hydrolysis reaction and a condensation reaction as needed. The solvent is not particularly limited as long as the hydrolysis reaction and the condensation reaction can be performed. For example, water, alcohols such as methanol, ethanol, and propanol, ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monopropyl ether And esters such as methyl acetate, ethyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate; and ketones such as acetone, methyl ethyl ketone, and methyl isoamyl ketone. Especially, it is preferable to apply the solvent different from the solvent which contains the siloxane resin mentioned later here, and it is more preferable to use a C1-C5 alcohol compound or a C2-C6 ether compound.

  Optimum conditions for the hydrolysis reaction and condensation reaction (temperature, time, amount of solvent) are appropriately selected according to the type of material used.

The weight average molecular weight of the siloxane resin used in the present embodiment is 1,000 to 50,000. Especially, 2,000-45,000 are preferable, 2,500-25,000 are more preferable, 3,000-25,000 are especially preferable.
In addition, a weight average molecular weight is a value when it measures using well-known GPC (gel permeation chromatography), and converts into standard polystyrene. Unless otherwise noted, for GPC measurement, Waters 2695 and Shodex GPC column KF-805L (3 columns directly connected) were used, and 50 μl of a tetrahydrofuran solution having a column temperature of 40 ° C. and a sample concentration of 0.5 mass% was injected. Then, tetrahydrofuran was flowed as an elution solvent at a flow rate of 1 ml / min, and the sample peak was detected by an RI detector (Waters 2414) and a UV detector (Waters 2996).

The content of the siloxane resin in the composition of the present embodiment (the curable composition for forming a low refractive index film) is preferably more than 5% by mass and 50% by mass or less based on the total amount of the composition material , Especially, 10-45 mass% is more preferable, and 15-40 mass% is especially preferable.
For this reason, in this invention, 15-40 mass% of siloxane resins are contained in the curable composition for low refractive index film | membrane formation.

(Surfactant)
The resin composition for forming a low refractive index film (curable composition) of the present embodiment preferably contains a surfactant having a polyoxyalkylene structure from the viewpoint of further improving applicability. 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 include an ethylene oxide (EO) structure and a propylene oxide (PO) structure. . As the surfactant having a polyoxyalkylene structure, various surfactants such as a fluorosurfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone surfactant as long as they have the polyoxyalkylene structure. Surfactants can be used. Among these, nonionic surfactants, anionic surfactants, and silicone surfactants are preferable, nonionic surfactants and anionic surfactants are more preferable, and anionic surfactants are most preferable.

In the case of forming a film using a coating liquid to which the low refractive index film forming resin composition of the present embodiment is applied, wetting the coated surface by reducing the interfacial tension between the coated surface and the coating liquid. The coating property is improved and the coating property to the coated surface is improved.
Examples of the fluorosurfactant include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F479, F482, F554, F780, F781 (above, DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, S-141, S- 145, same SC-101, same SC-103, same SC-104, same SC-105, same SC1068, same SC-381, same SC-383, same S393, same KH-40 (above, manufactured by Asahi Glass Co., Ltd.) ), EFtop EF301, EF303, EF351, EF352 (above, manufactured by Gemco), PF636, PF656 PF6320, PF6520, PF7002 (OMNOVA Co., Ltd.), and the like.
Specific examples of the nonionic surfactant include glycerol, trimethylolpropane, trimethylolethane ethoxylate and propoxylate (for example, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Polyoxyethylene oleyl ether (Emulgen 404 manufactured by Kao Corporation), polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, ELEBASE manufactured by Aoki Oil & Fat Co., Ltd. BUB-3 etc. are mentioned.
Specific examples of anionic surfactants include W004, W005, W017 (manufactured by Yusho Co., Ltd.), EMULSOGEN COL-020, EMULSOGEN COA-070, EMULSOGEN COL-080, manufactured by Clariant Japan Co., Ltd., Daiichi Kogyo Examples include Prisurf A208B manufactured by Pharmaceutical Co., Ltd.
Examples of the silicone surfactant include “Toray Silicone DC3PA”, “Toray Silicone SH7PA”, “Tore Silicone DC11PA”, “Tore Silicone SH21PA”, “Tore Silicone SH28PA”, “Toray Silicone” manufactured by Toray Dow Corning Co., Ltd. “Silicone SH29PA”, “Toresilicone SH30PA”, “Toresilicone SH8400”, “TSF-4440”, “TSF-4300”, “TSF-4445”, “TSF-4460”, “TSF” manufactured by Momentive Performance Materials, Inc. -4552 "," KP341 "," KF6001 "," KF6002 "manufactured by Shin-Etsu Silicone Co., Ltd.," BYK307 "," BYK323 "," BYK330 ", manufactured by Big Chemie," DBE-22 "manufactured by GELEST ", Such as" DBE-621 ", and the like.
Only one type of surfactant may be used, or two or more types may be combined.

Moreover, as a surfactant having a preferred polyoxyalkylene structure of the present embodiment, a surfactant represented by the following formula (4) can be mentioned.
Formula (4): R ⁵ O (R ⁶ O) _m R ⁷
(In the above formula, R ⁵ represents an alkyl group having 1 to 20 carbon atoms, R ⁶ represents an alkylene group having 1 to 4 carbon atoms, and R ⁷ represents a hydrogen atom, a carboxyl group, or —PO ₃ H ₂ . M represents an integer of 1 to 8.)
More specifically, R ⁵ in formula (4) may be a linear or branched alkyl group. Especially, C5-C20 is preferable and C12-C18 is more preferable. R ⁶ in the formula (4) may be a linear or branched alkylene group, and examples thereof include a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, and an isobutylene group. Among them, an ethylene group and an isopropylene group (a group that forms an adjacent O atom and an ethylene oxide structure or a propylene oxide structure) are preferable. R ⁷ in formula (4) is preferably a hydrogen atom or a carboxyl group, and most preferably a carboxyl group.

  The addition amount of the surfactant is not particularly limited, but as its lower limit, it is preferably added in a range of 1 part by mass or more with respect to 100 parts by mass of the curable resin, and 1.5 parts by mass or more. More preferably, it is most preferably 7.5 parts by mass or more. Although an upper limit is not specifically limited, 30 mass parts or less are preferable and 15 mass parts or less are more preferable.

  In the resin composition of the present embodiment, other surfactants may be used together with or separately from the surfactant having the polyoxyalkylene structure. As the surfactant, those commonly used can be used, and among them, a silicone-based surfactant is preferably used. Preferable silicone surfactants include polysiloxane type surfactants in which an organic group is introduced into a side chain or a terminal, or a side chain and a terminal. As side chain group, amino group, epoxy group, carbinol group, mercapto group, carboxyl group, hydrogen group, polyether group, aralkyl group, fluoroalkyl group, phenyl group, as end group, amino group, epoxy group, Examples thereof include a carbinol group, a methacryl group, a polyether group, a mercapto group, a carboxyl group, a phenol group, a silanol group, and a diol group.

Alternatively, it is also preferable to contain an alkylalkoxysilane compound having a specific carbon number (hereinafter referred to as “alkoxysilane compound α”) together with the surfactant having the polyoxyalkylene structure. You may use together 3 types of surfactant of surfactant which has, silicone type surfactant, and alkoxysilane compound alpha. As the alkoxysilane compound α, an alkoxysilane compound having an alkyl group having 4 to 12 carbon atoms (more preferably 6 to 10 carbon atoms) is preferably used. When this is represented by a general formula, it is preferably a compound represented by the following formula (5).
Formula (5): Si (OR ⁵¹ ) _n-4 (R ⁵² ) _n
Here, R ⁵¹ is the same group as R ⁴ . R ⁵² is preferably an alkyl group having 4 to 12 carbon atoms, and more preferably an alkyl group having 6 to 10 carbon atoms. n is an integer of 1 to 3.
The amount of the surfactant used in combination with the surfactant having a polyoxyalkylene structure may be arbitrarily adjusted. For example, the surfactant used in combination with 100 parts by mass of the surfactant having a polyoxyalkylene structure. Is preferably used at 0.01 to 100 parts by mass, more preferably 1 to 100 parts by mass, and even more preferably 10 to 100 parts by mass.

(Hollow particles / Non-hollow particles)
The curable composition or a cured film obtained by curing the curable composition preferably contains hollow particles. As the hollow particles, not only hollow structures but also porous fine particles may be used. The hollow particle has a structure having a cavity inside and refers to a particle having a cavity surrounded by an outer shell, and the porous particle refers to a porous particle having a large number of cavities. Hereinafter, the hollow particles or the porous particles are appropriately referred to as “specific particles”. The specific particles may be organic particles or inorganic particles.

The porosity of the specific particles is preferably 10 to 80%, more preferably 20 to 60%, and most preferably 30 to 60%. The porosity of the specific particles is preferably in the above range from the viewpoint of reducing the refractive index and maintaining the durability of the particles.
Among the specific particles, hollow particles are more preferable from the viewpoint of easily reducing the refractive index. For example, when the hollow particles are made of silica, the hollow silica particles have air with a low refractive index (refractive index = 1.0), and therefore the refractive index is normal silica (refractive index = 1.6).

  As a method for producing the hollow particles, for example, a method described in JP-A-2001-233611 can be applied. Moreover, the manufacturing method of a porous particle can apply the method described in each gazette, such as Unexamined-Japanese-Patent No. 2003-327424, 2003-335515, 2003-226516, 2003-238140, etc., for example.

The specific particles preferably have an average primary particle diameter of 1 nm to 200 nm, and more preferably 10 nm to 100 nm.
The average primary particle diameter of the specific particles here can be determined from the photograph obtained by observing the dispersed particles with a transmission electron microscope. The projected area of the particles is obtained, and the equivalent circle diameter is obtained therefrom, which is the average primary particle diameter. The average primary particle diameter in this specification is calculated by measuring the projected area of 300 or more particles and obtaining the equivalent circle diameter.
The refractive index of the specific particles is preferably 1.10 to 1.40, more preferably 1.15 to 1.35, and most preferably 1.15 to 1.30.
In this specification, the refractive index represents the refractive index of the entire particle, and when the particle is a hollow particle, it does not represent the refractive index of only the outer shell forming the hollow particle. When the particles are porous particles, the refractive index of the porous particles can be measured with an Abbe refractometer (manufactured by Atago Co., Ltd.) (measurement temperature 25 ° C., wavelength 633 nm).

The specific particles are preferably hollow or porous inorganic particles from the viewpoint of lowering the refractive index. Examples of the inorganic low refractive index particles include magnesium fluoride and silica particles, and silica particles are more preferable from the viewpoint of low refractive index properties, dispersion stability, and cost.
The average primary particle diameter of these inorganic particles is preferably 1 nm to 100 nm, and more preferably 1 nm to 60 nm.
As long as the inorganic particles satisfy the required porosity, the crystal system may be either crystalline or amorphous, and may be monodispersed particles or aggregated particles that satisfy a predetermined particle diameter. The shape is most preferably a spherical shape, but may be a bead shape, a shape having a major axis / minor axis ratio of 1 or more, or an indefinite shape.
The specific surface area of the inorganic particles ^is preferably from 10m ² / g~2000m 2 / ^g, it is still more preferably ^{20m 2 / g~1800m 2 / g,} 50m 2 / g~1500m 2 / g Is most preferred.

Inorganic particles are treated with physical surface treatments such as plasma discharge treatment and corona discharge treatment in order to stabilize dispersion in the curable composition or to increase the affinity and binding properties with the binder component. Chemical surface treatment with a surfactant, a coupling agent, or the like may be performed. The use of a coupling agent is particularly preferred. As the coupling agent, an alkoxy metal compound (eg, titanium coupling agent, silane coupling agent) is preferably used. Of these, silane coupling treatment is particularly effective.
That is, when the inorganic particles are silica particles and the coupling agent is a silane compound, organosilyl groups (monoorganosilyl, diorganosilyl, triorganosilyl groups) are converted into silica particles by the reaction between the silane compound and the silanol group. It binds to the surface. Examples of the organic group that the surface-treated silica particles have on the surface include saturated or unsaturated hydrocarbon groups having 1 to 18 carbon atoms and halogenated hydrocarbon groups having 1 to 18 carbon atoms.
The above-mentioned coupling agent may be used as a surface treatment agent for inorganic particles in order to perform surface treatment in advance before the preparation of the coating solution for a low refractive index film, or may be added as an additive at the time of preparing the coating solution.
The inorganic particles are preferably dispersed in the medium in advance before the surface treatment in order to reduce the load of the surface treatment.

A more preferred embodiment of the specific particles is silica particles.
Commercially available particles can be preferably used as the specific particles made of silica.
For example, Julia Catalytic Chemical's through rear series (hollow particles, isopropanol (IPA) dispersion, 4-methyl-2-pentanone (MIBK) dispersion, etc., such as through rear 2320), OSCAL series, Nissan Chemical Co., Ltd. Snowtex series (porous particles, IPA dispersion, ethylene glycol dispersion, methyl ethyl ketone (MEK) dispersion, dimethylacetamide dispersion, MIBK dispersion, propylene glycol monomethyl acetate dispersion, propylene glycol monomethyl ether dispersion, methanol dispersion, ethyl acetate dispersion, butyl acetate) Dispersion, xylene-n-butanol dispersion, toluene dispersion, etc. For example, MIBK-SD-L, MIBK-ST, etc.), Sirenax (porous particles) manufactured by Nittetsu Mining Co., Ltd., PL manufactured by Fuso Chemical Industries, Ltd. series Porous particles, IPA dispersion, toluene dispersion, propylene glycol monomethyl ether dispersion, methyl ethyl ketone dispersion, etc. For example, PL-1-IPA, PL-2L-PGME, etc., EVONIK's Aerosil series (porous particles, propylene glycol acetate dispersion) Silica particles such as ethylene glycol dispersion and MIBK dispersion) can be used.

  When silica particles are added as a dispersion containing silica particles and a particle dispersant (details of the particle dispersant will be described later), the content of silica particles in the silica dispersion is 10% by mass to 50% by mass. Is preferable, 15 mass%-40 mass% is more preferable, and 15 mass%-30 mass% is further more preferable.

The content of the specific particles with respect to the total solid content in the curable composition (curable composition for forming a low refractive index film) is preferably 5% by mass to 95% by mass, and 10% by mass to 90% by mass. More preferably, it is more preferably 20% by mass to 80% by mass.
When the film is formed by a curable composition, coating amount of the specific particles is ^preferably from ^{1mg / m 2 ~100mg / m 2} , more preferably ^{5mg / m 2 ~80mg / m 2} , more preferably 10mg / M ^{2 to} 60 mg / m ² . When it is 1 mg / m ² or more, the effect of lowering the refractive index and the effect of improving scratch resistance can be reliably obtained, and when it is 100 mg / m ² or less, fine irregularities are formed on the surface of the cured film. It is possible to suppress the deterioration of the integrated reflectance due to the fact that

(Fluorine resin)
The curable composition or a cured film obtained by curing the curable composition preferably contains a fluororesin. For example, the fluorine-type siloxane polymer of Unexamined-Japanese-Patent No. 2004-21036 is mentioned.

Fluorine-based resin is a resin containing fluorine in a substance molecule. Specifically, polytetrafluoroethylene, polyhexafluoropropylene, tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene / perfluoro Examples thereof include alkyl vinyl ether copolymers, tetrafluoroethylene / ethylene copolymers, hexafluoropropylene / propylene copolymers, polyvinylidene fluoride, vinylidene fluoride / ethylene copolymers, and the like.
Among them, polytetrafluoroethylene and tetrafluoroethylene / ethylene copolymer are preferable, polytetrafluoroethylene is more preferable, and polytetrafluoroethylene-containing mixed powder composed of polytetrafluoroethylene particles and an organic polymer is also preferably used. It is done.
Amorphous fluororesins are also preferably used, and examples of commercially available products include CYTOP (manufactured by Asahi Glass). The molecular weight of fluorine-based resin such as polytetrafluoroethylene is preferably in the range of 100,000 to 10,000,000, more preferably in the range of 100,000 to 1,000,000, which is particularly effective for extrusion moldability and flame retardancy. Commercially available products of polytetrafluoroethylene include “Teflon (registered trademark)” 6-J, “Teflon (registered trademark)” 6C-J, and “Teflon (registered trademark)” 62 manufactured by Mitsui DuPont Fluorochemical Co., Ltd. -J, “Full-on” CD1 and CD076 manufactured by Asahi IC Fluoropolymers Co., Ltd. are commercially available. In addition, as a commercial product of a polytetrafluoroethylene-containing mixed powder composed of polytetrafluoroethylene particles and an organic polymer, it is commercially available as “Metabrene (registered trademark)” A series from Mitsubishi Rayon Co., Ltd. METABLEN (registered trademark) “A-3000”, “METABBRENE (registered trademark)” A-3800, and the like are commercially available.

  Further, as the fluororesin, an amorphous fluororesin, a copolymer oligomer containing a perfluoroalkyl group-containing acrylate or methacrylate, a fluorocoating agent, a fluorosurfactant, a fluorocarbon surface treatment containing an electron beam or an ultraviolet curing component A fluorine-based surface treatment agent containing an agent and a thermosetting component is also preferable. As the other copolymerization component of the copolymer oligomer containing a perfluoroalkyl group-containing acrylate or methacrylate, alkyl acrylate or alkyl methacrylate is preferable.

  Specific examples are shown below. Examples of the amorphous fluororesin include Lumiflon manufactured by Asahi Glass Co., Ltd. and CYTOP. Copolymer oligomers containing perfluoroalkyl group-containing (meth) acrylate and alkyl (meth) acrylate as main components include Nippon Oil & Fats Modiper F Series, Daikin Industries Unidyne, Dainippon Ink & Chemicals Examples thereof include F470 series, F480 series, F110 series, and the like, and block copolymerization is more preferable. As a fluorine-type coating agent, Sumitomo 3M EGC1700 is mentioned. Examples of the fluorosurfactant include Megafac F114, F410 series, 440 series, 450, 490 series and the like manufactured by Dainippon Ink and Chemicals, Inc. Examples of the fluorine-based surface treating agent containing an electron beam or an ultraviolet curable component include Polynova PF-3320 manufactured by Omninova Solutions, Cheminox FAMAC-8 manufactured by Unimatec, and EGC1720 manufactured by Sumitomo 3M. Examples of the fluorine-based surface treating agent containing a thermosetting component include EGC 1720 manufactured by Sumitomo 3M, NH-10 and NH-15 manufactured by Dainippon Ink and Chemicals, Inc.

The fluororesin may be a mixture of a plurality of types of fluorine-containing compounds.
The addition amount of the fluorine-based resin is not particularly limited, but from the same viewpoint as the siloxane resin, the content is preferably in the same range as the siloxane resin in the low refractive index film-forming curable composition.

(Curing agent)
The resin composition for forming a low refractive index film of the present embodiment may further contain a curing agent. As a hardening | curing agent, the hardening | curing agent which consists of Al, Mg, Mn, Ti, Cu, Co, Zn, Hf, and Zr is preferable, and these can also be used together.

  These curing agents can be easily obtained by reacting a metal alkoxide with a chelating agent. Examples of chelating agents include β-diketones such as acetylacetone, benzoylacetone, and dibenzoylmethane; β-keto acid esters such as ethyl acetoacetate and ethyl benzoylacetate.

  Preferable specific examples of the metal group chelate compound include ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate), alkyl acetoacetate aluminum diisopropylate, aluminum monoacetylacetate bis (ethyl acetoacetate), aluminum tris Aluminum chelate compounds such as (acetylacetonate), ethyl acetoacetate magnesium monoisopropylate, magnesium bis (ethylacetoacetate), alkylacetoacetate magnesium monoisopropylate, magnesium chelate compounds such as magnesium bis (acetylacetonate), zirconium tetra Acetylacetonate, zirconium tributoxyacetylacetonate, jill Um acetylacetonate bis (ethylacetoacetate), manganese acetylacetonate, cobalt acetylacetonate, copper acetylacetonate, titanium acetylacetonate and titanium oxy acetylacetonate. Of these, aluminum tris (acetylacetonate), aluminum tris (ethylacetoacetate), magnesium bis (acetylacetonate), magnesium bis (ethylacetoacetate), and zirconium tetraacetylacetonate are preferred, and storage stability Considering availability, aluminum tris (acetylacetonate) and aluminum tris (ethyl acetoacetate) are particularly preferable.

  The total content of the curing agent is preferably 0.001 to 10 parts by mass, and more preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the total content of the siloxane resin. Especially preferably, it is 0.01 mass part-0.5 mass part.

<Solvent>
In general, the resin composition for forming a low refractive index film (curable composition) of the present embodiment can be constituted using an organic solvent. The organic solvent is basically not particularly limited as long as it satisfies the solubility of each component and the coating property of the resin composition for forming a low refractive index film, but in particular, considers the solubility, coating property, and safety of the binder. Is preferably selected. Moreover, when preparing the resin composition for low refractive index film | membrane formation in this embodiment, you may contain two types of organic solvents.

Examples of organic solvents include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, and ethyl lactate. , Alkyl oxyacetate (eg, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate)), alkyl 3-oxypropionate Esters (eg, methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.) )), 2- Xylpropionic acid alkyl esters (eg, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxy) Propyl propionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate (eg 2-methoxy-2- Methyl methyl propionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc. And as ethers For example, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene Glycol mono n-butyl ether, propylene glycol mono tert-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and ketones For example, methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and the like, and aromatic hydrocarbons include, for example, toluene and xylene.
Particularly preferably, the above-mentioned methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate Butyl carbitol acetate, propylene glycol methyl ether, dipropylene glycol dimethyl ether, propylene glycol mono n-butyl ether, propylene glycol mono tert-butyl ether, and propylene glycol methyl ether acetate.

In the curable composition of the present invention, the applied solvent is preferably 50 to 99.9% by mass and more preferably 60 to 95% by mass in the total amount of the composition. When the amount of the compound is equal to or more than the above lower limit value, the coating property is good, which is preferable. In the case where it is not more than the above upper limit value, the coating property is also good, which is preferable.
In addition, the solvent of the curable composition of the present invention may be a solvent of a dispersion composition containing a high refractive index material to be described later, or a mixed solvent thereof.

(viscosity)
The viscosity of the resin composition for forming a low refractive index film of the present embodiment is preferably adjusted from the viewpoint of forming a thick permeable film. The specific viscosity range is not particularly limited, but is preferably 1 to 20 cP, more preferably 2 to 15 cP, and particularly preferably 4 to 6 cP. Unless otherwise specified, the viscosity value in this specification is based on the measurement method described later.
-Measuring method It measures at room temperature (about 25 degreeC) using E type viscometer "TV-20 type viscometer and cone plate type TVE-20L" (made by Toki Sangyo). Sampling is the average of the values measured for viscosity 5 times every 100 seconds.

  In the present invention, the composition means that two or more components exist substantially uniformly in a specific composition. Here, “substantially uniform” means that each component may be unevenly distributed within the range where the effects of the invention are exerted. The composition is not particularly limited as long as the above definition is satisfied, is not limited to a fluid liquid or a paste, and includes a solid or powder composed of a plurality of components. Furthermore, even when there is a sediment, it means that the composition maintains a dispersion state for a predetermined time by stirring.

<High refractive index material>
The curable composition of this embodiment contains a high refractive index material. The refractive index exhibited by the high refractive index material is preferably more than 1.45, more preferably 1.46 or more, further preferably 1.50 or more, and further preferably 1.55 or more. Preferably, it is 1.6 or more, more preferably 1.7 or more, still more preferably 1.8 or more, and particularly preferably 1.85 or more. The upper limit is preferably 2 or less, more preferably 1.97 or less, still more preferably 1.95 or less, and particularly preferably 1.93 or less.

  The difference between the refractive index of the low refractive index material and the high refractive index material is not particularly limited, but is preferably 0.3 to 0.75, and more preferably 0.35 to 0.7.

The Abbe number of the high refractive index material is preferably 5 or more, more preferably 7 or more, further preferably 10 or more, and particularly preferably 12 or more. The upper limit is preferably 40 or less, more preferably 35 or less, further preferably 30 or less, further preferably 25 or less, and particularly preferably 20 or less. By setting the Abbe number of the high refractive index material within this range, when the film is combined with the low refractive index material, good optical characteristics can be exhibited.
Unless otherwise specified, the Abbe number is evaluated by the refractive index measured by the solvent and measurement method employed in Examples below.
However, in the present invention, the refractive index of the high refractive index material is 1.6 to 2, and the Abbe number is 5 to 40.

Hereinafter, preferred embodiments of the high refractive index material in the present embodiment will be described in detail. However, the present invention is not limited to such an embodiment.
In the present invention, a commercially available curable resin can be suitably used in addition to the resin composition of the embodiment described later. The product names (product numbers) are listed below.
(1) Ultra-high refractive index, high heat-resistant coating material: UR-108, UR-202, UR-501, HR-102 (manufactured by Nissan Chemical Industries)
(2) High refractive index coating material for thick film: UR-108, UR-204, HR-201 (manufactured by Nissan Chemical Industries)
(3) Thioepoxy resin LPH1101 (Mitsubishi Gas Chemical Co., Ltd.)
(4) Episulfide resin MR-174 (Mitsui Chemicals)
(5) Thiourethane resin MR-7 (Mitsui Chemicals)

In the present embodiment, the composition containing a high refractive index material is preferably formed from at least one dispersion composition selected from dispersion compositions I, II, or III described below.
(Dispersion composition I)
The dispersion composition I refers to a metal oxide particle (A) having a primary particle diameter of 1 nm to 100 nm and a graft copolymer (B) having a graft chain in which the number of atoms excluding hydrogen atoms is in the range of 40 to 10,000. And a solvent (C), wherein the content of the metal oxide particles (A) is 50% by mass or more and 90% by mass or less based on the total solid content of the dispersion composition. Refers to things.

(A) Metal oxide particles The metal oxide particles are inorganic particles having a high refractive index, such as titanium (Ti), zirconium (Zr), aluminum (Al), silicon (Si), zinc (Zn) or magnesium ( Mg) oxide particles, and preferably titanium dioxide (TiO ₂ ) particles, zirconium dioxide (ZrO ₂ ) particles, or silicon dioxide (SiO ₂ ) particles. It is more preferable that the
The colorless or transparent titanium dioxide particles can be represented by the chemical formula TiO ₂ , preferably have a purity of 70% or more, more preferably have a purity of 80% or more, and have a purity of 85% or more. preferable. The low-order titanium oxide, titanium oxynitride and the like represented by the formula Ti _n O _2n-1 (n represents a number of 2 to 4) are preferably 30% by mass or less, and 20% by mass or less. Is more preferable, and it is still more preferable that it is 15 mass% or less.
The metal oxide particles are not particularly limited as long as the primary particle diameter is 1 nm to 100 nm. For example, the metal oxide particles can be appropriately selected from commercially available metal oxide particles. The primary particle diameter of the metal oxide particles is preferably 1 nm to 80 nm, and particularly preferably 1 nm to 50 nm. If the primary particle diameter of the metal oxide particles exceeds 100 nm, the refractive index and the transmittance may decrease. When the thickness is less than 1 nm, dispersibility and dispersion stability may be reduced due to aggregation.
The primary particle size of the metal oxide particles is obtained as the average particle size of the metal oxide particles. The average particle diameter of the metal oxide particles is measured by using a dynamic light scattering method for a diluted solution obtained by diluting a mixed solution or dispersion containing the metal oxide particles 80 times with propylene glycol monomethyl ether acetate. The value obtained by doing.
The measurement of the average particle diameter here is the number average particle diameter obtained by using Microtrack UPA-EX150 manufactured by Nikkiso Co., Ltd. The same applies to the following embodiments.

The refractive index of the metal oxide particles is not particularly limited, but is preferably 1.75 to 2.70, more preferably 1.90 to 2.70 from the viewpoint of obtaining a high refractive index. The method for measuring the refractive index is the same as that for the hollow particles.
The specific surface area of the metal oxide particles ^is preferably 10m ² / g~400m 2 / ^g, more preferably from ^{20m 2 / g~200m 2 / g,} 30m 2 / g~150m 2 / g Most preferably.
Moreover, there is no restriction | limiting in particular in the shape of a metal oxide particle. For example, it can be a rice grain shape, a spherical shape, a cubic shape, a spindle shape, or an indefinite shape.

The metal oxide particles may have been surface-treated with an organic compound. Examples of the organic compound used for the surface treatment include polyols, alkanolamines, stearic acid, silane coupling agents, and titanate coupling agents. Of these, silane coupling agents are preferred.
The surface treatment may be carried out by using a single surface treatment agent or a combination of two or more surface treatment agents.
It is also preferable that the surface of the metal oxide particles is covered with an oxide such as aluminum, silicon, or zirconia. Thereby, a weather resistance improves more.

As a metal oxide particle, what is marketed can be used preferably.
Examples of commercially available titanium dioxide particles include TTO series (TTO-51 (A), TTO-51 (C), etc.), TTO-S, and V series (TTO-S-1, TTO-) manufactured by Ishihara Sangyo Co., Ltd. S-2, TTO-V-3, and the like), MT series (MT-01, MT-05, etc.) manufactured by Teika Co., Ltd., and the like.
Examples of commercially available zirconium dioxide particles include UEP (Daiichi Rare Element Chemical Co., Ltd.), PCS (Nippon Denko Co., Ltd.), JS-01, JS-03, JS-04 (Nippon Denko ( Co., Ltd.), UEP-100 (Daiichi Rare Element Chemical Co., Ltd.) and the like.
Examples of commercially available silicon dioxide particles include OG502-31 manufactured by Clariant Co., Ltd.
The metal oxide particles may be used alone or in combination of two or more.

  Further, when constituting the dispersion composition (I) of the present embodiment, in order to obtain a very high refractive index, the content of the metal oxide particles in the composition is determined from the viewpoint of dispersion stability. It is preferable that it is 10-90 mass% with respect to a minute, It is more preferable that it is 10-50 mass%, More preferably, it is 12-40 mass%, Especially preferably, it is 15-35 mass%. On the other hand, particularly for high-refractive-index microlenses, it is 50% by mass to 90% by mass, more preferably 52% by mass to 85% by mass, and most preferably, based on the total solid content of the dispersion composition. It is 55 mass%-80 mass%.

(B) Graft Copolymer The dispersion composition of the present embodiment includes a graft copolymer (hereinafter also referred to as “specific resin”). The graft copolymer of this embodiment has a graft chain in which the number of atoms excluding hydrogen atoms is in the range of 40 to 10,000. The graft chain in this case indicates from the base of the main chain of the copolymer (the atom bonded to the main chain in a group branched from the main chain) to the end of the group branched from the main chain. In the dispersion composition, the specific resin is a dispersion resin that imparts dispersibility to the metal oxide particles, and has an affinity for the solvent due to the graft chain. Excellent dispersion stability. Moreover, when it is set as a dispersion composition, it is thought that it is suppressed that the uniformity of the film thickness in a coating film deteriorates because a graft chain and a solvent show favorable interaction.

(B) The graft copolymer preferably has 40 to 10,000 atoms excluding hydrogen atoms per graft chain, and 100 to 500 atoms excluding hydrogen atoms per graft chain. It is more preferable that the number of atoms excluding hydrogen atoms per graft chain is 150 to 260. If this number is too small, the graft chain is short, so that the steric repulsion effect is reduced and the dispersibility and dispersion stability may be lowered. On the other hand, if the number of atoms excluding hydrogen atoms per graft chain exceeds 10,000 when the number is too large, the graft chain becomes too long, and the adsorptive power to the metal oxide particles decreases, resulting in dispersibility and dispersion stability. May decrease.
The number of atoms excluding hydrogen atoms per graft chain is included from the base atom bonded to the polymer chain constituting the main chain to the end of the branch polymer branched from the main chain. The number of atoms other than hydrogen atoms. When the graft copolymer contains two or more types of graft chains, it is sufficient that the number of atoms excluding hydrogen atoms of at least one type of graft chain satisfies the above requirements.

  As the polymer structure of the graft chain, a poly (meth) acrylic structure, a polyester structure, a polyurethane structure, a polyurea structure, a polyamide structure, a polyether structure, etc. can be used, but the interaction between the graft chain and the solvent is improved. In order to increase the dispersibility and dispersion stability thereby, a graft chain having a poly (meth) acrylic structure, a polyester structure and a polyether structure is preferable, and a polyester structure and a polyether structure are more preferable.

  The graft copolymer preferably has a structural unit having a graft chain (repeating unit), and can be obtained, for example, by polymerizing a macromonomer having a polymer structure as a graft chain based on a conventional method, The structure of such a macromonomer is not particularly limited as long as it has a substituent capable of reacting with the polymer main chain and has a graft chain that satisfies the requirements, but preferably a reactive double bond A macromonomer having a functional group can be preferably used.

  Commercially available macromonomers suitably used for the synthesis of the specific resin include AA-6 (manufactured by Toagosei), AA-10 (manufactured by Toagosei), AB-6 (manufactured by Toagosei), and AS-6 (Toagosei). Synthesizer), AN-6 (Toagosei), AW-6 (Toagosei), AA-714 (Toagosei), AY-707 (Toagosei), AY-714 (Tojo) SK-5 (manufactured by Toagosei), AK-30 (manufactured by Toagosei), AK-32 (manufactured by Toagosei), Blemmer PP-100 (manufactured by NOF Corporation), Blemmer PP-500 (Manufactured by NOF Corporation), BLEMMER PP-800 (manufactured by NOF Corporation), BLEMMER PP-1000 (manufactured by NOF Corporation), BLEMMER 55-PET-800 (manufactured by NOF Corporation), Blemmer PME-4000 (manufactured by NOF Corporation) Manufactured), Blemmer PSE-400 (manufactured by NOF Corporation), Blemma PSE-1300 (manufactured by NOF Corporation), BLEMMER 43PAPE-600B (manufactured by NOF Corporation), and the like. Among these, Preferably, AA-6 (made by Toagosei), AA-10 (made by Toagosei), AB-6 (made by Toagosei), AS-6 (made by Toagosei), AN-6 ( Toagosei Co., Ltd.) and Bremer PME-4000 (manufactured by NOF Corporation).

  The specific resin used in the present embodiment preferably includes at least a structural unit represented by any one of the following formulas (1) to (4) as the structural unit having a graft chain. It is more preferable to include a structural unit represented by any one of (1A), the following formula (2A), the following formula (3), and the following formula (4).

In the formulas (1) to (4), X ¹ , X ² , X ³ , X ⁴ , and X ⁵ each independently represent a hydrogen atom or a monovalent organic group. From the viewpoint of restrictions on synthesis, a hydrogen atom or an alkyl group having 1 to 12 carbon atoms is preferable, a hydrogen atom or a methyl group is more preferable, and a methyl group is particularly preferable.
In the formulas (1) to (4), W ¹ , W ² , W ³ , and W ⁴ each independently represent an oxygen atom or NH, and particularly preferably an oxygen atom.
In Formula (3), R ³ represents a branched or straight chain alkylene group (the carbon number is preferably 1 to 10, more preferably 2 or 3), and —CH ₂ from the viewpoint of dispersion stability. A group represented by —CH (CH ₃ ) — or a group represented by —CH (CH ₃ ) —CH ₂ — is preferred.
Further, as R ³ in the formula (3), two or more types of R ³ having different structures may be mixed and used in the specific resin.
In Formula (1) to Formula (4), Y ¹ , Y ² , Y ³ , and Y ⁴ are each independently a divalent linking group and are not particularly limited in structure. Specific examples include the following (Y-1) to (Y-21) linking groups. In the following structures, A and B each represent a bond with the left terminal group and the right terminal group in formulas (1) to (4). Of the structures shown below, (Y-2) and (Y-13) are more preferable from the viewpoint of ease of synthesis.

In Formula (1) to Formula (4), Z ¹ , Z ² , Z ³ , and Z ⁴ are each independently a hydrogen atom or a monovalent substituent, and the structure of the substituent is not particularly limited. Specific examples include an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group, and an amino group. Among these, it is preferable to have a steric repulsion effect particularly from the viewpoint of improving dispersibility, and the monovalent substituents represented by Z ^{1 to} Z ³ are each independently an alkyl group having 5 to 24 carbon atoms or carbon. An alkoxy group having 5 to 24 carbon atoms is preferable, and among them, an alkoxy group having a branched alkyl group having 5 to 24 carbon atoms or a cyclic alkyl group having 5 to 24 carbon atoms is particularly preferable. The monovalent substituent represented by Z ⁴ is preferably an alkyl group having 5 to 24 carbon atoms, and among them, each independently a branched alkyl group having 5 to 24 carbon atoms or a cyclic group having 5 to 24 carbon atoms. Alkyl groups are preferred.
In Formula (1)-Formula (4), n, m, p, and q are integers of 1-500, respectively.
In Formula (1) and Formula (2), j and k each independently represent an integer of 2 to 8.
J and k in Formula (1) and Formula (2) are preferably integers of 4 to 6, and most preferably 5, from the viewpoint of dispersion stability.

In formula (4), R ⁴ represents a hydrogen atom or a monovalent organic group and is not particularly limited in terms of structure, but is preferably a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, more preferably A hydrogen atom and an alkyl group. When R is an alkyl group, the alkyl group is preferably a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms. A linear alkyl group having 1 to 20 carbon atoms is more preferable, and a linear alkyl group having 1 to 6 carbon atoms is particularly preferable.
Further, as R ⁴ in the formula (4), two or more types of R ⁴ having different structures may be mixed and used in the specific resin.

  The structural unit represented by the formula (1) is more preferably a structural unit represented by the following formula (1A) or (2A) from the viewpoint of dispersion stability.

Wherein ^(1A), X ^1, Y 1, ^{Z 1} and n are as defined ^{X 1,} Y 1, ^{Z 1} and n in Formula (1), and preferred ranges are also the same.
Wherein ^(2A), X ^2, Y 2, ^{Z 2} and m are as defined ^{X 2,} Y 2, ^{Z 2} and m in the formula (2), and preferred ranges are also the same.

  The specific resin is more preferably one having a structural unit represented by the formula (1A).

  In the specific resin, the structural unit (repeating unit) having the graft chain is preferably included in a range of 10% to 75% and in a range of 12% to 50% with respect to the total mass of the specific resin in terms of mass. It is more preferable that it is included in a range of 15% to 40%. Within this range, the dispersibility and dispersion stability of the metal oxide particles are high, and the uniformity of the film thickness in the coating film formed using the dispersion composition is further improved. The specific resin may be a combination of two or more types of graft copolymers having different structures.

Moreover, it is preferable that specific resin is a polymer which has the structural unit (repeating unit) which has an acid group with 25 mass% or more and 90 mass% or less with respect to the total mass of specific resin. The content of the structural unit having an acid group is more preferably 50% by mass or more and 80% by mass or less, and most preferably 60% by mass or more and 75% by mass or less with respect to the total mass of the specific resin. When the content of the structural unit having an acid group is less than 25 masses with respect to the total mass of the specific resin, the adsorptivity of the specific resin to the metal oxide particles becomes insufficient and the dispersion stability is deteriorated.
When the content of the structural unit having an acid group is more than 90% by mass with respect to the total mass of the specific resin, the amount of the graft chain introduced into the specific resin becomes insufficient, resulting in poor dispersion stability. In addition, it is difficult to form a film having a small film thickness difference between the center and the periphery of the wafer.
Moreover, the acid value of specific resin can be suitably adjusted in the following preferable range because content of the structural unit which has an acid group exists in the said range.

The acid group can also function as a functional group capable of forming an interaction with the metal oxide particles in addition to the graft chain.
Examples of the acid group include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phenolic hydroxyl group, and the like. From the viewpoints of adsorption power to metal oxide particles and dispersibility / dispersion stability, the carboxylic acid group It is preferably at least one selected from a group, a sulfonic acid group, and a phosphoric acid group, and a carboxylic acid group is particularly preferable.
Furthermore, the acid group structure is preferably a structure separated by 5 atoms or more from the main chain of the resin structure. Furthermore, as the acid group, a carboxylic acid bonded to an aromatic ring is most preferable.
As said acid group, these can be used individually by 1 type or in combination of 2 or more types.
The acid value of the specific resin is preferably in the range of 70 mgKOH / g to 350 mgKOH / g, more preferably in the range of 80 mgKOH / g to 300 mgKOH / g, and still more preferably in the range of 100 mgKOH / g to 250 mgKOH / g. It is a range. By setting the acid value within the above range, even when the dispersion composition is applied to a large size (for example, 12 inches) wafer, a film having a small difference in film thickness between the central portion and the peripheral portion of the wafer can be obtained more reliably. be able to.
The acid value of the specific resin can be calculated from, for example, the average content of acid groups in the specific resin. Moreover, resin which has a desired acid value can be obtained by changing content of the monomer unit containing the acid group which comprises specific resin.

The specific resin may further have a structural unit (repeating unit) having a functional group capable of forming an interaction with the metal oxide particle other than the graft chain and the acid group. Such a structural unit having a functional group capable of interacting with other metal oxide particles is not particularly limited in terms of structure. For example, a structural unit having a basic group or a structural unit having a coordinating group And structural units having a reactive group.
Examples of the basic group include a primary amino group, a secondary amino group, a tertiary amino group, a heterocyclic ring containing an N atom, and an amide group. Particularly preferred is a tertiary amino group having good adsorption power to metal oxide particles and high dispersibility and dispersion stability. As said basic group, these can be used individually by 1 type or in combination of 2 or more types.
The specific resin may or may not contain a structural unit having a basic group (repeating unit), but when it is contained, the content of the structural unit having a basic group is 0 with respect to the total mass of the specific resin. 0.1 mass% or more and 50 mass% or less, and particularly preferably 0.1 mass% or more and 30 mass% or less.
Examples of the coordinating group and the reactive group include acetylacetoxy group, trialkoxysilyl group, isocyanate group, acid anhydride residue, acid chloride residue and the like. Particularly preferred is an acetylacetoxy group having good adsorption power to metal oxide particles and high dispersibility and dispersion stability. As the coordinating group and the reactive group, these can be used alone or in combination of two or more.
The specific resin may or may not contain a structural unit (repeating unit) having a coordinating group or a reactive group, but if included, a structure having a coordinating group or a reactive group. The unit content is 0.1% by mass or more and 50% by mass or less, and particularly preferably 0.1% by mass or more and 30% by mass or less with respect to the total mass of the specific resin.

  Further, the specific resin is different from the structural unit having the graft chain and the structural unit having the acid group as a structural unit having a functional group capable of forming an interaction with the metal oxide particles, represented by the following formulas (i) to You may have at least 1 sort (s) of the repeating unit obtained from the monomer represented by either (iii).

In the above formulas (i) to (iii), R ¹ , R ² , and R ³ are each independently a hydrogen atom, a halogen atom (eg, fluorine, chlorine, bromine, etc.), or a carbon atom number of 1-6. An alkyl group (for example, a methyl group, an ethyl group, a propyl group, etc.).
R ¹ , R ² , and R ³ are more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and most preferably a hydrogen atom or a methyl group. R ² and R ³ are particularly preferably a hydrogen atom.
X represents an oxygen atom (—O—) or an imino group (—NH—), and is preferably an oxygen atom.

L is a single bond or a divalent linking group. As the divalent linking group, a divalent aliphatic group (for example, alkylene group, substituted alkylene group, alkenylene group, substituted alkenylene group, alkynylene group, substituted alkynylene group), divalent aromatic group (for example, arylene group) , Substituted arylene groups), divalent heterocyclic groups and their oxygen atoms (—O—), sulfur atoms (—S—), imino groups (—NH—), substituted imino groups (—NR ³¹ —, where R ³¹ may be a combination with an aliphatic group, aromatic group or heterocyclic group) or a carbonyl group (—CO—).

The divalent aliphatic group may have a cyclic structure or a branched structure. 1-20 are preferable, as for the carbon atom number of the said aliphatic group, 1-15 are more preferable, and 1-10 are still more preferable.
The aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. Further, the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an aromatic group, and a heterocyclic group.
6-20 are preferable, as for the carbon atom number of the said bivalent aromatic group, 6-15 are more preferable, and 6-10 are the most preferable. The aromatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an aliphatic group, an aromatic group, and a heterocyclic group.
The divalent heterocyclic group preferably has a 5-membered or 6-membered ring as a heterocycle. Another heterocyclic ring, aliphatic ring or aromatic ring may be condensed with the heterocyclic ring. Moreover, the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxy groups, oxo groups (═O), thioxo groups (═S), imino groups (═NH), substituted imino groups (═N—R ³² , where R ³² is a fatty acid. Aromatic group, aromatic group or heterocyclic group), aliphatic group, aromatic group and heterocyclic group.

L is preferably a single bond, an alkylene group or a divalent linking group containing an oxyalkylene structure. The oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure. L may contain a polyoxyalkylene structure containing two or more oxyalkylene structures. The polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure. The polyoxyethylene structure is represented by — (OCH ₂ CH ₂ ) _n —, and n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.

In the above formulas (i) to (iii), Z represents a functional group that can form an interaction with the metal oxide particles, and is preferably an acid group, a basic group, or a reactive group as described above. , A carboxylic acid group or a tertiary amino group is more preferable, and a carboxylic acid group is still more preferable. Y represents a methine group or a nitrogen atom.
In the above formula (iii), R ⁴ , R ⁵ , and R ⁶ are each independently a hydrogen atom, a halogen atom (for example, fluorine, chlorine, bromine, etc.), or an alkyl group having 1 to 6 carbon atoms (for example, , Methyl group, ethyl group, propyl group, etc.), Z, or -LZ. Here, L and Z are as defined above. As R < ⁴ >, R < ⁵ > and R < ⁶ >, a hydrogen atom or a C1-C3 alkyl group is preferable, and a hydrogen atom is more preferable.

As the monomer represented by the above formula (i), R ¹ , R ² , and R ³ are a hydrogen atom or a methyl group, and L is a divalent linking group containing an alkylene group or an oxyalkylene structure. A compound in which X is an oxygen atom or imino group and Z is a carboxylic acid group is preferred.
Further, as the monomer represented by the above formula (ii), R ¹ is a hydrogen atom or a methyl group, L is an alkylene group, Z is a carboxylic acid group, and Y is a methine group. Certain compounds are preferred. The monomer represented by the above formula (iii) is preferably a compound in which R ⁴ , R ⁵ , and R ⁶ are a hydrogen atom or a methyl group and Z is a carboxylic acid group.

  Examples of typical compounds represented by formulas (i) to (iii) include methacrylic acid, crotonic acid, isocrotonic acid, compounds having an addition polymerizable double bond and a hydroxyl group in the molecule (for example, methacrylic acid 2 -Hydroxyethyl) and succinic anhydride reaction product, compound having addition polymerizable double bond and hydroxyl group in the molecule and phthalic anhydride reaction compound, compound having addition polymerizable double bond and hydroxyl group in the molecule And a reaction product of tetrahydroxyphthalic anhydride, a compound having an addition polymerizable double bond and a hydroxyl group in the molecule and trimellitic anhydride, a compound having an addition polymerizable double bond and a hydroxyl group in the molecule, and pyro Reaction with merit anhydride, acrylic acid, acrylic acid dimer, acrylic acid oligomer, maleic acid, itaconic acid, fumaric acid, 4-vinylbenzoic acid, vinyl phenol , 4-hydroxyphenyl methacrylamide.

  Furthermore, the specific resin contained in the dispersion composition of metal oxide particles is a structural unit having the graft chain and the acid group as long as the effects of the present invention are not impaired for the purpose of improving various performances. In addition to structural units having functional groups capable of interacting with metal oxide particles, which are different from these structural units, other structural units having various functions, such as dispersions, are used. A structural unit having a functional group having an affinity for the dispersion medium to be obtained can be included as a structural unit derived from the copolymerization component.

  Examples of the copolymerizable component copolymerizable with the specific resin include radical polymerizable compounds selected from (meth) acrylic acid esters, styrenes, acrylonitriles, methacrylonitriles, acrylamides, methacrylamides, and the like. It is done.

  Specifically, for example, acrylic acid esters such as alkyl acrylate (the alkyl group preferably has 1 to 20 carbon atoms) (specifically, for example, benzyl acrylate, 4-biphenyl acrylate, butyl Acrylate, sec-butyl acrylate, t-butyl acrylate, 4-t-butylphenyl acrylate, 4-chlorophenyl acrylate, pentachlorophenyl acrylate, 4-cyanobenzyl acrylate, cyanomethyl acrylate, cyclohexyl acrylate, 2-ethoxyethyl acrylate, ethyl acrylate 2-ethylhexyl acrylate, heptyl acrylate, hexyl acrylate, isobornyl acrylate, isopropyl acrylate, methyl acrylate, 3,5-dimethyl Adamantyl acrylate, 2-naphthyl acrylate, neopentyl acrylate, octyl acrylate, phenethyl acrylate, phenyl acrylate, propyl acrylate, tolyl acrylate, amyl acrylate, tetrahydrofurfuryl acrylate, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxy Propyl acrylate, 4-hydroxybutyl acrylate, 5-hydroxypentyl acrylate, allyl acrylate, 2-allyloxyethyl acrylate, propargyl acrylate, etc.)

Methacrylic acid esters (eg, benzyl methacrylate, 4-biphenyl methacrylate, butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, 4- t-butylphenyl methacrylate, 4-chlorophenyl methacrylate, pentachlorophenyl methacrylate, 4-cyanophenyl methacrylate, cyanomethyl methacrylate, cyclohexyl methacrylate, 2-ethoxyethyl methacrylate, ethyl methacrylate, 2-ethylhexyl methacrylate, heptyl methacrylate, hexyl methacrylate, isobol Nyl methacrylate, isopropyl methacrylate, methyl methacrylate, 3,5- Methyl adamantyl methacrylate, 2-naphthyl methacrylate, neopentyl methacrylate, octyl methacrylate, phenethyl methacrylate, phenyl methacrylate, propyl methacrylate, tolyl methacrylate, amyl methacrylate, tetrahydrofurfuryl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 2- Hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, allyl methacrylate, 2-allyloxyethyl methacrylate, propargyl methacrylate, 2-diethylaminoethyl methacrylate, 2-dimethylamino methacrylate, etc.)

Styrenes such as styrene and alkyl styrene (for example, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl styrene, Trifluoromethyl styrene, ethoxymethyl styrene, acetoxymethyl styrene etc.), alkoxy styrene (eg methoxy styrene, 4-methoxy-3-methyl styrene, dimethoxy styrene etc.), halogen styrene (eg chlorostyrene, dichlorostyrene, trichlorostyrene, tetra Chlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluoros Ren, 2-bromo-4-trifluoromethyl styrene, 4-fluoro-3-trifluoromethyl styrene etc.), acrylonitrile, methacrylonitrile, and the like.

  Among these radical polymerizable compounds, methacrylic acid esters, acrylamides, methacrylamides, and styrenes are preferably used.

  These radically polymerizable compounds can be used alone or in combination of two or more. The specific resin may or may not contain the above-mentioned radical polymerizable compound, but when it is contained, the content of the structural unit corresponding to these radical polymerizable compounds is 0.000 relative to the total mass of the specific resin. It is 1 mass% or more and 50 mass% or less, Most preferably, it is 0.1 mass% or more and 30 mass% or less. The specific resin can be synthesized by a conventionally known method.

  Specific examples of the specific resin include the following exemplary compounds 1 to 32, but the present invention is not limited thereto. In the following exemplary compounds, the numerical value written together with each structural unit (the numerical value written together with the main chain repeating unit) represents the content of the structural unit [mass%: described as (wt%)]. The numerical value written together with the repeating part of the side chain indicates the number of repetitions of the repeating part.

  The weight average molecular weight (polystyrene equivalent value measured by GPC method) of the specific resin is preferably 5,000 or more and 300,000 or less, more preferably 7,000 or more and 100,000 or less. It is especially preferable that it is 000 or more and 50,000 or less.

In dispersion composition (I), specific resin can be used individually by 1 type or in combination of 2 or more types.
The content of the specific resin relative to the total solid content of the dispersion composition (I) is preferably in the range of 10 to 50% by mass, more preferably in the range of 11 to 40% by mass, from the viewpoints of dispersibility and dispersion stability. The range of ˜30% by mass is more preferable.

-Other dispersion resins-
The dispersion composition (I) contains a dispersion resin other than the specific resin (hereinafter may be referred to as “other dispersion resin”) for the purpose of adjusting the dispersibility of the metal oxide particles. May be.
Other dispersion resins that can be used in the present invention include polymer dispersants [for example, polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly ( (Meth) acrylate, (meth) acrylic copolymer, naphthalene sulfonic acid formalin condensate], polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl amine, alkanol amine, pigment derivative and the like.
Other dispersion resins can be further classified into linear polymers, terminal-modified polymers, graft polymers, and block polymers based on their structures.

Specific examples of other dispersion resins include “Disperbyk-101 (polyamidoamine phosphate), 107 (carboxylic acid ester), 110 (copolymer containing an acid group), 130 (polyamide), 161, manufactured by BYK Chemie. 162, 163, 164, 165, 166, 170 (polymer copolymer) ”,“ BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid) ”,“ EFKA 4047, 4050, 4010, 4165 (polyurethane type) manufactured by EFKA ), EFKA 4330, 4340 (block copolymer), 4400, 4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (Azo pigment derivative) "Ajinomoto Fintechno" Addisper PB821, PB822 ", Kyoeisha Chemical Co., Ltd." Floren TG-710 (urethane oligomer) "," Polyflow No. 50E, No. 300 (acrylic copolymer) ", Enomoto Kasei Co., Ltd. “Dispalon KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyetherester), DA-703-50, DA-705, DA-725”, “Demol RN manufactured by Kao Corporation” , N (naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate), “homogenol L-18 (polymeric polycarboxylic acid)”, “Emulgen 920, 930” , 935, 985 (polyoxyethylene nonylphenyl ether) "," acetamine 86 (su Allylamine acetate) ”, Lubrizol Corporation“ Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 17000, 27000 (polymer having a functional part at the end), 24000, 28000 32000, 38500 (graft type polymer) ”,“ Nikkor T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate) ”manufactured by Nikko Chemicals, and the like.
These other resins may be used alone or in combination of two or more.

  The dispersion composition (I) may or may not contain other dispersion resin, but when it is contained, the content of the other dispersion resin with respect to the total solid content of the dispersion composition (I) is 1 to 20 masses. % Range is preferable, and the range of 1 to 10% by mass is more preferable.

(C) Solvent Although the dispersion composition (I) contains a solvent, the solvent can be composed of various organic solvents.
Organic solvents that can be used here include acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether. , Acetylacetone, cyclohexanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol monomethyl ether Diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, methyl lactate, Examples include ethyl lactate.
These organic solvents can be used alone or in combination. It is preferable that the density | concentration of solid content in dispersion composition (I) is 2-60 mass%.

  The dispersible composition (I) of the present embodiment preferably includes a polymerizable compound (D) and a polymerization initiator, and includes other components as necessary.

(D) Polymerizable compound (D) The polymerizable compound is an addition polymerizable compound having a polymerizable group such as at least one ethylenically unsaturated double bond, an epoxy group, or an oxetanyl group, and has at least a polymerizable group. It is selected from compounds having one, preferably two or more. Such compounds are widely known in the technical field, and can be used without particular limitation in the present invention.
These have chemical forms such as monomers, prepolymers, ie, multimers and oligomers such as dimers and trimers, or mixtures thereof and copolymers thereof. Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amides thereof. In this case, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used. Further, an addition reaction product of an unsaturated carboxylic acid ester or unsaturated carboxylic acid amide having a nucleophilic substituent such as a hydroxyl group, an amino group or a mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and A dehydration condensation reaction product with a monofunctional or polyfunctional carboxylic acid is also preferably used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or unsaturated carboxylic acid amide having an electrophilic substituent such as an isocyanate group or an epoxy group and a monofunctional or polyfunctional alcohol, amine, or thiol; Furthermore, a substitution reaction product of an unsaturated carboxylic acid ester or unsaturated carboxylic acid amide having a leaving group such as a halogen group or a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. It is. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid. As these specific compounds, the compounds described in paragraphs 0095 to 0108 of JP-A-2009-288705 can also be suitably used in the present invention.

  A first preferred form of the polymerizable compound is a monomer having at least one ethylenically unsaturated double bond (polymerizable monomer) or an oligomer having a polymerizable group (polymerizable oligomer) (hereinafter, polymerizable with a polymerizable monomer). In some embodiments, the polymerizable oligomers may be collectively referred to as “polymerizable monomers”.

The polymerizable monomer or the like is also preferably a compound having at least one addition-polymerizable ethylene group and having an ethylenically unsaturated group having a boiling point of 100 ° C. or higher under normal pressure. Examples include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethanetri (Meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (Meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) iso (Meth) acrylate obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohols such as anurate, glycerin and trimethylolethane, JP-B-48-41708, JP-B-50-6034, JP-A-51- Urethane (meth) acrylates as described in JP-B-37193, polyester acrylates described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, Mention may be made of polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of epoxy polymers and (meth) acrylic acid, and mixtures thereof.
A polyfunctional (meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group such as glycidyl (meth) acrylate and an ethylenically unsaturated group can also be used.
Further, as other preferable polymerizable monomers, etc., compounds having a fluorene ring and having two or more functional ethylenic polymerizable groups described in JP 2010-160418 A, JP 2010-129825 A, Patent 4364216, etc. Polymers can also be used.

Further, compounds having a boiling point of 100 ° C. or higher under normal pressure and having at least one addition-polymerizable ethylenically unsaturated group are disclosed in paragraphs [0254] to [0257] of JP-A-2008-292970. The compounds described are also suitable.
Further, compounds described in JP-A-10-62986 as formulas (1) and (2) together with specific examples thereof, which are (meth) acrylated after adding ethylene oxide or propylene oxide to the polyfunctional alcohol, It can be used as a polymerizable monomer.

（式中、ｎは、それぞれ、０〜１４であり、ｍは、それぞれ、１〜８である。一分子内に複数存在するＲ、ＴおよびＺは、それぞれ、同一であっても、異なっていてもよい。Ｔがオキシアルキレン基の場合には、炭素原子側の末端がＲに結合する。Ｒのうち少なくとも１つは、重合性基である。） The polymerizable monomer used in the present invention is preferably a polymerizable monomer represented by the following formulas (MO-1) to (MO-6).

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

が好ましく、

がより好ましい。
上記式（ＭＯ−１）〜（ＭＯ−６）で表される、ラジカル重合性モノマーの具体例としては、特開２００７−２６９７７９号公報の段落番号０２４８〜段落番号０２５１に記載されている化合物を本発明においても好適に用いることができる。 n is preferably 0 to 5, and more preferably 1 to 3.
m is preferably 1 to 5, and more preferably 1 to 3.
R is

Is preferred,

Is more preferable.
Specific examples of the radically polymerizable monomer represented by the above formulas (MO-1) to (MO-6) include compounds described in paragraph numbers 0248 to 0251 of JP-A-2007-26979. It can be suitably used in the present invention.

Among them, as a polymerizable monomer, dipentaerythritol triacrylate (KAYARAD D-330 as a commercially available product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercially available product, KAYARAD D-320; Nippon Kayaku) Dipentaerythritol penta (meth) acrylate (manufactured by K.K.) and dipentaerythritol hexa (meth) acrylate (commercially available KAYARAD DPHA; Nippon Kayaku Co., Ltd.) Company), and the structure in which these (meth) acryloyl groups are mediated by ethylene glycol and propylene glycol residues, diglycerin EO (ethylene oxide) modified (meth) acrylate (as a commercial product, M-460; manufactured by Toa Gosei) ) Preferred. These oligomer types can also be used.
For example, RP-1040 (made by Nippon Kayaku Co., Ltd.) etc. are mentioned.

  As a polymerizable monomer etc., it is a polyfunctional monomer, Comprising: You may have acid groups, such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Therefore, if the ethylenic compound has an unreacted carboxyl group as in the case of a mixture as described above, this can be used as it is. The acid group may be introduced by reacting the group with a non-aromatic carboxylic acid anhydride. In this case, specific examples of the non-aromatic carboxylic acid anhydride used include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, alkylated hexahydrophthalic anhydride, succinic anhydride, anhydrous Maleic acid is mentioned.

In the present invention, the monomer having an acid group is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. A polyfunctional monomer having an acid group is preferable, and in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. Examples of commercially available products include Aronix series M-305, M-510, and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.
A preferable acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mg-KOH / g, and particularly preferably 5 to 30 mg-KOH / g. When two or more polyfunctional monomers having different acid groups are used in combination, or when a polyfunctional monomer having no acid group is used in combination, it is essential that the acid value of the entire polyfunctional monomer is within the above range. It is.

Moreover, it is preferable to contain the polyfunctional monomer which has a caprolactone modified structure as a polymerizable monomer.
The polyfunctional monomer having a caprolactone-modified structure is not particularly limited as long as it has a caprolactone-modified structure in the molecule. For example, trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane , Obtained by esterifying polyhydric alcohol such as pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, trimethylolmelamine, (meth) acrylic acid and ε-caprolactone, Mention may be made of functional (meth) acrylates. Among these, a polyfunctional monomer having a caprolactone-modified structure represented by the following formula (1) is preferable.

（式中、６個のＲは全てが下記式（２）で表される基であるか、または６個のＲのうち１〜５個が下記式（２）で表される基であり、残余が下記式（３）で表される基である。）

(In the formula, all 6 Rs are groups represented by the following formula (2), or 1 to 5 of 6 Rs are groups represented by the following formula (2), The remainder is a group represented by the following formula (3).)

（式中、Ｒ^１は水素原子またはメチル基を示し、ｍは１または２の数を示し、「＊」は結合手であることを示す。）

(In the formula, R ¹ represents a hydrogen atom or a methyl group, m represents a number of 1 or 2, and “*” represents a bond.)

（式中、Ｒ^１は水素原子またはメチル基を示し、「＊」は結合手であることを示す。）

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and “*” represents a bond.)

The polyfunctional monomer having such a caprolactone-modified structure is commercially available, for example, as KAYARAD DPCA series from Nippon Kayaku Co., Ltd., and DPCA-20 (m = 1, number of groups represented by formula (2) = 2, compound in which R ¹ is all hydrogen atoms, DPCA-30 (same formula, m = 1, number of groups represented by formula (2) = 3, compound in which R ¹ is all hydrogen atoms), DPCA-60 (same formula, m = 1, number of groups represented by formula (2) = 6, compound in which R ¹ is all hydrogen atoms), DPCA -120 (a compound in which m = 2 in the formula, the number of groups represented by formula (2) = 6, and all R ¹ are hydrogen atoms).
In this invention, the polyfunctional monomer which has a caprolactone modified structure can be used individually or in mixture of 2 or more types.

  In addition, the polymerizable monomer or the like in the present invention is preferably at least one selected from the group of compounds represented by the following formula (i) or (ii).

In the formula (i) and (ii), E are each _{independently, - ((CH 2) yCH} 2 O) -, or _{- ((CH 2) y CH} (CH 3) O) - represents, y Each independently represents an integer of 0 to 10, and each X independently represents an acryloyl group, a methacryloyl group, a hydrogen atom, or a carboxyl group.
In said formula (i), the sum total of an acryloyl group and a methacryloyl group is 3 or 4, m represents the integer of 0-10 each independently, and the sum total of each m is an integer of 0-40. However, when the total of each m is 0, any one of X is a carboxyl group.
In said formula (ii), the sum total of an acryloyl group and a methacryloyl group is 5 or 6, each n represents the integer of 0-10 each independently, and the sum total of each n is an integer of 0-60. However, when the total of each n is 0, any one of X is a carboxyl group.

In the formula (i), m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4. Moreover, the integer of 2-40 is preferable, the integer of 2-16 is more preferable, and the integer of 4-8 is especially preferable as the sum total of each m.
In the formula (ii), n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4. Further, the total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12.
Further,-((CH ₂ ) _y CH ₂ O)-or-((CH ₂ ) _y CH (CH ₃ ) O)-in formula (i) or formula (ii) is such that the end on the oxygen atom side is X Preferred is a form that binds to.

  The compounds represented by the formula (i) or (ii) may be used alone or in combination of two or more. In particular, in the formula (ii), a form in which all six Xs are acryloyl groups is preferable.

Among the compounds represented by the formula (i) or (ii), a pentaerythritol derivative and / or a dipentaerythritol derivative is more preferable.
Specific examples include compounds represented by the following formulas (a) to (f) (hereinafter also referred to as “exemplary compounds (a) to (f)”), and among them, exemplary compounds (a) and ( b), (e) and (f) are preferred.

  Examples of commercially available monomers such as polymerizable monomers represented by formulas (i) and (ii) include SR-494, a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer, manufactured by Nippon Kayaku Co., Ltd. DPCA-60, which is a hexafunctional acrylate having six pentyleneoxy chains, and TPA-330, which is a trifunctional acrylate having three isobutyleneoxy chains.

Examples of polymerizable monomers include urethane acrylates as described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, Urethane compounds having an ethylene oxide skeleton described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 are also suitable. Furthermore, as polymerizable monomers, addition polymerizable monomers having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, JP-A-1-105238 Can be used to obtain a curable composition having a very high photosensitive speed.
Commercially available products such as polymerizable monomers include urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 "(manufactured by Shin-Nakamura Chemical Co., Ltd., DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA -306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha) and the like.

  A polyfunctional thiol compound having two or more mercapto (SH) groups in the same molecule is also suitable as the polymerizable monomer. In particular, those represented by the following formula (I) are preferable.

（式中、Ｒ^１はアルキル基、Ｒ^２は炭素以外の原子を含んでもよいｎ価の脂肪族基、Ｒ^０はＨではないアルキル基、ｎは２〜４を表す。）

(In the formula, R ¹ is an alkyl group, R ² is an n-valent aliphatic group that may contain atoms other than carbon, R ⁰ is an alkyl group that is not H, and n is 2 to 4.)

  If the polyfunctional thiol compound represented by the above formula (I) is specifically exemplified, 1,4-bis (3-mercaptobutyryloxy) butane having the following structural formula [formula (II)], 1 , 3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triasian-2,4,6 (1H, 3H5H) -trione [formula (III)] and pentaerythritol tetrakis (3- Mercaptobutyrate) [formula (IV)] and the like. These polyfunctional thiols can be used alone or in combination.

  In the present invention, it is also preferable to use a polymerizable monomer or oligomer having two or more epoxy groups or oxetanyl groups in the molecule as the polymerizable monomer.

<< C: Compound having epoxy group or oxetanyl group >>
In a third preferred embodiment of the present invention, a compound having an epoxy group or an oxetanyl group may be used as the polymerizable compound. Specific examples of the compound having an epoxy group or oxetanyl group include a polymer having an epoxy group in the side chain, and a polymerizable monomer or oligomer having two or more epoxy groups in the molecule, and a bisphenol A type epoxy resin, Bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, aliphatic epoxy resin and the like can be mentioned.
These compounds may be used as commercial products or can be obtained by introducing an epoxy group into the side chain of the polymer.

  As a commercial product, for example, as bisphenol A type epoxy resin, JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1055, JER1007, JER1009, JER1010 (above, Japan Epoxy Resin Co., Ltd.), EPICLON860, EPICLON1050, EPICLON1051, EPICLON1055 (manufactured by DIC Corporation), etc., and bisphenol F type epoxy resin is JER806, JER807, JER4004, JER4005, JER4007, JER4010 (above, Japan Epoxy Resin Co., Ltd.), EPICLON830, EPICLON835. (Above, manufactured by DIC Corporation), LCE-21, RE-602S (above, Nippon Kayaku) As a phenol novolac type epoxy resin, JER152, JER154, JER157S70, JER157S65 (manufactured by Japan Epoxy Resins Co., Ltd.), EPICLON N-740, EPICLON N-740, EPICLON N- 770, EPICLON N-775 (manufactured by DIC Corporation) and the like, and cresol novolac type epoxy resins include EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N- 680, EPICLON N-690, EPICLON N-695 (manufactured by DIC Corporation), EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd.), etc., and as an aliphatic epoxy resin, ADEK RESIN EP-4080S, EP-4085S, EP-4088S (above, manufactured by ADEKA) Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, EHPE3150, EPOLEEAD PB 3600, PB 4700 (above, Daicel Chemical Industries) (Manufactured by Nagase ChemteX Corp.), etc., Denacol EX-212L, EX-214L, EX-216L, EX-321L, EX-850L. In addition, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4010S, EP-4011S (above, manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above, manufactured by ADEKA Co., Ltd.), JER1031S (manufactured by Japan Epoxy Resin Co., Ltd.) and the like.

  Specific examples of the polymer having an oxetanyl group in the side chain and the polymerizable monomer or oligomer having two or more oxetanyl groups in the molecule include Aronoxetane OXT-121, OXT-221, OX-SQ, PNOX ( As described above, Toagosei Co., Ltd.) can be used.

In the case of synthesizing by introducing into a polymer side chain, for example, the introduction reaction includes tertiary amines such as triethylamine and benzylmethylamine, quaternary ammonium salts such as dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, pyridine, The reaction can be carried out in an organic solvent at a reaction temperature of 50 to 150 ° C. for several to several tens of hours using triphenylphosphine or the like as a catalyst. The introduction amount of the alicyclic epoxy unsaturated compound is preferably controlled so that the acid value of the obtained polymer is in a range satisfying 5 to 200 KOH · mg / g. Further, the molecular weight is preferably 500 to 5000000, more preferably 1000 to 500000 in terms of weight average.
As the epoxy unsaturated compound, those having a glycidyl group as an epoxy group such as glycidyl (meth) acrylate and allyl glycidyl ether can be used, but preferred are unsaturated compounds having an alicyclic epoxy group. Examples of such compounds include the following compounds.

Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide and the like.
Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B No. 54-21726.

In addition, urethane-based addition polymerizable compounds produced by using an addition reaction of isocyanate and hydroxyl group are also suitable, and specific examples thereof include, for example, one molecule described in JP-B-48-41708. A vinylurethane compound containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer having a hydroxyl group represented by the following formula (V) to a polyisocyanate compound having two or more isocyanate groups: Etc.
In the following formula (V), R ⁷ and R ⁸ each independently represent a hydrogen atom or a methyl group.

H ₂ C═CR ⁷ COOCH ₂ CH (R ⁸ ) OH Formula (V)

  Also, urethane acrylates such as those described in JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, JP-B-58-49860, JP-B-56- Urethane compounds having an ethylene oxide skeleton described in Japanese Patent No. 17654, Japanese Patent Publication No. 62-39417, and Japanese Patent Publication No. 62-39418 are also suitable. Furthermore, by using polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238. Can obtain a curable composition having a very high photosensitive speed.

  Other examples include polyester acrylates, epoxy resins and (meth) acrylic acid as described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, and JP-A-52-30490. Mention may be made of polyfunctional acrylates and methacrylates such as epoxy acrylates obtained by reaction. Also, specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337, JP-B-1-40336, vinylphosphonic acid compounds described in JP-A-2-25493, and the like Can be mentioned. In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, the Japan Adhesion Association magazine vol. 20, no. 7, 300-308 (1984), photocurable monomers and oligomers can also be used.

About these polymeric compounds, the details of usage methods, such as the structure, single use, combined use, and addition amount, can be arbitrarily set according to the final performance design of a curable composition. For example, it is selected from the following viewpoint.
From the viewpoint of sensitivity, a structure having a large unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Further, in order to increase the strength of the cured film, those having three or more functionalities are preferable, and further, different functional numbers and different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrene compound, vinyl ether compound, epoxy) It is also effective to adjust both sensitivity and strength by using a combination of a compound based on a compound and an oxetane compound).
In addition, the selection and use of the polymerizable compound is also an important factor for compatibility and dispersibility with other components (for example, polymerization initiator, metal oxide particles, etc.) contained in the curable composition. For example, the compatibility may be improved by using a low-purity compound or using two or more other components in combination. In addition, a specific structure may be selected for the purpose of improving adhesion to a hard surface such as a substrate.

The content of the polymerizable compound (D) is preferably in the range of 1% by mass to 50% by mass with respect to the total solid content of the curable composition for forming a high refractive index layer, and is preferably 3% by mass to 40% by mass. % Is more preferable, and a range of 5% by mass to 30% by mass is even more preferable.
Within this range, the curability is good and preferable without lowering the refractive index.

(E) Polymerization initiator (E) The polymerization initiator is a compound that initiates and accelerates the polymerization of the (D) polymerizable compound, and is stable up to 45 ° C., but has a good polymerization initiation ability when heated at high temperatures. It is preferable.
The polymerization initiator preferably contains at least one compound having a molecular extinction coefficient of at least about 50 within a range of about 300 nm to 800 nm (more preferably 330 nm to 500 nm).
Moreover, a polymerization initiator can be used individually or in combination of 2 or more types.

(E) As the polymerization initiator, for example, organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, metallocene compounds, Examples include hexaarylbiimidazole compounds, organic boric acid compounds, disulfonic acid compounds, oxime ester compounds, onium salt compounds, and acylphosphine (oxide) compounds.
As specific examples of these, the description after paragraph [0135] of JP 2010-106268 A (corresponding US Patent Application Publication No. 2011/0124824 [0163]) can be referred to. Incorporated into.

As the polymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be suitably used. More specifically, for example, aminoacetophenone initiators described in JP-A-10-291969 and acylphosphine oxide initiators described in Japanese Patent No. 4225898 can also be used.
As the hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (trade names: all manufactured by BASF) can be used.
As the aminoacetophenone-based initiator, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF) can be used. As the aminoacetophenone-based initiator, a compound described in JP-A-2009-191179 in which an absorption wavelength is matched with a long-wave light source such as 365 nm or 405 nm can also be used.
As the acylphosphine initiator, commercially available products such as IRGACURE-819, Darocur 4265, and DAROCUR-TPO (trade names: all manufactured by BASF) can be used.

(E) As a polymerization initiator, an oxime compound is preferable from the viewpoints of curability, stability over time, and difficulty in coloring during post-heating.
Examples of oxime compounds include J.M. C. S. Perkin II (1979) 1653-1660), J. MoI. C. S. Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, Journal of Applied Polymer Science (2012) pp. 725-731, compounds described in JP-A No. 2000-66385, compounds described in JP-A No. 2000-80068, JP-T 2004-534797, and the like.
Further, as oxime ester compounds other than those described above, compounds described in JP-T 2009-519904, in which an oxime is linked to the N-position of carbazole, compounds described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety, A compound described in Japanese Patent Application Laid-Open No. 2010-15025 and US Patent Publication No. 2009-292039 in which a nitro group is introduced at the dye site, a ketoxime compound described in International Patent Publication No. 2009-131189, the triazine skeleton and the oxime skeleton are identical A compound described in US Pat. No. 7,556,910 contained in the molecule, a compound described in JP-A-2009-221114 having an absorption maximum at 405 nm and good sensitivity to a g-line light source, and the like may be used. .
Furthermore, the cyclic oxime compounds described in JP2007-231000A and JP2007-322744A can also be suitably used. Among the cyclic oxime compounds, in particular, the cyclic oxime compounds fused to the carbazole dyes described in JP2010-32985A and JP2010-185072A have high light absorption and high sensitivity. preferable.
Further, the compound described in JP-A-2009-242469 having an unsaturated bond at a specific site of the oxime compound can be preferably used because it can achieve high sensitivity by regenerating active radicals from polymerization inert radicals. it can.

  In addition, an oxime compound having a specific substituent as disclosed in JP 2007-269979 A and an oxime compound having a thioaryl group as disclosed in JP 2009-191061 A can be given.

式（ＯＸ）中、Ｒ及びＢは後記式（ＯＸ−１）と同義である。Ａ^１は式（ＯＸ−１）の−Ａ−ＳＡｒまたはアルキル基であることが好ましい。アルキル基は、炭素数１〜１２が好ましく、１〜６であることがより好ましく、１〜３であることが特に好ましい。

In the formula (OX), R and B are as defined in the following formula (OX-1). A ¹ is preferably -A-SAr of formula (OX-1) or an alkyl group. The alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms.

In formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.
In the formula (OX-1), the monovalent substituent represented by R is preferably a monovalent nonmetallic atomic group.
Examples of the monovalent nonmetallic atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group. Moreover, these groups may have one or more substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.
Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group.

  In the formula (OX-1), the monovalent substituent represented by B represents an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group. These groups may be bonded to the methylene group via a linking group, and examples of the linking group include a single bond, a carbonyl group, a substituent Y described later, an alkyl group, or a combination thereof. These groups may have one or more substituents. Examples of the substituent include the above-described substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.

Of these, the structures shown below are particularly preferred.
In the following structure, Y, X, and n have the same meanings as Y, X, and n in formula (OX-2) described later, and preferred examples are also the same.
As the oxime initiator, paragraph 0513 of JP 2012-208494 A (corresponding US Patent Application Publication No. 2012/235099, [0632]) and the following formulas (OX-1), (OX-2) or ( Description of the compound represented by OX-3) can be referred to, and the contents thereof are incorporated in the present specification.

  Specific examples (PIox-1) to (PIox-13) of oxime compounds that can be suitably used are shown below, but the present invention is not limited thereto.

  The oxime compound has a function as a thermal polymerization initiator that decomposes by heat to start and accelerate polymerization. In particular, the oxime compound represented by the formula (a) is less colored by post-heating and has good curability.

The oxime compound preferably has a maximum absorption wavelength in the wavelength region of 350 nm to 500 nm, more preferably has an absorption wavelength in the wavelength region of 360 nm to 480 nm, and has high absorbance at 365 nm and 455 nm. Particularly preferred.
The molar extinction coefficient at 365 nm or 405 nm of the oxime compound is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, more preferably 5,000 to 200, from the viewpoint of sensitivity. Is particularly preferred. A known method can be used for the molar extinction coefficient of the compound. Specifically, for example, in an ultraviolet-visible spectrophotometer (Varian's Carry-5 spectrophotometer), an ethyl acetate solvent is used, and 0.01 g It is preferable to measure at a concentration of / L.
Moreover, as oxime compounds, commercially available products such as IRGACURE OXE01 and IRGACURE OXE02 (both manufactured by BASF) can be suitably used.

  (E) As a polymerization initiator, from the viewpoint of curability, a trihalomethyltriazine compound, a benzyldimethyl ketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound Oxime compounds, triallylimidazole dimer, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, 3- Compounds selected from the group consisting of aryl substituted coumarin compounds are preferred.

  (E) The content of the polymerization initiator (in the case of two or more types, the total content) is preferably 0.1% by mass or more and 10% by mass or less, more preferably, based on the total solid content of the curable composition. Is 0.3 mass% or more and 8 mass% or less, More preferably, it is 0.5 mass% or more and 5 mass% or less. Within this range, good curability can be obtained.

  Furthermore, you may contain further the arbitrary components explained in full detail as needed.

[Polymerization inhibitor]
In order to prevent unnecessary polymerization of a compound having an ethylenically unsaturated double bond that can be polymerized during production or storage, a polymerization inhibitor is preferably added.
Polymerization inhibitors include phenolic hydroxyl group-containing compounds, N-oxide compounds, piperidine 1-oxyl free radical compounds, pyrrolidine 1-oxyl free radical compounds, N-nitrosophenylhydroxylamines, diazonium compounds, and cations Examples include dyes, sulfide group-containing compounds, nitro group-containing compounds, transition metal compounds such as FeCl ₃ and CuCl ₂ . As the polymerization inhibitor, specifically, description of JP 2010-106268 A, paragraphs 0260 to 0280 (corresponding to [0284] to [0296] of US 2011/0124824) can be referred to. The contents of which are incorporated herein by reference.

A preferable addition amount of the polymerization inhibitor is preferably 0.01 parts by weight or more and 10 parts by weight or less, and more preferably 0.01 parts by weight or more and 8 parts by weight or less with respect to 100 parts by weight of the polymerization initiator (E). It is preferable that it is in the range of 0.05 parts by mass or more and 5 parts by mass or less.
By setting it as the said range, the curing reaction suppression in a non-image part and the curing reaction acceleration in an image part are fully performed, and image forming property and a sensitivity become favorable.

[Binder polymer]
It is preferable that the dispersion composition of this embodiment further contains a binder polymer.
It is preferable to use a linear organic polymer as the binder polymer. As such a linear organic polymer, a well-known thing can be used arbitrarily. Preferably, a linear organic polymer that is soluble or swellable in water or weak alkaline water is selected to enable water development or weak alkaline water development. The linear organic polymer is selected and used not only as a film forming agent but also according to the use as water, weak alkaline water or an organic solvent developer. For example, when a water-soluble organic polymer is used, water development becomes possible. Examples of such linear organic polymers include radical polymers having a carboxylic acid group in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, and JP-B-sho. No. 54-25957, JP-A-54-92723, JP-A-59-53836, JP-A-59-71048, ie, a monomer having a carboxyl group alone or Copolymerized resin, acid anhydride monomer alone or copolymerized, acid anhydride unit hydrolyzed, half esterified or half amidated, epoxy resin unsaturated monocarboxylic acid and acid anhydride Examples include modified epoxy acrylate. Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 4-carboxylstyrene, and the monomer having an acid anhydride includes maleic anhydride. It is done.
Similarly, there is an acidic cellulose derivative having a carboxylic acid group in the side chain. In addition, those obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group are useful.

  When a copolymer is used as the binder polymer, monomers other than the monomers listed above can be used as the compound to be copolymerized. Examples of other monomers include the following compounds (1) to (12).

(1) 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate Acrylic acid esters and methacrylic acid esters having an aliphatic hydroxyl group such as
(2) Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, benzyl acrylate, acrylic acid-2- Alkyl acrylates such as chloroethyl, glycidyl acrylate, 3,4-epoxycyclohexylmethyl acrylate, vinyl acrylate, 2-phenylvinyl acrylate, 1-propenyl acrylate, allyl acrylate, 2-allyloxyethyl acrylate, propargyl acrylate;

(3) Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, amyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, methacrylic acid-2- Alkyl methacrylates such as chloroethyl, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, vinyl methacrylate, 2-phenylvinyl methacrylate, 1-propenyl methacrylate, allyl methacrylate, 2-allyloxyethyl methacrylate, and propargyl methacrylate.
(4) Acrylamide, methacrylamide, N-methylolacrylamide, N-ethylacrylamide, N-hexylmethacrylamide, N-cyclohexylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-nitrophenylacrylamide, N-ethyl- Acrylamide or methacrylamide such as N-phenylacrylamide, vinylacrylamide, vinylmethacrylamide, N, N-diallylacrylamide, N, N-diallylmethacrylamide, allylacrylamide, allylmethacrylamide.

(5) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, and phenyl vinyl ether.
(6) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate.
(7) Styrenes such as styrene, α-methylstyrene, methylstyrene, chloromethylstyrene, and p-acetoxystyrene.
(8) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.
(9) Olefins such as ethylene, propylene, isobutylene, butadiene, and isoprene.
(10) N-vinylpyrrolidone, acrylonitrile, methacrylonitrile and the like.
(11) Unsaturated imides such as maleimide, N-acryloylacrylamide, N-acetylmethacrylamide, N-propionylmethacrylamide, N- (p-chlorobenzoyl) methacrylamide.
(12) A methacrylic acid monomer having a hetero atom bonded to the α-position. For example, the compounds described in JP-A-2002-309057, JP-A-2002-311569 and the like can be mentioned.

  The binder polymer preferably contains a repeating unit obtained by polymerizing a monomer component essentially comprising a compound represented by the following formula (ED) (hereinafter sometimes referred to as “ether dimer”).

(In formula (ED), R ₁ and R ₂ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.)

Thereby, the curable composition for high refractive index layer formation of this embodiment can form the cured coating film which was very excellent also in heat resistance and transparency. In the formula (ED) showing the ether dimer, the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ₁ and R ₂ is not particularly limited. Linear or branched alkyl group; aryl group; alicyclic group such as cyclohexyl, t-butylcyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl, 2-methyl-2-adamantyl; alkoxy An alkyl group substituted with an aryl group such as benzyl; and the like. Among these, an acid such as methyl, ethyl, cyclohexyl, benzyl or the like, or a primary or secondary carbon substituent which is difficult to be removed by heat is preferable from the viewpoint of heat resistance.

Specific examples of the ether dimer include specific examples of the ether dimer described in paragraph [0565] of JP2012-208494A (corresponding to [0694] of the corresponding US Patent Application Publication No. 2012/235099), These contents are incorporated herein.
Specific examples of the ether dimer include dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2, 2 ′-[oxybis (methylene)] bis-2-propenoate and dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate are preferred. These ether dimers may be used alone or in combination of two or more. The structure derived from the compound represented by the formula (ED) may be copolymerized with other monomers.

  Other monomers that can be copolymerized with the ether dimer include, for example, a monomer for introducing an acid group, a monomer for introducing a radical polymerizable double bond, and an epoxy group. Monomers and other copolymerizable monomers other than these may be mentioned. Only 1 type may be used for such a monomer and it may use 2 or more types.

Examples of the monomer for introducing an acid group include monomers having a carboxyl group such as (meth) acrylic acid and itaconic acid, monomers having a phenolic hydroxyl group such as N-hydroxyphenylmaleimide, maleic anhydride, and anhydride. And monomers having a carboxylic anhydride group such as itaconic acid. Among these, (meth) acrylic acid is particularly preferable.
The monomer for introducing an acid group may be a monomer that can give an acid group after polymerization, for example, a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, Examples thereof include a monomer having an epoxy group such as glycidyl (meth) acrylate, and a monomer having an isocyanate group such as 2-isocyanatoethyl (meth) acrylate. When using a monomer for introducing a radical polymerizable double bond, when using a monomer capable of imparting an acid group after polymerization, it is necessary to perform a treatment for imparting an acid group after polymerization. The treatment for adding an acid group after polymerization varies depending on the type of monomer, and examples thereof include the following treatment. In the case of using a monomer having a hydroxyl group, for example, a treatment of adding an acid anhydride such as succinic anhydride, tetrahydrophthalic anhydride, maleic anhydride or the like can be mentioned. In the case of using a monomer having an epoxy group, for example, a compound having an amino group and an acid group such as N-methylaminobenzoic acid or N-methylaminophenol is added, or, for example, (meth) acrylic For example, a treatment of adding an acid anhydride such as succinic acid anhydride, tetrahydrophthalic acid anhydride, maleic acid anhydride to the hydroxyl group generated after adding an acid such as an acid can be mentioned. In the case of using a monomer having an isocyanate group, for example, a treatment of adding a compound having a hydroxyl group and an acid group such as 2-hydroxybutyric acid can be mentioned.

  When the polymer obtained by polymerizing the monomer component containing the compound represented by the formula (ED) contains a monomer for introducing an acid group, the content ratio is not particularly limited. In the monomer component, 5 to 70% by mass is preferable, and 10 to 60% by mass is more preferable.

  Examples of the monomer for introducing a radical polymerizable double bond include, for example, monomers having a carboxyl group such as (meth) acrylic acid and itaconic acid; carboxylic acid anhydrides such as maleic anhydride and itaconic anhydride Monomers having a group; monomers having an epoxy group such as glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbenzyl glycidyl ether; . When using a monomer for introducing a radical polymerizable double bond, it is necessary to perform a treatment for imparting a radical polymerizable double bond after polymerization. The treatment for imparting a radical polymerizable double bond after polymerization differs depending on the type of monomer that can impart a radical polymerizable double bond to be used, and examples thereof include the following treatment. If a monomer having a carboxyl group such as (meth) acrylic acid or itaconic acid is used, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p- ) Treatment of adding a compound having an epoxy group such as vinylbenzyl glycidyl ether and a radically polymerizable double bond. In the case of using a monomer having a carboxylic anhydride group such as maleic anhydride or itaconic anhydride, a treatment for adding a compound having a hydroxyl group and a radical polymerizable double bond such as 2-hydroxyethyl (meth) acrylate Is mentioned. If a monomer having an epoxy group such as glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbenzylglycidyl ether is used, (meth) The process which adds the compound which has acid groups, such as acrylic acid, and a radically polymerizable double bond is mentioned.

  When the polymer obtained by polymerizing the monomer component containing the compound represented by the formula (ED) contains a monomer for introducing a radical polymerizable double bond, the content ratio is not particularly limited. However, 5-70 mass% is preferable in all the monomer components, More preferably, it is 10-60 mass%.

Examples of the monomer for introducing an epoxy group include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbenzyl glycidyl ether, and the like. Can be mentioned.
When the polymer obtained by polymerizing the monomer component containing the compound represented by the formula (ED) contains a monomer for introducing an epoxy group, the content ratio is not particularly limited. In the monomer component, 5 to 70% by mass is preferable, and 10 to 60% by mass is more preferable.

  Examples of other copolymerizable monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and (meth) acrylate n. -Butyl, isobutyl (meth) acrylate, t-butyl (meth) acrylate, methyl 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2- (meth) acrylic acid 2- (Meth) acrylic acid esters such as hydroxyethyl; aromatic vinyl compounds such as styrene, vinyltoluene and α-methylstyrene; N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide; butadiene, isoprene and the like Butadiene or substituted butadiene compounds; ethylene, propylene, vinyl chloride Ethylene or substituted ethylene compound such as acrylonitrile, vinyl esters such as vinyl acetate; and the like. Among these, methyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, and styrene are preferable in terms of good transparency and resistance to heat resistance.

  When the polymer obtained by polymerizing the monomer component containing the compound represented by the formula (ED) contains another copolymerizable monomer, the content ratio is not particularly limited, but is 95% by mass or less. Is preferable, and it is more preferable that it is 85 mass% or less.

The weight average molecular weight of the polymer obtained by polymerizing the monomer component containing the compound represented by the formula (ED) is not particularly limited, but is formed by the viscosity of the colored radiation-sensitive composition and the composition. From a viewpoint of the heat resistance of a coating film, Preferably it is 2000-200000, More preferably, it is 5000-100000, More preferably, it is 5000-20000.
Moreover, when the polymer formed by polymerizing the monomer component containing the compound represented by the formula (ED) has an acid group, the acid value is preferably 30 to 500 mgKOH / g, more preferably 50 to It should be 400 mg KOH / g.

A polymer obtained by polymerizing a monomer component containing a compound represented by the formula (ED) can be easily obtained by polymerizing at least the above-mentioned monomer essentially containing an ether dimer. At this time, the cyclization reaction of the ether dimer proceeds simultaneously with the polymerization to form a tetrahydropyran ring structure.
The polymerization method applied to the synthesis of the polymer obtained by polymerizing the monomer component containing the compound represented by the formula (ED) is not particularly limited, and various conventionally known polymerization methods can be employed. However, it is particularly preferable to use a solution polymerization method. Specifically, for example, a polymer obtained by polymerizing a monomer component containing a compound represented by the formula (ED) according to the synthesis method of the polymer (a) described in JP-A-204-300204 Can be synthesized

  Hereinafter, although the exemplary compound of the polymer formed by superposing | polymerizing the monomer component containing the compound represented by a formula (ED) is shown, this invention is not limited to these. The composition ratio of the exemplary compounds shown below is mol%.

In the present invention, in particular, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate (hereinafter referred to as “DM”), benzyl methacrylate (hereinafter referred to as “BzMA”), methyl methacrylate (hereinafter referred to as “MMA”). ), Methacrylic acid (hereinafter referred to as “MAA”), and glycidyl methacrylate (hereinafter referred to as “GMA”). In particular, the molar ratio of DM: BzMA: MMA: MAA: GMA is preferably 5-15: 40-50: 5-15: 5-15: 20-30. It is preferable that 95% by mass or more of the components constituting the copolymer used in the present invention is these components. Moreover, it is preferable that the weight average molecular weights of this polymer are 9000-20000.
The polymer used in the present invention preferably has a weight average molecular weight (polystyrene conversion value measured by GPC method) of 1000 to 2 × 10 ⁵ , more preferably 2000 to 1 × 10 ⁵ , and 5000 to More preferably, it is 5 × 10 ⁴ .

  Among these, a (meth) acrylic resin having an allyl group, a vinyl ester group, and a carboxyl group in the side chain and a side chain described in JP-A Nos. 2000-187322 and 2002-62698 are doubled. An alkali-soluble resin having a bond and an alkali-soluble resin having an amide group in the side chain described in JP-A No. 2001-242612 are preferable because of excellent balance of film strength, sensitivity, and developability. Examples of the above-described polymers include: NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (COOH-containing polyurethane acrylic oligomer. Diamond Shamrock Co. Ltd., biscort R-264, KS resist 106 (all) Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series such as Cyclomer P ACA230AA, Plaxel CF200 series (both manufactured by Daicel Chemical Industries, Ltd.), Ebecryl 3800 (manufactured by Daicel UCB Co., Ltd.), and the like.

Also, Japanese Patent Publication No. 7-12004, Japanese Patent Publication No. 7-120041, Japanese Patent Publication No. 7-120042, Japanese Patent Publication No. 8-12424, Japanese Patent Publication No. 63-287944, Japanese Patent Publication No. 63-287947. Urethane binder polymer containing an acid group described in JP-A No. 1-271741 and the like, and urethane binder having an acid group and a double bond in a side chain described in JP-A No. 2002-107918 Since the polymer is very excellent in strength, it is advantageous in terms of film strength.
Acetal-modified polyvinyl alcohol-based binder polymers having an acid group described in European Patent No. 993966, European Patent No. 1204000, and Japanese Patent Application Laid-Open No. 2001-318463 are also preferable because of their excellent film strength.
In addition, polyvinyl pyrrolidone, polyethylene oxide, and the like are useful as the water-soluble linear organic polymer. In order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful.

The weight average molecular weight (polystyrene equivalent value measured by GPC method) of the binder polymer is preferably 5,000 or more, more preferably 10,000 to 300,000, and the number average molecular weight is preferably It is 1,000 or more, More preferably, it is the range of 2,000 or more and 250,000 or less. The polydispersity (weight average molecular weight / number average molecular weight) is preferably 1 or more, more preferably 1.1 or more and 10 or less.
These binder polymers may be any of random polymers, block polymers, graft polymers and the like.

  The content of the binder polymer is preferably 1% by mass or more and 40% by mass or less, more preferably 3% by mass or more and 30% by mass or less, and more preferably 4% by mass or more and 20% by mass with respect to the total solid content. More preferably, it is as follows.

[Surfactant]
Various dispersion agents may be added to the dispersion composition (I) of the present embodiment. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used. In particular, the use of a fluorosurfactant is preferred. Specific examples of the surfactant may be the same as those described in the resin composition for forming a low refractive index film, and only one type may be used or two or more types may be combined. The fluorine content in the fluorosurfactant is preferably 3% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, and particularly preferably 7% by mass to 25% by mass. A fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and has good solubility.
The addition amount of the surfactant in the dispersion composition is preferably 0.001% by mass to 2.0% by mass, more preferably 0.005% by mass to 1.0% by mass with respect to the total mass of the curable composition. % By mass.

[Other additives]
Furthermore, you may add well-known additives, such as a plasticizer and a fat-sensitizing agent, with respect to a dispersion composition.
Examples of plasticizers include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, and triacetyl glycerin. , 10% by mass or less can be added with respect to the total mass of the polymerizable compound and the binder polymer.

[Ultraviolet absorber]
The dispersion composition of this embodiment may contain an ultraviolet absorber. As the ultraviolet absorber, a compound represented by the following formula (I) which is a conjugated diene compound is particularly preferable.

In the formula (I), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and R ¹ and R ² May be the same or different from each other, but do not represent a hydrogen atom at the same time. In the formula (I), R ³ and R ⁴ represent an electron withdrawing group. Here, the electron withdrawing group is an electron withdrawing group having a Hammett's substituent constant σp value (hereinafter, simply referred to as “σp value”) of 0.20 or more and 1.0 or less. Preferably, it is an electron withdrawing group having a σp value of 0.30 or more and 0.8 or less.
Paragraphs 0024 to 0033 of WO2009 / 123109 (corresponding [0040] to [0057] of US 2011/0039195) corresponding to the description of the substituent of the ultraviolet absorber represented by the formula (I). The contents of which are incorporated herein by reference. Preferable specific examples of the compound represented by the formula (I) include the exemplified compound (1) of WO2009 / 123109, paragraphs 0034 to 0039 (corresponding to US Pat. Appl. No. 2011/0039195, [0060]). The description of (14) can be referred to and the contents thereof are incorporated in the present specification.

The content of the ultraviolet absorber in the dispersion composition (I) of the present embodiment is preferably 0.1% by mass to 10% by mass and more preferably 0.1% by mass to 5% by mass with respect to the total solid content. Preferably, 0.1 mass%-3 mass% are especially preferable.
Further, the composition containing a high refractive index material may be a dispersion composition II described below.
The dispersion composition II refers to a dispersion composition containing metal oxide particles (A) having a primary particle diameter of 1 nm to 100 nm, a specific dispersion resin (B), and a solvent (C). Here, the components other than the specific dispersion resin (B) are the same as those of the dispersion composition I.

・ Specific dispersion resin (B)
As the dispersant for dispersing the high refractive index particles, it is preferable to use an oligoimine-based dispersant containing a nitrogen atom in at least one of the main chain and the side chain. The oligoimine-based dispersant has a repeating unit having a partial structure X having a functional group of pKa14 or less, and a side chain containing a side chain Y having 40 to 10,000 atoms, and has a main chain and a side chain. A dispersion resin having a basic nitrogen atom in at least one (hereinafter referred to as “specific dispersion resin (B)” as appropriate) is preferred. Here, the basic nitrogen atom is not particularly limited as long as it is a basic nitrogen atom.
The specific resin (B), the partial structure X, etc. and may have a partial structure W paired is preferably the partial structure W is a structure having a pK b ₁₄ or less nitrogen atoms, pK _b It is more preferable to contain a structure having 10 or less nitrogen atoms. The base strength pK _b, means a pK _b at a water temperature 25 ° C., is one of the index for quantitatively indicating the strength of the base, is synonymous with basicity constants. The base strength pK _b and the acid strength pK _a described later have _a relationship of pK _b = 14−pK _a . When partial structure X and partial structure W are paired to form a salt structure, a dissociated structure is assumed, and proton (H ⁺ ) or hydroxide ion (OH ⁻ ) is present there. The pKa and pKb are evaluated as ion-bonded compounds. The details of the partial structure X will be described later.

  The details of the preferable range of the partial structure X are the same as those of the partial structure X described later. Similarly, the details of the preferred range of the side chain Y are the same as those of the side chain Y described later. The W preferably has a structure in which the linking part of the side chain Y is dissociated to become an ion binding site.

  An example of the specific dispersion resin (B) is a resin represented by the following formula [B].

  In said formula, x, y, and z show the polymerization molar ratio of a repeating unit, respectively, x is 5-50, y is 5-60, and it is preferable that z is 10-90. l represents the number of linked polyester chains, and is an integer capable of forming a side chain having 40 to 10,000 atoms. l is preferably 5 to 100,000, more preferably 20 to 20,000, and 40 to More preferably, it is 2,000. The repeating unit whose copolymerization ratio is defined by x in the formula is the partial structure X, and the repeating unit whose copolymerization ratio is defined by z in the formula is the partial structure Y.

  The specific dispersion resin (B) includes (i) a poly (lower alkyleneimine) -based repeating unit, a polyallylamine-based repeating unit, a polydiallylamine-based repeating unit, a metaxylenediamine-epichlorohydrin polycondensate-based repeating unit, and a polyvinylamine-based repeating unit A repeating unit (i) having at least one repeating unit having a basic nitrogen atom selected from the units and having a partial structure X bonded to the basic nitrogen atom and having a functional group of pKa14 or less; And a side chain (ii) containing a side chain Y having 40 to 10,000 atoms (hereinafter referred to as “specific dispersion resin (B1)” as appropriate).

  The specific dispersion resin (B1) has the repeating unit (i). Thereby, the adsorption | suction power of dispersion resin to the particle | grain surface improves, and the interaction between particle | grains can be reduced. The poly (lower alkyleneimine) may be a chain or a network. Here, the lower alkylene imine means an alkylene imine containing an alkylene chain having 1 to 5 carbon atoms. The repeating unit (i) preferably forms a main chain portion in the specific dispersion resin. The number average molecular weight of the main chain portion, that is, the number average molecular weight of the portion excluding the side chain including the side chain Y portion from the specific dispersion resin (B1) is preferably 100 to 10,000, and 200 to 5,000. Is more preferable, and 300 to 2,000 is most preferable. The number average molecular weight of the main chain portion can be measured by a polystyrene conversion value by GPC method.

  As specific dispersion resin (B1), the repeating unit represented by the following formula (I-1) and the repeating unit represented by formula (I-2), or the repeating unit represented by formula (I-1) And a dispersion resin containing a repeating unit represented by the formula (I-2a).

Ｒ^１及びＲ^２は、各々独立に、水素原子、ハロゲン原子又はアルキル基（炭素数１〜６が好ましい）を表す。ａは、各々独立に、１〜５の整数を表す。＊は繰り返し単位間の連結部を表す。
Ｒ^８及びＲ^９はＲ^１と同義の基である。
Ｌは単結合、アルキレン基（炭素数１〜６が好ましい）、アルケニレン基（炭素数２〜６が好ましい）、アリーレン基（炭素数６〜２４が好ましい）、ヘテロアリーレン基（炭素数１〜６が好ましい）、イミノ基（炭素数０〜６が好ましい）、エーテル基、チオエーテル基、カルボニル基、またはこれらの組合せに係る連結基である。なかでも、単結合もしくは−ＣＲ^５Ｒ^６−ＮＲ^７−（イミノ基がＸもしくはＹの方になる）であることが好ましい。ここで、Ｒ^５Ｒ^６は各々独立に、水素原子、ハロゲン原子、アルキル基（炭素数１〜６が好ましい）を表す。Ｒ^７は水素原子または炭素数１〜６のアルキル基である。
Ｌ^ａはＣＲ^８ＣＲ^９とＮとともに環構造形成する構造部位であり、ＣＲ^８ＣＲ^９の炭素原子と合わせて炭素数３〜７の非芳香族複素環を形成する構造部位であることが好ましい。さらに好ましくはＣＲ^８ＣＲ^９の炭素原子及びＮ（窒素原子）を合わせて５〜７員の非芳香族複素環を形成する構造部位であり、より好ましくは５員の非芳香族複素環を形成する構造部位であり、ピロリジンを形成する構造部位であることが特に好ましい。ただし、当該構造部位はさらにアルキル基等の置換基を有していてもよい。
ＸはｐＫａ１４以下の官能基を有する基を表す。
Ｙは原子数４０〜１０，０００の側鎖を表す。

R ¹ and R ² each independently represents a hydrogen atom, a halogen atom or an alkyl group (preferably having 1 to 6 carbon atoms). a represents the integer of 1-5 each independently. * Represents a connecting part between repeating units.
R ⁸ and R ⁹ are the same groups as R ¹ .
L is a single bond, an alkylene group (preferably having 1 to 6 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), an arylene group (preferably having 6 to 24 carbon atoms), a heteroarylene group (having 1 to 6 carbon atoms). Are preferred), an imino group (preferably having 0 to 6 carbon atoms), an ether group, a thioether group, a carbonyl group, or a linking group thereof. Among these, a single bond or —CR ⁵ R ⁶ —NR ⁷ — (where the imino group is X or Y) is preferable. Here, R ⁵ R ⁶ each independently represents a hydrogen atom, a halogen atom, or an alkyl group (preferably having 1 to 6 carbon atoms). R ⁷ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
L ^a is a structural site ring structure formed together with ^CR 8 CR ⁹ and N, it is preferable together with the carbon atom of ^CR 8 CR ⁹ is a structural site that form a non-aromatic heterocyclic ring having 3 to 7 carbon atoms . More preferably, it is a structural part that forms a 5- to 7-membered non-aromatic heterocycle by combining the carbon atom of CR ⁸ CR ⁹ and N (nitrogen atom), more preferably forms a 5-membered non-aromatic heterocycle It is particularly preferred that it is a structural site that forms pyrrolidine. However, the structural site may further have a substituent such as an alkyl group.
X represents a group having a functional group of pKa14 or less.
Y represents a side chain having 40 to 10,000 atoms.

  The specific dispersion resin (B1) preferably further has a repeating unit represented by the formula (I-3), the formula (I-4), or the formula (I-5) as a copolymerization component. When the specific dispersion resin (B1) includes such a repeating unit, the dispersion performance can be further improved.

Ｒ^１、Ｒ^２、Ｒ^８、Ｒ^９、Ｌ、Ｌａ、及びａは式（Ｉ−１）、（Ｉ−２）、（Ｉ−２ａ）における規定と同義である。

R ¹ , R ² , R ⁸ , R ⁹ , L, La, and a are as defined in formulas (I-1), (I-2), and (I-2a).

  Ya represents a side chain having 40 to 10,000 atoms having an anionic group. The repeating unit represented by the formula (I-3) is reacted by adding an oligomer or polymer having a group that reacts with an amine to form a salt to a resin having a primary or secondary amino group in the main chain. Can be formed. It is preferable that Ya is a postscript formula (III-2).

In formula (I-1) to formula (I-5), R ¹ and R ² are particularly preferably hydrogen atoms. a is preferably 2 from the viewpoint of obtaining raw materials.

  The specific dispersion resin (B1) may further contain a lower alkyleneimine containing a primary or tertiary amino group as a repeating unit. In addition, the group shown by said X, Y, or Ya may couple | bond with the nitrogen atom in such a lower alkyleneimine repeating unit. Resins containing both a repeating unit having a group represented by X and a repeating unit having Y bonded to such a main chain structure are also included in the specific dispersion resin (B1).

The repeating unit represented by the formula (I-1) is preferably contained in an amount of 1 to 80 mol% in all repeating units contained in the specific dispersion resin (B1) from the viewpoint of storage stability and developability. It is most preferable to contain ~ 50 mol%. The repeating unit represented by the formula (I-2) is preferably contained in an amount of 10 to 90 mol% in all repeating units contained in the specific dispersion resin (B1) from the viewpoint of storage stability, Most preferably, it is contained in mol%. From the viewpoint of the balance between dispersion stability and hydrophilicity / hydrophobicity, the content ratio [(I-1) :( I-2)] of the repeating unit (I-1) and the repeating unit (I-2) is 10 in molar ratio. Is preferably in the range of 1: 1 to 1: 100, and more preferably in the range of 1: 1 to 1:10. The repeating unit represented by the formula (I-3) used together as desired is contained in an amount of 0.5 to 20 mol% from the viewpoint of the effect in all the repeating units contained in the specific dispersion resin (B1). Is preferable, and it is most preferable to contain 1-10 mol%. In addition, it can confirm that the polymer chain Ya has couple | bonded ionically by infrared spectroscopy or base titration.
In addition, the description regarding the copolymerization ratio of said Formula (I-2) is synonymous also about the repeating unit represented by Formula (I-2a), Formula (I-4), and Formula (I-5). Means the total amount.

・ Partial structure X
The partial structure X in each of the above formulas has a functional group having a pKa of 14 or less at a water temperature of 25 ° C. Here, “pKa” has the definition described in Chemical Handbook (II) (4th revised edition, 1993, edited by The Chemical Society of Japan, Maruzen Co., Ltd.). The “functional group of pKa14 or less” is not particularly limited as long as the physical properties satisfy this condition, and examples thereof include those having a pKa satisfying the above range with known functional groups. The following functional groups are preferred, and those having a pKa of 11 or less are particularly preferred. Although there is no particular lower limit, it is practical that it is −5 or more. Specific examples of the partial structure X include, for example, a carboxylic acid group (pKa: about 3 to 5), a sulfonic acid (pKa: about −3 to −2), —COCH ₂ CO— (pKa: about 8 to 10), —COCH ₂ CN (pKa: about 8 to 11), —CONHCO—, phenolic hydroxyl group, —R _F CH ₂ OH or — (R _F ) ₂ CHOH (R _F represents a perfluoroalkylene group or a perfluoroalkyl group. PKa. : About 9-11), a sulfonamide group (pKa: about 9-11), etc. are mentioned, especially a carboxylic acid group (pKa: about 3-5), a sulfonic acid group (pKa: about -3-2), -COCH ₂ CO- (pKa: approximately 8 to 10) are preferred.

  When the pKa of the functional group included in the partial structure X is 14 or less, interaction with the highly refractive particles can be achieved. The partial structure X is preferably directly bonded to the basic nitrogen atom in the repeating unit having the basic nitrogen atom. The partial structures X may be linked not only by a covalent bond but also in a form in which a salt is formed by ionic bonding. As the partial structure X, those having a structure represented by the following formula (V-1), formula (V-2) or formula (V-3) are particularly preferable.

Ｕは単結合又は２価の連結基を表す。
ｄ及びｅは、それぞれ独立して０又は１を表す。
Ｑはアシル基又はアルコキシカルボニル基を表す。

U represents a single bond or a divalent linking group.
d and e each independently represents 0 or 1;
Q represents an acyl group or an alkoxycarbonyl group.

Examples of the divalent linking group represented by U include alkylene (more specifically, for example, —CH ₂ —, —CH ₂ CH ₂ —, —CH ₂ CHMe— (Me is a methyl group), — (CH ₂ ) ₅ —, —CH ₂ CH (n—C ₁₀ H ₂₁ ) —, etc.), oxygen-containing alkylene (more specifically, for example, —CH ₂ OCH ₂ —, —CH ₂ CH ₂ OCH ₂ CH ₂ -, etc.), an arylene group, but alkyleneoxy, etc., particularly preferably an alkylene group or an arylene group having 6 to 20 carbon atoms having 1 to 30 carbon atoms, the number alkylene or C 1 to 20 carbon atoms 6 Most preferred are ˜15 arylene groups.
Further, from the viewpoint of productivity, d is preferably 1, and e is preferably 0.

Q represents an acyl group or an alkoxycarbonyl group. As the acyl group in Q, an acyl group having 1 to 30 carbon atoms is preferable, and acetyl is particularly preferable. As the alkoxycarbonyl group in Q, Q is particularly preferably an acyl group, and an acetyl group is preferable from the viewpoint of ease of production and availability of ^a raw material (precursor X ^a of X).

  The partial structure X is preferably bonded to the basic nitrogen atom in the repeating unit having a basic nitrogen atom. Thereby, the dispersibility and dispersion stability of titanium dioxide particles are dramatically improved. Partial structure X is also considered to contribute to dispersion stability by imparting solvent solubility and suppressing resin precipitation over time. Furthermore, since the partial structure X contains a functional group of pKa14 or less, it also functions as an alkali-soluble group. Thereby, developability is improved, and it is considered that both dispersibility, dispersion stability, and developability can be achieved.

Although there is no restriction | limiting in particular in content of the functional group below pKa14 in the partial structure X, It is preferable that it is 0.01-5 mmol with respect to 1 g of specific dispersion resin (B1), and it is especially 0.05-1 mmol. preferable. From the viewpoint of developability, it is preferable that the acid value of the specific dispersion resin (B1) is contained in an amount of about 5 to 50 mgKOH / g.
・ Side chain Y
Examples of Y include known polymer chains such as polyester, polyamide, polyimide, and poly (meth) acrylate that can be connected to the main chain portion of the specific dispersion resin (B1). The binding site with the specific dispersion resin (B1) in Y is preferably the terminal of the side chain Y.

Y is at least one selected from a poly (lower alkyleneimine) -based repeating unit, a polyallylamine-based repeating unit, a polydiallylamine-based repeating unit, a metaxylenediamine-epichlorohydrin polycondensate-based repeating unit, and a polyvinylamine-based repeating unit. It is preferably bonded to the nitrogen atom of the repeating unit having a nitrogen atom. At least one basic selected from a poly (lower alkyleneimine) -based repeating unit, a polyallylamine-based repeating unit, a polydiallylamine-based repeating unit, a metaxylenediamine-epichlorohydrin polycondensate-based repeating unit, and a polyvinylamine-based repeating unit. The bonding mode between the main chain portion such as a repeating unit having a nitrogen atom and Y is a covalent bond, an ionic bond, or a mixture of a covalent bond and an ionic bond. The ratio of the binding mode between Y and the main chain is covalent bond: ionic bond = 100: 0 to 0: 100, preferably 95: 5 to 5:95, particularly preferably 90:10 to 10:90. .
Y is preferably ionically bonded to the nitrogen atom of the repeating unit having the basic nitrogen atom as an amide bond or carboxylate.

The number of atoms of the side chain Y is preferably 50 to 5,000, more preferably 60 to 3,000, from the viewpoint of dispersibility, dispersion stability, and developability.
Moreover, the number average molecular weight of Y can be measured by the polystyrene conversion value by GPC method. At this time, it is practical to measure the molecular weight of Y before being incorporated into the resin. The number average molecular weight of Y is particularly preferably 1,000 to 50,000, and most preferably 1,000 to 30,000 from the viewpoints of dispersibility, dispersion stability, and developability. The molecular weight of Y can be specified from the polymer compound used as the raw material for Y, and the measurement method conforms to the measurement conditions by GPC described later.
It is preferable that two or more side chain structures represented by Y are connected to the main chain in one molecule of the resin, and more preferably five or more are connected.

  In particular, Y preferably has a structure represented by the formula (III-1).

  In formula (III-1), Z is a polymer or oligomer having a polyester chain as a partial structure, and represents a residue obtained by removing a carboxyl group from a polyester having a free carboxylic acid represented by HO-CO-Z. When specific dispersion resin (B1) contains the repeating unit represented by Formula (I-3)-(I-5), it is preferable that Ya is Formula (III-2).

  In formula (III-2), Z has the same meaning as Z in formula (III-1). In the partial structure Y, a polyester having a carboxyl group at one end is obtained by polycondensation of a carboxylic acid and a lactone, polycondensation of a hydroxy group-containing carboxylic acid, a polyhydric alcohol and a divalent carboxylic acid (or a cyclic acid anhydride). It can be obtained by condensation or the like.

Z is preferably-(L ^B ) _nB -Z ^B.
Z ^B represents a hydrogen atom or a monovalent organic group. When Z ^B is an organic group, an alkyl group (preferably having 1 to 30 carbon atoms), an aryl group, and heterocyclic group. Z ^B may further have a substituent, and examples of the substituent include an aryl group having 6 to 24 carbon atoms and a heterocyclic group having 3 to 24 carbon atoms.
L ^B is an alkylene group (preferably having from 1 to 6 carbon atoms), an alkenylene group (2 to 6 carbon atoms is preferred), an arylene group (having 6 to 24 carbon atoms is preferred), heteroarylene groups (having from 1 to 6 carbon atoms Preferred), an imino group (preferably having 0 to 6 carbon atoms), an ether group, a thioether group, a carbonyl group, or a combination group thereof. Especially, it is preferable that it is a coupling group which concerns on an alkylene group (C1-C6 is preferable), an ether group, a carbonyl group, or these combination. The alkylene group may be branched or linear. The alkylene group may have a substituent, and preferred substituents include an alkyl group (preferably 1 to 6 carbon atoms), an acyl group (preferably 2 to 6 carbon atoms), an alkoxy group (preferably 1 to 6 carbon atoms). Or an alkoxycarbonyl group (preferably having 2 to 8 carbon atoms). nB is an integer of 5 to 100,000. nB number of L ^B may have a different structure, respectively.

Specific embodiments of the specific dispersion resin (B) are shown below by the specific structure of the repeating unit of the resin and the combination thereof, but the present invention is not limited to this (see JP 2010-6932 A). The description after the paragraph 0075 of the publication can be referred to, and the contents thereof are incorporated in the present specification.) In the following formula, k, l, m, and n each represent a polymerization molar ratio of repeating units, k is 1-80, l is 10-90, m is 0-80, n is 0-70, and k + l + m + n = 100. Those defined by k, l, and m, and those defined only by k and l mean k + l + m = 100 and k + l = 100, respectively. p and q represent the number of linked polyester chains, and each independently represents 5 to 100,000. R ^a represents a hydrogen atom or an alkoxycarbonyl group.

  To synthesize the specific dispersion resin (B1), (1) a method of reacting a resin having a primary or secondary amino group with a precursor x of a partial structure X and a precursor y of Y, (2) a portion It can be produced by a method of polymerization of a monomer containing a structure corresponding to the structure X and a macromonomer containing Y. First, a resin having a primary or secondary amino group in the main chain is synthesized, and then a precursor X of X and a precursor y of Y are reacted with the resin to polymerize nitrogen atoms existing in the main chain. It is preferable to produce by introducing by reaction. For details of the manufacturing method, refer to JP2009-203462A.

The molecular weight of the specific dispersion resin B is preferably 3,000 to 100,000 in terms of weight average molecular weight, and if the 5,000 to 55,000 weight average molecular weight is within the above range, The effects of the plurality of introduced adsorption sites are sufficiently exhibited, and performance with excellent adsorptivity to the surface of the titanium dioxide particles can be exhibited. In this specification, unless otherwise specified, GPC was measured using HLC-8020GPC (manufactured by Tosoh Corp.) and columns as TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ200 (manufactured by Tosoh Corporation). The carrier may be selected as appropriate, but tetrahydrofuran is used as long as it can be dissolved.
In the photosensitive composition of the present invention, the dispersant for high refractive index particles can be used alone or in combination of two or more.

  In dispersion composition (II) of this embodiment, specific resin can be used individually by 1 type or in combination of 2 or more types.

  The content of the specific resin with respect to the total solid content of the dispersion composition (II) is preferably in the range of 10 to 50% by mass, more preferably in the range of 11 to 40% by mass, from the viewpoints of dispersibility and dispersion stability. The range of ˜30% by mass is more preferable.

Further, the high refractive index material may be a dispersion composition III described below.
<Dispersion composition III>
The dispersion composition III contains metal oxide particles (A) having a primary particle diameter of 1 nm to 100 nm, a polymer compound dispersant (B) represented by the following formula (1), and a solvent (C). Refers to a dispersion composition. Here, the components other than the polymer compound (B) represented by the following formula (1) are the same as those in the dispersion compositions I and II.

In the above formula (1), R ¹ represents an (m + n) -valent linking group, and R ² represents a single bond or a divalent linking group. A ¹ is an acid group, a urea group, a urethane group, a group having a coordinating oxygen atom, a group having a basic nitrogen atom, a phenol group, an alkyl group, an aryl group, a group having an alkyleneoxy chain, an imide group, a heterocyclic ring A monovalent substituent having at least one group selected from the group consisting of a group, an alkyloxycarbonyl group, an alkylaminocarbonyl group, a carboxylate group, a sulfonamide group, an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxyl group Represent. The n A ¹ and R ² may be the same or different. m represents a positive number of 8 or less, n represents 1 to 9, and m + n satisfies 3 to 10. P ¹ represents a polymer chain. The m P ¹ may be the same or different.

In the dispersion composition of the present invention, since the substituent A ¹ of the polymer compound (B) can interact with the metal oxide particles (A), the polymer compound (B) has n (1 By having (˜9) substituents A ¹ , the metal oxide particles (A) can be strongly interacted. Further, m polymer chains P ¹ of the polymer compound (B) can function as steric repulsion groups, and by having m, the polymer compound P ¹ exhibits a favorable steric repulsion force and uniformly disperses the metal oxide particles. be able to. Further, it is presumed that the polymer compound (B) does not cause adverse effects such as aggregation of particles due to cross-linking between particles, which can be generated with a dispersant having a conventional graft random structure, in terms of molecular structure.

<(A) Metal Oxide Particles with a Primary Particle Diameter of 1 nm to 100 nm> As the metal oxide particles (A) in the present invention, the same as the dispersion composition I can be used. The content of the metal oxide particles in the dispersion composition (or curable composition described later) of the present invention is 65% by mass or more based on the total solid content of the dispersion composition from the viewpoint of obtaining a high refractive index. Is more preferable, and 70% by mass or more is more preferable. Although there is no restriction | limiting in particular as an upper limit of content, It is preferable that it is 90 mass% or less with respect to dispersion composition total solid, and it is more preferable that it is 85 mass% or less.

<(B) Polymer Compound Represented by Formula (1)> Hereinafter, each group in Formula (1) will be described in detail. A ¹ is a monovalent substitution having at least one type of functional group having an adsorption ability for the metal oxide particles (A) or a structure capable of adsorbing the metal oxide particles (A) such as a heterocyclic structure. Represents a group. Hereinafter, the site having the ability to adsorb to the metal oxide particles (A) (the functional group and the structure) will be collectively referred to as “adsorption site” as appropriate.

It is sufficient that at least one adsorption site is included in one A ¹ , and two or more adsorption sites may be included. As an aspect in which two or more adsorption sites are included in one A ¹ , a chain saturated hydrocarbon group (which may be linear or branched and preferably has 1 to 10 carbon atoms). ), A saturated cyclic hydrocarbon group (preferably having 3 to 10 carbon atoms), an aromatic group (preferably having 5 to 10 carbon atoms, for example, a phenylene group), etc. There embodiment and the like to form a bond with a monovalent substituent a ^1, embodiment 2 or more adsorption sites via a chain saturated hydrocarbon groups form with a monovalent substituent a ¹ bond is preferred . In the case where adsorption sites themselves constitute a monovalent substituent, adsorption sites themselves may also be a monovalent substituent represented by A ^1. First, the adsorption site constituting A ¹ will be described below.

Preferred examples of the “acid group” include a carboxylic acid group, a sulfonic acid group, a monosulfate group, a phosphoric acid group, a monophosphate group, a phosphonic acid group, a phosphinic acid group, and a boric acid group. An acid group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, and a phosphinic acid group are more preferable, and a carboxylic acid group is particularly preferable.

Examples of the “urea group” include —NR ¹⁵ CONR ¹⁶ R ¹⁷ (wherein R ¹⁵ , R ¹⁶ , and R ¹⁷ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or 6 carbon atoms). The above aryl group or an aralkyl group having 7 or more carbon atoms may be mentioned as a preferred example, and —NR ¹⁵ CONHR ¹⁷ (wherein R ¹⁵ and R ¹⁷ are each independently a hydrogen atom or 1 carbon atom). More preferably an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms.) —NHCONHR ¹⁷ (wherein R ¹⁷ represents a hydrogen atom or 1 to 10 carbon atoms) An alkyl group, an aryl group having 6 or more carbon atoms, and an aralkyl group having 7 or more carbon atoms are particularly preferable.

Examples of the “urethane group” include —NHCOOR ¹⁸ , —NR ¹⁹ COOR ²⁰ , —OCONHR ²¹ , —OCONR ²² R ²³ (wherein R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² and R ²³ are Each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms), and the like. -NHCOOR ¹⁸ , -OCONHR ²¹ (here And R ¹⁸ and R ²¹ each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms), and the like, more preferably —NHCOOR ¹⁸ , -OCONHR ^{21 (wherein,} R ^{18, R 21} each independently represents an alkyl group having from 1 to 10 carbon atoms, 6 or more arylene carbon Group, the number 7 or aralkyl group having a carbon.), Etc. are particularly preferred.

Examples of the “group having a coordinating oxygen atom” include an acetylacetonato group and a crown ether. Examples of the “group having a basic nitrogen atom” include an amino group (—NH ₂ ), a substituted imino group (—NHR ⁸ , —NR ⁹ R ¹⁰ , wherein R ⁸ , R ⁹ , and R ¹⁰ are each Independently, an alkyl group having 1 to 20 carbon atoms (preferably 1 to 5 carbon atoms), an aryl group having 6 or more carbon atoms (preferably 6 to 30 carbon atoms), an aralkyl group having 7 or more carbon atoms (preferable carbon number) Represents 7 to 30).), A guanidyl group represented by the following formula (a1), an amidinyl group represented by the following formula (a2), and the like.

In formula (a1), R ¹¹ and R ¹² are each independently an alkyl group having 1 to 20 carbon atoms (preferably 1 to 5 carbon atoms), an aryl group having 6 or more carbon atoms (preferably 6 to 30 carbon atoms). ), An aralkyl group having 7 or more carbon atoms (preferably 7 to 30 carbon atoms). In formula (a2), R ¹³ and R ¹⁴ are each independently an alkyl group having 1 to 20 carbon atoms (preferably 1 to 5 carbon atoms), an aryl group having 6 or more carbon atoms (preferably 6 to 30 carbon atoms). ), An aralkyl group having 7 or more carbon atoms (preferably 7 to 30 carbon atoms).

The alkyl group represented by the substituent A ¹ may be linear or branched, and is preferably an alkyl group having 1 to 40 carbon atoms, and an alkyl group having 4 to 30 carbon atoms. It is more preferably a group, and further preferably an alkyl group having 10 to 18 carbon atoms. The aryl group represented by the substituent A ¹ is preferably an aryl group having 6 to 10 carbon atoms. As the “group having an alkyleneoxy chain”, the terminal preferably forms an alkyloxy group or a hydroxyl group, and more preferably an alkyloxy group having 1 to 20 carbon atoms. The alkyleneoxy chain is not particularly limited as long as it has at least one alkyleneoxy group, but is preferably composed of an alkyleneoxy group having 1 to 6 carbon atoms. The alkylene group, for _{example, -CH 2 CH 2 O -,} - CH 2 CH 2 CH 2 O- and the like. The alkyl group moiety in the “alkyloxycarbonyl group” and “alkylaminocarbonyl group” is preferably an alkyl group having 1 to 20 carbon atoms. Examples of the “carboxylic acid base” include groups composed of ammonium salts of carboxylic acids. In the “sulfonamide group”, a hydrogen atom bonded to a nitrogen atom may be substituted with an alkyl group (such as a methyl group) or an acyl group (such as an acetyl group or a trifluoroacetyl group).

Examples of the “heterocyclic structure” include thiophene, furan, xanthene, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, pyrazolidine, imidazole, oxazole, thiazole, oxadiazole, triazole, thiadiazole, pyran, pyridine, piperidine Preferred examples include dioxane, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindoline, isoindolinone, benzimidazolone, benzothiazole, hydantoin, indole, quinoline, carbazole, acridine, acridone and anthraquinone. Examples of the “imide group” include succinimide, phthalimide, naphthalimide and the like.

The “heterocyclic structure” and the “imide group” may further have a substituent. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, and 6 to 16 carbon atoms. Aryl groups, hydroxyl groups, amino groups, carboxyl groups, sulfonamido groups, N-sulfonylamido groups, acetoxy groups and the like, acyloxy groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, halogen atoms, methoxy Examples thereof include C2-C7 alkoxycarbonyl groups such as carbonyl group, ethoxycarbonyl group and cyclohexyloxycarbonyl group, cyano groups, and carbonate ester groups such as t-butyl carbonate.

The “alkoxysilyl group” may be any of monoalkoxysilyl group, dialkoxysilyl group and trialkoxysilyl group, but is preferably trialkoxysilyl group, for example, trimethoxysilyl group, triethoxysilyl group Etc. Examples of the “epoxy group” include a substituted or unsubstituted oxiranyl group (ethylene oxide group).

In particular, A ¹ is preferably a monovalent substituent having at least one functional group having a pKa of 5 or more, and more preferably a monovalent substituent having at least one functional group having a pKa of 5 to 14. Here, “pKa” has the definition described in Chemical Handbook (II) (4th revised edition, 1993, edited by The Chemical Society of Japan, Maruzen Co., Ltd.). The functional group having a pKa of 5 or more includes a group having a coordinating oxygen atom, a group having a basic nitrogen atom, a phenol group, a urea group, a urethane group, an alkyl group, an aryl group, an alkyloxycarbonyl group, and an alkylaminocarbonyl group. A group having an alkyleneoxy chain, an imide group, a carboxylate group, a sulfonamide group, a hydroxyl group, a heterocyclic group and the like. Specifically as a functional group of pKa5 or more, for example, a phenol group (about pKa 8-10), an alkyl group (about pKa 46-53), an aryl group (about pKa 40-43), a urea group (pKa 12-14) degree), about urethane group (pKa 11 to 13), -COCH ₂ CO- (about pKa 8 to 10 as a coordinating oxygen atom), a sulfonamido group (about pKa 9 to 11), hydroxyl group (pKa 15 to 17 Degree), a heterocyclic group (about pKa 12 to 30), and the like. Among the above, as A ¹ , an acid group, a phenol group, an alkyl group, an aryl group, a group having an alkyleneoxy chain, a hydroxyl group, a urea group, a urethane group, a sulfonamide group, an imide group, and a coordinating oxygen atom It is preferably a monovalent substituent having at least one group selected from the group consisting of the having groups.

In the formula (1), R ² represents a single bond or a divalent linking group. n R ² may be the same or different. The divalent linking group represented by R ² includes 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, and 1 to 200 carbon atoms. A group consisting of a hydrogen atom and 0 to 20 sulfur atoms is included, which may be unsubstituted or may further have a substituent.

R ² may be a single bond or 1 to 10 carbon atoms, 0 to 5 nitrogen atoms, 0 to 10 oxygen atoms, 1 to 30 hydrogen atoms, and A divalent linking group consisting of 0 to 5 sulfur atoms is preferred. R ² is a chain saturated hydrocarbon group (which may be linear or branched and preferably has 1 to 20 carbon atoms), or a cyclic saturated hydrocarbon group (having 3 to 20 carbon atoms). Selected from the group consisting of an aromatic group (preferably having 5 to 20 carbon atoms, for example, a phenylene group), a thioether bond, an ester bond, an amide bond, an ether bond, a nitrogen atom, and a carbonyl group. More preferably a group or a combination of two or more of these, selected from the group consisting of a chain saturated hydrocarbon group, a cyclic saturated hydrocarbon group, an aromatic group, a thioether bond, an ester bond, an ether bond, and an amide bond Or a combination of two or more of these, a chain saturated hydrocarbon group, a thioether bond, an ester bond, an ether bond, and an amide A group selected from the group consisting of a bond, or a group obtained by combining two or more of these is particularly preferable.

Among the above, when the divalent linking group represented by R ² has a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 16 carbon atoms, C1-C6 acyloxy groups, C1-C6 alkoxy groups such as hydroxyl, amino, carboxyl, sulfonamido, N-sulfonylamido, acetoxy, etc., halogen atoms, methoxycarbonyl, ethoxy Examples thereof include C2-C7 alkoxycarbonyl groups such as carbonyl group and cyclohexyloxycarbonyl group, carbonate groups such as cyano group and t-butyl carbonate.

In the formula (1), R ¹ represents a (m + n) -valent linking group. m + n satisfies 3-10. Examples of the (m + n) -valent linking group represented by R ¹ include 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, and 1 to 200. Groups consisting of up to 0 hydrogen atoms and 0 to 20 sulfur atoms are included, which may be unsubstituted or further substituted.

The (m + n) -valent linking group represented by R ¹ is preferably a group represented by any of the following formulae.

In the above formula, L ₃ represents a trivalent group. T ₃ represents a single bond or a divalent linking group, and three T _{3 s} may be the same or different from each other. L ₄ represents a tetravalent group. T ₄ represents a single bond or a divalent linking group, and the four T _{4 s} may be the same or different from each other. L ₅ represents a pentavalent group. T ₅ represents a single bond or a divalent linking group, and five T _{5 s} may be the same or different from each other. L ₆ represents a hexavalent group. T ₆ represents a single bond or a divalent linking group, and six T _{6 s} may be the same or different from each other. Specific examples (specific examples (1) to (17)) of the (m + n) -valent linking group represented by R ¹ are shown below. However, the present invention is not limited to these.

Among the above specific examples, the most preferable (m + n) -valent linking groups are the following (1), (2), (10), from the viewpoint of availability of raw materials, ease of synthesis, and solubility in various solvents. (11), (16) and (17).

In the formula (1), m represents a positive number of 8 or less. As m, 0.5-5 are preferable, 1-4 are more preferable, and 1-3 are especially preferable. Moreover, in said Formula (1), n represents 1-9. As n, 2-8 are preferable, 2-7 are more preferable, and 3-6 are especially preferable.

In the formula (1), P ¹ represents a polymer chain and can be selected from known polymers according to the purpose and the like. The m P ¹ may be the same or different. Among the polymers, a vinyl monomer polymer or copolymer, an ester polymer, an ether polymer, a urethane polymer, an amide polymer, an epoxy polymer, a silicone polymer, and modifications thereof are used to form a polymer chain. Or copolymer [for example, polyether / polyurethane copolymer, copolymer of polyether / vinyl monomer polymer, etc. (any of random copolymer, block copolymer, graft copolymer, etc. May also be included). At least one selected from the group consisting of vinyl monomers, selected from the group consisting of polymers or copolymers of vinyl monomers, ester polymers, ether polymers, urethane polymers, and modified products or copolymers thereof. At least one kind is more preferred, and a polymer or copolymer of vinyl monomers is particularly preferred. The polymer or copolymer of vinyl monomer, the ester-based polymer, and the ether-based polymer that the polymer chain P ¹ may have have structures represented by the following formulas (L), (M), and (N), respectively. It is preferable.

In the above formula,
X ¹ represents a hydrogen atom or a monovalent organic group. From the viewpoint of restrictions on synthesis, a hydrogen atom or an alkyl group having 1 to 12 carbon atoms is preferable, a hydrogen atom or a methyl group is more preferable, and a methyl group is particularly preferable.
R ¹⁰ represents a hydrogen atom or a monovalent organic group, and is not particularly limited in terms of structure, but is preferably a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, more preferably a hydrogen atom or an alkyl group. is there. When R ¹⁰ is an alkyl group, the alkyl group may be a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms. Preferably, a linear alkyl group having 1 to 20 carbon atoms is more preferable, and a linear alkyl group having 1 to 6 carbon atoms is particularly preferable. It may have the formula (L) with different R ¹⁰ structurally more in.
R ¹¹ and R ^{12 each} represent a branched or straight chain alkylene group (the number of carbon atoms is preferably 1 to 10, more preferably 2 to 8, and still more preferably 3 to 6). Different R ¹¹ or R ¹² of the structure may have two or more in each formula.
k1, k2, and k3 each independently represents a number of 5 to 140.

The polymer chain P ¹ preferably contains at least one repeating unit. The number k of the at least one repeating unit in the polymer chain P ¹ is preferably 5 or more, and more preferably 7 or more, from the viewpoint of exhibiting steric repulsion and improving dispersion stability. . In addition, from the viewpoint of suppressing the bulk of the polymer compound (B), causing the metal oxide particles (A) to be densely present in the cured film (transparent film), and achieving a high refractive index, the at least one type of repetition is performed. The number k of repeating units is preferably 140 or less, more preferably 130 or less, and still more preferably 60 or less.

The polymer is preferably soluble in an organic solvent. When the affinity with the organic solvent is low, the affinity with the dispersion medium is weakened, and it may be impossible to secure an adsorption layer sufficient for stabilizing the dispersion. The vinyl monomer is not particularly limited. For example, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, vinyl monomers having an acid group, maleic acid diesters, fumaric acid diesters, itaconic acid diesters. , (Meth) acrylamides, styrenes, vinyl ethers, vinyl ketones, olefins, maleimides, (meth) acrylonitrile, etc. are preferred, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, acid groups More preferred are vinyl monomers having a (meth) acrylic acid ester and crotonic acid ester. Preferable examples of these vinyl monomers include paragraphs 0089 to 0094, 0096 and 0097 of JP-A-2007-277514 (paragraphs 0105 to 0117 and 0119 to 0120 in the corresponding US Patent Application Publication No. 2010/233595). ), The contents of which are incorporated herein.

In addition to the above compounds, for example, vinyl monomers having a functional group such as a urethane group, a urea group, a sulfonamide group, a phenol group, and an imide group can also be used. Such a monomer having a urethane group or a urea group can be appropriately synthesized using, for example, an addition reaction between an isocyanate group and a hydroxyl group or an amino group. Specifically, an addition reaction between an isocyanate group-containing monomer and a compound containing one hydroxyl group or a compound containing one primary or secondary amino group, or a hydroxyl group-containing monomer or primary or secondary amino group containing It can be appropriately synthesized by an addition reaction between a monomer and monoisocyanate.

Among the polymer compounds (B) represented by the formula (1), a polymer compound represented by the following formula (2) is preferable.

In the formula (2), A ² has the same meaning as the A ¹ in the formula (1), and the preferred embodiment is also the same.

In the formula (2), R ⁴ and R ⁵ each independently represents a single bond or a divalent linking group. The n R ^{4 s} may be the same or different. The m R ^{5 s} may be the same or different. As the divalent linking group represented by R ⁴ or R ⁵ , the same divalent linking groups as those represented by R ² in the formula (1) can be used, and a preferred embodiment is also used. It is the same. Especially, as a bivalent coupling group represented by R < ⁴ >, R < ⁵ >, it is a chain | strand-shaped saturated hydrocarbon group (It may be linear or branched and it is preferable that it is C1-C20.) , Cyclic saturated hydrocarbon group (preferably having 3 to 20 carbon atoms), aromatic group (preferably having 5 to 20 carbon atoms, for example, phenylene group), ester bond, amide bond, ether bond, nitrogen A group selected from the group consisting of an atom and a carbonyl group, or a group in which two or more of these are combined is preferable, a chain saturated hydrocarbon group, a cyclic saturated hydrocarbon group, an aromatic group, an ester bond, an ether bond, And a group selected from the group consisting of amide bonds, or a combination of two or more thereof, more preferably a group consisting of a chain saturated hydrocarbon group, an ester bond, an ether bond, and an amide bond. -Option is the group, or a group formed by combining two or more of these more preferred.

In the formula (2), R ³ represents a (m + n) -valent linking group. m + n satisfies 3-10. The (m + n) -valent linking group represented by R ³ may be unsubstituted or may further have a substituent, and the (m + n) -valent linking group represented by R ¹ in the formula (1). The same as those mentioned above are used, and preferred embodiments are also the same. In the formula (2), m and n have the same meanings as m and n in the formula (1), respectively, and the preferred embodiments are also the same. Further, ^{P 2} in the formula (2) has the same meaning as ^{P 1} in formula (1), a preferable embodiment thereof is also the same. the m P ² can be the same or different. Among the polymer compounds represented by the formula (2), those satisfying all of R ³ , R ⁴ , R ⁵ , P ² , m, and n shown below are most preferable. R ³ : Specific examples (1), (2), (10), (11), (16), or (17) R ⁴ : A single bond, a chain saturated hydrocarbon group, or a cyclic saturated hydrocarbon group , An aromatic group, an ester bond, an amide bond, an ether bond, a nitrogen atom, and a group selected from the group consisting of a carbonyl group, or a combination of two or more of these R ⁵ : a single bond, an ethylene group, a propylene group The following group (a) or the following group (b) In the following groups, R ¹² represents a hydrogen atom or a methyl group, and l represents 1 or 2.

P ² : Polymer or copolymer of vinyl monomer, ester polymer, ether polymer, urethane polymer and modified products thereof m: 1 to 3 n: 3 to 6

Among the polymer compounds (B) represented by the formula (1) or (2), a polymer compound represented by the following formula (5) is more preferable from the viewpoints of dispersion stability, coated surface shape, and the like.

In the above formula (5), R ⁶ represents a (m + n1 + n2) -valent linking group, and R ^{7 to} R ⁹ each independently represent a single bond or a divalent linking group. A ³ represents a monovalent substituent having at least one acid group. A ⁴ represents a monovalent substituent different from A ³ . The n1 A ³ and R ⁷ may be the same or different from each other. The n2 A ⁴ and R ⁸ may be the same or different from each other. m is synonymous with m in the formula (1), and the preferred embodiment is also the same. n1 represents 1 to 8, n2 represents 1 to 8, and m + n1 + n2 satisfies 3 to 10. P ³ has the same meaning as P ² in formula (2), and the preferred embodiment is also the same. The m P ³ and R ⁹ may be the same or different. The (m + n1 + n2) -valent linking group for R ⁶ is the same as those exemplified as the (m + n) -valent linking group represented by R ^{1 in the} formula (1) or R ³ in the formula (2). The preferred embodiment is the same. Examples of the divalent linking group for R ⁷ to R ^9, the formula (2) of R ^4, R ⁵ a divalent similar to those listed as a linking group of those represented may be used, preferred embodiments Is the same. Specific examples and preferred examples of the acid group that the substituent A ³ may have include those similar to the specific examples and preferred examples described above for the acid group in the formula (1). The substituent A ³ is more preferably a monovalent substituent having at least one acid group having a pKa of less than 5; from a sulfonic acid group, a carboxylic acid group, a phosphoric acid group, a phosphonic acid group, and a phosphinic acid group. Particularly preferred is a monovalent substituent having at least one group selected from the group consisting of carboxylic acid groups. Specific examples and preferred examples of the monovalent substituent A ⁴ different from A ³ include those similar to the groups other than the acid group in the specific examples and preferred examples described above for A ¹ in the formula (1). Can be mentioned. Among these, the substituent A ⁴ is more preferably a monovalent substituent having at least one functional group having a pKa of 5 or more, a group having a coordinating oxygen atom, a group having a basic nitrogen atom, and a phenol group. , Urea group, urethane group, alkyl group, aryl group, alkyloxycarbonyl group, alkylaminocarbonyl group, group having an alkyleneoxy chain, imide group, carboxylate group, sulfonamide group, hydroxyl group and heterocyclic group More preferably, it is a monovalent substituent having at least one selected group, an alkyl group, an aryl group, a group having a coordinating oxygen atom, a group having a basic nitrogen atom, a urea group or a urethane group. It is particularly preferred.

As a combination of the substituent A ³ and the substituent A ⁴ , the substituent A ³ is a monovalent substituent having at least one functional group having a pKa smaller than 5, and the substituent A ⁴ is a pKa 5 A monovalent substituent having at least one of the above functional groups is preferable. The substituent A ³ is a monovalent substituent having at least one group selected from the group consisting of a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, and a phosphinic acid group, and the substitution Group A ⁴ is a group having a coordinating oxygen atom, a group having a basic nitrogen atom, a phenol group, a urea group, a urethane group, an alkyl group, an aryl group, an alkyloxycarbonyl group, an alkylaminocarbonyl group, an alkyleneoxy chain. More preferably, it is a monovalent substituent having at least one group selected from the group consisting of a group having an imide group, an imide group, a carboxylate group, a sulfonamide group, a hydroxyl group and a heterocyclic group. The substituent A ³ is a monovalent substituent having a carboxylic acid group, and the substituent A ⁴ is an alkyl group, an aryl group, a group having a coordinating oxygen atom, or a group having a basic nitrogen atom. More preferably, it is a urea group or a urethane group. And later of the metal oxide particles (A) (Very particular titanium dioxide particles), in view adsorption is good with an alkyl group substituent A ^3, the substituents A ³ is a carboxylic acid group, and the It is particularly preferable that the substituent A ⁴ is an alkyl group. Adsorption of alkyl group substituents A ⁴ and titanium dioxide particles in the range of good, such as when titanium dioxide particles are surface treated with stearic acid, alkyl group and substituted alkyl group of group A ⁴ of the stearic acid Is presumed to interact with each other. As a molecular weight of a high molecular compound (B), 1000-50000 are preferable at a weight average molecular weight, 3000-30000 are more preferable, 3000-20000 are especially preferable. When the weight average molecular weight is within the above range, the effects of the plurality of adsorption sites introduced at the ends of the polymer are sufficiently exhibited, and the performance excellent in the adsorptivity to the surface of the metal oxide fine particles can be exhibited.

(Synthesis Method of Polymer Compound (B)) The polymer compound represented by the formula (1) or (2) is not particularly limited, but in JP-A-2007-277514, paragraphs 0114 to 0140 and 0266 to 0348. It can be synthesized according to the synthesis method described. In the dispersion composition of the present invention, the polymer compound (B) can be used alone or in combination of two or more. The content of the polymer compound (B) with respect to the total solid content of the dispersion composition (or curable composition described later) of the present invention is in the range of 5 to 40% by mass from the viewpoint of dispersion stability and high refractive index. Preferably, the range of 10-35 mass% is more preferable, and the range of 12-30 mass% is still more preferable.

—Other Dispersion Resin— The dispersion composition of the present invention may be a dispersion resin other than the specific resin (hereinafter referred to as “other dispersion resin”) for the purpose of adjusting the dispersibility of the metal oxide particles. May be contained). Other dispersion resins that can be used in the present invention include polymer dispersants [for example, polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly ( (Meth) acrylate, (meth) acrylic copolymer, naphthalene sulfonic acid formalin condensate], polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl amine, alkanol amine, pigment derivative and the like. Other dispersion resins can be further classified into linear polymers, terminal-modified polymers, graft polymers, and block polymers based on their structures. The other dispersion resin is adsorbed on the surface of the metal oxide particles and acts to prevent re-aggregation. Therefore, a terminal-modified polymer, a graft polymer, and a block polymer having an anchor site to the surface of the metal oxide particles can be cited as preferred structures. On the other hand, other dispersion resins have the effect of promoting the adsorption of the dispersion resin by modifying the surface of the metal oxide particles.

Specific examples of other dispersion resins include “DISPERBYK101 (polyamideamine phosphate), 107 (carboxylic acid ester), 110, 180 (copolymer containing an acid group), 130 (polyamide), 161, manufactured by BYK Chemie. 162, 163, 164, 165, 166, 170 (polymer copolymer) ”,“ BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid) ”,“ EFKA 4047, 4050, 4010, 4165 (polyurethane type) manufactured by EFKA ), EFKA 4330, 4340 (block copolymer), 4400, 4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (Azo pigment Conductor) "," Ajisper PB821, PB822 "manufactured by Ajinomoto Fintechno Co., Ltd.," Floren TG-710 (urethane oligomer) "manufactured by Kyoeisha Chemical Co., Ltd.," Polyflow No. 50E, No. 300 (acrylic copolymer) ", Enomoto Kasei “Disparon KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyetherester), DA-703-50, DA-705, DA-725”, manufactured by Kao Corporation DEMAL RN, N (naphthalene sulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate), “homogenol L-18 (polymer polycarboxylic acid)”, “Emulgen 920 , 930, 935, 985 (polyoxyethylene nonylphenyl ether) "," acetamine 8 6 (stearylamine acetate) ", Lubrizol" Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 17000, 27000 (polymer having a functional part at the end), 24000, 28000, 32000, 38500 (graft type polymer) ”,“ Nikkor T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate) ”manufactured by Nikko Chemical Co., Ltd., and the like. In addition, as other dispersion resins, compounds represented by the formula (ED) after the paragraph 0562 of JP2012-208494A (corresponding US Patent Application Publication No. 2012/235099 [0692]) (ether dimer) May be mentioned as an essential monomer component, and the contents thereof are incorporated in the present specification. As a specific example of the ether dimer, the description of the ether dimer in paragraph 0565 of JP2012-208494A (corresponding US Patent Application Publication No. 2012/235099, [0694]) can be referred to, and the contents thereof are described in this application. Incorporated in the description. Specific examples of the polymer obtained by polymerizing the compound represented by the formula (ED) as an essential monomer component include the compound represented by the formula (ED) described later in the section of the binder polymer as an essential monomer. The thing similar to the specific example of the polymer polymerized as a component is mentioned. These other resins may be used alone or in combination of two or more.

  The content of the polymer compound (dispersion resin) (B) relative to the total solid content of the dispersion composition of the present invention is preferably in the range of 5 to 40% by mass from the viewpoints of dispersibility, high refractive index, and coated surface shape. The range of 10-35 mass% is more preferable, and the range of 12-30 mass% is still more preferable.

<(C) Solvent>
Although the dispersion composition of this invention contains a solvent, this solvent can be comprised using various organic solvents.
As the organic solvent that can be used here, those similar to the dispersion compositions I and II can be used, and the preferred range is also the same.

  There is no restriction | limiting in particular as a manufacturing method of the dispersion composition of this invention, The manufacturing method of the dispersion composition normally used can be applied. For example, the metal oxide particles (A), the polymer compound (B), and the solvent (C) can be mixed and dispersed using a circulation type dispersion device (bead mill) or the like.

The curable composition of the present embodiment is preferably filtered with a filter for the purpose of removing foreign substances and reducing defects. If it is conventionally used for the filtration use etc., it can use without being specifically limited. For example, fluorine resins such as PTFE (polytetrafluoroethylene), polyamide resins such as nylon-6 and nylon-6,6, polyolefin resins such as polyethylene and polypropylene (PP) (including high density and ultra high molecular weight), etc. Filter. Among these materials, polypropylene (including high density polypropylene) is preferable.
The filter has a pore diameter of about 0.01 to 7.0 μm, preferably about 0.01 to 2.5 μm, and more preferably about 0.01 to 1.5 μm. By setting it as this range, it is possible to surely remove fine foreign matters that are mixed in the dissolved pigment and the like and inhibit the preparation of a uniform and smooth curable composition in the subsequent step.
When using filters, different filters may be combined. At that time, the filtering by the first filter may be performed only once or may be performed twice or more. When filtering two or more times by combining different filters, it is preferable that the second and subsequent pore sizes are larger than the pore size of the first filtering. Moreover, you may combine the 1st filter of a different hole diameter within the range mentioned above. The pore diameter here can refer to the nominal value of the filter manufacturer. 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 Japan Microlith Co., Ltd.) or KITZ Micro Filter Co., Ltd. .
As the second filter, a filter formed of the same material as the first filter described above can be used. The pore size of the second filter is suitably about 0.5 to 7.0 μm, preferably about 2.5 to 7.0 μm, more preferably about 4.5 to 6.0 μm. By setting it within this range, the component particles contained in the mixed solution remain mixed and mixed in the mixed solution, and foreign matters that hinder the preparation of a uniform and smooth curable composition in the subsequent step are removed. Can be removed.
For example, the filtering by the first filter may be performed only with the dispersion, and the second filtering may be performed after mixing other components.

<Low refractive index film>
The light transmissive cured film in the present invention can be formed of a curable composition containing the specific low refractive index material and high refractive index material in a solvent.
The low refractive index film according to the present invention exhibits excellent low refractive index properties. Specifically, the refractive index of the low refractive index film is 1.5 or less, more preferably 1.46 or less, further preferably 1.43 or less, and 1.42 or less. Is particularly preferred. As a lower limit, it is 1.3 or more, and it is especially preferable that it is 1.32 or more. Within the above range, it is useful as an antireflection film described later. The antireflection film is preferably lower than the refractive index of an optical member (for example, an optical lens body) to which it is formed. Thereby, an effective antireflection effect is obtained.

The Abbe number of the low refractive index film according to the present invention is 5 or more, preferably 10 or more, more preferably 15 or more, further preferably 17 or more, and preferably 20 or more. Particularly preferred. The upper limit is 40 or less, preferably 38 or less, more preferably 35 or less, and particularly preferably 33 or less. The Abbe number of the films within this range, compatibility with the high refractive index film which is widely (microlenses) may, Ru uniform antireflection effect can be obtained in a wide range of the visible light region.

The thickness of the low refractive index film is not particularly limited, but is preferably 0.025 μm or more, more preferably 0.05 μm or more, and more preferably 0.075 μm or more. The upper limit of the thickness is preferably 3 μm or less, and more preferably 2.5 μm or less.
The thickness of the high refractive index film is not particularly limited, but is preferably 0.1 μm or more, more preferably 0.2 μm or more, and more preferably 0.3 μm or more. The upper limit of the thickness is preferably 6 μm or less, and more preferably 4 μm or less. A particularly preferable range when the lens body is used will be described later.

  When the cured film is used as a low refractive index film, by setting the film thickness within this range, it is excellent in durability as a microlens unit, and also excellent in adhesion to a cover glass when used as a solid-state imaging device described later. Therefore, it is preferable. In particular, in the case of thick coating, it may be more than 1.0 μm. The film thickness here refers to the thickness from the height of the longest point of the lens body.

<Optical member set>
As an example of the optical member set according to a preferred embodiment of the present invention, there is a structure in which different first optical members and second optical members are combined.
Hereinafter, the microlens unit will be described as an example of the optical member set, the light curable cured film will be described as an example of the first optical member, and the microlens body will be described as an example of the second optical member.
The microlens unit is incorporated in a solid-state imaging device and includes a microlens body and a light-transmitting cured film that covers the microlens body. The term “microlens body” includes the meaning of a microlens array, and may be collectively referred to simply as “lens members” or “lens members”. When the microlens array is used as a microlens body, it is ideal that the groove, which is the gap between the microlens bodies, is embedded in the light-transmitting cured film without any gap, and no voids are generated. . In such an aspect, the microlens unit does not generate void-derived noise in the light passing through the unit, and exhibits good quality performance.

<First optical member>
An example of the first optical member according to this embodiment is a light transmissive cured film. The light transmissive cured film is composed of a cured film of the curable composition.

<Second optical member>
An example of the second optical member according to this embodiment is a microlens body. The shape of the microlens body is not particularly limited, but a convex lens is preferably used. In the present invention, the term “convex lens” refers to a lens including a plano-convex lens, a biconvex lens, a convex meniscus lens, etc., and having a portion bulging in at least one direction unless otherwise specified. Specific examples of the shape of the convex lens include a polyhedron shape, a spherical shape, and an aspherical shape (a shape without a spherical aberration formed by a free-form surface). Examples of the shape of the polyhedron include a regular polyhedron shape, a semi-regular polyhedron shape, a cylindrical shape, and a cylindrical shape. Further, if there is a light collecting effect, a Fresnel lens or the like is also included in the convex lens in the present invention.

In the present invention, the high refractive index film (lens body) is preferably made of a material exhibiting a high refractive index. Specifically, the refractive index of the high refractive index film is preferably 1.7 or more, and more preferably 1.8 or more. The upper limit is preferably 2 or less, and more preferably 1.95 or less. When the refractive index is within this range, a lens unit with good quality performance can be obtained when used in combination with the above-described antireflection film (low refractive index film).
From the viewpoint of compatibility with the low refractive index film according to the present invention, the Abbe number of the high refractive index film is preferably 5 or more, more preferably 7 or more, and particularly preferably 10 or more. . The upper limit is preferably 90 or less, more preferably 80 or less, further preferably 70 or less, further preferably 50 or less, and particularly preferably 40 or less.

As in the present embodiment, as a form in which the microlens bodies are used as a microlens array, it is preferable that the bulging directions are arranged substantially in the same direction. Here, the arrangement means that two or more are arranged side by side at a predetermined interval, and the interval may be uniform or different. Preferably, it is two-dimensionally arranged in one plane, and more preferably two-dimensionally arranged at equal intervals. In addition, the distance between the lenses (the distance between the centers of the lenses) is usually in the range of 100 to 1,000 nm, and more preferably 100 to 400 nm when densely arranged. Between the lens it is mostly the concave portion is formed, as the shape determined by the shape of the bulged convex lens. In the case of a convex lens having an arcuate shape (a surface defined by an arc and a chord) in a cross section, a concave portion having a cross section in which two V-shaped lines are formed by reverse arcs is formed.
The height (thickness) of the lens body is not particularly limited, but is practically 200 to 1000 nm. The width of the lens body is not particularly limited, but it is practically 70 to 80% of the lower color filter size (for example, when the color filter size is 1400 nm, it is 980 to 1190 nm). The height of the lens body here refers to the height of the longest point of the lens body.
When the lens body is a convex lens, the radius of curvature is not particularly limited as long as it is within a range where a desired effect is achieved.

<Method for producing optical member set>
There is no restriction | limiting in particular as an embodiment of an optical member set in this invention, According to a use and the objective, it can select suitably. Specific examples include the following, but the present invention is not limited to these configurations. In this specification, the term “coating” includes not only the case where the object is directly in contact with the object but also covering with another layer.
1st aspect: The aspect in which a 2nd optical member is directly coat | covered with the 1st optical member 2nd aspect: The 2nd optical member is coat | covered with the overcoat layer, and also in the 1st optical member, Aspect formed by coating A third aspect: an aspect in which a layer of the first optical member is formed between the second optical member and the semiconductor light receiving unit Among the above, the first aspect is preferable. Hereinafter, the manufacturing method is demonstrated in detail about a 1st aspect.

(Application of composition)
The curable composition of this embodiment is preferably used as a material for forming an antireflection film or a low refractive index film. A method of applying to a workpiece such as a lens body in order to form a cured film is not particularly limited, and any appropriate known application method can be applied. For example, a spin coating method, a dip coating method, a roller blade method, a spray method, or the like can be applied. As needed, it is preferable to heat-treat etc. to the apply | coated coating film and to remove the solvent contained in a coating film.
The coating amount is preferably a condition that the film thickness after curing is 3 μm or less, more preferably a condition that is 2.5 μm or less, and even more preferably a condition that is 2 μm or less. Although a lower limit is not specifically limited, The conditions which become 0.1 micrometer or more are preferable, The conditions which become 0.2 micrometers or more are more preferable, The conditions which become 0.5 micrometers or more are especially preferable. When the workpiece has, for example, a concavo-convex shape in which a large number of convex lenses are arranged in a solid-state imaging device, the gap width of the trench-like portion (the width of the middle of a V-shaped groove) is typically about 100 to 300 nm. is there.

(Formation of cured film)
It is preferable to apply the resin composition for forming a light transmissive cured film on the workpiece, and then remove the solvent to form a cured film. For this purpose, the coated film is preferably left at 60 to 200 ° C., more preferably 100 to 150 ° C., preferably 1 to 10 minutes, more preferably 1 to 5 minutes. The solvent removal may be performed twice or more under different conditions.

  In this embodiment, it is preferable that the applied resin composition for forming a light transmissive cured film is heated to further promote curing. By doing in this way, a more stable form can be realized and development resistance can be enhanced. Although the heating temperature will not be restrict | limited especially if a coating film hardens | cures, it is preferable that it is 150-400 degreeC normally. Especially, 150-280 degreeC is preferable and 150-240 degreeC is more preferable. If it is the said heating conditions, a coating film will fully harden | cure and it can be set as the outstanding film | membrane. Although it does not restrict | limit especially as heating time, It is preferable that it is 1 to 60 minutes, and it is more preferable that it is 1 to 30 minutes. The heating method is not particularly limited, and heating by a hot plate, oven, furnace, or the like can be applied.

The atmosphere during heating is not particularly limited, and an inert atmosphere, an oxidizing atmosphere, or the like can be applied. The inert atmosphere can be realized by an inert gas such as nitrogen, helium, or argon. The oxidizing atmosphere can be realized by a mixed gas of these inert gas and oxidizing gas, or air may be used. Examples of the oxidizing gas include oxygen, carbon monoxide, and oxygen dinitride. The heating step can be performed under pressure, normal pressure, reduced pressure, or vacuum.
The cured film obtained by the heat treatment is mainly composed of organic silicon oxide (SiOC). Thereby, for example, even if it is a fine pattern, a to-be-processed object and a cured film can be etched precisely, and it can respond suitably also to the manufacturing process of a fine solid-state image sensor.

(Antireflection film)
As a suitable usage mode of the cured film obtained using the composition according to the present invention described above, an antireflection film can be mentioned. In particular, it is suitable as an antireflection film for an optical device using a solid-state imaging device or the like, for example, a microlens for an image sensor, a plasma display panel, a liquid crystal display, or organic electroluminescence. The lower the reflectance when used as an antireflection film, the better. Specifically, the specular average reflectance in the wavelength region of 400 to 700 nm is preferably 3% or less, more preferably 2% or less, and most preferably 1% or less. The reflectance is preferably as small as possible, and most preferably 0.
The haze of the antireflection film is preferably 3% or less, more preferably 1% or less, and most preferably 0.5% or less. The reflectance is preferably as small as possible, and most preferably substantially zero.

<Solid-state imaging device>
A solid-state imaging device according to a preferred embodiment of the present invention includes a microlens unit on a semiconductor light receiving unit, and is incorporated so that a microlens body and a color filter are in contact with each other. The light receiving element receives light passing through the light-transmitting cured film, the lens body, and the color filter in this order, and functions as an image sensor. Specifically, the light-transmitting cured film functions as an antireflection film, improves the light collection efficiency of the lens body, and the light collected efficiently by the lens body is detected by the light receiving element through the color filter. . Since these function throughout the elements that detect light corresponding to RGB, an extremely clear image can be obtained even when the light receiving elements and the lens bodies are arranged at high density.

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

The microlens unit according to a preferred embodiment of the present invention preferably has the following configuration. That is, a plurality of convex lenses are applied as the microlens body, the plurality of convex lenses are arranged with their bulging directions substantially in the same direction, and the plurality of convex lenses are covered from the bulging direction. The light-transmitting cured film is covered with the light-transmitting cured film, and the recessed portions formed between the plurality of convex lenses are filled with the light-transmitting cured film substantially without any gaps. The opposite side of the lens body is a flat surface.
In this specification, “substantially the same direction” means that even if the bulging direction does not completely match, even if there is a deviation in the bulging direction, such as a mismatch in direction, within the range where the desired effect is achieved. The idea is to allow good things. On the other hand, “substantially no gap” is intended to allow a minute gap between the first optical member and the second optical member within a range in which a desired effect is achieved. is there.

  In the present invention, the microlens unit can be suitably used for applications other than those for solid-state imaging devices. Other applications include, for example, various OA devices, liquid crystal display elements such as liquid crystal televisions, mobile phones, and projectors, and imaging optical systems for on-chip color filters such as facsimiles, electronic copying machines, and solid-state image sensors. These can be used for various applications.

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

<Low refractive index material>
(Synthesis of hydrolysis condensate)
A preparation example of composition A02 is shown as a representative example. Hydrolysis / condensation reaction was performed using methyltriethoxysilane. The solvent used at this time was ethanol. The obtained hydrolysis condensate A-1 had a weight average molecular weight of about 10,000. The weight average molecular weight was confirmed by GPC according to the procedure described above. Components of the following composition 1 were mixed with a stirrer to prepare composition A02. Other compositions were prepared in the same manner as A02 except that the components in the amounts shown in Table A below were used.

(Composition 1)
Hydrolysis condensate (A-1) ... 10 parts propylene glycol monomethyl ether acetate
(PGMEA) 72 parts ethyl 3-ethoxypropionate (EEP) 18 parts EMULSOGEN-COL-020
(Manufactured by Clariant Japan) 2 parts Thru rear 2320 25 parts

(Application of composition)
The composition A02 obtained above was applied onto a silicon wafer and then pre-baked (100 ° C. for 2 minutes) and post-baked (230 ° C. for 10 minutes) to form a coating film.

ただし
ｎ_Ｄ：フラウンホーファーのＤ線（５８９．３ｎｍ）に対する屈折率
ｎ_Ｆ：フラウンホーファーのＦ線（４８６．１ｎｍ）に対する屈折率
ｎ_Ｃ：フラウンホーファーのＣ線（６５６．３ｎｍ）に対する屈折率 [Refractive index evaluation]
The refractive index of the obtained film was measured with an ellipsometer (VUV-base [trade name] manufactured by JA Woollam) (wavelength 633 nm, measurement temperature 25 ° C.). The Abbe number was calculated from the refractive index value measured in the same manner with the measuring apparatus. The calculation formula is as follows.

Where n _D : refractive index with respect to Fraunhofer's D line (589.3 nm) n _F : refractive index with respect to Fraunhofer's F line (486.1 nm) n _C : refractive index with respect to Fraunhofer's C line (656.3 nm)

<Notes on the table>
Blending amount: parts by mass (raw material of siloxane resin)
MTES: methyltriethoxysilane TEOS: tetraethoxysilane γ-GP-TMS: γ-glycidoxypropyltrimethoxysilane TFP-TMS: trifluoropropyltrimethoxysilane TDFO-TMS: tridecafluorooctyltrimethoxy Silane (surfactant)
EMUL-020 ... EMULSOGEN COL-020
(Anionic surfactant, manufactured by Clariant)
(Fluorine resin)
CYTOP: Product name, Asahi Glass (silica particles)
Through rear 2320
... Thru rear 2320: 20% by mass dispersion of hollow silica manufactured by JGC Catalysts & Chemicals, Inc. SD-L
・ ・ ・ Snowtex MIBK-SD-L: 30% by mass dispersion of porous silica manufactured by Nissan Chemical Industries, Ltd. ST
・ ・ ・ Snowtex MIBK-ST: 20% by mass dispersion of porous silica PL-1 manufactured by Nissan Chemical Co., Ltd. PL-1
... PL-1-IPA: 12.5 mass% dispersion of porous silica manufactured by Fuso Chemical Co., Ltd. PL-2L
... PL-2L-PGME: 20% by mass dispersion of porous silica manufactured by Fuso Chemical Co., Ltd.

<High refractive index material>
[Preparation of titanium dioxide dispersion (dispersion composition)]
Using a NPM manufactured by Shinmaru Enterprises Co., Ltd. as a circulation type dispersion device (bead mill), a mixture treatment having the following composition was subjected to a dispersion treatment as follows to obtain a titanium dioxide dispersion as a dispersion composition. .
~composition~
・ Titanium dioxide (Ishihara Sangyo Co., Ltd. TTO-51 (C)): 150.0 parts ・ The following dispersion resin 1 (solid content 20% PGMEA solution): 165.0 parts ・ Propylene glycol monomethyl ether acetate: 142.5 Part

The dispersing device was operated under the following conditions.
・ Bead diameter: φ0.05mm
・ Bead filling rate: 60% by volume
・ Peripheral speed: 10m / sec
・ Pump supply amount: 30Kg / hour
・ Cooling water: Tap water ・ Bead mill annular passage volume: 1.0L
・ Amount of liquid mixture to be dispersed: 10kg

After the start of dispersion, the average particle size was measured at 30 minute intervals (one pass time).
The average particle diameter decreased with the dispersion time (pass number), but the amount of change gradually decreased. Dispersion was terminated when the average particle size change when the dispersion time was extended by 30 minutes became 5 nm or less. The average particle size of the titanium dioxide particles in this dispersion was 40 nm.
Moreover, the average particle diameter of the titanium dioxide particles contained in the obtained dispersion was 40 nm.

In addition, the average particle diameter of titanium dioxide or the like in this example is obtained by diluting a mixed liquid or dispersion containing titanium dioxide 80 times with propylene glycol monomethyl ether acetate, and subjecting the obtained diluted liquid to a dynamic light scattering method. The value obtained by using and measuring.
This measurement was performed using Nikkiso Co., Ltd. Microtrac UPA-EX150.

[High Refractive Index Material: Preparation of Titanium Dioxide-Containing Curable Composition B01]
-Titanium dioxide dispersion prepared above (dispersion composition)-80.5 parts-Solvent: propylene glycol
Monomethyl ether acetate 15 parts ・ Polymerizable compound: KAYARAD DPHA
(Nippon Kayaku Co., Ltd.) ... 3.6 parts Polymerization initiator: IRGACURE OXE 01 (trade name) manufactured by BASF
... 0.10 parts-Polymer: benzyl methacrylate / methacrylic acid copolymer (copolymerization ratio: 80/20 (wt%), weight average molecular weight: 12,000)
(Manufactured by FFFC) 0.5 parts Surfactant: Megafac F781 (manufactured by DIC Corporation) 0.30 parts

[Formation of cured film]
After the titanium dioxide-containing curable composition was applied on a silicon wafer, pre-baking (100 ° C. for 2 min) and post-baking (230 ° C. for 10 min) were performed to prepare a cured film B-1. When the refractive index of this coating film was measured using an ellipsometry manufactured by JA Woollam Japan, the refractive index at 633 nm was 1.91.

  The raw material ratio in the curable composition to be used was changed to the following composition ratio, and various titanium dioxide-containing curable compositions were prepared by the same steps as the titanium dioxide-containing curable composition B-1. In addition, the refractive index measurement result of each cured film is also described.

<Meaning of abbreviations>
Blending amount: parts by mass 157S65 JER157S65 (manufactured by Japan Epoxy Resin Co., Ltd.)
JER-157S65: manufactured by Japan Epoxy Resins Co. ZrO _2: zirconium oxide (Nippon Denko Co. PCS)

  The sample B03 was prepared in the same manner as the B01 composition except that the titanium oxide was changed to zirconium oxide (PCS manufactured by Nippon Electric Works Co., Ltd.).

<Creation of base film>
After applying the titanium dioxide-containing curable composition (B01) on a glass substrate, pre-baking (100 ° C. for 2 min) and post-baking (230 ° C. for 10 min) were performed to prepare a base film D-1. The base film (high refractive index film) had a refractive index of 1.91 and an Abbe number of 13.6. The thickness of the base film was 1.2 μm.

<Adjustment of curable composition>
A02 and B01 were mixed as follows to prepare a curable composition AB01.
A02 ... 80 parts B01 ... 20 parts Other curable compositions were prepared in the same manner as AB01 except that the components in the amounts shown in Table 1 below were used.

<Creation of cured film>
After applying the curable composition AB01 prepared above on the base film D-1, pre-baking (100 ° C. for 2 min) and post-baking (230 ° C. for 10 min) were performed to form an antireflective low refractive index film. The thickness of the low refractive index film was 0.1 μm.

[Reflectance evaluation]
Measurement was performed using a spectrophotometer U-4100 manufactured by Hitachi, Ltd. The light was incident in the direction of 5 degrees with respect to the vertical direction of the substrate, and the intensity of the light reflected from the film was compared with the value of the blank without the substrate having the base film. Wavelengths of 450 nm, 550 nm, and 650 nm were used. The results are shown in Table 1.

試験Ｎｏ．：ｃで始まるものが比較例

Test No. : Starting with c is a comparative example

  Ac1 was prepared in the same manner as A01 except that 80 parts MTES and 20 parts TEOS were changed to 100 parts MTES (Table A) and PL-1 was not added.

Comparative examples c12 and c13 are examples in which a low refractive index material and a high refractive index material are not mixed, and a low refractive index film is produced using only the low refractive index materials in the table. c14 to c16 are examples using commercially available products.
MP1: CYTOP (trade name) manufactured by Asahi Glass Co., Ltd. [Fluororesin]
MP2: JSR Opstar JN (trade name)
[Fluorine organic inorganic hybrid material]
MP3: DIC defender OP (trade name)
[UV curable resin for optics]

  For B05, an ultra-high refractive index, high heat-resistant coating material UR-202 (manufactured by Nissan Chemical Industries) was used.

  The low refractive index film (Example) formed from the curable composition of the present invention achieved a desired refractive index and Abbe number, and exhibited good antireflection properties in a wide visible light region. From this result, it can be seen that excellent optical performance is exhibited as an optical member such as a solid-state imaging device.

(Example 2)
(Titanium dioxide-less high refractive index material composition)
In order to form a layer having a refractive index (1.68), the following composition was prepared. In addition, when using the following composition C01, prebaking (100 degreeC2min) and postbaking (230 degreeC10min) are implemented and a cured film is formed.
Solvent: Propylene glycol monomethyl ether acetate 15 parts Cyclohexanone 30 parts Resin: Ultra high refractive index coating material UR202 manufactured by Nissan Chemical Industries, Ltd. 32 parts Curing accelerator: SB-A (Mitsubishi Gas Chemical) .... 5 parts epoxy resin: 157S65 (Mitsubishi Chemical Corporation) ... 17.5 parts Surfactant: Megafak F-781 (DIC) ... 0.5 parts

  The antireflective low refractive index film was formed as shown in Table 2 below using the high refractive index material C01. In any test, it was confirmed that a good reflectance with no variation was obtained in the range of 450 to 650 nm.

(Example 3)
A test body 301 was obtained in the same manner as the test body 201 except that the UR202 of the high refractive index material C01 of the test body 201 was changed to thioepoxy resin LPH1101 (manufactured by Mitsubishi Gas Chemical Company). About the test body 301, the reflectance of the range of 450-650 nm was evaluated similarly to the test body 101, and it confirmed that it was a favorable result.

Example 4
A specimen 401 was obtained in the same manner as the specimen 201 except that the UR202 of the high refractive index material C01 of the specimen 201 was changed to episulfide resin MR-174 (manufactured by Mitsui Chemicals). About the test body 401, the reflectance of the range of 450-650 nm was evaluated similarly to the test body 101, and it confirmed that it was a favorable result.

(Example 5)
A test body 501 was obtained in the same manner as the test body 201 except that the UR202 of the high refractive index material C01 of the test body 201 was changed to thiourethane resin MR-7 (Mitsui Chemicals). About the test body 501, the reflectance in the range of 450-650 nm was evaluated similarly to the test body 101, and it confirmed that it was a favorable result.

(Example 6)
The reflectance of each wavelength was measured in the same manner except that the thicknesses of the high refractive index film (underlying film) and the low refractive index film were changed as follows. As a result, it was confirmed that uniform antireflection performance was obtained in the visible light region as in Example 1.
――――――――――――――――――――
Test High refractive index film Low refractive index film ――――――――――――――――――――
101 1.2 μm 0.1 μm
601 1.5 μm 0.15 μm
602 0.75 μm 0.075 μm
603 1.25 μm 0.2 μm
604 2.0 μm 0.3 μm
――――――――――――――――――――

The thicknesses of the high refractive index film and the low refractive index film were measured as follows.
The thickness of the obtained film was measured with an ellipsometer (VUV-base [trade name] manufactured by JA Woollam).

Claims (14)

  Curing for forming a low refractive index film comprising a low refractive index material having an Abbe number of 40 to 80 and a refractive index of 1.2 to 1.4 and a high refractive index material having an Abbe number of 5 to 40 and a refractive index of 1.6 to 2. A low refractive index film-forming composition, wherein the low refractive index material contains a siloxane resin, and the curable composition for forming a low refractive index film contains 15 to 40% by mass of the siloxane resin. Sex composition. The curable composition for forming a low refractive index film according to claim 1 , wherein the low refractive index material contains hollow particles or non-hollow particles. The high refractive index material, the low refractive index film-forming curable composition according to claim 1 or 2 containing titania or zirconia. The curable composition for forming a low refractive index film according to any one of claims 1 to 3 , further comprising at least one of a dispersant, a surfactant, a polymerizable compound, and a polymer thereof. Any of claims 1 to 4, the number of atoms other than hydrogen atoms contains a polymer compound dispersant represented by the graft copolymer or the following formula (1) having a graft chain in the range of 40 to 10,000 1 The curable composition for forming a low refractive index film according to Item.

In formula (1), R ¹ represents an (m + n) -valent linking group, and R ² represents a single bond or a divalent linking group. A ¹ represents a monovalent substituent having at least one acid group. The n A ¹ and R ² may be the same or different. m represents a positive number of 8 or less, n represents 1 to 9, and m + n satisfies 3 to 10. P ¹ represents a polymer chain. The m P ¹ may be the same or different. 6. The curing for forming a low refractive index film according to claim 5 , wherein the polymer structure of the graft chain of the graft copolymer is a poly (meth) acrylic structure, a polyester structure, a polyurethane structure, a polyurea structure, a polyamide structure or a polyether structure. Sex composition. The graft copolymer is a poly (alkylene imine containing an alkylene chain having 1 to 5 carbon atoms) -based repeating unit, a polyallylamine-based repeating unit, a polydiallylamine-based repeating unit, a metaxylenediamine-epichlorohydrin polycondensate-based repeating unit, And a repeating unit having a basic nitrogen atom, at least one selected from polyvinylamine-based repeating units, having a partial structure having a functional group of pKa14 or less, and a side having 40 to 10,000 atoms The curable composition for forming a low refractive index film according to claim 5 having a chain. The graft copolymer is a repeating unit represented by the following formula (I-1) and a repeating unit represented by the formula (I-2), or a repeating unit and a formula represented by the formula (I-1). (I-2a) a low refractive index film-forming curable composition according to claim 5 or 7 containing a repeating unit represented by.

In the formula, R ¹ and R ² each independently represents a hydrogen atom, a halogen atom or an alkyl group. a represents the integer of 1-5 each independently. * Represents a connecting part between repeating units. R ⁸ and R ⁹ are the same groups as R ¹ . L represents a single bond, an alkylene group, an alkenylene group, an arylene group, heteroarylene group, an imino group, an ether group, a thioether group, a carbonyl group or a linking group according to a combination thereof,, L ^a is CR ⁸ CR ⁹ and N And a structural site that forms a ring structure. X represents a group having a functional group having a pKa of 14 or less, and Y represents a side chain having 40 to 10,000 atoms. The curable composition for forming a low refractive index film according to claim 5 , wherein the polymer compound represented by the formula (1) is represented by the following formula (2).

In formula (2), A ² has the same meaning as A ¹ in formula (1). R ⁴ and R ⁵ each independently represents a single bond or a divalent linking group. The n R ^{4 s} may be the same or different. The m R ^{5 s} may be the same or different. R ³ represents a (m + n) -valent linking group. m + n satisfies 3-10. P ² has the same meaning as P ¹ in the formula (1). the m P ² can be the same or different. The curable composition for forming a low refractive index film according to any one of claims 1 to 9, comprising a fluorine-based surfactant and a nonionic surfactant. The curable composition for forming a low refractive index film according to any one of claims 1 to 10 , comprising a polymerizable compound represented by any one of the following formulas (a) to (f).

The curable composition for forming a low refractive index film according to any one of claims 1 to 11 , comprising an oxime compound as a polymerization initiator. A method for producing an optical member set comprising a first optical member and a second optical member coated thereon,
A step of preparing the curable composition for forming a low refractive index film according to any one of claims 1 to 12 ,
Applying the curable composition onto the second optical member;
The manufacturing method of an optical member set including the process of hardening this curable composition and forming the 1st optical member which is a low refractive index film | membrane. A method for producing a curable composition prepared by mixing a first composition and a second composition,
The curable composition is a curable composition for forming a low refractive index film,
The first composition includes a low refractive index material having an Abbe number of 40 to 80 and a refractive index of 1.2 to 1.4, and the second composition has an Abbe number of 5 to 40, a refractive index of 1. Including a high refractive index material exhibiting 6-2, and
The method for producing a curable composition, wherein the low refractive index material contains a siloxane resin, and the curable composition contains 15 to 40% by mass of the siloxane resin.