JP2017151321A - Curable composition, production method of cured film, cured film, touch panel and display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition that has excellent storage stability and excels in development adhesiveness of a cured film to be obtained therefrom, in surface smoothness of the film after heating, and in suppressing a development residue, a cured film obtained by curing the above curable composition and a production method of the cured film, and an organic EL display device and a liquid crystal display device having the cured film.SOLUTION: A curable composition comprises an ethylenically unsaturated compound, a photopolymerization initiator, a polymer having an acid group, a polyfunctional thiol compound, metal oxide particles, a silane coupling agent and an organic solvent. The polymer having an acid group has an acid value of 100 to 300 mgKOH/g. A content A1 of the polyfunctional thiol compound with respect to the whole solid content of the composition, and a content A2 of the silane coupling agent with respect to the whole solid content of the composition satisfy formula 1: 0.2≤(A1/A2)≤5.0 and formula 2: 0.5≤(A1+A2)≤15.0.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a curable composition, a method for producing a cured film, a cured film, and various display devices such as a touch panel, a liquid crystal display device, an organic EL display device, and a touch panel display device using the cured film.

In recent years, transparent curable compositions have been used to form interlayer insulating films, protective films, light extraction layers, spacer members, microlens members, and the like. A cured product obtained by using a transparent curable composition is used as a member of many electronic devices such as various display devices such as liquid crystal display devices and organic EL display devices, touch panels, imaging devices, and solar cells.
As a conventional curable composition, the composition described in patent documents 1-3 is known.
Patent Document 1 contains a polymerizable compound having an ethylenically unsaturated bond, a polymerization initiator, an alkoxysilane compound, and an organic solvent, and has at least six functional groups in the solid content excluding inorganic substances from the total solid content of the composition. The curable composition characterized by the ratio of urethane (meth) acrylate being 70 mass%-100 mass% is described.
Patent Document 2 contains a polymerizable compound having an ethylenically unsaturated bond as Component A, a polymerization initiator as Component B, a mercapto compound as Component S, and an organic solvent as Component D. A contains 6 or more functional urethane (meth) acrylate, the ratio of the 6 or more functional urethane (meth) acrylate in component A is 70 to 100% by mass, and the content of component S is curable. The curable composition characterized by being 1-20 mass% with respect to the total solid of a composition is described.
Patent Document 3 contains a polymerizable compound having an ethylenically unsaturated bond as Component A, a polymerization initiator as Component B, a blocked isocyanate compound as Component C, and an organic solvent as Component D, Component A contains 6 or more functional urethane (meth) acrylates, the ratio of the 6 or more functional urethane (meth) acrylates in Component A is 70 to 100% by mass, Component A, Component B and Component C And the total amount of the curable composition is 85% by mass or more based on the total organic solid content of the curable composition.

  It is also known to adjust the refractive index of a transparent curable composition for the purpose of further improving the light extraction efficiency of the organic EL display device and preventing the touch detection electrode of the touch panel from being seen.

International Publication No. 2015/072532 International Publication No. 2015/072533 International Publication No. 2015/072534

  The problem to be solved by the present invention is a curable composition excellent in storage stability and development adhesion of the resulting cured film, surface smoothness after heating, and suppression of development residue, the above curing It is providing the cured film which hardened the curable composition, its manufacturing method, and the organic electroluminescent display device and liquid crystal display device which have the said cured film.

The above-described problems of the present invention have been solved by means described in the following <1>, <8>, <9>, <10>, or <12> to <15>. It describes below with <2>-<7> and <11> which are preferable embodiments.
<1> An ethylenically unsaturated compound, a photopolymerization initiator, a polymer having an acid group, a polyfunctional thiol compound, a metal oxide particle, a silane coupling agent, and an organic solvent, and having the above acid group. The acid value of the polymer is 100 to 300 mgKOH / g, the content A1 of the polyfunctional thiol compound with respect to the total solid content of the composition, and the content A2 of the silane coupling agent with respect to the total solid content of the composition Satisfying the following formula 1 and formula 2,
Formula 1: 0.2 ≦ (A1 / A2) ≦ 5.0
Formula 2: 0.5 ≦ (A1 + A2) ≦ 15.0
<2> The content B1 of the ethylenically unsaturated compound with respect to the total solid content of the composition and the content B2 of the polymer having the acid group with respect to the total solid content of the composition are represented by the following formula 3 and formula: 4, the curable composition according to <1>,
Formula 3: 1.0 ≦ (B1 / B2) ≦ 15.0
Formula 4: 5 ≦ B2 ≦ 30
<3> The polyfunctional thiol compound is pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyryloxy) Ethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropane tris (3-mercaptobutyrate), trimethylolethane tris (3-mercaptobutyrate), Trimethylolpropane tris (3-mercaptopropionate), tris [(3-mercaptopropionyloxy) ethyl] isocyanurate, pentaerythritol tetrakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate) ) And dipentaerythrito The curable composition according to <1> or <2>, comprising at least one compound selected from the group consisting of hexhexakis (3-mercaptopropionate),
<4> The curable composition according to any one of <1> to <3>, wherein the metal oxide particles have a refractive index of 1.80 to 2.80 at a wavelength of 550 nm.
<5> The curable composition according to any one of <1> to <4>, wherein the metal oxide particles include titanium oxide particles or zirconium oxide particles.
<6> The curable composition according to any one of <1> to <5>, wherein the content of the metal oxide particles is 30% by mass or more based on the total solid content of the composition,
<7> The curable composition according to any one of <1> to <6>, wherein the silane coupling agent includes a compound represented by the following formula SC-2 or formula SC-3.

上記式ＳＣ−２及び式ＳＣ−３中、Ｒはそれぞれ独立に、炭素数１〜３のアルキル基を表し、Ｌは２価の連結基を表し、Ｒ¹は水素原子又はメチル基を表す、
＜８＞ 少なくとも工程ａ〜工程ｄをこの順で含む硬化膜の製造方法、
工程ａ：＜１＞〜＜７＞のいずれか１つに記載の硬化性組成物を基板上に塗布する塗布工程
工程ｂ：塗布された硬化性組成物から溶剤を除去する溶剤除去工程
工程ｃ：溶剤が除去された硬化性組成物の少なくとも一部を活性光線により露光する露光工程
工程ｄ：硬化性組成物を熱処理する熱処理工程
＜９＞ 少なくとも工程１〜工程５をこの順で含む硬化膜の製造方法、
工程１：＜１＞〜＜７＞のいずれか１つに記載の硬化性組成物を基板上に塗布する塗布工程
工程２：塗布された硬化性組成物から溶剤を除去する溶剤除去工程
工程３：溶剤が除去された硬化性組成物の少なくとも一部を活性光線により露光する露光工程
工程４：露光された硬化性組成物を水性現像液により現像する現像工程
工程５：現像された硬化性組成物を熱処理する熱処理工程
＜１０＞ ＜１＞〜＜７＞のいずれか１つに記載の硬化性組成物を硬化してなる硬化膜、
＜１１＞ 層間絶縁膜又はオーバーコート膜である、＜１０＞に記載の硬化膜、
＜１２＞ ＜１０＞又は＜１１＞に記載の硬化膜を有する、液晶表示装置、
＜１３＞ ＜１０＞又は＜１１＞に記載の硬化膜を有する、有機ＥＬ表示装置、
＜１４＞ ＜１０＞又は＜１１＞に記載の硬化膜を有する、タッチパネル、
＜１５＞ ＜１０＞又は＜１１＞に記載の硬化膜を有する、タッチパネル表示装置。

In the above formula SC-2 and formula SC-3, R each independently represents an alkyl group having 1 to 3 carbon atoms, L represents a divalent linking group, and R ¹ represents a hydrogen atom or a methyl group.
<8> A method for producing a cured film including at least steps a to d in this order,
Step a: Application step of applying the curable composition according to any one of <1> to <7> on the substrate Step b: Solvent removal step of removing the solvent from the applied curable composition Step c : An exposure step in which at least a part of the curable composition from which the solvent has been removed is exposed with actinic rays Step d: a heat treatment step in which the curable composition is heat-treated <9> Manufacturing method,
Process 1: Application | coating process which apply | coats the curable composition as described in any one of <1>-<7> on a board | substrate Process 2: The solvent removal process of removing a solvent from the apply | coated curable composition Process 3 : Exposure step of exposing at least a part of the curable composition from which the solvent has been removed with actinic rays Step 4: development step of developing the exposed curable composition with an aqueous developer Step 5: developed curable composition Heat treatment step for heat-treating a product <10> A cured film obtained by curing the curable composition according to any one of <1> to <7>,
<11> The cured film according to <10>, which is an interlayer insulating film or an overcoat film,
<12> A liquid crystal display device having the cured film according to <10> or <11>,
<13> An organic EL display device having the cured film according to <10> or <11>,
<14> A touch panel having the cured film according to <10> or <11>,
<15> A touch panel display device having the cured film according to <10> or <11>.

  According to the present invention, there is provided a curable composition excellent in storage stability and having excellent development adhesion of the resulting cured film, surface smoothness after heating, and suppression of development residue, and the above curable composition. It was possible to provide a cured film and a method for producing the cured film, and an organic EL display device and a liquid crystal display device having the cured film.

1 is a conceptual diagram of a configuration of an example of a liquid crystal display device. The schematic sectional drawing of the active matrix substrate in a liquid crystal display device is shown, and it has the cured film 17 which is an interlayer insulation film. 1 shows a conceptual diagram of a configuration of an example of an organic EL display device. A schematic cross-sectional view of a substrate in a bottom emission type organic EL display device is shown, and a planarizing film 4 is provided. It is a top view which shows the electrode pattern of the touchscreen in an example of the display apparatus with a touchscreen. FIG. 4 is a cross-sectional view showing a cross-sectional structure along the line A1-A2 shown in FIG. 3. FIG. 4 is a cross-sectional view showing a cross-sectional structure along the line B1-B2 shown in FIG.

Hereinafter, the contents of the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the specification of the present application, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value. The organic EL element in the present invention refers to an organic electroluminescence element.
In the notation of groups (atomic groups) in this specification, the notation that does not indicate substitution and non-substitution includes not only those having no substituent but also those having a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present specification, “(meth) acrylate” represents acrylate and methacrylate, “(meth) acryl” represents acryl and methacryl, and “(meth) acryloyl” represents acryloyl and methacryloyl.
In the present invention, “mass%” and “wt%” are synonymous, and “part by mass” and “part by weight” are synonymous.
Moreover, in this invention, the combination of a preferable aspect is a more preferable aspect.

(Curable composition)
The curable composition of the present invention (hereinafter also simply referred to as “composition”) includes an ethylenically unsaturated compound, a photopolymerization initiator, a polymer having an acid group, a polyfunctional thiol compound, metal oxide particles, and silane. A polymer containing a coupling agent and an organic solvent, the acid value of the polymer having an acid group is 100 to 300 mgKOH / g, and the content A1 of the polyfunctional thiol compound with respect to the total solid content of the composition The content A2 of the silane coupling agent with respect to the total solid content of the composition satisfies the following formulas 1 and 2.
Formula 1: 0.2 ≦ (A1 / A2) ≦ 5.0
Formula 2: 0.5 ≦ (A1 + A2) ≦ 15.0
In addition, "solid content" in a curable composition represents the component except volatile components, such as an organic solvent.

The present inventors have found that a cured film formed using a conventional curable composition deteriorates the surface smoothness of the cured film when exposed to high temperatures in the production process after the cured film is formed. Found that there is a case.
The deterioration of the surface smoothness is because the chemical composition on the surface of the cured film becomes non-uniform or irregularities are formed after the cured film is exposed to a high temperature. It is presumed that the shape becomes non-uniform or crystallizes non-uniformly.
As described above, the surface smoothness of the cured film is deteriorated, for example, the surface smoothness of the wiring formed in a state in contact with the cured film is also deteriorated, and the electrical resistance value of the wiring is increased. The characteristics of the display device and the like may be adversely affected.
As a result of intensive studies, the present inventors contain an ethylenically unsaturated compound, a photopolymerization initiator, a polymer having an acid group, a polyfunctional thiol compound, metal oxide particles, a silane coupling agent, and an organic solvent. The acid value of the polymer having an acid group is 100 to 300 mgKOH / g, the content A1 of the polyfunctional thiol compound with respect to the total solid content of the composition, and the silane with respect to the total solid content of the composition When the coupling agent content A2 satisfies the formulas 1 and 2 described later, the storage stability is excellent, and the adhesion of the cured film obtained, the surface smoothness after heating, and the development residue It has been found that a curable composition excellent in suppression of the above can be obtained.
Although the detailed mechanism is unknown, it is presumed that the above-mentioned effects are obtained as a result of each component acting in concert by the presence of each specific component as described above at a specific ratio. Yes.

  The curable composition of the present invention is preferably a composition in which the strength of the cured product is increased by heat-treating the cured product such as the obtained cured film after polymerization or subsequent to polymerization, More preferably, the composition contains a photopolymerization initiator, and after the polymerization by light, the resulting cured product is heat-treated to increase the strength of the cured product.

In the curable composition of the present invention, the content A1 of the polyfunctional thiol compound with respect to the total solid content of the composition and the content A2 of the silane coupling agent with respect to the total solid content of the composition are the following formulae: 1 is satisfied, the following formula 1-1 is preferably satisfied, and it is more preferable that the following formula 1-2 is satisfied.
When A1 / A2 is within the above range, a curable composition excellent in development adhesion of the resulting cured film can be obtained.
Formula 1: 0.2 ≦ (A1 / A2) ≦ 5.0
Formula 1-1: 0.3 ≦ (A1 / A2) ≦ 4.0
Formula 1-2: 0.5 ≦ (A1 / A2) ≦ 2.0
In addition, when a curable composition contains 2 or more types of polyfunctional thiol compounds, A1 is taken as the total content of 2 or more types of polyfunctional thiol compounds. The same applies to the silane coupling agent in A2.
In the curable composition of the present invention, the content A1 of the polyfunctional thiol compound with respect to the total solid content of the composition and the content A2 of the silane coupling agent with respect to the total solid content of the composition are: It is preferable to satisfy the following formula 2, satisfy the following formula 2-1, and more preferably satisfy the following formula 2-2.
When A1 + A2 is within the above range, a curable composition having excellent surface smoothness after heating of the resulting cured film can be obtained.
Formula 2: 0.5 ≦ (A1 + A2) ≦ 15.0
Formula 2-1: 1.0 ≦ (A1 + A2) ≦ 10.0
Formula 2-2: 2.0 ≦ (A1 + A2) ≦ 8.0

From the viewpoint of coexistence of development adhesion and surface smoothness after heating, in the curable composition of the present invention, the content B1 of the ethylenically unsaturated compound and the acid group with respect to the total solid content of the composition are included. The content B2 of the polymer preferably satisfies the following formulas 3 and 4.
Formula 3: 1.0 ≦ (B1 / B2) ≦ 15.0
Formula 4: 5 ≦ B2 ≦ 30
In addition, when a curable composition contains 2 or more types of ethylenically unsaturated compounds, B1 is taken as the total content of 2 or more types of ethylenically unsaturated compounds. The same applies to the polymer having an acid group in B2.
In the curable composition of the present invention, the content B1 of the ethylenically unsaturated compound and the content B2 of the polymer having an acid group with respect to the total solid content of the composition satisfy the above formula 3. Preferably, the following formula 3-1 is more preferably satisfied, and the following formula 3-2 is more preferably satisfied.
Formula 3-1: 1.5 ≦ (B1 / B2) ≦ 6.0
Formula 3-2: 2.0 ≦ (B1 / B2) ≦ 4.0
In the curable composition of the present invention, the content B of the polymer having an acid group preferably satisfies the above formula 4, more preferably satisfies the following formula 4-1, and the following formula 4-2. It is further preferable to satisfy
Formula 4-1: 7 ≦ B2 ≦ 20
Formula 4-2: 10 ≦ B2 ≦ 15
Hereinafter, each component which the curable composition of this invention contains is demonstrated.

<Ethylenically unsaturated compound>
The curable composition of the present invention contains an ethylenically unsaturated compound.
The ethylenically unsaturated compound may be a low molecular compound, an oligomer, or a polymer, but the molecular weight of the ethylenically unsaturated compound is preferably 100 to 10,000, and 150 to 5 1,000 is more preferable, and 200 to 3,000 is still more preferable.
In the present invention, the molecular weight of the ethylenically unsaturated compound is measured by ESI-MS (electrospray ionization mass spectrometry). In the present invention, unless otherwise specified, the polymer component is a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent.
In addition, even if it is an ethylenically unsaturated compound, about the compound of molecular weight 5,001 or more, the weight average molecular weight of polystyrene conversion measured by gel permeation chromatography (GPC) when tetrahydrofuran (THF) is used as a solvent. It is.
In addition, an ethylenically unsaturated compound that corresponds to a polymer having an acid group is included in a polymer having an acid group, and a compound that corresponds to a silane coupling agent is included in a silane coupling agent. Shall.

  The ethylenically unsaturated compound in the present invention is preferably a compound having at least one ethylenically unsaturated double bond, preferably a compound having at least one terminal ethylenically unsaturated bond, More preferably, the compound is selected from compounds having two or more unsaturated unsaturated bonds. Such compounds are widely known in this technical field, and these can be used without particular limitation in the present invention.

  These have chemical forms such as monomers, prepolymers, i.e. dimers, trimers and oligomers, 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 an unsaturated carboxylic acid amide having a nucleophilic substituent such as a hydroxy 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.

  Specific examples of the monomer of an ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol. Diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tris (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate , Tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate , Pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tris (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer, isocyanur Examples include acid ethylene oxide (EO) -modified triacrylate.

  Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy- 2-hydroxypro ) Phenyl] dimethyl methane, there are bis [p- (methacryloxyethoxy) phenyl] dimethyl methane.

  In addition, itaconic acid esters, crotonic acid esters, maleic acid esters, other esters, and monomers of amides of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include paragraphs 0132 to 0134 of International Publication No. 2014/084190. The compounds described in (1) can be preferably used.

Examples of the urethane compound include urethane chain polymerizable compounds produced by the addition reaction of isocyanate and hydroxyl group. For example, urethanized products of pentaerythritol triacrylate and hexamethylene diisocyanate, pentaerythritol triacrylate. Urethanes of toluene and diisocyanates, Urethanes of pentaerythritol triacrylate and isophorone diisocyanate, Urethanes of dipentaerythritol pentaacrylate and hexamethylene diisocyanate, Urethanes of dipentaerythritol pentaacrylate and toluene diisocyanate, Dipentaerythritol Examples include urethanized products of pentaacrylate and isophorone diisocyanate.
Specifically, they are described in International Publication No. 2015/072532, Japanese Patent Application Laid-Open No. 2011-126921, Japanese Patent Application Laid-Open No. 51-37193, Japanese Patent Publication No. 2-32293, and Japanese Patent Publication No. 2-16765. Such urethane acrylates are exemplified and these descriptions are incorporated herein.

  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.

[Ethylenically unsaturated compound having two or more aromatic rings]
The ethylenically unsaturated compound in the present invention preferably contains an ethylenically unsaturated compound having two or more aromatic rings from the viewpoint of achieving both refractive index and surface smoothness.
The aromatic ring may be included as a single ring or may form a polycycle. In the present invention, the naphthalene ring is assumed to have two benzene rings.
The ethylenically unsaturated compound having two or more aromatic rings is preferably a compound having a refractive index of 1.54 or more at a wavelength of 550 nm.
The refractive index at a wavelength of 550 nm of the ethylenically unsaturated compound having two or more aromatic rings means that 3 parts by mass of Irgacure 184 (manufactured by BASF) is added to 97 parts by mass of the ethylenically unsaturated compound having two or more aromatic rings. A film dissolved in an organic solvent (PGMEA) was applied onto a silicon wafer, dried, and then photocured in a nitrogen atmosphere with an exposure amount (i-line) of 350 mJ / cm ^2. The rate is a value measured using an ellipsometer VUV-VASE (manufactured by JA Woollam Japan Co., Ltd.).

The ethylenically unsaturated compound having two or more aromatic rings is preferably a polyfunctional ethylenically unsaturated compound having two or more aromatic rings, and is a bifunctional ethylenically unsaturated compound having two or more aromatic rings. It is more preferable.
As the ethylenically unsaturated compound having two or more aromatic rings, an ethylenically unsaturated compound having a biphenyl skeleton, a bisphenol skeleton, or a fluorene skeleton is preferable, and an ethylenically unsaturated compound having a bisphenol skeleton or a fluorene skeleton is preferable. More preferred is an ethylenically unsaturated compound having a fluorene skeleton.

-Ethylenically unsaturated compound having biphenyl skeleton-
The ethylenically unsaturated compound having a biphenyl skeleton is not particularly limited, but is preferably a compound represented by the following formula B-1.

In formula B-1, X ¹¹ and X ¹² each independently represent a single bond or an oxygen atom, L ¹¹ and L ¹² each independently represent a single bond or a divalent linking group, and A ¹¹ and A ¹² Each independently represents a polymerizable group, n11 represents an integer of 0 to 5, n12 represents an integer of 0 to 5, n11 and n12 are not both 0, R ¹¹ and R ¹² are Each independently represents a monovalent substituent, p represents an integer of 0 to (5-n11), and q represents an integer of 0 to (5-n12).

X ¹¹ and X ¹² are preferably each independently a group represented by —O—.
L ¹¹ and L ¹² are each independently a single bond, an alkylene group having 1 to 8 carbon atoms, an arylene group having 6 to 10 carbon atoms, an alkyleneoxy group having 1 to 4 carbon atoms, or an aryleneoxy group having 6 to 10 carbon atoms. Or it is preferable that it is a C1-C4 polyalkyleneoxy group, It is more preferable that it is a C1-C4 alkyleneoxy group or a C1-C4 polyalkyleneoxy group, and it is C2-C3. More preferably, it is an alkyleneoxy group or a C2-C3 polyalkyleneoxy group.
A ¹¹ and A ¹² are preferably each independently a (meth) acryloyl group.

  Examples of the ethylenically unsaturated compound having a biphenyl skeleton include A-LEN-10 (manufactured by Shin-Nakamura Chemical Co., Ltd.).

-Ethylenically unsaturated compound having bisphenol skeleton-
The ethylenically unsaturated compound having a bisphenol skeleton is not particularly limited, but is preferably a compound represented by the following formula B-2.

In formula B-2, R ²¹ and R ²² each independently represent a hydrogen atom, an alkyl group or an aryl group, and R ²¹ and R ²² may be bonded to each other to form an alicyclic ring or an aromatic ring, R ²³ and R ²⁴ each independently represents an alkyl group, an aryl group or a halogen atom, p and q each independently represents an integer of 0 to 4, L ²¹ and L ²² each independently represent an alkylene group, An arylene group, an alkyleneoxy group or a polyalkyleneoxy group is represented, and A ²¹ and A ²² each independently represent a polymerizable group.

In formula B-2, R ²¹ and R ²² are each independently preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, and a hydrogen atom, a methyl group or a phenyl group More preferably, it is more preferably a methyl group.
When R ²¹ and R ²² are bonded to each other to form an alicyclic ring or an aromatic ring, it is preferable to form an alicyclic ring, and it is more preferable to form a cyclohexane ring.
R ²³ and R ²⁴ are each independently preferably an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms or a halogen atom, and may be a methyl group, a phenyl group, a fluorine atom or a chlorine atom. Is more preferable, and a methyl group is still more preferable.
p and q are each independently preferably 0 or 1, more preferably 0.
L ²¹ and L ²² are each independently an alkylene group having 1 to 4 carbon atoms, an arylene group having 6 to 10 carbon atoms, an alkyleneoxy group having 1 to 4 carbon atoms, or a polyalkyleneoxy group having 1 to 4 carbon atoms. It is preferable that it represents, It is more preferable to represent a C1-C4 alkylene group, a C1-C4 alkyleneoxy group, or a C1-C4 polyalkyleneoxy group, C1-C4 More preferably, it represents a polyalkyleneoxy group.
A ²¹ and A ²² are preferably each independently a (meth) acryloyl group.

  The ethylenically unsaturated compound having a bisphenol skeleton is preferably an ethylenically unsaturated compound having a bisphenol A skeleton, for example, BPE-80N, BPE-100, BPE-200, BPE-500, BPE-900, and BPE-1300N. (Manufactured by Shin-Nakamura Chemical Co., Ltd.).

[Ethylenically unsaturated compound having a fluorene skeleton]
Although it does not specifically limit as an ethylenically unsaturated compound which has a fluorene skeleton, It is preferable that it is a compound represented by the following formula B-3.

In Formula B-3, Ar ³¹ and Ar ³² each independently represent an arylene group, and R ³¹ and R ³² each independently represent a hydroxy group, a carboxy group, an alkoxy group, or a hydroxy group, a carboxy group, and R represents a monovalent organic group having at least one group selected from the group consisting of (meth) acryloyl groups, R ³³ and R ³⁴ each independently represent a monovalent organic group, R ³¹ , R ³² , At least one of R ³³ and R ³⁴ represents a polymerizable group, p and q each independently represents an integer of 0 to 4, and different R ³³ and different R ³⁴ are bonded to each other to form an alicyclic ring. Or you may form an aromatic ring.

Ar ³¹ and Ar ³² are each independently preferably a divalent aromatic hydrocarbon group, more preferably a phenylene group or a naphthylene group, and a 1,4-phenylene group or a 2,6-naphthylene group. More preferably, it is particularly preferably a 1,4-phenylene group. Ar ³¹ and Ar ³² are each independently preferably a naphthylene group, more preferably a 2,6-naphthylene group, from the viewpoint of refractive index.
R ³¹ and R ³² are each independently a monovalent group having at least one group selected from the group consisting of a hydroxy group, a carboxy group, an alkoxy group, or a hydroxy group, a carboxy group, and a (meth) acryloyl group. The organic group is preferably a monovalent organic group having at least one group selected from the group consisting of a hydroxy group, a carboxy group, and a (meth) acryloyl group, and has a (meth) acryloyl group. A valent organic group is more preferable.
Further, R ³¹ and R ³² are particularly preferably the same group from the viewpoint of synthesis.

The monovalent organic group having at least one group selected from the group consisting of a hydroxy group, a carboxy group, and a (meth) acryloyl group in R ³¹ and R ³² has a hydroxy group, a carboxy group, and ( It is preferably a monovalent organic group having at least one group selected from the group consisting of (meth) acryloyl groups.
Moreover, as a partial structure other than the hydroxy group, carboxy group, and (meth) acryloyl group in the monovalent organic group, an alkylene group, an ether bond, a thioether bond, a carbonyl group, an amide bond, and a combination thereof Preferred is the structure.
The monovalent organic group is preferably a group having an ether bond, an alkyleneoxy group or a polyalkyleneoxy group, and more preferably an ether bond or an alkyleneoxy group.

R ³¹ and R ³² are each independently preferably a hydroxy group, a (meth) acryloyloxy group, a (meth) acryloyloxyalkyleneoxy group, or a (meth) acryloyloxypolyalkyleneoxy group. It is more preferably an acryloyloxy group or a (meth) acryloyloxyalkyleneoxy group, more preferably a (meth) acryloyloxy group or a (meth) acryloyloxyalkyleneoxy group, and a (meth) acryloyloxyalkylene. Particularly preferred is an oxy group.

R ³³ and R ³⁴ each independently represents a monovalent substituent.
Preferred examples of the monovalent substituent in R ³³ and R ³⁴ include a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, and an arylthio group. A halogen atom, an alkyl group, and an alkoxy group Can be illustrated more preferably, and an alkyl group can be illustrated more preferably.
Further, the monovalent substituent in R ³³ and R ³⁴ may be a (meth) acryloyl group or a group containing a (meth) acryloyl group. Examples of the group containing a (meth) acryloyl group include a (meth) acryloyloxy group, a (meth) acryloyloxyalkyleneoxy group, and a (meth) acryloyloxypolyalkyleneoxy group.
At least one of R ³¹ , R ³² , R ³³ , and R ³⁴ represents a polymerizable group, and R ³¹ or R ³² preferably represents a polymerizable group. Examples of the polymerizable group include a group containing a (meth) acryloyl group.
p and q each independently represents an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 0 or 2, and particularly preferably 0.
It is also possible to form an alicyclic or aromatic ring by bonding different R ³³ together and different R ³⁴ together. When forming the ring, it is preferable to form an aromatic ring, and it is more preferable to form the following ring together with the fluorene ring.

The compound represented by Formula B-3 preferably has 4 to 8 benzene rings, more preferably 5 to 8, and still more preferably 6 to 8. In the above embodiment, the refractive index is more excellent.
The molecular weight of the compound represented by Formula B-3 is preferably less than 1,000, more preferably from 400 to less than 1,000, from the viewpoint of solubility in a developer and optical properties. It is preferably 400 to 800, more preferably 400 to 600.

  Examples of the ethylenically unsaturated compound having a fluorene skeleton include EA-0200, EA-F5003, EA-F5503, EA-F5510 (manufactured by Osaka Gas Chemical Co., Ltd.), NK ester A-BPEF, and NK ester A-. BPEF-4E (manufactured by Shin-Nakamura Chemical Co., Ltd.) and the like can be mentioned.

An ethylenically unsaturated compound can be used 1 type or in combination of 2 or more types.
The total amount of the ethylenically unsaturated compound in the curable composition of the present invention is preferably 3 to 60% by mass, more preferably 5 to 50% by mass, based on the total solid content of the curable composition. More preferably, it is 10 to 40% by mass.

<Other polymerizable compounds>
The curable composition of this invention may contain other polymeric compounds other than the said ethylenically unsaturated compound.
The other polymerizable compound preferably includes a polymerizable compound having two or more aromatic rings.
The aromatic ring may be included as a single ring or may form a polycycle. In the present invention, the naphthalene ring is assumed to have two benzene rings.
The polymerizable compound having two or more aromatic rings is preferably a compound having a refractive index of 1.54 or more at a wavelength of 550 nm.
The refractive index at a wavelength of 550 nm of the polymerizable compound having two or more aromatic rings means that 3 parts by mass of Irgacure 184 (manufactured by BASF) is added to 97 parts by mass of the polymerizable compound having two or more aromatic rings, and an organic solvent ( The liquid dissolved in PGMEA) was applied onto a silicon wafer, dried, and then the refractive index at 550 nm of a film that was photocured at an exposure dose (i-line) of 350 mJ / cm ² under a nitrogen atmosphere This is a value measured using a meter VUV-VASE (manufactured by JA Woollam Japan Co., Ltd.).

The polymerizable compound having two or more aromatic rings is preferably a polymerizable compound having two or more aromatic rings, and more preferably a bifunctional polymerizable compound having two or more aromatic rings.
As the polymerizable compound having two or more aromatic rings, a polymerizable compound having a biphenyl skeleton, a bisphenol skeleton, or a fluorene skeleton is preferable, a polymerizable compound having a bisphenol skeleton or a fluorene skeleton is more preferable, and a fluorene skeleton is preferable. More preferred is a polymerizable compound.

-Polymerizable compound having biphenyl skeleton-
The polymerizable compound having a biphenyl skeleton is not particularly limited, but is preferably a compound represented by the following formula C-1.

In the formula ^{C-1, X 11, X} 12, L 11, L 12, n11, n12, R 11, R 12, p, and, q is X ¹¹ in the formula ^{B-1, X 12, L} 11, ^{L 12, n11, n12, R} 11, R 12, p and has the same meaning as q, preferable embodiments thereof are also the same.
A ⁴¹ and A ⁴² each independently represent a polymerizable group, and is preferably a glycidyl group.

-Polymerizable compound having bisphenol skeleton-
The polymerizable compound having a bisphenol skeleton is not particularly limited, but is preferably a compound represented by the following formula C-2.

In the formula C-2, R ²¹ , R ²² , R ²³ , R ²⁴ , p, q, L ²¹ , and L ²² are R ²¹ , R ²² , R ²³ , R ²⁴ , p in the formula B-2. , Q, L ²¹ , and L ²² , and preferred embodiments are also the same.
A ⁵¹ and A ⁵² each independently represent a polymerizable group, and is preferably a glycidyl group.

[Polymerizable compound having a fluorene skeleton]
The polymerizable compound having a fluorene skeleton is not particularly limited, but is preferably a compound represented by the following formula C-3.

In the formula ^{C-3, Ar 31, Ar} 32, p and q are as defined Ar ^31, Ar ^32, p and q in the formula B-3, preferable embodiments thereof are also the same.
In formula C-3, R ⁴¹ and R ⁴² are each independently at least one selected from the group consisting of a hydroxy group, a carboxy group, an alkoxy group, or a hydroxy group, a carboxy group, an epoxy group, and an oxetanyl group. Represents a monovalent organic group having a group, R ⁴³ and R ⁴⁴ each independently represents a monovalent organic group, and at least one of R ⁴¹ and R ⁴² represents a polymerizable group.

R ⁴¹ and R ⁴² are each independently a monovalent group having at least one group selected from the group consisting of a hydroxy group, a carboxy group, an alkoxy group, or a hydroxy group, a carboxy group, an epoxy group, and an oxetanyl group. The organic group is preferably a monovalent organic group having at least one group selected from the group consisting of a hydroxy group, a carboxy group, an epoxy group, and an oxetanyl group, and an epoxy group and an oxetanyl group, More preferably, it is a monovalent organic group having at least one group selected from the group consisting of:
Further, R ⁴¹ and R ⁴² are particularly preferably the same group from the viewpoint of synthesis.

The monovalent organic group having at least one group selected from the group consisting of a hydroxy group, a carboxy group, an epoxy group, and an oxetanyl group in R ⁴¹ and R ⁴² is terminated with a hydroxy group, a carboxy group, an epoxy group, And it is preferably a monovalent organic group having at least one group selected from the group consisting of oxetanyl groups.
Moreover, as a partial structure other than the hydroxy group, carboxy group, epoxy group, and oxetanyl group in the monovalent organic group, an alkylene group, an ether bond, a thioether bond, a carbonyl group, an amide bond, and a combination thereof are combined. Preferred is the structure.
The monovalent organic group is preferably a group having an ether bond, an alkyleneoxy group or a polyalkyleneoxy group, and more preferably an ether bond or an alkyleneoxy group.

R ⁴¹ and R ⁴² are each independently preferably a hydroxy group, a glycidyloxy group, a 3-alkyl-3-oxetanylmethyloxy group, a glycidyloxyalkyleneoxy group, or a glycidyloxypolyalkyleneoxy group. An oxy group and a glycidyloxyalkyleneoxy group are more preferable, a glycidyloxy group and a glycidyloxyalkyleneoxy group are more preferable, and a glycidyloxyalkyleneoxy group is particularly preferable.

R ⁴³ and R ⁴⁴ each independently represents a monovalent substituent.
Preferred examples of the monovalent substituent in R ⁴³ and R ⁴⁴ include a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, and an arylthio group. A halogen atom, an alkyl group, and an alkoxy group Can be illustrated more preferably, and an alkyl group can be illustrated more preferably.
At least one of R ⁴¹ and R ⁴² represents a polymerizable group, and examples of the polymerizable group include a group containing an oxetanyl group or a glycidyl group.
It is also possible to form an alicyclic or aromatic ring by bonding different R ⁴³ together and different R ⁴⁴ together. When forming the ring, it is preferable to form an aromatic ring, and it is more preferable to form the following ring together with the fluorene ring.

The compound represented by Formula C-3 preferably has 4 to 8 benzene rings, more preferably 5 to 8, and still more preferably 6 to 8. In the above embodiment, the refractive index is more excellent.
The molecular weight of the compound represented by Formula C-3 is preferably less than 1,000, more preferably from 400 to less than 1,000, from the viewpoint of solubility in a developer and optical properties. It is preferably 400 to 800, more preferably 400 to 600.

Other polymerizable compounds can be used alone or in combination of two or more.
The total amount of other polymerizable compounds in the curable composition of the present invention is preferably 3 to 60% by mass, more preferably 5 to 50% by mass, based on the total solid content of the curable composition. More preferably, it is 10 to 40% by mass.

<Photopolymerization initiator>
The photopolymerization initiator preferably contains a photoradical polymerization initiator.
The radical photopolymerization initiator that can be used in the present invention is a compound that can initiate and accelerate the polymerization of an ethylenically unsaturated compound by light.
“Light” is not particularly limited as long as it is an active energy ray capable of imparting energy capable of generating an initiation species from a photo radical polymerization initiator by irradiation, and widely used as α ray, γ ray, X It includes rays, ultraviolet rays (UV), visible rays, electron beams, and the like. Among these, light containing at least ultraviolet rays is preferable.

  Examples of the photopolymerization initiator include oxime ester compounds, organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, metallocenes. Examples include compounds, hexaarylbiimidazole compounds, organic boric acid compounds, disulfonic acid compounds, onium salt compounds, and acylphosphine (oxide) compounds. Among these, oxime ester compounds and hexaarylbiimidazole compounds are preferable from the viewpoint of sensitivity, and oxime ester compounds are more preferable.

Examples of the oxime ester compound include compounds described in JP-A No. 2000-80068, JP-A No. 2001-233842, JP-T No. 2004-534797, JP-A No. 2007-231000, and JP-A No. 2009-134289. Can be used.
The oxime ester compound is preferably a compound represented by the following formula D-1 or formula D-2.

In Formula D-1 or Formula D-2, Ar represents an aromatic group or a heteroaromatic group, R ^D1 represents an alkyl group, an aromatic group, or an alkoxy group, R ^D2 represents a hydrogen atom or an alkyl group, Further, R ^D2 may be bonded to an Ar group to form a ring.

Ar represents an aromatic group or a heteroaromatic group, and is preferably a group obtained by removing one hydrogen atom from a benzene ring, naphthalene ring or carbazole ring, and a naphthalenyl group or carbazoyl group which forms a ring together with R ^D2 More preferred. Preferable examples of the hetero atom in the heteroaromatic group include a nitrogen atom, an oxygen atom, and a sulfur atom. Of these, a nitrogen atom is preferable.
R ^D1 represents an alkyl group, an aromatic group or an alkoxy group, preferably a methyl group, an ethyl group, a benzyl group, a phenyl group, a naphthyl group, a methoxy group or an ethoxy group, and a methyl group, an ethyl group, a phenyl group or a methoxy group Is more preferable.
R ^D2 represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or a substituted alkyl group, and more preferably a substituted alkyl group or a toluenethioalkyl group that forms a ring with the hydrogen atom or Ar.
Ar is preferably a group having 4 to 20 carbon atoms, R ^D1 is preferably a group having 1 to 30 carbon atoms, and R ^D2 is a group having 1 to 50 carbon atoms. It is preferable.

  The oxime ester compound is more preferably a compound represented by the following formula D-3, formula D-4 or formula D-5, and particularly preferably a compound represented by the following formula D-5.

In Formula D-3 to Formula D-5, R ^D1 represents an alkyl group, an aromatic group, or an alkoxy group, X represents —CH ₂ —, —C ₂ H ₄ —, —O—, or —S—, R ^D3 each independently represents a halogen atom, R ^D4 each independently represents an alkyl group, a phenyl group, an alkyl-substituted amino group, an arylthio group, an alkylthio group, an alkoxy group, an aryloxy group or a halogen atom, R ^D5 Represents a hydrogen atom, an alkyl group or an aryl group, R ^D6 represents an alkyl group, n1 and n2 each independently represents an integer of 0 to 6, and n3 represents an integer of 0 to 5.

R ^D1 represents an alkyl group, an aromatic group, or an alkoxy group, and a group represented by R ^D11 —X′-alkylene group— is preferable. R ^D11 represents an alkyl group or an aryl group, and X ′ represents a sulfur atom or an oxygen atom. R ^D11 is preferably an aryl group, more preferably a phenyl group. The alkyl group and aryl group as R ^D11 may be substituted with a halogen atom (preferably a fluorine atom, a chlorine atom or a bromine atom) or an alkyl group.
X is preferably a sulfur atom.
R ^D3 and R ^D4 can be bonded at any position on the aromatic ring.
R ^D4 represents an alkyl group, a phenyl group, an alkyl-substituted amino group, an arylthio group, an alkylthio group, an alkoxy group, an aryloxy group or a halogen atom, preferably an alkyl group, a phenyl group, an arylthio group or a halogen atom, an alkyl group, an arylthio group A group or a halogen atom is more preferred, and an alkyl group or a halogen atom is still more preferred. As an alkyl group, a C1-C5 alkyl group is preferable and a methyl group or an ethyl group is more preferable. As a halogen atom, a chlorine atom, a bromine atom, or a fluorine atom is preferable.
The number of carbon atoms of R ^D4 is preferably 0 to 50, and more preferably from 0 to 20.
R ^D5 represents a hydrogen atom, an alkyl group or an aryl group, preferably an alkyl group. As an alkyl group, a C1-C5 alkyl group is preferable and a methyl group or an ethyl group is more preferable. As the aryl group, an aryl group having 6 to 10 carbon atoms is preferable.
R ^D6 represents an alkyl group, preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group or an ethyl group.
n1 and n2 each represent the number of substitutions of R ^D3 on the aromatic ring in Formula D-3 or Formula D-4, and n3 represents the number of substitutions of R ^D4 on the aromatic ring in Formula D-5.
n1 to n3 are each independently preferably an integer of 0 to 2, and more preferably 0 or 1.

  Below, the example of the oxime ester compound preferably used by this invention is shown. However, it goes without saying that the oxime ester compound used in the present invention is not limited to these compounds. Me represents a methyl group and Ph represents a phenyl group. Further, the cis-trans isomerism of the double bond of oxime in these compounds may be either one of EZ or a mixture of EZ.

  Specific examples of the organic halogenated compounds include Wakabayashi et al., “Bull Chem. Soc. Japan” 42, 2924 (1969), US Pat. No. 3,905,815, and Japanese Examined Patent Publication No. 46-4605. JP, 48-34881, JP 55-3070, JP 60-239736, JP 61-169835, JP 61-169837, JP 62-58241, JP-A 62-212401, JP-A 63-70243, JP-A 63-298339, M.S. P. Hutt “Journal of Heterocyclic Chemistry” vol. 7, 511-518, (1970) and the like, and in particular, an oxazole compound substituted with a trihalomethyl group and an s-triazine compound.

  Examples of hexaarylbiimidazole compounds include, for example, JP-B-6-29285, US Pat. Nos. 3,479,185, 4,311,783, and 4,622,286. Examples include various compounds described in the specification.

Examples of the acylphosphine (oxide) compound include a monoacylphosphine oxide compound and a bisacylphosphine oxide compound. Specific examples include IRGACURE 819, Darocur 4265, Darocur TPO, and the like manufactured by BASF.
Examples of the acetophenone compound include IRGACURE 127 manufactured by BASF.

A photoinitiator can be used 1 type or in combination of 2 or more types. Moreover, when using the photoinitiator which does not have absorption in an exposure wavelength, a sensitizer can also be used.
The total amount of the photopolymerization initiator in the curable composition of the present invention is preferably 0.5 to 30% by mass and more preferably 1 to 20% by mass with respect to the total solid content in the composition. Preferably, it is 1-10 mass%, More preferably, it is 2-5 mass%.

[Sensitizer]
A sensitizer can be added to the curable composition of the present invention in addition to the photopolymerization initiator and the photoacid generator described below.
The sensitizer absorbs actinic rays or radiation and enters an excited state. The excited sensitizer is capable of initiating and accelerating polymerization due to the action of electron transfer, energy transfer, heat generation and the like due to the interaction with the photopolymerization initiator.
Examples of preferred sensitizers include compounds belonging to the following compounds and having an absorption wavelength in the 350 nm to 450 nm region. Polynuclear aromatics (eg, pyrene, perylene, triphenylene, anthracene, phenanthrene), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), xanthones (eg, xanthone, thioxanthone, dimethylthioxanthone, Diethylthioxanthone, isopropylthioxanthone, 2-chlorothioxanthone), cyanines (eg thiacarbocyanine, oxacarbocyanine), merocyanines (eg merocyanine, carbomerocyanine), rhodocyanines, oxonols, thiazines (eg thionine) , Methylene blue, toluidine blue), acridines (eg, acridine orange, chloroflavin, acriflavine, benzoflavin), acridones For example, acridone, 10-butyl-2-chloroacridone), anthraquinones (eg, anthraquinone, 9,10-dibutoxyanthracene), squariums (eg, squalium), styryls, base styryls, coumarins (eg, , 7-diethylamino-4-methylcoumarin, ketocoumarin), carbazoles (for example, N-vinylcarbazole), camphorquinones, phenothiazines.
In addition, typical sensitizers that can be used in the present invention include those disclosed in Crivello [JV Crivello, Adv. In Polymer Sci., 62, 1 (1984)].
Preferred specific examples of the sensitizer include pyrene, perylene, acridine orange, thioxanthone, 2-chlorothioxanthone, benzoflavin, N-vinylcarbazole, 9,10-dibutoxyanthracene, anthraquinone, coumarin, ketocoumarin, phenanthrene, camphorquinone. And phenothiazines. The sensitizer is preferably added at a ratio of 30 to 200 parts by mass with respect to 100 parts by mass of the polymerization initiator.

<Polymer having acid group>
The curable composition of the present invention contains a polymer having an acid group.
By containing a polymer having an acid group, there are few coarse particles when the metal oxide particles are dispersed, and aggregation is suppressed even in the presence of the polymer component, so that it has excellent storage stability and high refractive index. Thus, a curable composition capable of forming a cured film having excellent transparency can be obtained.
The acid value of the polymer having an acid group is 100 to 300 mgKOH / g, and preferably 150 to 250 mg / KOH.
When the acid value is within the above range, a curable composition having excellent storage stability and excellent development adhesion of the resulting cured film can be obtained.
The acid value of the polymer having an acid group can be measured according to the method described in JIS K2501 (2003).

The polymer having an acid group is preferably an addition polymerization type resin, and more preferably a polymer containing a structural unit derived from (meth) acrylic acid and / or an ester thereof. In addition, you may have structural units other than the structural unit derived from (meth) acrylic acid and / or its ester, for example, the structural unit derived from styrene, the structural unit derived from a vinyl compound, etc.
The “structural unit derived from (meth) acrylic acid and / or its ester” is also referred to as “acrylic structural unit”. Further, “(meth) acrylic acid” means “methacrylic acid and / or acrylic acid”.
The polymer having an acid group is preferably a polymer having at least one selected from the group consisting of a carboxy group, a phenolic hydroxyl group, a sulfonamide group, a phosphonic acid group, a sulfonic acid group, and a sulfonylimide group. From the viewpoint of dispersibility of the metal oxide particles, a polymer having a carboxy group is more preferable.
The molecular weight of the polymer having an acid group is preferably 2,000 to 200,000, more preferably 2,000 to 15,000, and still more preferably 2,500 to 10,000 in terms of weight average molecular weight.

  The curable composition of the present invention preferably contains a polymer represented by the following formula S-1 and having at least one acid group as a polymer having an acid group.

In formula S-1, R ³ represents an (m + n) -valent linking group, R ⁴ and R ⁵ each independently represents a single bond or a divalent linking group, and A ² represents an organic dye structure or a heterocyclic structure. , An acid group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxyl group Represents a monovalent organic group containing at least one partial structure selected from n, n A ² and R ⁴ may be the same or different, m represents 0 to 8, n Represents 2 to 9, m + n is 3 to 10, P ² represents a polymer skeleton, and m P ² and R ⁵ may be the same or different.

The polymer represented by the formula S-1 and having at least one acid group is presumed to act as an adsorbing group for the metal oxide particles by having an acid group, and is excellent in dispersibility of the metal oxide particles. .
Examples of the acid group include a carboxy group, a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group. From the viewpoint of the adsorptive power and dispersibility to the metal oxide particles, a carboxy group, a sulfonic acid group, and a phosphoric acid group. It is preferably at least one selected from the group consisting of, and a carboxy group is particularly preferable. The acid groups in the polymer represented by the above formula S-1 and having at least one acid group may have these alone or in combination of two or more.
The acid group in the polymer represented by the formula S-1 and having at least one acid group may have any structure of the formula S-1. Specifically, for example, acid groups, both of the above formulas may be included in the A ² in S-1, also may be included in the polymer backbone represented by P ^2, A ² and P ² it may be included in, from the viewpoint of effect, it is preferably included in a ^2.

In the formula S-1, A ² represents an organic dye structure, a heterocyclic structure, an acid group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, or a group having 4 or more carbon atoms. A monovalent organic group containing at least one partial structure selected from the group consisting of a hydrocarbon group, an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxyl group. Further, n A ² present in the formula S-1 may be the same or different.

That is, the above A ² is a structure having an adsorption ability for metal oxide particles such as an organic dye structure or a heterocyclic structure, an acid group, a group having a basic nitrogen atom, a urea group, a urethane group, or a coordinating oxygen. A monovalent group containing at least one functional group capable of adsorbing to metal oxide particles, such as a group having an atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxyl group. Represents an organic group.
Hereinafter, the partial structure having the ability to adsorb to the metal oxide particles (the above structure and functional group) will be collectively referred to as “adsorption site” as appropriate.

The adsorption sites are in one A ^2, it may be contained at least one, may contain two or more kinds.
Further, in the present invention, the “monovalent organic group containing at least one kind of adsorption site” means the aforementioned adsorption site, 1 to 200 carbon atoms, 0 to 20 nitrogen atoms, 0 To 100 oxygen atoms, 1 to 400 hydrogen atoms, and a linking group consisting of 0 to 40 sulfur atoms are monovalent organic groups. In the case where adsorption sites themselves may constitute a monovalent organic group, adsorption sites itself may be a monovalent organic group represented by A ^2.
First, the adsorption site constituting A ² will be described below.

  Examples of the “organic dye structure” include, for example, phthalocyanine, insoluble azo, azo lake, anthraquinone, quinacridone, dioxazine, diketopyrrolopyrrole, anthrapyridine, ansanthrone, indanthrone, flavan. Examples of preferable dye structures of throne, perinone, perylene, and thioindigo are phthalocyanine, azo lake, anthraquinone, dioxazine, and diketopyrrolopyrrole, and phthalocyanine and anthraquinone. A diketopyrrolopyrrole dye structure is particularly preferred.

  The “heterocyclic structure” may be a group having at least one heterocyclic ring. Examples of the heterocyclic ring in the “heterocyclic structure” include, for example, thiophene, furan, xanthene, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, pyrazolidine, imidazole, oxazole, thiazole, oxadiazole, triazole, thiadiazole, pyran, Pyridine, piperidine, dioxane, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindoline, isoindolinone, benzimidazolone, benzothiazole, succinimide, phthalimide, naphthalimide, hydantoin, indole, quinoline, carbazole, acridine, acridone And a heterocyclic ring selected from the group consisting of anthraquinone is a preferred example, pyrroline, pyrrolidine, pyrazole Pyrazoline, pyrazolidine, imidazole, triazole, pyridine, piperidine, morpholine, pyridazine, pyrimidine, piperazine, triazine, isoindoline, isoindolinone, benzimidazolone, benzothiazole, succinimide, phthalimide, naphthalimide, hydantoin, carbazole, acridine, acridone And a heterocyclic ring selected from the group consisting of anthraquinone is more preferable.

  The “organic dye structure” or “heterocyclic structure” may further have a substituent. Examples of the substituent include alkyl groups having 1 to 20 carbon atoms such as a methyl group and an ethyl group. An acyloxy group having 1 to 6 carbon atoms, such as an aryl group having 6 to 16 carbon atoms such as a group, phenyl group or naphthyl group, a hydroxyl group, an amino group, a carboxy group, a sulfonamide group, an N-sulfonylamide group, or an acetoxy group. Alkoxy groups having 1 to 20 carbon atoms such as methoxy group and ethoxy group, halogen atoms such as chlorine atom and bromine atom, alkoxy having 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group and cyclohexyloxycarbonyl group And carbonic acid ester groups such as a carbonyl group, a cyano group, and a t-butyl carbonate group. Here, these substituents may be bonded to an organic dye structure or a heterocyclic structure via a linking group constituted by combining the following structural units or the above structural units.

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

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 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), a guanidyl group represented by the following formula a1, or a formula represented by the following formula a2. Preferred examples include amidinyl group.

In formula a1, R ¹¹ and R ¹² 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.
In formula a2, R ¹³ and R ¹⁴ 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.

Among these, an amino group (—NH ₂ ), a substituted imino group (—NHR ⁸ , —NR ⁹ R ¹⁰ , where R ⁸ , R ⁹ and R ¹⁰ are each independently an alkyl having 1 to 10 carbon atoms. A guanidyl group represented by the above formula a1 (in the formula a1, R ¹¹ and R ¹² are each independently an alkyl group having 1 to 10 carbon atoms, a phenyl group, a benzyl group). Amidinyl group represented by the formula a2 (in the formula a2, R ¹³ and R ¹⁴ each independently represents an alkyl group having 1 to 10 carbon atoms, a phenyl group, or a benzyl group). Is more preferable.
In particular, 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 5 carbon atoms, A phenyl group and a benzyl group), and a guanidyl group represented by the formula a1 (in the formula a1, R ¹¹ and R ¹² are each independently an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a benzyl group. And an amidinyl group represented by the formula a2 (in the formula a2, R ¹³ and R ¹⁴ each independently represents an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a benzyl group). Used.

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, a carbon number of 6 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, carbon number 1). To 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 is more preferable, and —NHCONHR ¹⁷ (where R ¹⁷ is a hydrogen atom, 1 to 10 carbon atoms). Or an alkyl group having 6 or more carbon atoms or an aralkyl group having 7 or more carbon atoms) is particularly preferable.

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

  Examples of the “group having a coordinating oxygen atom” include an acetylacetonato group and a group having a crown ether structure.

  Preferred examples of the “hydrocarbon group having 4 or more carbon atoms” include an alkyl group having 4 or more carbon atoms, an aryl group having 6 or more carbon atoms, an aralkyl group having 7 or more carbon atoms, and the like. More preferably, an alkyl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an alkyl group having 4 to 15 carbon atoms (for example, an octyl group, a dodecyl group, etc.), and 6 to 15 carbon atoms. Particularly preferred are aryl groups (for example, phenyl group, naphthyl group and the like), aralkyl groups having 7 to 15 carbon atoms (for example, benzyl group and the like), and the like.

  Examples of the “alkoxysilyl group” include a trimethoxysilyl group and a triethoxysilyl group.

  The linking group bonded to the adsorption site may be a single bond or 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200. A linking group comprising up to 0 hydrogen atoms and 0 to 20 sulfur atoms is preferred, and this linking group may be unsubstituted or may further have a substituent. Specific examples of this linking group include the following structural units or groups constituted by combining the above structural units.

  When the linking group has a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, and an aryl group having 6 to 16 carbon atoms such as a phenyl group and a naphthyl group. Group, hydroxyl group, amino group, carboxy group, sulfonamido group, N-sulfonylamido group, acetoxy group and other C1-C6 acyloxy groups, methoxy group, ethoxy group and other C1-C6 alkoxy groups , Halogen atoms such as chlorine atom and bromine atom, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group and cyclohexyloxycarbonyl group, carbonate ester groups such as cyano group and t-butyl carbonate group, etc. Is mentioned.

In the above, as A ² , a portion selected from the group consisting of an organic dye structure, a heterocyclic structure, an acid group, a group having a basic nitrogen atom, a urea group, and a hydrocarbon group having 4 or more carbon atoms A monovalent organic group containing at least one structure is preferable, and a monovalent organic group containing at least one acid group is particularly preferable.

As the A ^2, and more preferably a monovalent organic group represented by the following formula 4.

In Formula 4, B ¹ represents the adsorption site (that is, organic dye structure, heterocyclic structure, acid group, group having basic nitrogen atom, urea group, urethane group, group having coordinating oxygen atom, carbon number 4 represents a partial structure selected from the group consisting of 4 or more hydrocarbon groups, alkoxysilyl groups, epoxy groups, isocyanate groups, and hydroxyl groups, and R ²⁴ represents a single bond or a (a + 1) -valent linking group. a represents an integer of 1 to 10, and a B ¹ existing in Formula 4 may be the same or different.

Examples of the adsorption site represented by B ¹ include those similar to the adsorption site constituting A ² of the formula S-1, and preferred examples are also the same.
Among these, a partial structure selected from the group consisting of an organic dye structure, a heterocyclic structure, an acid group, a group having a basic nitrogen atom, a urea group, and a hydrocarbon group having 4 or more carbon atoms is preferable, and an acid group is particularly preferable preferable.

R ²⁴ represents a single bond or a (a + 1) -valent linking group, a represents an integer of 1 to 10, preferably an integer of 1 to 7, more preferably an integer of 1 to 5, An integer of 1 to 3 is particularly preferable.
(A + 1) valent linking groups include 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, In addition, a group composed of 0 to 20 sulfur atoms is included, which may be unsubstituted or may further have a substituent.

  Specific examples of the (a + 1) -valent linking group include the following structural units or groups formed by combining the above structural units (which may form a ring structure).

R ²⁴ may be a single bond or 1 to 50 carbon atoms, 0 to 8 nitrogen atoms, 0 to 25 oxygen atoms, 1 to 100 hydrogen atoms, And a (a + 1) -valent linking group consisting of 0 to 10 sulfur atoms, preferably a single bond or 1 to 30 carbon atoms, 0 to 6 nitrogen atoms, 0 More preferred are (a + 1) -valent linking groups consisting of from 1 to 15 oxygen atoms, from 1 to 50 hydrogen atoms, and from 0 to 7 sulfur atoms, a single bond or from 1 to 10 Consisting of up to 5 carbon atoms, 0 to 5 nitrogen atoms, 0 to 10 oxygen atoms, 1 to 30 hydrogen atoms, and 0 to 5 sulfur atoms ( The a + 1) -valent linking group is particularly preferable.

  Among the above, when the (a + 1) -valent linking group has a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a phenyl group, and a naphthyl group. Carbons having 1 to 6 carbon atoms, such as aryl groups, hydroxyl groups, amino groups, carboxy groups, sulfonamido groups, N-sulfonylamido groups, acetoxy groups, etc. having 6 to 16 carbon atoms, methoxy groups, ethoxy groups, etc. Alkoxy groups having 1 to 6 carbon atoms, halogen atoms such as chlorine atoms and bromine atoms, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl groups, ethoxycarbonyl groups and cyclohexyloxycarbonyl groups, cyano groups, and t-butyl And carbonate ester groups such as carbonate groups.

In the above formula S-1, R ⁴ and R ⁵ each independently represents a single bond or a divalent linking group. n R ^{4 s} may be the same or different. Further, m R ^{5 s} may be the same or different.
Examples of the divalent linking group in R ⁴ and R ⁵ include 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, and 1 to 200. And a group consisting of 0 to 20 sulfur atoms, may be unsubstituted or may further have a substituent.

  Specific examples of the divalent linking group include the following structural units or groups formed by combining the structural units.

R ⁴ and R ⁵ are each independently a single bond, or 1 to 50 carbon atoms, 0 to 8 nitrogen atoms, 0 to 25 oxygen atoms, 1 to 100 Divalent linking groups consisting of up to 10 hydrogen atoms and 0 to 10 sulfur atoms are preferred, single bonds or 1 to 30 carbon atoms, 0 to 6 nitrogen atoms More preferred are divalent linking groups consisting of atoms, 0 to 15 oxygen atoms, 1 to 50 hydrogen atoms, and 0 to 7 sulfur atoms, a single bond or 1 From 0 to 10 carbon atoms, 0 to 5 nitrogen atoms, 0 to 10 oxygen atoms, 1 to 30 hydrogen atoms, and 0 to 5 sulfur atoms. Particularly preferred are divalent linking groups.

  Among the above, when the divalent linking group has a substituent, examples of the substituent include carbon numbers such as an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a phenyl group, and a naphthyl group. 1 to 6 carbon atoms such as aryl group, hydroxyl group, amino group, carboxy group, sulfonamido group, N-sulfonylamido group, acetoxy group and the like having 6 to 16 carbon atoms, methoxy group, ethoxy group and the like To 6 alkoxy groups, halogen atoms such as chlorine atom and bromine atom, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group, cyclohexyloxycarbonyl group, cyano group, t-butyl carbonate group And the like, and the like.

In the above formula S-1, R ³ represents a (m + n) -valent linking group. m + n satisfies 3-10.
The (m + n) -valent linking group represented by R ³ includes 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to Groups comprising up to 100 hydrogen atoms and 0 to 20 sulfur atoms are included, which may be unsubstituted or may further have a substituent.

  Specific examples of the (m + n) -valent linking group include the following structural units or groups formed by combining the above structural units (which may form a ring structure).

  (M + n) -valent linking group includes 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 40 oxygen atoms, 1 to 120 hydrogen atoms, And preferred are groups consisting of 0 to 10 sulfur atoms, preferably 1 to 50 carbon atoms, 0 to 10 nitrogen atoms, 0 to 30 oxygen atoms, 1 to More preferred are groups consisting of up to 100 hydrogen atoms and 0 to 7 sulfur atoms, 1 to 40 carbon atoms, 0 to 8 nitrogen atoms, 0 to 20 atoms. Particularly preferred are groups consisting of up to oxygen atoms, 1 to 80 hydrogen atoms, and 0 to 5 sulfur atoms.

  Among the above, when the (m + n) -valent linking group has a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a phenyl group, and a naphthyl group. Carbons having 1 to 6 carbon atoms, such as aryl groups, hydroxyl groups, amino groups, carboxy groups, sulfonamido groups, N-sulfonylamido groups, acetoxy groups, etc. having 6 to 16 carbon atoms, methoxy groups, ethoxy groups, etc. Alkoxy groups having 1 to 6 carbon atoms, halogen atoms such as chlorine atoms and bromine atoms, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl groups, ethoxycarbonyl groups and cyclohexyloxycarbonyl groups, cyano groups, and t-butyl Examples thereof include carbonate groups such as carbonate groups.

Specific examples [specific examples (1) to (17)] of the (m + n) -valent linking group represented by R ³ are shown below. However, the present invention is not limited to these.

  Among the above specific examples, the most preferable (m + n) -valent linking group is the following group from the viewpoint of availability of raw materials, ease of synthesis, and solubility in various solvents.

In said formula S-1, m represents 0-8. As m, 0.5-5 are preferable, 0.5-4 are more preferable, and 0.5-3 are especially preferable.
Moreover, in said formula S-1, n represents 2-9. As n, 2-8 are preferable, 2-7 are more preferable, and 3-6 are especially preferable.

P ² in the formula S-1 represents a polymer skeleton, and can be selected from known polymers according to the purpose and the like. M P ² present in Formula S-1 may be the same or different.
Among polymers, in order to constitute a polymer skeleton, a polymer or copolymer of vinyl monomers, ester polymers, ether polymers, urethane polymers, amide polymers, epoxy polymers, silicone polymers, and these Modified products or copolymers of [for example, polyether / polyurethane copolymers, copolymers of polyether / vinyl monomers, etc. (any of random copolymers, block copolymers, and graft copolymers). May be included). And at least one selected from the group consisting of vinyl monomers, polymers or copolymers, ester polymers, ether polymers, urethane polymers, and their modified products or copolymers. At least one selected is more preferable, a polymer or copolymer of a vinyl monomer is further preferable, and an acrylic resin (a polymer or copolymer of a (meth) acryl monomer) is particularly preferable.
Furthermore, the polymer is preferably soluble in an organic solvent. The polymer represented by the formula S-1 and having at least one acid group is preferably soluble in an organic solvent. When the affinity with the organic solvent is low, for example, the affinity with the dispersion medium is weakened, which is sufficient for stabilizing the dispersion, and is represented by the formula S-1 on the surface of the metal oxide particles, and has at least one acid group. The adsorbing layer formed by the polymer may not be secured.

In the present invention, the polymer skeleton in P ² may or may not have an acid group, but preferably has at least one acid group.
Examples of the polymer having an acid group constituting the polymer skeleton include, for example, a polyamidoamine and salt thereof, a polycarboxylic acid and salt thereof, a high molecular weight unsaturated acid ester, a modified polyurethane, a modified polyester, and a modified polymer having an acid group. (Meth) acrylate, (meth) acrylic copolymer, naphthalene sulfonic acid formalin condensate), polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl amine, alkanol amine, pigment derivative and the like. Among these, a (meth) acrylic acid copolymer is preferable.

The means for introducing an acid group into the polymer skeleton is not particularly limited. For example, a means for introducing an acid group with a vinyl monomer, a means for introducing an acid group using a crosslinkable side chain, and the like are adopted. However, as will be described later, the mode in which the acid group is introduced by the constitution of the polymer skeleton including a structural unit derived from a vinyl monomer having an acid group makes it easy to control the amount of acid group introduced. From the viewpoint of synthesis cost.
Here, the “acid group” may be the same as those mentioned as the “acid group” in the description of A ² above, and is preferably a carboxy group.

Although it does not restrict | limit especially as said vinyl monomer, For example, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, (meth) acrylamides Styrenes, vinyl ethers, vinyl ketones, olefins, maleimides, (meth) acrylonitrile, vinyl monomers having an acid group, and the like are preferable.
Hereinafter, preferable examples of these vinyl monomers will be described.

  Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, amyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, (Meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid t-octyl, (meth) acrylic acid dodecyl, (meth) acrylic acid octadecyl, (meth) acrylic acid acetoxyethyl, (meth) acrylic acid phenyl, (meth) 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, (meth 3-hydroxypropyl acrylate, 4-hydroxybutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) (meth) acrylate Ethyl, 3-methoxy-2-hydroxypropyl (meth) acrylate, 2-chloroethyl (meth) acrylate, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, (meth) acrylic acid Vinyl, 2-phenylvinyl (meth) acrylate, 1-propenyl (meth) acrylate, allyl (meth) acrylate, 2-allyloxyethyl (meth) acrylate, propargyl (meth) acrylate, (meth) acrylic Benzyl acid, (meth) acrylic acid diethylene glycol monomethyl ether (Meth) acrylic acid diethylene glycol monoethyl ether, (meth) acrylic acid triethylene glycol monomethyl ether, (meth) acrylic acid triethylene glycol monoethyl ether, (meth) acrylic acid polyethylene glycol monomethyl ether, (meth) acrylic acid polyethylene glycol Monoethyl ether, β-phenoxyethoxyethyl (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, (meth) acrylic acid Trifluoroethyl, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, (meth) a Acrylic acid tribromophenyl, (meth) tribromophenyl oxyethyl acrylate, and (meth) acrylic acid γ- butyrolactone-2-yl.

Examples of the crotonic acid esters include butyl crotonic acid and hexyl crotonic acid.
Examples of vinyl esters include vinyl acetate, vinyl chloroacetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate and the like.
Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.
Examples of fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.
Examples of itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

  (Meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and Nn-butyl. Acrylic (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N -Diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-nitrophenyl acrylamide, N-ethyl-N-phenyl acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide, N- Methylo Acrylamide, N- hydroxyethyl acrylamide, vinyl (meth) acrylamide, N, N- diallyl (meth) acrylamide, such as N- allyl (meth) acrylamide.

  Examples of styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethyl Examples thereof include styrene, hydroxystyrene protected with a group deprotectable by an acidic substance (for example, t-butoxycarbonyl group (t-Boc) and the like), methyl vinylbenzoate, and α-methylstyrene.

Examples of vinyl ethers include methyl vinyl ether, ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, octyl vinyl ether, methoxyethyl vinyl ether, and phenyl vinyl ether.
Examples of vinyl ketones include methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.
Examples of olefins include ethylene, propylene, isobutylene, butadiene, isoprene and the like.
Examples of maleimides include maleimide, butyl maleimide, cyclohexyl maleimide, and phenyl maleimide.

  (Meth) acrylonitrile, heterocyclic groups substituted with vinyl groups (for example, vinylpyridine, N-vinylpyrrolidone, vinylcarbazole, etc.), N-vinylformamide, N-vinylacetamide, N-vinylimidazole, vinylcaprolactone, etc. are also used. it can.

  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 urea group can be appropriately synthesized by utilizing an addition reaction between an isocyanate group and a hydroxyl group or an amino group, for example. 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, primary or It can be appropriately synthesized by an addition reaction between a secondary amino group-containing monomer and monoisocyanate.

Next, a vinyl monomer having an acid group used for introducing an acid group into the polymer skeleton P ² will be described.
Examples of the vinyl monomer having an acid group include a vinyl monomer having a carboxy group and a vinyl monomer having a sulfonic acid group.
Examples of the vinyl monomer having a carboxy group include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid dimer. Further, an addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic anhydride, ω-carboxypolycaprolactone mono (Meth) acrylate and the like can also be used. Moreover, you may use anhydride containing monomers, such as maleic anhydride, itaconic anhydride, and citraconic anhydride, as a precursor of a carboxy group. Of these, (meth) acrylic acid is particularly preferable from the viewpoints of copolymerizability, cost, solubility, and the like.

  Examples of the vinyl monomer having a sulfonic acid group include 2-acrylamido-2-methylpropanesulfonic acid, and examples of the vinyl monomer having a phosphoric acid group include phosphoric acid mono (2-acryloyloxyethyl ester) and phosphoric acid mono (1-methyl-2-acryloyloxyethyl ester) and the like.

Furthermore, as the vinyl monomer having an acid group, a vinyl monomer containing a phenolic hydroxy group or a vinyl monomer containing a sulfonamide group can be used.
When the polymer skeleton P ² includes a monomer unit derived from a vinyl monomer containing an acid group, the content of the monomer unit derived from a vinyl monomer having an acid group in the polymer skeleton is expressed in terms of mass in the entire polymer skeleton. On the other hand, it is preferably 3 to 40% by mass, and more preferably 5 to 20% by mass.

Of the polymers represented by the above formula S-1 and having at least one acid group, those satisfying all of R ³ , R ⁴ , R ⁵ , P ² , m and n shown below are most preferable.
R ³ : Specific example (1), (2), (10), (11), (16) or (17) above
R ⁴ : a single bond, or the following structural unit or a combination of the above structural units: “1 to 10 carbon atoms, 0 to 5 nitrogen atoms, 0 to 10” A divalent linking group comprising an oxygen atom, 1 to 30 hydrogen atoms, and 0 to 5 sulfur atoms (which may have a substituent, For example, an alkyl group having 1 to 20 carbon atoms such as a methyl group or an ethyl group, an aryl group having 6 to 16 carbon atoms such as a phenyl group or a naphthyl group, a hydroxyl group, an amino group, a carboxy group, a sulfonamide group, N- C1-C6 acyloxy groups such as sulfonylamide groups and acetoxy groups, C1-C6 alkoxy groups such as methoxy groups and ethoxy groups, halogen atoms such as chlorine and bromine atoms, methoxycarbo Group, an ethoxycarbonyl group, an alkoxycarbonyl group having from 2 to 7 carbon atoms such as cyclohexyl oxycarbonyl group, a cyano group, such as carbonic acid ester group such as t- butyl carbonate group.

R ⁵ : single bond, ethylene group, 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 : a copolymer of a vinyl monomer having a carboxy group and another vinyl monomer; a polymer or copolymer of a vinyl monomer having no acid group; an ester-based polymer, an ether-based polymer, and a urethane-based polymer; and , A polymer selected from the group consisting of these modified products and may contain at least one acid group m: 0.5-3
n: 3-6

  The content of the acid group in the polymer represented by Formula S-1 and having at least one acid group is appropriately determined depending on the acid value of the polymer represented by Formula S-1 and having at least one acid group. It is determined. The acid value of the polymer represented by the formula S-1 and having at least one acid group is preferably 20 to 300 mgKOH / g, more preferably 50 to 250 mgKOH / g, and 50 to 210 mgKOH / g. Particularly preferred. If the acid value is 20 mgKOH / g or more, sufficient alkali developability of the curable composition is obtained, and if the acid value is 300 mgKOH / g or less, the dispersibility and dispersion stability of the metal oxide particles are excellent. .

  The molecular weight of the polymer represented by the formula S-1 and having at least one acid group is preferably 2,000 to 200,000, more preferably 2,000 to 15,000 in terms of weight average molecular weight. , 500 to 10,000 are particularly preferred. 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 adsorptivity to the solid surface is exhibited. The polymer represented by Formula S-1 contained in the curable composition of the present invention and having at least one kind of acid group may be one kind or two or more kinds. In the case of two or more types, it is preferable that the weight average molecular weight of any polymer is also within the above range.

  Examples of the polymer represented by the formula S-1 and having at least one acid group are listed below, but the present invention is not limited thereto, and any compounds are included as long as they are included in the formula S-1. Can take structure. Moreover, in the following exemplary compounds, P1 and P2 can take arbitrary values in terms of mass as long as they do not deviate from the preferred ranges of the acid value and molecular weight described in paragraphs 0081 and 0082, respectively. In addition, the polymer chain in the following compound may be bonded to any monomer unit with a sulfur atom, and when the polymer chain includes two types of monomer units, even if the polymer chain is obtained by random polymerization, It may be a block copolymer chain.

Among the exemplary compounds of the polymer represented by the formula S-1 and having at least one acid group, the content ratio of the monomer unit having a carboxylic acid ester and the monomer unit having a carboxy group in the polymer skeleton (P1: P2) ) Is preferably in the range of 100: 0 to 80:20 in terms of mass. Moreover, the structure of the other end of the polymer chain in the exemplified compound is not particularly limited, and may be a known structure.
The polymer represented by the formula S-1 and having at least one acid group can be synthesized with reference to the method described in JP-A-2006-278118, for example.

The polymer which has an acid group may be used individually by 1 type, or may be used together 2 or more types.
The content of the polymer having an acid group in the curable composition of the present invention is preferably in the range of 5 to 70% by mass and more preferably in the range of 10 to 50% by mass with respect to the total solid content of the curable composition. preferable.

<Multifunctional thiol compound>
The curable composition of the present invention contains a polyfunctional thiol compound.
By containing a polyfunctional thiol compound, the curable composition which is excellent in storage stability and from which a cured product having a higher refractive index can be obtained.
In the present invention, the polyfunctional thiol compound means a compound having two or more thiol groups (mercapto groups) in the molecule. As the polyfunctional thiol compound, a low molecular compound having a molecular weight of 100 or more is preferable, specifically, a molecular weight of 100 to 1,500 is more preferable, and 150 to 1,000 is still more preferable.
As the number of functional groups of the polyfunctional thiol compound, 2 to 10 functions are preferable, 2 to 8 functions are more preferable, and 2 to 4 functions are more preferable. When the number of functional groups is large, the film strength is excellent, while when the number of functional groups is small, the storage stability is excellent. In the case of the said range, these can be made compatible.
As the polyfunctional thiol compound, an aliphatic polyfunctional thiol compound is preferable. A preferred example of the aliphatic polyfunctional thiol compound is a compound composed of a combination of an aliphatic hydrocarbon group and -O-, -C (= O)-, wherein at least 2 hydrogen atoms of the aliphatic hydrocarbon group are present. Examples are compounds in which one is substituted with a thiol group.
Furthermore, the thiol group in the polyfunctional thiol compound may be a primary thiol group, a secondary thiol group, or a tertiary thiol group, but from the viewpoint of sensitivity and chemical resistance Therefore, it is preferably a primary or secondary thiol group, more preferably a secondary thiol group. From the viewpoint of storage stability, it is preferably a secondary or tertiary thiol group, more preferably a secondary thiol group.

  As the aliphatic polyfunctional thiol compound, a compound having two or more groups represented by the following formula E-1 is preferable.

In Formula E-1, R ^1E represents a hydrogen atom or an alkyl group, A ^1E represents —CO— or —CH ₂ —, and a wavy line represents a bonding position with another structure.

As the polyfunctional thiol compound, a compound having 2 to 6 groups represented by the formula E-1 is preferable, and a compound having 2 to 4 groups represented by the formula E-1 is more preferable.
As an alkyl group in R ^<1E> in Formula E-1, it is a linear, branched, and cyclic alkyl group, As a carbon number range, 1-16 are preferable and 1-10 are more preferable. Specific examples of the alkyl group include methyl group, ethyl group, propyl group, i-propyl group, butyl group, s-butyl group, t-butyl group, pentyl group, hexyl group, and 2-ethylhexyl group. And a methyl group, an ethyl group, a propyl group or an i-propyl group is preferred.
R ^1E is particularly preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, or an i-propyl group, and most preferably a methyl group or an ethyl group.

  In the present invention, the polyfunctional thiol compound is particularly preferably a compound represented by the following formula E-2 having a plurality of groups represented by the above formula E-1.

In Formula E-2, each R ^1E independently represents a hydrogen atom or an alkyl group, each A ^1E independently represents —CO— or —CH ₂ —, L ^1E represents an nE-valent linking group, nE represents an integer of 2-6. From the viewpoint of synthesis, R ^1E is preferably the same group, and A ^1E is preferably the same group.

R ^1E in formula E-2 has the same meaning as R ^1E in formula E-1, and the preferred range is also the same. nE is preferably an integer of 2 to 4.
As L ^1E which is an nE-valent linking group in Formula E-2, for example, a divalent linking group such as — (CH ₂ ) _mE — (mE represents an integer of 2 to 6), trimethylolpropane residue, etc. A trivalent linking group such as an isocyanuric ring having three groups, — (CH ₂ ) _pE — (pE represents an integer of 2 to 6), a tetravalent linking group such as a pentaerythritol residue, or a pentavalent linking group. Examples include a linking group and a hexavalent linking group such as a dipentaerythritol residue.

Examples of the aliphatic polyfunctional thiol compound include pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyryl). Oxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropane tris (3-mercaptobutyrate), trimethylolethane tris (3-mercaptobutyrate) , Trimethylolpropane tris (3-mercaptopropionate), tris [(3-mercaptopropionyloxy) ethyl] isocyanurate, pentaerythritol tetrakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate) Nate) and dipentae It preferably contains at least one compound selected from the group consisting of sitolitol hexakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis (3-mercapto) Group consisting of butyryloxy) butane and 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione It is more preferable to contain at least one compound selected from the group consisting of:
Examples of commercially available products include Karenz MT-PE-1, Karenz MT-BD-1, Karenz MT-NR-1, TPMB, TEMB (manufactured by Showa Denko KK), TMMP, TEMPIC, PEMP, EGMP- 4 and DPMP (above, manufactured by Sakai Chemical Industry Co., Ltd.).

It is preferable that the curable composition of this invention contains a polyfunctional thiol compound in the range of 0.1-20 mass% with respect to the total solid of a composition, and contains it in the range of 0.5-10 mass%. It is more preferable, and it is still more preferable to include in 1-5 mass%.
The curable composition of the present invention may contain only one type of polyfunctional thiol compound, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

<Metal oxide particles>
The curable composition of the present invention contains metal oxide particles for the purpose of adjusting the refractive index and light transmittance. Since the metal oxide particles have high transparency and light transmittance, a curable composition having a high refractive index and excellent transparency can be obtained.
The metal oxide particles preferably have a refractive index higher than the refractive index of the curable composition made of a material excluding the metal oxide particles. Specifically, the refractive index at a wavelength of 550 nm is 1.50 or more. Particles having a refractive index of 1.70 or more are more preferable, particles having a refractive index of 1.80 or more are more preferable, and particles having a refractive index of 1.90 or more are particularly preferable. The upper limit of the refractive index is not particularly limited, but may be 2.80 or less.
In addition, in this invention, the refractive index in wavelength 550nm means the measured value of the refractive index measured using the light of wavelength 550nm, and the ellipsometer VUV-VASE (made by JA Woollam Japan Co., Ltd.) is used. Can be used to measure.

In addition, the metal of the metal oxide particles in the present invention includes semimetals such as B, Si, Ge, As, Sb, and Te.
The light-transmitting and high refractive index metal oxide particles include Be, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Gd, Tb, Dy, Yb, Lu, Ti, Zr, Hf, and Nb. Oxide particles containing atoms such as Mo, W, Zn, B, Al, Si, Ge, Sn, Pb, Sb, Bi, Te are preferable, titanium oxide particles, titanium composite oxide particles, zinc oxide particles, oxidation Zirconium particles, indium / tin oxide particles, or antimony / tin oxide particles are more preferable, titanium oxide particles, titanium composite oxide particles, or zirconium oxide particles are more preferable, titanium oxide particles, or zirconium oxide particles. Is particularly preferred, and titanium oxide particles are most preferred. As the titanium oxide particles, a rutile type having a particularly high refractive index is preferable. The surface of these metal oxide particles can be treated with an organic material in order to impart dispersion stability.

  From the viewpoint of transparency of the curable composition, the average primary particle diameter of the metal oxide particles is preferably 1 to 200 nm, more preferably 3 to 80 nm, and particularly preferably 5 to 50 nm. Here, the average primary particle diameter of the particles refers to an arithmetic average obtained by measuring the particle diameter of 200 arbitrary particles with an electron microscope. When the particle shape is not spherical, the equivalent circle diameter calculated from the projected area is taken as the diameter.

Moreover, a metal oxide particle may be used individually by 1 type, and can also use 2 or more types together.
The content of the metal oxide particles in the curable composition of the present invention may be appropriately determined in consideration of the refractive index required for the optical member obtained from the curable composition, light transmittance, etc. It is preferable that it is 20 mass% or more with respect to the total solid of the curable composition of this invention, and it is more preferable that it is 30 mass% or more. The content of the metal oxide particles is preferably 80% by mass or less, more preferably 70% by mass or less, and 50% by mass or less with respect to the total solid content of the curable composition. Is more preferable.
If content of a metal oxide particle is in the said range, the curable composition excellent in the storage stability and excellent in the refractive index of the cured film obtained will be obtained.

In the present invention, the metal oxide particles can be used as a dispersion prepared by mixing and / or dispersing in a suitable dispersant and solvent using a mixing device such as a ball mill or a rod mill.
Examples of the solvent used for the preparation of the dispersion include 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-2-propanol, and 1-pentanol in addition to the organic solvents described later. , 2-pentanol, 3-pentanol, 3-methyl-1-butanol, 2-methyl-2-butanol, neopentanol, cyclopentanol, 1-hexanol, cyclohexanol and the like. it can.
These solvents can be used singly or in combination of two or more.

<Silane coupling agent>
The curable composition of the present invention contains a silane coupling agent. When the curable composition of the present invention contains a silane coupling agent, the adhesiveness between the formed film and the substrate is improved, or the taper angle between the film formed of the curable composition of the present invention and the substrate. Can be adjusted.
As the silane coupling agent, a compound represented by the following formula SC-1 is preferable.

In Formula SC-1, R ¹ and R ² each independently represents an alkyl group or an aryl group, n represents an integer of 0 to 2, L ¹ represents a single bond or a divalent linking group, and A ¹ Represents a functional group.
R ¹ is preferably an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 18 carbon atoms. 1-10 are preferable, as for carbon number of an alkyl group, 1-5 are more preferable, and 1-3 are still more preferable. 6-12 are preferable and, as for carbon number of an aryl group, 6 is more preferable.
R ² is preferably an alkyl group having 1 to 3 carbon atoms or a phenyl group, more preferably an alkyl group having 1 to 3 carbon atoms, and still more preferably a methyl group.
n represents an integer of 0 to 2, and 0 or 1 is preferable.
When L ¹ represents a divalent linking group, a group consisting of — (CH ₂ ) _n1 — or a combination of — (CH ₂ ) _n1 — and —O— is preferable. Here, n1 is preferably from 1 to 10, more preferably from 1 to 6, and even more preferably from 1 to 3. A ¹ is vinyl group, epoxy group, styryl group, methacryloxy group, acryloxy group, amino group, ureido group, mercapto. At least one functional group selected from a group, a sulfide group and an isocyanate group is preferable, and an epoxy group, a methacryloxy group or an acryloxy group is more preferable.

  The silane coupling agent preferably includes a compound represented by the following formula SC-2 or formula SC-3.

In formula SC-2 and formula SC-3, R each independently represents an alkyl group having 1 to 3 carbon atoms, L represents a divalent linking group, and R ¹ represents a hydrogen atom or a methyl group.
R represents a C1-C3 alkyl group each independently, and a C1-C2 alkyl group is preferable.
L represents a divalent linking group and is preferably an alkylene group. 1-10 are preferable, as for carbon number of the said alkylene group, 1-6 are more preferable, and 1-3 are still more preferable.
R ¹ represents a hydrogen atom or a methyl group, and a methyl group is more preferable.

  Specific examples of the silane coupling agent include, for example, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrialkoxysilane, γ-glycidoxypropyl dialkoxysilane, γ- Methacryloxypropyltrialkoxysilane, γ-methacryloxypropyl dialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, vinyltrialkoxy Examples include silane, 3-acryloxypropyltriethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, and the like.

  50-500 are preferable and, as for the molecular weight of a silane coupling agent, 100-300 are more preferable.

The curable composition of the present invention preferably contains the silane coupling agent in the range of 0.1 to 20% by mass, and in the range of 0.5 to 10% by mass of the total solid content of the composition. More preferably, it is more preferable to contain in 1-5 mass%.
The curable composition of the present invention may contain only one type of polyfunctional thiol compound, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

<Organic solvent>
The curable composition of the present invention contains an organic solvent. The curable composition of the present invention is preferably prepared as a liquid obtained by dissolving or dispersing the essential components of the present invention and further optional components described below in an organic solvent.
As the organic solvent used in the curable composition of the present invention, known organic solvents can be used, such as ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoester. Alkyl ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl Examples include ether acetates, esters, ketones, amides, lactones and the like. Specific examples of the organic solvent used in the curable composition of the present invention include organic solvents described in paragraphs 0174 to 0178 of JP2011-221494A, paragraphs 0167 to 0168 of JP2012-194290A. The organic solvents described in the above are also included, the contents of which are incorporated herein.

In addition, benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, caprylic acid, 1-octanol, Organic solvents such as nonal, benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate, and propylene carbonate can also be added.
These organic solvents can be used individually by 1 type or in mixture of 2 or more types. The organic solvent that can be used in the present invention is preferably a single type or a combination of two types.

The organic solvent is preferably an organic solvent having a boiling point of 130 ° C. or higher and lower than 160 ° C., an organic solvent having a boiling point of 160 ° C. or higher, or a mixture thereof.
Examples of organic solvents having a boiling point of 130 ° C. or higher and lower than 160 ° C. include propylene glycol monomethyl ether acetate (boiling point 146 ° C.), propylene glycol monoethyl ether acetate (boiling point 158 ° C.), propylene glycol methyl-n-butyl ether (boiling point 155 ° C.), propylene Examples thereof include glycol methyl-n-propyl ether (boiling point 131 ° C.).
Examples of organic solvents having a boiling point of 160 ° C. or higher include ethyl 3-ethoxypropionate (boiling point 170 ° C.), diethylene glycol methyl ethyl ether (boiling point 176 ° C.), propylene glycol monomethyl ether propionate (boiling point 160 ° C.), dipropylene glycol methyl ether. Acetate (bp 213 ° C), 3-methoxybutyl ether acetate (bp 171 ° C), diethylene glycol diethyl ether (bp 189 ° C), diethylene glycol dimethyl ether (bp 162 ° C), propylene glycol diacetate (bp 190 ° C), diethylene glycol monoethyl ether Acetate (boiling point 220 ° C), dipropylene glycol dimethyl ether (boiling point 175 ° C), 1,3-butylene glycol diacetate (boiling point 232 ° C) It can be exemplified.
Among these, as the organic solvent, propylene glycol monoalkyl ether acetates are preferable, and propylene glycol monomethyl ether acetate is particularly preferable.

  The content of the organic solvent in the curable composition of the present invention is preferably contained so that the total solid content of the curable composition is 3 to 30% by mass from the viewpoint of adjusting the viscosity to be suitable for coating. More preferably, it is 5-20 mass%, and it is still more preferable that it is 8-15 mass%. That is, the total solid content: total solvent (mass ratio) is preferably 3:97 to 30:70, more preferably 5:95 to 20:80, and 8:92 to 15:85. Is more preferable.

The viscosity at 20 ° C. of the curable composition of the present invention is 1 to 30 mPa · s. When the viscosity of the curable composition is less than 1 mPa · s, the viscosity is low and printability is poor. On the other hand, when it exceeds 30 mPa · s, the viscosity is too high, and the inkjet dischargeability and in-plane uniformity are poor.
The viscosity at 20 ° C. of the curable composition of the present invention is preferably 5 to 30 mPa · s, more preferably 10 to 25 mPa · s, and still more preferably 10 to 20 mPa · s.
The viscosity is preferably measured at 20 ± 0.2 ° C. using a RE-80L rotational viscometer manufactured by Toki Sangyo Co., Ltd., for example. The rotation speed during measurement is 1,000 to 100 rpm for less than 5 mPa · s, 50 rpm for 5 mPa · s to less than 10 mPa · s, 20 rpm for 10 mPa · s to less than 30 mPa · s, and 10 rpm for more than 30 mPa · s, respectively. It is preferable.

<Surfactant>
The curable composition of the present invention may contain a surfactant.
As the surfactant, any of anionic, cationic, nonionic, or amphoteric surfactants can be used, but a preferred surfactant is a nonionic surfactant. Moreover, as the surfactant, a fluorine-based surfactant is preferable, and a fluorine-based nonionic surfactant is more preferable.
As the surfactant that can be used in the present invention, for example, commercially available products such as MegaFuck F142D, F172, F173, F176, F177, F183, F479, F482, F554, and F780 are commercially available. F781, F781-F, R30, R08, F-472SF, BL20, R-61, R-90 (manufactured by DIC Corporation), Florard FC-135, FC-170C, FC-430, FC-431, Novec FC-4430 (Sumitomo 3M), Asahi Guard AG 7105, 7000, 950, 7600, Surflon S-112, S-113, S-131, S -141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-1 05, the same SC-106 (Asahi Glass Co., Ltd.), F-top EF351, 352, 801, 802 (Mitsubishi Materials Electronics Chemical Co., Ltd.), and Footent 250 (Neos Co., Ltd.). . In addition to the above, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F-Top (manufactured by Mitsubishi Materials Denka Kasei Co., Ltd.), MegaFuck (manufactured by DIC Corporation) , FLORARD (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), PolyFox (manufactured by OMNOVA), and the like.

  Further, the surfactant includes a structural unit A and a structural unit B represented by the following formula F-1, and has a polystyrene-reduced weight average molecular weight (Mw) of 1 measured by gel permeation chromatography using tetrahydrofuran as a solvent. As a preferable example, a copolymer having a molecular weight of 1,000 or more and 10,000 or less can be given.

In Formula F-1, R ⁴⁰¹ and R ⁴⁰³ each independently represent a hydrogen atom or a methyl group, R ⁴⁰² represents a linear alkylene group having 1 to 4 carbon atoms, and R ⁴⁰⁴ represents a hydrogen atom or 1 carbon atom. Represents an alkyl group having 4 or less, L represents an alkylene group having 3 to 6 carbon atoms, p and q are mass percentages representing a polymerization ratio, and p represents a numerical value of 10% by mass to 80% by mass. Q represents a numerical value of 20% by mass or more and 90% by mass or less, r represents an integer of 1 or more and 18 or less, and s represents an integer of 1 or more and 10 or less.

L is preferably a branched alkylene group represented by the following formula F-2. R ⁴⁰⁵ in Formula F-2 represents an alkyl group having 1 to 4 carbon atoms, and is preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability with respect to the coated surface. More preferred is an alkyl group of 3.
The sum (p + q) of p and q in Formula F-1 is preferably p + q = 100, that is, 100% by mass.

The weight average molecular weight (Mw) of the copolymer is more preferably from 1,500 to 5,000.
These surfactants can be used singly or in combination of two or more.
When blended, the content of the surfactant in the curable composition of the present invention is preferably 0.001 to 5.0 mass% with respect to the total solid content of the curable composition, and 0.01 to 2. 0 mass% is more preferable.

<Crosslinking agent>
The curable composition of this invention may contain a crosslinking agent as needed. By adding a crosslinking agent, the cured film obtained by the curable composition of the present invention can be made a stronger film.
The cross-linking agent is not limited as long as it causes a cross-linking reaction by heat (however, the above-described components are excluded), and a known cross-linking agent can be used. For example, it is preferable to include a compound having two or more blocked isocyanate groups in the molecule (a compound having a protected isocyanate group) and a compound having two or more alkoxymethyl groups in the molecule.
When the curable composition of the present invention has a crosslinking agent, the content of the crosslinking agent is preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of the total solid content in the curable composition, It is more preferable that it is 0.1-30 mass parts, and it is still more preferable that it is 0.5-20 mass parts. By adding in this range, a cured film excellent in mechanical strength and solvent resistance can be obtained. A plurality of different kinds of crosslinking agents can be used in combination, and in that case, the content is calculated by adding all the crosslinking agents.

<Antioxidant>
The curable composition of the present invention may contain an antioxidant. As an antioxidant, a well-known antioxidant can be contained. By adding an antioxidant, there is an advantage that coloring of the cured film can be prevented, or a decrease in film thickness due to decomposition can be reduced, and heat resistant transparency is excellent.
Examples of such antioxidants include phosphorus antioxidants, amides, hydrazides, hindered amine antioxidants, sulfur antioxidants, phenol antioxidants, ascorbic acids, zinc sulfate, sugars, Examples thereof include nitrates, sulfites, thiosulfates, and hydroxylamine derivatives. Among these, phenolic antioxidants (hindered phenols), hindered amine antioxidants, phosphorus antioxidants (alkyl phosphites), sulfur oxidation, etc., in particular from the viewpoint of coloring the cured film and reducing the film thickness Inhibitors (thioethers) are preferred, and phenolic antioxidants are most preferred. These may be used individually by 1 type and may mix 2 or more types.
Specific examples include the compounds described in paragraphs 0026 to 0031 of JP-A-2005-29515, and the compounds described in paragraphs 0106 to 0116 of JP-A-2011-227106. Embedded in the book.
Preferred commercial products include ADK STAB AO-60, ADK STAB AO-80 (manufactured by ADEKA Corporation), Irganox 1035, Irganox 1098, Irganox 1726, IRGAFOS 168 (manufactured by BASF).

  When the curable composition of the present invention contains an antioxidant, the content of the antioxidant is 0.1 to 10 parts by mass with respect to 100 parts by mass of all solid components in the curable composition. Preferably, it is 0.2-5 mass parts, More preferably, it is 0.5-4 mass parts.

<Other ingredients>
In the curable composition of the present invention, as necessary, a plasticizer, a polymerization inhibitor, a thermal acid generator, an acid proliferating agent, a binder polymer, and a structural unit having a group in which an acid group is protected by an acid-decomposable group Other components such as a polymer having a photoacid generator, a dispersing agent, and a heterocyclic compound having two or more nitrogen atoms can be added. As for these components, for example, those described in JP2009-98616A, JP2009-244801A, JP2014132292A, paragraphs 0203-0298, Kokukai Kogyo 2014 / The thing of paragraphs 0025-0050 of 1999967 gazette and other publicly known things can be used. Further, various ultraviolet absorbers described in “New Development of Polymer Additives (Nikkan Kogyo Shimbun Co., Ltd.)”, metal deactivators, and the like may be added to the curable composition of the present invention.

(Polymerization inhibitor)
The curable composition of the present invention may contain a polymerization inhibitor.
With the polymerization inhibitor, hydrogen donation (or hydrogen donation), energy donation (or energy donation), electron donation (or electron donation), etc. are performed on the polymerization initiation radical component generated from the polymerization initiator, It is a substance that plays a role of deactivating polymerization initiation radicals and prohibiting polymerization initiation. For example, compounds described in paragraphs 0154 to 0173 of JP2007-334322A can be used.
Preferable compounds include phenothiazine, phenoxazine, hydroquinone, and 3,5-dibutyl-4-hydroxytoluene.
Although there is no restriction | limiting in particular in content of a polymerization inhibitor, It is preferable that it is 0.0001-5 mass% with respect to the total solid of a curable composition.

<Method for preparing curable composition>
There is no restriction | limiting in particular as a preparation method of the curable composition of this invention, It can prepare by a well-known method, For example, each component is mixed by a predetermined ratio and arbitrary methods, and stir-dissolves and / or It can be dispersed to prepare a curable composition. For example, after making each component into the solution which respectively melt | dissolved in the solvent previously, these can be mixed in a predetermined ratio and a curable composition can also be prepared. The curable composition prepared as described above can be used after being filtered using, for example, a filter having a pore diameter of 0.2 μm.

(Curing film and manufacturing method thereof)
The cured product of the present invention is a cured product obtained by curing the curable composition of the present invention. Moreover, it is preferable that the hardened | cured material of this invention is a cured film. The cured film of the present invention is preferably a cured film obtained by the method for producing a cured film of the present invention.
The method for producing a cured film of the present invention is not particularly limited as long as it is a method for producing a cured film by curing the curable composition of the present invention, but may include the following steps a to d in this order. preferable.
Step a: Application step of applying the curable composition of the present invention onto a substrate Step b: Solvent removal step of removing the solvent from the applied curable composition Step c: At least the curable composition from which the solvent has been removed The exposure process which exposes a part by actinic rays Process d: The heat processing process which heat-processes a curable composition Moreover, it is preferable that the manufacturing method of the cured film of this invention includes the following processes 1-5 in this order.
Process 1: Application | coating process which apply | coats the curable composition of this invention on a board | substrate Process 2: The solvent removal process of removing a solvent from the apply | coated curable composition Process 3: At least curable composition from which the solvent was removed An exposure process in which a part is exposed with actinic rays Step 4: A development process in which the exposed curable composition is developed with an aqueous developer Step 5: A heat treatment process in which the developed curable composition is heat-treated

  In the method for producing a cured film including steps a to d, the development step is an optional step. For example, when a refractive index adjustment layer is provided on one surface of the substrate, patterning is not required. Is done.

In the coating step, it is preferable to apply the curable composition of the present invention on a substrate to form a wet film containing a solvent. Before applying the curable composition to the substrate, the substrate can be cleaned such as alkali cleaning or plasma cleaning. Furthermore, the substrate surface can be treated with hexamethyldisilazane or the like after cleaning the substrate. By performing this treatment, the adhesiveness of the curable composition to the substrate tends to be improved.
Examples of the substrate include inorganic substrates, resins, and resin composite materials.
Examples of the inorganic substrate include glass, quartz, silicon, silicon nitride, and a composite substrate in which molybdenum, titanium, aluminum, copper, or the like is vapor-deposited on such a substrate.
Examples of resins include polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, polyethersulfone, polyarylate, allyl diglycol carbonate resin, polyamide, polyimide, polyamideimide, polyetherimide, Fluorine resin such as polybenzazole, polyphenylene sulfide, polycycloolefin, norbornene resin, polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, silicone resin, ionomer resin, cyanate resin, crosslinked fumaric acid diester, cyclic polyolefin, Synthetic trees such as aromatic ether resin, maleimide-olefin copolymer, cellulose, episulfide resin A substrate made of, and the like. These substrates are rarely used in the above-described form, and usually, a multilayer laminated structure such as a TFT element is formed depending on the form of the final product.

  Since the curable composition of the present invention has good adhesion to a metal film or metal oxide formed by sputtering, the substrate preferably includes a metal film formed by sputtering. The metal is preferably titanium, copper, aluminum, indium, tin, manganese, nickel, cobalt, molybdenum, tungsten, chromium, silver, neodymium and oxides or alloys thereof, molybdenum, titanium, aluminum, copper and More preferably, these alloys are used. In addition, a metal and a metal oxide may be used individually by 1 type, or may use multiple types together.

The coating method on the substrate is not particularly limited. For example, a slit coating method, a spray method, a roll coating method, a spin coating method, a casting coating method, a slit and spin method, an ink jet method, a printing method (flexo, gravure, screen, etc.) ) Etc. can be used. The ink jet method and the printing method are preferable because the composition can be placed in a necessary position and the composition can be saved.
Among these, the curable composition of the present invention is suitably used for a printing method and an inkjet method, and particularly suitable for a screen printing method and an inkjet method.
The wet film thickness when applied is not particularly limited and can be applied with a film thickness according to the application, but is preferably in the range of 0.05 to 10 μm.
Furthermore, before applying the curable composition of the present invention to the substrate, a so-called prewetting method as described in JP-A-2009-145395 can be applied.

In the solvent removal step, the solvent is removed from the applied film by vacuum (vacuum) and / or heating to form a dry coating film on the substrate. The heating conditions for the solvent removal step are preferably 70 to 130 ° C. and about 30 to 300 seconds.
In addition, the said application | coating process and the said solvent removal process may be performed in this order, may be performed simultaneously, or may be repeated alternately. For example, the solvent removal step may be performed after the inkjet coating in the coating step is completed, or the substrate is heated and the solvent is discharged while the curable composition is discharged by the inkjet coating method in the coating step. Removal may be performed.

The above exposure step generates a polymerization initiating species from a photopolymerization initiator using actinic rays, polymerizes an ethylenically unsaturated compound such as a compound having an ethylenically unsaturated group, and removes the solvent. A step of curing at least a part of the product is preferable.
As an exposure light source that can be used in the above exposure process, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a chemical lamp, an LED (light emitting diode) light source, an excimer laser generator, and the like can be used, i-line (365 nm), Actinic rays having a wavelength of from 300 nm to 450 nm, such as h-line (405 nm) and g-line (436 nm), can be preferably used. Moreover, irradiation light can also be adjusted through spectral filters, such as a long wavelength cut filter, a short wavelength cut filter, and a band pass filter, as needed.
As the exposure apparatus, various types of exposure apparatuses such as a mirror projection aligner, a stepper, a scanner, a proximity, a contact, a microlens array, a lens scanner, and a laser exposure can be used.
Further, even if the exposure amount in the exposure step is not particularly limited, it is preferably from 1~3,000mJ / cm ^2, more preferably 1 to 500 mJ / cm ^2.
The exposure in the exposure step is preferably performed in a state where oxygen is blocked from the viewpoint of curing acceleration. Examples of means for blocking oxygen include exposure in a nitrogen atmosphere and provision of an oxygen blocking film.
Moreover, the exposure in the said exposure process should just be performed to at least one part of the curable composition from which the solvent was removed, for example, may be whole surface exposure or pattern exposure.
Further, after the exposure step, post-exposure heat treatment (Post Exposure Bake (hereinafter also referred to as “PEB”)) can be performed. The temperature for performing PEB is preferably 30 ° C. or higher and 130 ° C. or lower, more preferably 40 ° C. or higher and 120 ° C. or lower, and particularly preferably 50 ° C. or higher and 110 ° C. or lower.
The heating method is not particularly limited, and a known method can be used. For example, a hot plate, an oven, an infrared heater, etc. are mentioned.
The heating time is preferably about 1 to 30 minutes in the case of a hot plate, and is preferably about 20 to 120 minutes in other cases. Within this range, the substrate and the apparatus can be heated without damage.

It is preferable that the manufacturing method of the cured film of this invention further includes the image development process which develops the exposed curable composition with a developing solution.
In the development step, the pattern-exposed curable composition is developed with a solvent or an alkaline developer to form a pattern. The developer used in the development step preferably contains a basic compound. Examples of the basic compound include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkalis such as sodium bicarbonate and potassium bicarbonate Metal bicarbonates; ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, and choline hydroxide; An aqueous solution of sodium silicate, sodium metasilicate, or the like can be used. An aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the alkaline aqueous solution can also be used as a developer.
As a preferred developing solution, a 0.4 to 2.5% by mass aqueous solution of tetramethylammonium hydroxide can be mentioned.
The pH of the developer is preferably 10.0 to 14.0. The development time is preferably 30 to 500 seconds, and the development method may be any of a liquid piling method (paddle method), a shower method, a dip method, and the like.
A rinsing step can also be performed after development. In the rinsing step, the developed substrate and the development residue are removed by washing the developed substrate with pure water or the like. A known method can be used as the rinsing method. For example, a shower rinse, a dip rinse, etc. can be mentioned.
For pattern exposure and development, a known method or a known developer can be used. For example, the pattern exposure method and the development method described in JP 2011-186398 A and JP 2013-83937 A can be suitably used.

It is preferable that the manufacturing method of the cured film of this invention includes the process of heat-processing a curable composition after the said exposure process. By performing a heat treatment after exposing the curable composition of the present invention, a cured film having higher strength can be obtained.
As temperature of the said heat processing, it is preferable that it is 80 to 300 degreeC, It is more preferable that it is 100 to 280 degreeC, It is especially preferable that it is 120 to 250 degreeC. In the above embodiment, it is estimated that condensation of the ethylenically unsaturated compound occurs moderately, and the physical properties of the cured film are superior.
The time for the heat treatment is not particularly limited, but is preferably 1 minute to 360 minutes, more preferably 5 minutes to 240 minutes, and still more preferably 10 minutes to 120 minutes.
Moreover, the curing by light and / or heat in the method for producing a cured film of the present invention may be performed continuously or sequentially.
In addition, when the heat treatment is performed in a nitrogen atmosphere, the transparency can be further improved.
Prior to the heat treatment step (post-bake), the heat treatment step can be performed after baking at a relatively low temperature (addition of a middle bake step). When performing middle baking, it is preferable to post-bake at a high temperature of 200 ° C. or higher after heating at 90 to 150 ° C. for 1 to 60 minutes. Further, middle baking and post baking can be heated in three or more stages. The taper angle of the pattern can be adjusted by devising such middle baking and post baking. These heating methods can use well-known heating methods, such as a hotplate, oven, and an infrared heater.
Prior to post-baking, the entire surface of the patterned substrate is re-exposed (post-exposure) with actinic rays and then post-baked to leave the condensation reaction between ethylenically unsaturated compounds and / or the exposed portion. It is presumed that the photopolymerization initiator generates an initiating species by thermal decomposition and functions as a catalyst for accelerating the crosslinking step, and can promote film curing. As a preferable exposure amount when the post-exposure step is included, 100 to 3,000 mJ / cm ² is preferable, and 100 to 500 mJ / cm ² is particularly preferable.

(Cured film)
The cured film or cured product of the present invention (hereinafter sometimes referred to as a cured film) is obtained by curing the curable composition of the present invention.
The cured film or the like of the present invention may be a cured film or the like developed as described above, or a cured film or the like that has not been developed, but a developed cured film or the like that can further exert the effects of the present invention. Preferably there is.
Since the cured film of the present invention has a high refractive index and high transparency, the microlens, the optical waveguide, the antireflection film, the layer for improving the light intake / extraction efficiency of the solar cell or the organic EL light emitting element, the LED sealing It is suitably used as a protective film for a wiring electrode used in a touch panel, an optical member such as an LED chip coating material, a protective film or an insulating film used in a display device such as an organic EL display device or a liquid crystal display device. it can.
The cured film of the present invention is a protective film for a color filter in a liquid crystal display device or an organic EL display device, a spacer for keeping the thickness of a liquid crystal layer in the liquid crystal display device constant, and for MEMS (Micro Electro Mechanical Systems). It can be suitably used for a structural member of a device.

Moreover, the cured film of this invention can be used for visibility reduction layers, such as a wiring electrode used for a touch panel. Note that the visibility reduction layer of the wiring electrode used for the touch panel is a layer that reduces the visibility of the wiring electrode used for the touch panel, that is, the layer that makes the wiring electrode etc. difficult to see. Examples thereof include interlayer insulating films (for example, made of indium tin oxide (ITO)), electrode protective films (overcoat films), and the like. It is also suitable for an index matching layer (sometimes referred to as an IM layer or a refractive index adjustment layer). The index matching layer is a layer for adjusting the light reflectance and transmittance of the display device. The index matching layer is described in detail in Japanese Patent Application Laid-Open No. 2012-146217, the contents of which are incorporated herein. An excellent visibility touch panel can be obtained by using the cured film of the present invention for the visibility-reducing layer.
Among these, the cured film of the present invention is suitable as an interlayer insulating film or an overcoat film in a display device or the like.
When used as an interlayer insulating film or a protective film between touch detection electrodes, the refractive index of the cured film is preferably close to the refractive index of the electrode from the viewpoint of improving visibility, and specifically, the refractive index at a wavelength of 550 nm is It is preferably 1.60 to 1.90, more preferably 1.62 to 1.85.

(Liquid crystal display device)
The liquid crystal display device of the present invention has the cured film of the present invention.
The liquid crystal display device of the present invention is not particularly limited except that it has a flattening film and an interlayer insulating film formed using the curable composition of the present invention, and known liquid crystal display devices having various structures are used. Can be mentioned.
For example, as specific examples of TFT (Thin-Film Transistor) included in the liquid crystal display device of the present invention, amorphous silicon TFT, low temperature polysilicon TFT, oxide semiconductor TFT (for example, indium gallium zinc oxide, so-called, IGZO) and the like. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.
Further, liquid crystal driving methods that can be taken by the liquid crystal display device of the present invention include TN (Twisted Nematic) method, VA (Vertical Alignment) method, IPS (In-Plane-Switching) method, FFS (Fringe Field Switching) method, OCB (OCB) method. Optically Compensated Bend) method.
In the panel configuration, the cured film of the present invention can also be used in a COA (Color Filter on Array) type liquid crystal display device. For example, the organic insulating film (115) of Japanese Patent Laid-Open No. 2005-284291, -346054 can be used as the organic insulating film (212). Specific examples of the alignment method of the liquid crystal alignment film that can be taken by the liquid crystal display device of the present invention include a rubbing alignment method and a photo alignment method. Further, the polymer alignment may be supported by the PSA (Polymer Sustained Alignment) technique described in JP2003-149647A or JP2011-257734A.
Moreover, the curable composition of this invention and the cured film of this invention are not limited to the said use, but can be used for various uses. For example, in addition to the planarization film and interlayer insulating film, a protective film for the color filter, a spacer for keeping the thickness of the liquid crystal layer in the liquid crystal display device constant, a microlens provided on the color filter in the solid-state imaging device, etc. Can be suitably used.

FIG. 1 is a conceptual cross-sectional view showing an example of an active matrix liquid crystal display device 10. The color liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on the back surface, and the liquid crystal panel includes all pixels disposed between two glass substrates 14 and 15 having a polarizing film attached thereto. The elements of the TFT 16 corresponding to are arranged. Each element formed on the glass substrate is wired with an ITO transparent electrode 19 that forms a pixel electrode through a contact hole 18 formed in the cured film 17. On the ITO transparent electrode 19, an RGB color filter 22 in which a liquid crystal 20 layer and a black matrix are arranged is provided.
The light source of the backlight is not particularly limited, and a known light source can be used. For example, white LED, multicolor LED such as blue, red and green, fluorescent lamp (cold cathode tube), organic EL and the like can be mentioned.
Further, the liquid crystal display device can be a 3D (stereoscopic) type or a touch panel type. Further, a flexible type can also be used, and it is used as the second interlayer insulating film (48) described in JP2011-145686A or the interlayer insulating film (520) described in JP2009-258758A. Can do.

(Organic EL display device)
The organic EL display device of the present invention has the cured film of the present invention.
The organic EL display device of the present invention is not particularly limited except that it has a planarizing film and an interlayer insulating film formed using the curable composition of the present invention, and various known organic EL devices having various structures. A display device and a liquid crystal display device can be given.
For example, specific examples of TFT (Thin-Film Transistor) included in the organic EL display device of the present invention include amorphous silicon-TFT, low-temperature polysilicon-TFT, and oxide semiconductor TFT. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.

FIG. 2 is a conceptual diagram of an example of an organic EL display device. A schematic cross-sectional view of a substrate in a bottom emission type organic EL display device is shown, and a planarizing film 4 is provided.
A bottom gate type TFT 1 is formed on a glass substrate 6, and an insulating film 3 made of Si ₃ N ₄ is formed so as to cover the TFT 1. A contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height: 1.0 μm) connected to the TFT 1 through the contact hole is formed on the insulating film 3. The wiring 2 is used to connect the TFT 1 with an organic EL element formed between the TFTs 1 or in a later process.
Further, in order to flatten the unevenness due to the formation of the wiring 2, a planarizing film 4 is formed on the insulating film 3 in a state where the unevenness due to the wiring 2 is embedded.
On the planarizing film 4, a bottom emission type organic EL element is formed. That is, the first electrode 5 made of ITO is formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7. The first electrode 5 corresponds to the anode of the organic EL element.
An insulating film 8 having a shape covering the periphery of the first electrode 5 is formed. By providing the insulating film 8, a short circuit between the first electrode 5 and the second electrode formed in the subsequent process is prevented. can do.
Further, although not shown in FIG. 2, a hole transport layer, an organic light emitting layer, and an electron transport layer are sequentially deposited through a desired pattern mask, and then a second layer made of Al is formed on the entire surface above the substrate. An active matrix organic material in which two electrodes are formed and sealed by bonding using a sealing glass plate and an ultraviolet curable epoxy resin, and each organic EL element is connected to a TFT 1 for driving it. An EL display device is obtained.

(Touch panel and touch panel display device)
The touch panel of the present invention is a touch panel in which all or part of the insulating layer and / or protective layer is made of a cured product of the curable composition of the present invention. Moreover, it is preferable that the touch panel of this invention has a transparent substrate, an electrode, an insulating layer, and / or a protective layer at least.
The touch panel display device of the present invention is preferably a touch panel display device having the touch panel of the present invention. As the touch panel of the present invention, any of known methods such as a resistive film method, a capacitance method, an ultrasonic method, and an electromagnetic induction method may be used. Among these, the electrostatic capacity method is preferable.
Examples of the capacitive touch panel include those disclosed in JP 2010-28115 A and those disclosed in International Publication No. 2012/057165. As another touch panel, a so-called in-cell type (for example, FIG. 5, FIG. 6, FIG. 7 and FIG. 8 of JP-T-2012-517051), a so-called on-cell type (for example, JP-A-2012-43394). FIG. 14, International Publication No. 2012/141148, FIG. 2 (b)), OGS (one glass solution) type, TOL (Touch on lens) type, and other configurations (for example, FIG. 6 of JP2013-164871A) ).

  The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, “part” and “%” are based on mass.

  Various components used in Examples and Comparative Examples are as follows.

<Ethylenically unsaturated compound>
-Ethylenically unsaturated compound 1: Dipentaerythritol hexaacrylate, A-DPH, manufactured by Shin-Nakamura Chemical Co., Ltd.-Ethylenically unsaturated compound 2: Ethoxylated bisphenol A diacrylate, ABE-300, Shin-Nakamura Chemical ( Co., Ltd., ethylenically unsaturated compound 3: Ethoxylated-o-phenylphenol acrylate, A-LEN-10, Shin-Nakamura Chemical Co., Ltd., ethylenically unsaturated compound 4: 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene, A-BPEF, manufactured by Shin-Nakamura Chemical Co., Ltd., ethylenically unsaturated compound 5: tricyclodecane dimethanol diacrylate, A-DCP, Shin-Nakamura Chemical Co., Ltd. Made)
-Ethylenically unsaturated compound 6: Ethoxylated isocyanuric acid triacrylate, A-9300, manufactured by Shin-Nakamura Chemical Co., Ltd.-Ethylenically unsaturated compound 7: Ethoxylated bisphenol A dimethacrylate, BPE-80N, Shin-Nakamura Chemical Made by

<Photopolymerization initiator>
Photopolymerization initiator 1: IRGACURE OXE 01, manufactured by BASF Co., Ltd. Photopolymerization initiator 2: Compound 1, compound having the following structure, a method similar to the method described in paragraphs 0135 to 0141 of International Publication No. 2015/072532. Was synthesized.

<Polymer having acid group>
Polymer having acid group 1: Polymer 1 having the following structure, acid value 50 mgKOH / g, synthetic product, comparative example Polymer having acid group 2: Polymer 2 having the following structure, acid value 50 mgKOH / g, synthesis Product, Comparative Example / Polymer having acid group 3: Polymer 3 having the following structure, acid value 100 mgKOH / g, Synthetic product / Polymer having acid group 4: Polymer 4 having the following structure, acid value 200 mgKOH / g, Synthetic product / polymer having acid group 5: polymer 5 having the following structure, acid value 200 mgKOH / g, synthetic product / polymer having acid group 6: polymer 6 having the following structure, acid value 300 mgKOH / g, synthetic product -Polymer 7 having an acid group: Polymer 7 having the following structure, acid value 400 mgKOH / g, synthetic product, comparative example-Polymer 8 having an acid group: Polymer 8 having the following structure, acid value 200 mgKOH / g
-Polymer 9 having an acid group: Polymer 9 having the following structure, acid value 200 mgKOH / g, synthetic product

In the above structural formulas, l, m, p, q, i, and j represent the molar ratio of each structural unit, a and b represent the molar ratio of each structural unit, and c and d represent the number of repetitions. Mw represents the weight average molecular weight of each polymer.
Polymers 1 to 7 were synthesized by a method similar to the method described in paragraphs 0322 to 0382 of JP-A-2008-096678.
Polymers 8 and 9 were synthesized by the same method as described in paragraphs 0281 to 0295 of JP-A-2014-066221.

<Multifunctional thiol compound>
Polyfunctional thiol compound 1: pentaerythritol tetrakis (3-mercaptobutyrate), Karenz MT (registered trademark) PE1, manufactured by Showa Denko KK Multifunctional thiol compound 2: 1,4-bis (3-mercaptobutyryl) Oxy) butane, Karenz MT (registered trademark) BD1, manufactured by Showa Denko KK, polyfunctional thiol compound 3: 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine- 2,4,6 (1H, 3H, 5H) -trione, Karenz MT (registered trademark) NR1, manufactured by Showa Denko KK, monofunctional thiol compound 1: 1-phenyl-2-mercaptobenzimidazole, Kawaguchi Chemical Co., Ltd. Company Phenyl MB (1,3-dihydro-1-phenyl-2H-benzimidazole-2-thione)

<Metal oxide particles>
Metal oxide particles 1: Titanium oxide, average primary particle size 10-30 nm, TTO-51 (C), manufactured by Ishihara Sangyo Co., Ltd.

<Silane coupling agent>
Silane coupling agent 1: 3-methacryloxypropyltrimethoxysilane, KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd. Silane coupling agent 2: 3-glycidoxypropyltrimethoxysilane, KBM-403, Shin-Etsu Chemical Made by Kogyo Co., Ltd.

<Organic solvent>
・ PGMEA: Propylene glycol monomethyl ether acetate

<Surfactant>
・ Surfactant 1: Fluorosurfactant MegaFuck F-554 (manufactured by DIC Corporation)

<Polymerization inhibitor>
-Polymerization inhibitor 1: Phenothiazine, manufactured by Tokyo Chemical Industry Co., Ltd.

Example 1
<Preparation of Metal Oxide Particle Dispersion Composition 4>
A metal containing the polymer 4 having an acid group is subjected to dispersion treatment under the following dispersion conditions using a Ultra Apex mill manufactured by Kotobuki Kogyo Co., Ltd. as a circulation type dispersion device (bead mill) for a mixed solution having the following composition. The oxide particle dispersion composition 4 was obtained.

[Composition of the mixture]
Titanium dioxide (Ishihara Sangyo Co., Ltd. TTO-51 (C)) (purity 75% or more): 150 parts Polymer 4 having an acid group (30% by mass solution): 150 parts Propylene glycol monomethyl ether acetate ( PGMEA): 300 parts

[Distribution conditions]
・ Bead diameter: 0.05mm
・ Bead filling rate: 75% by volume
・ Peripheral speed: 10 m / sec ・ Pump supply: 10 kg / hour ・ Cooling water: Tap water ・ Bead mill annular passage volume: 0.15 L
・ Amount of liquid mixture to be dispersed: 0.44 kg

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 change in the primary particle size when the dispersion time was extended by 30 minutes became 5 nm or less. The primary particle diameter of the titanium dioxide particles in this dispersion was 40 nm.
In addition, the primary particle diameter of titanium dioxide in the present example is a mixture or dispersion containing titanium dioxide diluted with propylene glycol monomethyl ether acetate 80 times, and a dynamic light scattering method is used for the obtained diluted liquid. The number average particle diameter obtained by using and measuring.
The number average particle diameter was measured by Nikkiso Co., Ltd. Microtrac UPA-EX150.

<Preparation of curable composition>
The following components were mixed, stirred for 1 hour using a magnetic stirrer, and then filtered through a polytetrafluoroethylene filter having a pore size of 0.3 μm to obtain the curable composition of Example 1.

[Composition of curable composition]
-PGMEA: 292.0 parts by mass-Ethylenically unsaturated compound 1: 44.2 parts by mass-Photopolymerization initiator 2: 1.5 parts by mass-Silane coupling agent 1: 1.0 parts by mass-Polymerization inhibitor 1 : 0.2 part by mass, polyfunctional thiol compound 1: 1.0 part by mass, surfactant 1: 0.1 part by mass, metal oxide particle dispersion composition 4 160 parts by mass (titanium oxide particles 40.0 parts by mass And 12.0 parts by mass of polymer 4 having an acid group)

<Evaluation of storage stability>
The initial viscosity of the curable composition obtained above was measured with “RE-85L” manufactured by Toki Sangyo Co., Ltd., and the curable composition was stored at room temperature (25 ° C.) for one month, and then time-lapsed. The viscosity was measured and evaluated according to the following evaluation criteria. The evaluation results are shown in Table 5. 3, 4, and 5 are practical levels, preferably 4 or 5, and more preferably 5.
Viscosity fluctuation was calculated by the following formula: Viscosity fluctuation (%) = | 1−viscosity / initial viscosity | × 100
Viscosity measurement was performed at 20 ° C.
5: Viscosity fluctuation after one month is within 5% 4: Viscosity fluctuation after one month is over 5% and within 10% 3: Viscosity fluctuation after one month is over 10% and within 20% 2: One Viscosity fluctuation after 20 months exceeds 50% and less than 1: 1: Viscosity fluctuation after one month is larger than 50%

<Evaluation of development adhesion>
The curable composition obtained above is applied to a glass substrate with a film thickness of 2.0 μm, and the mask is set to GAP (gap, distance between the coating surface of the curable composition and the mask) 150 μm with a proximity exposure machine. Through a 50 μm line and space (L & S) pattern with an exposure amount at which the line width becomes a mask bias + 5 μm, and subsequently a potassium hydroxide (KOH) developer (0.05 parts by weight of KOH, 99.95 parts by weight of pure water) ) For 60 seconds at a pressure of 0.15 MPa, washed with water and dried to obtain an image pattern (50 μm L & S pattern) of the curable composition. The undercut amount of the obtained image pattern was measured by cross-sectional SEM observation, and an average value of 5 points was evaluated according to the following evaluation criteria. The evaluation results are shown in Table 5. 3, 4, and 5 are practical levels, preferably 4 or 5, and more preferably 5.
5: Undercut is not observed 4: Undercut amount exceeds 0 μm and 0.5 μm or less 3: Undercut amount exceeds 0.5 μm and 1.0 μm or less 2: Undercut amount exceeds 1.0 μm and 5.0 μm Below 1: Image peels off and no pattern remains

<Evaluation of surface smoothness after heating>
The curable composition obtained above was applied to a glass substrate with a film thickness of 2.0 μm, exposed with a proximity exposure machine at 100 mJ / cm ² , and subsequently KOH developer (KOH 0.05 parts by mass, Shower development with a pressure of 0.15 MPa for 60 seconds with pure water (99.95 parts by mass), washed with water, dried, then heated in a heating oven at 230 ° C. for 60 minutes, and the surface roughness of the resulting curable composition solid pattern was Sa (Ra) was evaluated according to the following evaluation criteria using AFM (Dimension 3100, manufactured by Digital Instruments). The evaluation results are shown in Table 5. 3, 4, and 5 are practical levels, preferably 4 or 5, and more preferably 5.
5: Ra is 2.0 nm or less 4: Ra exceeds 2.0 nm and is 3.0 nm or less 3: Ra is more than 3.0 nm and is 5.0 nm or less 2: Ra is more than 5.0 nm and is 8.0 nm or less 1: Ra Is greater than 8.0 nm

<Evaluation of development residue>
The curable composition obtained above was applied to a glass substrate with a film thickness of 2.0 μm, and the line width when developed with a 50 μm L & S pattern for 60 seconds through a mask as a GAP of 150 μm with a proximity exposure machine is a mask. Exposure is performed with an exposure amount of bias +5 μm, and subsequently, 0.1 K with a development time of 30 seconds, 40 seconds, 50 seconds, and 60 seconds with a KOH developer (0.05 parts by weight of KOH, 99.95 parts by weight of pure water). Each of the development residues in the peripheral portion of the image pattern (50 μm L & S pattern) of the curable composition obtained by shower development at a pressure of 15 MPa, washing with water and drying was observed with an SEM and evaluated according to the following evaluation criteria. The evaluation results are shown in Table 5. 3, 4, and 5 are practical levels, preferably 4 or 5, and more preferably 5.
5: Development residue is not seen at any development time 4: Development residue is seen at development time of 30 seconds 3: Development residue is seen at development time of 30 seconds and 40 seconds 2: 30 seconds, 40 seconds, Development residue can be seen at development time of 50 seconds Development residue can be seen at development time of 1:30 seconds, 40 seconds, 50 seconds, 60 seconds

<Evaluation of refractive index>
The curable composition obtained above was applied to a glass substrate with a film thickness of 2.0 μm, exposed at 100 mJ / cm ² with a proximity exposure machine, and subsequently heated at 230 ° C. for 60 minutes in a heating oven, The refractive index in the light of 550 nm of the obtained curable composition was measured using an ellipsometer VUV-VASE (manufactured by JA Woollam Japan Co., Ltd.) and evaluated according to the following evaluation criteria. The evaluation results are shown in Table 5. 3, 4, and 5 are practical levels, preferably 4 or 5, and more preferably 5.
5: Refractive index is 1.80 or more 4: Refractive index is 1.76 or more and less than 1.80 3: Refractive index is 1.72 or more and less than 1.76 2: Refractive index is 1.68 or more and less than 1.72 1: Refractive index less than 1.68

(Examples 2-31 and Comparative Examples 1-15)
<Preparation of metal oxide particle dispersion compositions 1-3 and 5-9>
Except having changed the polymer 4 which has an acid group into the polymer which has an acid group of the following Table 1, it carried out similarly to Example 1, and carried out metal oxide particle dispersion composition 1-3 and 5-9. Prepared.

<Preparation of curable composition>
Except having changed each component mixed at the time of preparation of a curable composition into the compound of the following Table 2-Table 4, it carried out similarly to Example 1, and set the curable composition in each Example or a comparative example. Obtained.
In Tables 2 to 4, the numerical values in the column of each component represent the content (parts by mass) of the active ingredient, and “-” indicates that the corresponding component is not contained.
In Tables 2 to 4, in the columns of the metal oxide particle dispersion compositions 1 to 9, the total value of the solid content of the polymer containing the metal oxide particles and the acid group is described.
In Tables 2 to 4, in the column of “acid value of polymer having acid group (mgKOH / g)”, measurement was carried out by measuring the acid value of the polymer having acid group according to the method described in JIS K2501 (2003). Values are listed. When the composition does not contain a polymer having an acid group, “-” is described in the corresponding column.
In Tables 2 to 4, the numerical values described in the columns “A1 / A2”, “A1 + A2”, “B1 / B2”, and “B2” are calculated values from the following A1, A2, B1, and B2, and are necessary for the calculation. When the content of any of these components is 0, “-” is described in the corresponding column.
A1: Content of polyfunctional thiol compound A2: Content of silane coupling agent with respect to total solid content of composition B1: Content of ethylenically unsaturated compound with respect to total solid content of composition B2: Total content of composition Content of polymer having acid groups based on solid content

<Evaluation>
In each Example and Comparative Example, evaluation of development adhesion, surface smoothness after heating, development residue, and refractive index was performed in the same manner as in Example 1.
The evaluation results are shown in Table 5.

(Example 32)
3 to 5 except that an insulating layer W (hereinafter also referred to as a “pedestal layer W”) surrounding the Y electrode of FIG. 4 together with the substrate 111 is formed as follows. The touch panel of the present invention was obtained by forming in the same manner as described in JP-A-97692. Furthermore, using the touch panel, a display device with a touch panel was obtained in accordance with JP2013-97692A.
Formation of pedestal layer: The curable composition of Example 12 was applied on a substrate, pre-baked, exposed using an ultrahigh pressure mercury lamp, developed with an alkaline aqueous solution to form a pattern, and heated at 200 ° C for 30 minutes. Heat treatment was performed to form a pedestal layer W. The pedestal layer functions as an interlayer insulating film between the touch detection electrodes.
When a driving voltage was applied to the obtained display device, it was found that the display device had good display characteristics and touch detection performance and was highly reliable.

(Example 33)
3 to 5 except that the insulating layer W (pedestal layer W), the insulating layer 112, and the protective layer 113 surrounding the Y (102a) electrode of FIG. 4 together with the substrate 111 are formed as follows. The touch panel of the present invention was obtained by the same method as described in JP2013-97692A. Furthermore, using the touch panel, a display device with a touch panel was obtained in accordance with JP2013-97692A.
Formation of pedestal layer W, insulating layer 112 and protective layer 113: The curable composition of Example 12 was slit-coated on a substrate, pre-baked, exposed using an ultrahigh pressure mercury lamp, and developed with an alkaline aqueous solution. A pattern was formed, and heat treatment was performed at 200 ° C. for 30 minutes to form each layer.
When a driving voltage was applied to the obtained display device, it was found that the display device had good display characteristics and touch detection performance and was highly reliable.

  1: TFT (thin film transistor), 2: wiring, 3: insulating film, 4: flattening film, 5: first electrode, 6: glass substrate, 7: contact hole, 8: insulating film, 10: liquid crystal display device, 12 : Backlight unit, 14, 15: Glass substrate, 16: TFT, 17: Cured film, 18: Contact hole, 19: ITO transparent electrode, 20: Liquid crystal, 22: Color filter, 101a, 102a: Intersection, 101b, 102b: electrode part, 101X: electrode in X direction, 102: electrode in Y direction, 111: substrate, 112: insulating layer, 112a: contact hole, 113: protective layer, W: pedestal layer, X, Y: electrode

Claims (15)

Ethylenically unsaturated compounds,
Photopolymerization initiator,
A polymer having an acid group,
Polyfunctional thiol compounds,
Metal oxide particles,
A silane coupling agent, and
An organic solvent,
The acid value of the polymer having an acid group is 100 to 300 mgKOH / g,
The content A1 of the polyfunctional thiol compound with respect to the total solid content of the composition and the content A2 of the silane coupling agent with respect to the total solid content of the composition satisfy the following formulas 1 and 2. A curable composition.
Formula 1: 0.2 ≦ (A1 / A2) ≦ 5.0
Formula 2: 0.5 ≦ (A1 + A2) ≦ 15.0 The content B1 of the ethylenically unsaturated compound with respect to the total solid content of the composition and the content B2 of the polymer having an acid group with respect to the total solid content of the composition satisfy the following formulas 3 and 4. The curable composition according to claim 1.
Formula 3: 1.0 ≦ (B1 / B2) ≦ 15.0
Formula 4: 5 ≦ B2 ≦ 30   The polyfunctional thiol compound is pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyryloxyethyl)- 1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropane tris (3-mercaptobutyrate), trimethylolethanetris (3-mercaptobutyrate), trimethylolpropane Tris (3-mercaptopropionate), tris [(3-mercaptopropionyloxy) ethyl] isocyanurate, pentaerythritol tetrakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), and Dipentaerythritol Sakisu (3-mercaptopropionate) at least one compound selected from the group consisting of curable composition according to claim 1 or 2.   The curable composition of any one of Claims 1-3 whose refractive index in wavelength 550nm of the said metal oxide particle is 1.80-2.80.   The curable composition according to any one of claims 1 to 4, wherein the metal oxide particles include titanium oxide particles or zirconium oxide particles.   The curable composition according to any one of claims 1 to 5, wherein the content of the metal oxide particles is 30% by mass or more based on the total solid content of the composition. The curable composition of any one of Claims 1-6 in which the said silane coupling agent contains the compound represented by the following formula SC-2 or formula SC-3.

In formula SC-2 and formula SC-3, R each independently represents an alkyl group having 1 to 3 carbon atoms, L represents a divalent linking group, and R ¹ represents a hydrogen atom or a methyl group. A method for producing a cured film comprising at least step a to step d in this order.
Step a: Application step of applying the curable composition according to any one of claims 1 to 7 on a substrate Step b: Solvent removal step of removing the solvent from the applied curable composition Step c: Solvent An exposure step of exposing at least a part of the curable composition from which the resin has been removed with actinic rays Step d: a heat treatment step of heat-treating the curable composition A method for producing a cured film comprising at least Step 1 to Step 5 in this order.
Process 1: Application | coating process which apply | coats the curable composition of any one of Claims 1-7 on a board | substrate Process 2: The solvent removal process of removing a solvent from the apply | coated curable composition Process 3: Solvent An exposure step of exposing at least a part of the curable composition from which the polymer has been removed with actinic rays Step 4: a development step of developing the exposed curable composition with an aqueous developer Step 5: developing the developed curable composition Heat treatment process for heat treatment   The cured film formed by hardening | curing the curable composition of any one of Claims 1-7.   The cured film according to claim 10, which is an interlayer insulating film or an overcoat film.   A liquid crystal display device comprising the cured film according to claim 10.   An organic EL display device comprising the cured film according to claim 10.   A touch panel comprising the cured film according to claim 10.   A touch panel display device comprising the cured film according to claim 10.

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