JP2016056341A - Curable composition, manufacturing method of cured film, cured film, touch panel and display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition high in transparency, providing a cured film high in in-plane uniformity and excellent in printability, the cured film by curing the curable composition and a manufacturing method therefor, various display devices having the cured film and a touch panel.SOLUTION: There is provided a curable composition containing Component A:a specific titanium-containing compound and/or a zirconium-containing compound, Component B:a curable compound and Component C:a solvent, the Component C contains Component C-1:at least one kind of organic solvent having viscosity at 20°C of 50 mPa s to 200 mPa s and surface tension of 30 mN/m to 41 mN/m and Component C-2: at least one kind of organic solvent having viscosity at 20°C of less than 50 mPa s, the content of the Component C-1 is 20 to 95 mass% based on total mass of the Component C and viscosity at 20°C of the curable composition is 1 mPa s to 30 mPa s.SELECTED DRAWING: None

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.
It is also known to adjust the refractive index of the 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.
As a transparent curable composition having an adjusted refractive index, a composition using a metal oxide or a metal alkoxide is known (for example, see Patent Document 1).
Moreover, the composition described in patent document 2 is known as a transparent curable composition which adjusted the refractive index with patterning performance.

National Opening No. 2010/050580 JP 2012-203061 A

In recent years, from the viewpoint of liquid-saving properties and proper application to various substrates, it has been demanded that a composition used in manufacturing an electronic device such as a display device or a touch panel can be applied by a printing method. The compositions described in Patent Documents 1 and 2 have not yet been sufficiently printed.
The problem to be solved by the present invention is that a cured film having high transparency and high in-plane uniformity is obtained, a curable composition excellent in printability, a cured film obtained by curing the curable composition, and the same A manufacturing method and an organic EL display device, a liquid crystal display device, a touch panel, and a touch panel display device having the cured film.

The above-described problems of the present invention have been solved by means described in the following <1>, <9> to <11>, or <14> to <17>. It is described below together with <2> to <8>, <12> and <13> which are preferred embodiments.
<1> The component A contains at least one selected from the group consisting of the following a1 to a3, the component B as a curable compound, the component C as a solvent, and the component C as the component C- 1, at least one organic solvent having a viscosity at 20 ° C. of 50 mPa · s to 200 mPa · s and a surface tension of 30 mN / m to 41 mN / m, and as Component C-2, 20 ° C. And at least one organic solvent having a viscosity of less than 50 mPa · s, the content of the component C-1 is 20 to 95% by mass with respect to the total mass of the component C, and the curable composition A curable composition characterized in that the viscosity at 20 ° C. of the product is 1 mPa · s or more and 30 mPa · s or less,
a1: a titanium compound and / or a zirconium compound having an alkoxy group,
a2: titanoxane, zircoxane and / or titanoxane-zircoxane condensate having at least one alkoxy group directly bonded to a titanium atom or a zirconium atom,
a3: Metal oxide containing a titanium atom and / or a zirconium atom.

<2> The curable composition according to <1>, wherein component B is a polymerizable compound,
<3> Component C-1 is terpineol, dihydroterpineol, 4- (acetyloxy) -α, α, 4-trimethylcyclohexanemethanol acetate, and 2- [1-methyl-1- (4-methyl-3- The curable composition according to <1> or <2>, which contains at least one selected from the group consisting of cyclohexen-1-yl) ethoxy] ethanol,
<4> The total amount of solids in the curable composition is 2 to 15% by mass with respect to the total mass of the curable composition, according to any one of <1> to <3>. Curable composition,
<5> The curable composition according to any one of <1> to <4>, wherein Component B contains a polymerizable compound having 6 or more functional groups,
<6> At least one selected from the group consisting of a titanium compound having an alkoxy group, a zirconium compound having an alkoxy group, a titanium compound having a halogeno group, and a zirconium compound having a halogeno group is used as the titanium atom and zirconium. <1> It is a titanoxane, zircoxane and / or titanoxane-zircoxane condensate obtained by hydrolysis and condensation with 0.5 to 1.9 times molar equivalent of water with respect to 1.0 mol of the total molar amount of atoms. ~ <5> curable composition according to any one of the above,
<7> The curable composition according to any one of <1> to <6>, wherein the component A includes the a2.
<8> The curable composition according to any one of <1> to <7>, which contains a photopolymerization initiator as component D.

<9> 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 <8> onto the substrate Step b: Solvent removal step of removing the solvent from the applied curable composition Step c : Exposure step of exposing at least a part of the curable composition from which the solvent has been removed with actinic rays step d: heat treatment step of heat-treating the curable composition

<10> A method for producing a cured film including at least Step 1 to Step 5 in this order,
Process 1: Application | coating process which apply | coats curable composition as described in any one of <1>-<8> on a board | substrate Process 2: Solvent removal process which removes 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 process which heat-treats a thing <11> Cured film formed by hardening | curing the curable composition as described in any one of <1>-<8>,
<12> The cured film according to <11>, which is an interlayer insulating film or an overcoat film,
<13> The cured film according to <11> or <12>, wherein the refractive index at a wavelength of 550 nm is 1.6 to 1.9,
<14> A liquid crystal display device having the cured film according to any one of <11> to <13>,
<15> An organic EL display device having the cured film according to any one of <11> to <13>,
<16> A touch panel having the cured film according to any one of <11> to <13>,
<17> A touch panel display device having the cured film according to any one of <11> to <13>.

  According to the present invention, a cured film having high transparency and high in-plane uniformity is obtained, and a curable composition excellent in printability, a cured film obtained by curing the curable composition, a method for producing the same, and And an organic EL display device, a liquid crystal display device, a touch panel and a touch panel 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 description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what does not have a substituent and what has 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 addition, the chemical structural formula in this specification may be expressed as a simplified structural formula in which a hydrogen atom is omitted.
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, “at least one selected from the group consisting of a1 to a3” and the like are also simply referred to as “component A” and the like.
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.

  The weight average molecular weight and the number average molecular weight in the titanoxane, zircoxane and titanoxane-zircoxane condensate of the present invention are measured by gel permeation chromatography (GPC).

(Curable composition)
The curable composition of the present invention (hereinafter also simply referred to as “composition”) includes, as component A, at least one selected from the group consisting of the following a1 to a3, as component B, a curable compound, Component C contains a solvent, Component C-1 as Component C-1, has a viscosity at 20 ° C. of 50 mPa · s to 200 mPa · s and a surface tension of 30 mN / m to 41 mN / m. And at least one organic solvent having a viscosity at 20 ° C. of less than 50 mPa · s as the component C-2, and the content of the component C-1 is It is 20-95 mass% with respect to the total mass of C, and the viscosity in 20 degreeC of a curable composition is 1 mPa * s or more and 30 mPa * s or less, It is characterized by the above-mentioned.
a1: a titanium compound and / or a zirconium compound having an alkoxy group,
a2: titanoxane, zircoxane and / or titanoxane-zircoxane condensate having at least one alkoxy group directly bonded to a titanium atom or a zirconium atom,
a3: Metal oxide containing a titanium atom and / or a zirconium atom.
The curable composition of the present invention is suitable for applications such as a refractive index adjusting layer (index matching) for improving visibility, a refractive index adjusting insulating film or an overcoat layer for preventing the appearance of bone.

In the touch panel field, the appearance of polymer insulators and the appearance of wiring such as ITO (so-called bone appearance) are problematic. In order to solve this problem, a refractive index adjustment layer (index matching layer) is used.
Conventionally, sputter-type index matching layers, such as sputter-deposited layers of niobium oxide, have been used as the index matching layer. However, because of the high cost of materials and production, high refractive index titanium oxide and zirconium oxide A coating type in which a layer is formed by applying a metal oxide such as titanium alkoxide or metal alkoxide such as zirconia alkoxide, titanoxane or zirconia which is a condensate thereof, or the like as a coating solution has been studied.
As a result of intensive studies, the inventors have found that a coating solution using a normal solvent has a cloudy surface state when dried, resulting in deterioration of transparency, occurrence of cissing failure, or surface application when applied by flexographic printing or inkjet printing. It was found that problems such as internal distribution occurred.
The present inventors have found that by using a specific solvent in combination, a cured film with high transparency and high in-plane uniformity can be obtained, and a curable composition excellent in printability can be obtained. The present invention has been completed.
Although the detailed mechanism of the effect is unknown, in order to obtain a viscosity suitable for flexographic printing and inkjet printing, when using an alcohol-based high-viscosity solvent, the high-viscosity solvent generally has a high surface tension, and repelling. There was a problem that occurred. Further, when a solvent having a high surface tension is used, there is a problem that pinholes are generated depending on the compatibility with the substrate at the time of drying or after drying. Furthermore, the compatibility with the component A and the component B is low, and there is a problem that the phase separation occurs at the time of drying to cause cloudiness and the transparency is deteriorated. In the present invention, by using a combination of specific solvents as the solvent, the viscosity of the composition is high, the surface tension is low, and the occurrence of phase separation during drying and the associated cloudiness is suppressed. Although it is presumed, the detailed mechanism of the effect is unclear.

The curable composition of the present invention is preferably a photosensitive composition, and may be a positive photosensitive composition or a negative photosensitive composition, but a negative photosensitive composition. It is preferable that
When the curable composition of the present invention is a negative photosensitive composition, component B is preferably a polymerizable compound.
When the curable composition of the present invention is a positive photosensitive composition, it preferably contains a polymer having a structural unit having a group in which an acid group is protected by an acid-decomposable group, and a photoacid generator. Further, when the curable composition of the present invention is a positive photosensitive composition, it is preferably a chemically amplified positive photosensitive composition (chemically amplified positive photosensitive composition), and actinic rays. It may be a non-chemically amplified positive photosensitive composition using a 1,2-quinonediazide compound as a photoacid generator that is sensitive to water. In view of high sensitivity and excellent transparency, a chemically amplified positive photosensitive composition is preferred.

In addition, when the curable composition of the present invention is a negative photosensitive composition, a composition in which the strength of the cured product becomes higher by heat-treating the cured product such as a cured film obtained after polymerization with actinic rays. It is preferable that it is a thing.
Furthermore, when the curable composition of the present invention is a positive photosensitive composition, it is preferable that the unexposed portion is heated after the exposed portion is removed to cause a crosslinking reaction and cure.

The curable composition of the present invention is preferably a curable composition for producing a transparent cured product, and more preferably a curable composition for producing a transparent cured film.
Furthermore, the curable composition of the present invention is preferably a curable composition having a refractive index of 1.60 or more at a wavelength of 550 nm of the obtained cured product, and the refractive index of the obtained cured product at a wavelength of 550 nm is 1. More preferably, the curable composition is 0.62 or more. Moreover, it is preferable that the refractive index in wavelength 550nm of the hardened | cured material obtained is 1.90 or less, and it is more preferable that it is 1.85 or less.
Moreover, the curable composition of this invention can be used suitably as a curable composition for interlayer insulation films or overcoat films.
Furthermore, the curable composition of this invention can be used suitably as a curable composition for refractive index adjustment layers.

Component A: At least one selected from the group consisting of a1 to a3 The curable composition of the present invention contains, as Component A, at least one selected from the group consisting of the following a1 to a3. Content is 40-80 mass% with respect to the total solid of a curable composition.
a1: a titanium compound and / or a zirconium compound having an alkoxy group,
a2: titanoxane, zircoxane and / or titanoxane-zircoxane condensate having at least one alkoxy group directly bonded to a titanium atom or a zirconium atom,
a3: Metal oxide containing a titanium atom and / or a zirconium atom.
Further, it goes without saying to those skilled in the art that the above a1 is synonymous with “a titanium compound having an alkoxy group and / or a zirconium compound having an alkoxy group”, and the above a2 is “a titanium compound having a halogeno group”. And / or a zirconium compound having a halogeno group, wherein a2 is “a titanoxane having at least one alkoxy group directly bonded to a titanium atom, a zirconoxane having at least one alkoxy group directly bonded to a zirconium atom, or , A titanoxane-zircoxane condensate having at least one alkoxy group directly bonded to a titanium atom or a zirconium atom, and the above a3 is “a metal oxide containing a titanium atom and / or a metal oxide containing a zirconium atom” It is synonymous with "thing".

  It is preferable that content of the component A is 15-90 mass% with respect to the total solid of a curable composition. When the refractive index of the cured product (cured film) is 1.60 to 1.90, it is more preferably 15 to 60% by mass from the viewpoint of adjusting the refractive index, and 17.5 to 45% by mass. It is still more preferable and it is especially preferable that it is 20-35 mass%. Moreover, when using as a high refractive index material, it is preferable that it is 40-90 mass% from a viewpoint of refractive index adjustment, It is more preferable that it is 50-85 mass%, It is 60-80 mass%. More preferably. In addition, "solid content" in a curable composition represents the component except volatile components, such as a solvent. Needless to say, the solid content may be liquid instead of solid.

Component A may be any of a1 alone, a2 alone, a3 alone, a mixture of a1 and a2, a mixture of a1 and a3, a mixture of a2 and a3, or a mixture of a1, a2 and a3. From the viewpoint of the storage stability of the product, a2 alone, a3 alone, or a mixture of a1 and a2 is preferable, and a2 alone is more preferable.
Further, as a1, a titanium compound and a zirconium compound may be used in combination.
Component A preferably contains at least a2 from the viewpoints of refractive index and storage stability.
Component A is preferably selected from the group consisting of a titanium compound, titanoxane, and titanium oxide from the viewpoint of refractive index and developability, and from the viewpoint of low-temperature curability, curing speed, and stability. And selected from the group consisting of zirconium compounds, zirconia and zirconium oxide.

a1: Titanium compound and / or zirconium compound having an alkoxy group a1: As a titanium compound having an alkoxy group and a zirconium compound having an alkoxy group, titanium monoalkoxide, titanium dialkoxide, titanium trialkoxide, titanium tetraalkoxide, zirconium mono Alkoxides, zirconium dialkoxides, zirconium trialkoxides, and zirconium tetraalkoxides can be mentioned. From the viewpoint of film properties, titanium tetraalkoxides and zirconium tetraalkoxides are preferable, and titanium tetraalkoxides are more preferable.
In addition, a1 should just have at least 1 alkoxy group, and may have other groups, such as a halogeno group and an alkyl group.
The titanium tetraalkoxide is preferably a titanium tetraalkoxide represented by the following formula a1-1 from the viewpoint of film properties.
The zirconium tetraalkoxide is preferably a zirconium tetraalkoxide represented by the following formula a1-2 from the viewpoint of film properties.

In formula a1-1 and formula a1-2, R ^{1 to} R ⁴ each independently represents an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms. Represent.

R ^{1 to} R ⁴ in Formula a1-1 and Formula a1-2 are each independently preferably an alkyl group having 1 to 18 carbon atoms, and an alkyl group having 1 to 8 carbon atoms from the viewpoint of film properties. It is more preferable that it is a C1-C5 alkyl group.

The titanium tetraalkoxide represented by the formula a1-1 is not limited to the following specific examples. For example, titanium tetramethoxide, titanium tetraethoxide, titanium tetra n-propoxide, titanium tetraisopropoxide, titanium Examples include tetra n-butoxide, titanium tetraisobutoxide, titanium diisopropoxydi n-butoxide, titanium di-t-butoxydiisopropoxide, titanium tetra-t-butoxide, titanium tetraisooctyloxide, titanium tetrastearyl alkoxide, and the like.
The zirconium tetraalkoxide represented by the formula a1-2 is not limited to the following specific examples. For example, zirconium tetramethoxide, zirconium tetraethoxide, zirconium tetra n-propoxide, zirconium tetraisopropoxide, zirconium Examples include tetra n-butoxide, zirconium tetraisobutoxide, zirconium diisopropoxy di-n-butoxide, zirconium di-t-butoxy diisopropoxide, zirconium tetra-t-butoxide, zirconium tetraisooctyloxide, zirconium tetrastearyl alkoxide, and the like. .
These can be used individually by 1 type or in mixture of 2 or more types.

Titanoxane is also referred to as polytitanoxane and is a compound having two or more Ti—O—Ti bonds. Examples of the production method include a method obtained by hydrolyzing and condensing the titanium tetraalkoxide represented by the formula a1-1 with water. In addition, titanium halide such as titanium tetrachloride may be hydrolyzed and condensed. Of these, titanium alkoxides and titanium chlorides are preferable, and titanium alkoxides are more preferable because of ease of synthesis.
Zirconoxane is also referred to as polyzircoxane and is a compound having two or more Zr—O—Zr bonds. Moreover, as the manufacturing method, the same method as the manufacturing method of the said titanoxane is mentioned except changing a raw material into zirconium compounds, such as a zirconium alkoxide and a halogenated zirconium.
The titanoxane-zircoxoxane condensate is a condensate obtained by hydrolysis and condensation using both the titanium compound and the zirconium compound. Moreover, as the manufacturing method, the same method as the said manufacturing method is mentioned except using a titanium compound and a zirconium compound together as a raw material.

a2: Titanoxane, zirconoxane and / or titanoxane-zircoxane condensate having at least one alkoxy group directly bonded to a titanium atom or a zirconium atom The a2 is a titanium compound having an alkoxy group, a zirconium compound having an alkoxy group, and a halogeno group. At least one selected from the group consisting of a titanium compound having a halogen compound and a zirconium compound having a halogeno group is 0.5 to 1.9 times the molar equivalent of 1.0 mol of the total molar amount of titanium atom and zirconium atom. It is preferably a titanoxane, zircoxane and / or titanoxane-zircoxane condensate obtained by hydrolysis and condensation with water, and is selected from the group consisting of titanium compounds having an alkoxy group and zirconium compounds having an alkoxy group. At least one kind obtained by hydrolytic condensation with 0.5 to 1.9 times molar equivalent of water with respect to 1.0 mol of the total molar amount of titanium atom and zirconium atom-titanoxane, zircoxane and / or titanoxane- It is more preferable that it is a zircoxane condensation product.
When using a titanium compound having a halogeno group and / or a zirconium compound having a halogeno group, it is used in combination with a titanium compound having an alkoxy group and / or a zirconium compound having an alkoxy group, or has a titanium compound having a halogeno group and a halogeno group. It is preferable to use a compound which is a zirconium compound and has at least one alkoxy group or hydrolytically condenses by adding an alcohol compound in addition to water.
Examples of the titanium compound having a halogeno group and the zirconium compound having a halogeno group include titanium monohalide, titanium dihalide, titanium trihalide, titanium tetrahalide, zirconium monohalide, zirconium dihalide, zirconium trihalide, and zirconium tetrahalide. Among them, titanium tetrahalide and zirconium tetrahalide are preferable from the viewpoint of film physical properties, and titanium tetrahalide is more preferable. These can be used individually by 1 type or in mixture of 2 or more types.

Moreover, not only water but a solvent etc. may be used for the said hydrolysis condensation, and an alcohol compound may be used as an additive. Moreover, as a solvent, an alcohol compound is mentioned suitably.
From the viewpoint of the mechanical strength of the resulting film, the amount of water used for the hydrolysis condensation is 0.5 to 1.9 molar equivalents relative to 1.0 mole of the total molar amount of titanium atoms and zirconium atoms in the raw material. The lower limit is preferably 0.9 molar equivalent or more, more preferably 1.2 molar equivalent or more from the viewpoint of film strength, and the upper limit is preferably 1. from the viewpoint of film flexibility. It is preferably 8 molar equivalents or less, and more preferably 1.7 molar equivalents or less.
Component A includes a titanoxane having at least one alkoxy group directly bonded to a titanium atom (hereinafter also simply referred to as “titanoxan”) and an alkoxy group directly bonded to a zirconium atom from the viewpoint of storage stability and film properties of the composition. Zirconoxane having at least one (hereinafter, also simply referred to as “zircoxane”), or titanoxane-zircoxane condensate having at least one alkoxy group directly bonded to a titanium atom or zirconium atom (hereinafter, simply “titanoxan-zircoxane condensate”). It is also preferable to include titanoxane or zirconoxane, and it is more preferable to include titanoxane.

  The titanoxane, zirconoxane and titanoxane-zircoxane condensate may be in any polymer form such as linear, branched, three-dimensional network, pendant, ladder, cage, etc. Although it is not, it is preferable that it is titanoxane or zircoxane having compatibility with component B. Moreover, titanoxane and zircoxane may be solid or liquid at normal temperature (25 ° C.).

  Although it does not restrict | limit especially as a weight average molecular weight of a titanoxane, a zircoxane, and a titanoxane zircoxane condensate, 500-50,000 are preferable and 1,000-20,000 are more preferable.

The titanoxane is preferably a titanoxane represented by the following formula a2-1 from the viewpoint of film properties.
Moreover, it is preferable from a viewpoint of film | membrane physical property that the said zirconia is a zirconia represented by the following formula a2-2.
Ti _α O _β (OR) _γ (a2-1)
Zr _α O _β (OR) _γ (a2-2)
In formula a2-1 and formula a2-2, R each independently represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms. , Α, β, and γ satisfy the following conditions a ′ to c ′, α represents a positive integer, and β and γ represent a positive number.
a ′: 200 ≧ α ≧ 2,
b ′: 1.9α ≧ β ≧ 1.0α,
c ′: γ = 4α-2β

  The titanoxane, zircoxane and titanoxane-zircoxane condensate in a2 may be of a single composition or a mixture of two or more.

a3: Metal oxide containing titanium atom and / or zirconium atom Examples of a3 include titanium oxide, zirconium oxide, and composite oxide containing titanium atom and / or zirconium atom.
As the composite oxide containing a titanium atom and / or a zirconium atom, titanium oxide, titanium composite oxide, zirconium oxide, zirconium composite oxide is preferable, titanium oxide, titanium composite oxide, or zirconium oxide is more preferable, and titanium oxide. Zirconium oxide is more preferable, and titanium oxide is particularly preferable. Titanium oxide is particularly preferably a rutile type having a high refractive index. The surface of these metal oxide particles can be treated with an organic material in order to impart dispersion stability.
Examples of the composite oxide include tin oxide-titanium oxide composite particles, silicon oxide-titanium oxide composite particles, and tin oxide-zirconium oxide composite particles.
Titanium oxide is particularly preferably a rutile type having a high refractive index. The surface of these metal oxide particles can be treated with an organic material in order to impart dispersion stability.

  As a3, you may use what is marketed, for example, Ishihara Sangyo Co., Ltd. TTO series (TTO-51 (A), TTO-51 (C), etc.), TTO-S as titanium oxide particles. , V series (TTO-S-1, TTO-S-2, TTO-V-3, etc.), MT series (MT-01, MT-05, etc.) manufactured by Teika Co., Ltd., and tin oxide-titanium oxide composite particles Optlake TR-502, Optlake TR-504, Optolake TR-503, Optlake TR-513, Optlake TR-520, Optlake TR-521, Optlake TR-527, Zirconium oxide particles (manufactured by Kojundo Chemical Laboratory Co., Ltd.), tin oxide-zirconium oxide composite particles (manufactured by JGC Catalysts & Chemicals Co., Ltd.), etc. It is.

From the viewpoint of transparency of the curable composition, the average primary particle diameter of a3 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 longest side is the diameter.
Further, a3 can be used as a dispersion prepared by mixing and dispersing in a suitable dispersant and solvent using a mixing device such as a ball mill or a rod mill.

  In addition, the total content of titanium atoms and zirconium atoms with respect to the total solid content of the curable composition in the present invention is preferably 5 to 60% by mass and more preferably 10 to 50% by mass from the viewpoint of high refractive index and film properties. Preferably, 15 to 40% by mass is more preferable.

Component B: Curable Compound The curable composition of the present invention contains a curable compound as Component B.
The curable compound is a compound that is cured by at least one of heating, radical active species, cationic active species, and anionic active species.
Among these, a compound having an epoxy group, a compound having an oxetanyl group, and a polymerizable compound described below are preferable.

<Compound having epoxy group or oxetanyl group>
When the curable composition of the present invention is a positive photosensitive composition, the curable compound preferably contains a compound having an epoxy group and / or a compound having an oxetanyl group. It is more preferable to contain the compound which has the above epoxy groups, and / or the compound which has 2 or more oxetanyl groups in a molecule | numerator.
Further, when the curable composition of the present invention is a negative photosensitive composition and is cured by a cationic active species, it contains a compound having an epoxy group and / or a compound having an oxetanyl group as a polymerizable compound. It is preferable to contain a compound having two or more epoxy groups in the molecule and / or a compound having two or more oxetanyl groups in the molecule.
A compound having an epoxy group or oxetanyl group in the molecule reacts with an epoxy group or oxetanyl group by heating or reacts with an acid (such as a carboxylic acid) in the composition. In addition, coexistence with cationic active species causes cationic polymerization.
Specific examples of the compound having an epoxy group in the molecule include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, aliphatic epoxy resin, and epoxy group in the side chain. An acrylic resin etc. can be mentioned.
Acrylic resin is a polymer in which 70 mol% or more of the structural units are composed of the following structural units. The weight average molecular weight of the acrylic resin is preferably 3,000 to 300,000, and more preferably 7,000 to 50,000.

式中、Ｒ¹は、水素原子又はメチル基を表し、Ｒ²は、水素原子又は１価の有機基を表す。

In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² represents a hydrogen atom or a monovalent organic group.

In the formula, R ² represents a hydrogen atom or a monovalent organic group, and the monovalent organic group preferably comprises any of a hydrogen atom, a carbon atom, an oxygen atom, and a nitrogen atom.
The organic group preferably has 1 to 25 carbon atoms, and more preferably 1 to 15 carbon atoms.

These are available as commercial products. For example, JER152, JER157S70, JER157S65, JER806, JER828, JER1007 (manufactured by Mitsubishi Chemical Holdings Co., Ltd.) and the like are commercially available products described in paragraph No. 0189 of JP2011-221494A. EX-611, EX-612, EX-614, EX-614B, EX-622, EX-512, EX-521, EX-411, EX-421, EX-313, EX-314, EX-321, EX- 211, EX-212, EX-810, EX-811, EX-850, EX-851, EX-821, EX-830, EX-832, EX-841, EX-911, EX-941, EX-920, EX-931, EX-212L, EX-214L, EX-216L, X-321L, EX-850L, DLC-201, DLC-203, DLC-204, DLC-205, DLC-206, DLC-301, DLC-402 (above, manufactured by Nagase ChemteX Corporation), YH-300 YH-301, YH-302, YH-315, YH-324, YH-325 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.). These can be used alone or in combination of two or more.
Among these, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, acrylic resin and aliphatic epoxy resin having an epoxy group in the side chain are more preferable, and bisphenol A type epoxy resin, fat Particularly preferred are cyclic epoxy resins and acrylic resins having an epoxy group in the side chain.

As specific examples of the compound having an oxetanyl group, use of Aron Oxetane OXT-121, OXT-221, OX-SQ, PNOX (manufactured by Toagosei Co., Ltd.), an acrylic resin having an oxetanyl group in the side chain is used. Can do.
Moreover, it is preferable to use the compound containing an oxetanyl group individually or in mixture with the compound containing an epoxy group.

  Preferable specific examples of the acrylic resin having an epoxy group or oxetanyl group in the side chain include acrylic resins having the following structural units. In the structural units below, R represents a hydrogen atom or a methyl group.

<Polymerizable compound>
The curable composition of the present invention preferably contains the following polymerizable compound as Component B.
The polymerizable compound is not particularly limited, and either a radical polymerizable compound or a cationic polymerizable compound may be used, but a radical polymerizable compound is preferable from the viewpoint of curability. From the viewpoint of transparency, a cationically polymerizable compound is preferable.
The radically polymerizable compound is not particularly limited as long as it is a compound having at least one ethylenically unsaturated group, preferably a terminal ethylenically unsaturated group, and is appropriately selected from known ethylenically unsaturated compounds. The
Among these, component B preferably contains a polymerizable compound having 6 or more functional groups, component B-1: more preferably contains an ethylenically unsaturated compound having 6 or more functional groups, and urethane (meta) having 6 or more functional groups. More preferably, it includes an acrylate.

B-1: Ethylenically unsaturated compound having 6 or more functional groups The curable composition of the present invention preferably contains, as Component B, an ethylenically unsaturated compound having 6 or more functional components B-1. Examples of the ethylenically unsaturated compound having 6 or more functional groups include Component B-1-1: urethane (meth) acrylate having 6 or more functions, Component B-1-2: other ethylenically unsaturated compounds having 6 or more functions. The Among these, it is preferable to contain component B-1-1 as component B.
Hereinafter, Component B-1-1 and Component B-1-2 will be described.

Component B-1-1: Six or more functional urethane (meth) acrylate The curable composition of the present invention may contain, as Component B, component B-1-1: Six or more functional urethane (meth) acrylate. preferable.
The number of (meth) acryloxy groups in the hexafunctional or higher urethane (meth) acrylate is preferably 8 or more, more preferably 10 or more, and most preferably 12 or more. By adopting such a configuration, the effect of the present invention is more effectively exhibited.
Further, the upper limit of the number of the (meth) acryloxy groups is not particularly limited, but when it is not a polymer structure, it is preferably 50 or less, more preferably 30 or less, and 20 or less. Further preferred.
The curable composition of the present invention may contain only one type of hexafunctional or higher urethane (meth) acrylate, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

  Examples of the urethane (meth) acrylate having 6 or more functional groups that can be used in the present invention include urethane addition polymerizable compounds produced by using an addition reaction between an isocyanate and a hydroxyl group, Japanese Patent Application Laid-Open No. 51-37193, The urethane acrylates described in JP-B-2-32293 and JP-B-2-16765 are exemplified, and these descriptions are incorporated in the present specification.

The molecular weight of the hexafunctional or higher urethane (meth) acrylate is preferably 500 to 20,000, more preferably 650 to 6,000, and still more preferably 800 to 3,000, from the viewpoint of cured film hardness.
By adopting such a configuration, the effect of the present invention is more effectively exhibited.

The (meth) acryloxy group in the urethane (meth) acrylate having 6 or more functional groups may be either an acryloxy group or a methacryloxy group or both, but is preferably an acryloxy group from the viewpoint of curability.
The number of urethane bonds in the urethane (meth) acrylate having 6 or more functional groups is not particularly limited, but is preferably 1 to 30, more preferably 1 to 20, and still more preferably 2 to 10. 2 to 5 is particularly preferable, and 2 or 3 is most preferable.
The hexafunctional or higher urethane (meth) acrylate is preferably a hexafunctional or higher aliphatic urethane (meth) acrylate.
Moreover, it is preferable that hexafunctional or more urethane (meth) acrylate has an isocyanuric ring structure.
The hexafunctional or higher urethane (meth) acrylate is a compound comprising a core portion having one or more urethane bonds and a terminal portion bonded to the core portion and having one or more (meth) acryloxy groups. Preferably, the core part is more preferably a compound in which two or more of the terminal parts are bonded, more preferably a compound in which 2 to 5 terminal parts are bonded to the core part. A compound in which 2 or 3 of the above terminal moieties are bound to the core part is particularly preferred.

The hexa- or more functional urethane (meth) acrylate is preferably a compound having at least a group represented by the following formula Be-1 or formula Be-2, and a compound having at least a group represented by the following formula Be-1. It is more preferable that Further, the hexafunctional or higher urethane (meth) acrylate is a compound having two or more groups selected from the group consisting of a group represented by the following formula Be-1 and a group represented by the formula Be-2. More preferred.
Moreover, it is preferable that the said terminal part in 6 or more functional urethane (meth) acrylate is group represented by the following formula Be-1 or Formula Be-2.

  In Formula Be-1 and Formula Be-2, R represents an acryl group or a methacryl group each independently, and a wavy line portion represents a bonding position with another structure.

Further, the urethane (meth) acrylate having 6 or more functional groups is preferably a compound having at least a group represented by the following formula Bc-1 or Bc-2, and at least a group represented by the following formula Bc-1 More preferably, it is a compound having
Moreover, it is preferable that the said core part in urethane (meth) acrylate more than hexafunctional is group represented by the following formula Bc-1 or formula Bc-2.

In Formula Bc-1 and Formula Bc-2, L ^{1 to} L ⁴ each independently represent a divalent hydrocarbon group having 2 to 20 carbon atoms, and a wavy line represents a bonding position with another structure.
L ^{1 to} L ⁴ are each independently preferably an alkylene group having 2 to 20 carbon atoms, more preferably an alkylene group having 2 to 10 carbon atoms, and an alkylene group having 4 to 8 carbon atoms. Is more preferable. The alkylene group may have a branched or ring structure, but is preferably a linear alkylene group.
Further, the urethane (meth) acrylate having 6 or more functional groups was selected from the group consisting of a group represented by Formula Bc-1 or Formula Bc-2 and a group represented by Formula Be-1 and Formula Be-2. Particularly preferred is a compound in which 2 or 3 groups are bonded.

  Examples of urethane (meth) acrylates having 6 or more functionalities that are preferably used in the present invention are shown below, but it goes without saying that the present invention is not limited to these.

  Commercially available products of 6 or more functional urethane (meth) acrylates are U-6HA, UA-1100H, U-6LPA, U-15HA, U-6H, U-10HA, available from Shin-Nakamura Chemical Co., Ltd. U-10PA, UA-53H, UA-33H (all are registered trademarks) and UA-306H, UA-306T, UA-306I, UA-510H, available from BASF available from Kyoeisha Chemical Co., Ltd. Examples include Laromer UA-9048, UA-9050, PR9052, EBECRYL 220, 5129, 8301, KRM8200, 8200AE, and 8452 available from Daicel Ornex Co., Ltd.

Component B-1-2: Other hexafunctional or higher ethylenically unsaturated compound In the present invention, as Component B, Component B-1-2: Other hexafunctional or higher ethylenically unsaturated compound may be contained. . Component B-1-2 may be a polymer (for example, a molecular weight of 2,000 or more) or a monomer (for example, a molecular weight of less than 2,000, preferably a molecular weight of 100 or more and less than 2,000). The monomer is preferable.
Component B-1-2 is preferably a (meth) acrylate compound, and examples thereof include dipentaerythritol hexa (meth) acrylate.

B-2: Ethylenically unsaturated compound having less than 6 functions The curable composition of the present invention contains not only the above-described 6 or more functional ethylenically unsaturated compounds, but also an ethylenically unsaturated compound having less than 6 functions. Also good.
The B-2 is not particularly limited as long as it is a compound having less than 6 ethylenically unsaturated groups, and can be appropriately selected depending on the purpose. Examples include ester compounds, amide compounds, urethane compounds, and other compounds.
The compound having an ethylenically unsaturated group may be either a monofunctional ethylenically unsaturated compound or a 2-5 functional polyfunctional ethylenically unsaturated compound, but a 2-5 functional polyfunctional ethylenically unsaturated compound. It is preferable to contain a saturated compound, and it is more preferable that it is a 2-5 functional polyfunctional ethylenically unsaturated compound.

  Examples of the ester compound include (meth) acrylic acid ester, itaconic acid ester, crotonic acid ester, isocrotonic acid ester, maleic acid ester, and other ester compounds. Among these, polyfunctional (meth) acrylic acid ester (polyfunctional (meth) acrylate compound) and the like are preferable.

  Examples of the polyfunctional (meth) acrylate compound include polyethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, Tetramethylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate , Dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, sorbitol tri (meth) acrylate, sorbitol tetra Meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, hexanediol di (meth) acrylate. Among these, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol penta (meth) acrylate are particularly preferable.

  Other examples of the polyfunctional (meth) acrylic acid ester include those obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol such as glycerin, trimethylolethane, bisphenol A, and the like, and 48-41708, JP-B-50-6034, JP-A-51-37193, urethane acrylates, JP-A-48-64183, JP-B-49-43191, and JP-B-52 -30490, polyester acrylates, epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid, (meth) acrylic acid esters and urethanes described in JP-A-60-258539 Examples thereof include (meth) acrylate and vinyl ester.

  Other polyfunctional ethylenically unsaturated compounds include, for example, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, Japan Adhesion Association Vol. 20, no. 7, photocurable monomers and oligomers described on pages 300 to 308, and the like.

Examples of the amide compound include an amide (monomer) of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound. Specific examples include methylene bis (meth) acrylamide, 1,6-hexamethylene. Examples thereof include bis (meth) acrylamide, diethylenetriamine tris (meth) acrylamide, and xylylene bis (meth) acrylamide, and (meth) acrylic acid amide described in JP-A-60-258539.
Examples of the urethane compound include urethane chain polymerizable compounds produced by an addition reaction between isocyanate and a 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.
Specific examples include urethane acrylates as described in JP 2011-126921 A, JP 51-37193 A, JP 2-32293 A, and JP 2-16765 A. These descriptions are incorporated herein.

Examples of other polyfunctional ethylenically unsaturated compounds include allyl compounds and alkenyl group-containing compounds described in JP-A-60-258539 and International Publication No. 2010/050580.
Specifically, 1,2-divinylbenzene, 1,4-divinylbenzene, 1,2-diallylbenzene, 1,3-diallylbenzene, 1,4-diallylbenzene, 1,3,5-trivinylbenzene, 1,3,5-triallylbenzene, 1,2,4,5-tetraallylbenzene, hexallylbenzene, divinyltoluene, bisphenol A diallyl ether, 1,2-diallyloxybenzene, 1,4-diallyloxybenzene , Diallyl terephthalate, diallyl isophthalate, 1,4-bis (dimethylvinylsilyl) benzene, divinylmethylphenylsilane, divinyldiphenylsilane, diallyldiphenylsilane, and the like.

Monofunctional ethylenically unsaturated compounds include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid and their salts, (meth) acrylates, (meth) acrylamides, And monofunctional ethylenically unsaturated compounds such as (meth) acrylonitriles and styrenes.
In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having an nucleophilic substituent such as a hydroxyl group, an amino group or a mercapto group and an isocyanate or an epoxy, and a monofunctional or polyfunctional carboxylic acid A dehydration condensation reaction product of

Furthermore, isocyanato groups (isocyanate groups), addition reaction products of unsaturated carboxylic acid esters or amides having an electrophilic substituent such as an epoxy group and alcohols, amines, thiols, halogeno groups, and tosyloxy A substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a group and an alcohol, amine or thiol is also suitable.
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.
There is no restriction | limiting in particular as a monofunctional ethylenically unsaturated compound, In addition to the compound illustrated above, well-known various compounds can be used, For example, the compound etc. which are described in Unexamined-Japanese-Patent No. 2009-204962 are used. May be.

  Furthermore, as monofunctional ethylenically unsaturated compounds, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, carbitol (meth) acrylate, cyclohexyl (meth) Preferred are (meth) acrylic acid derivatives such as acrylate, benzyl (meth) acrylate, and epoxy (meth) acrylate, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, and derivatives of allyl compounds such as allyl glycidyl ether. Used.

The content of Component B-1 with respect to 100 parts by mass of Component B is preferably 70 to 100 parts by mass, more preferably 75 to 100 parts by mass, and 90 to 100 parts by mass. More preferred is 95 to 100 parts by mass. The effect of this invention is more effectively exhibited as it is the said aspect.
In the curable composition of the present invention, the content of Component B is 5 to 85% by mass with respect to the total solid content of the curable composition from the viewpoint of achieving both the refractive index of the cured film and the developability. Is preferable, it is more preferable that it is 10-82.5 mass%, and it is still more preferable that it is 15-80 mass%.

Component C: Solvent The curable composition of the present invention contains a solvent as Component C, Component C has Component C-1, a viscosity at 20 ° C. of 50 mPa · s to 200 mPa · s, and the surface. Containing at least one organic solvent having a tension of 30 mN / m or more and 41 mN / m or less and, as Component C-2, at least one organic solvent having a viscosity at 20 ° C. of less than 50 mPa · s, and The content of Component C-1 is 20 to 95% by mass with respect to the total mass of Component C.
The curable composition of the present invention is preferably prepared as a solution or dispersion in which essential components and optional components described below are dissolved or dispersed in a solvent.
Hereinafter, component C-1 and component C-2 will be described.

Component C-1: At least one organic solvent having a viscosity at 20 ° C. of 50 mPa · s or more and 200 mPa · s or less and a surface tension of 30 mN / m or more and 41 mN / m or less The curable composition of the present invention is And component C-1. Component C-1 is an organic solvent having a relatively high viscosity and a low surface tension. By containing Component C-1, a composition having a low surface tension can be obtained while increasing the viscosity of the entire composition.

The viscosity of Component C-1 at 20 ° C. is 50 mPa · s or more and 200 mPa · s or less. When the viscosity at 20 ° C. is 50 mPa · s or less, the viscosity of the composition as a whole is low, and it does not have printability. On the other hand, if it exceeds 200 mP · s, the viscosity of the composition as a whole becomes too high, and similarly, it does not have printability.
The viscosity of Component C-1 at 20 ° C. is preferably 80 to 200 mPa · s.
The viscosity of Component C-1 is measured at 20 ° C. according to JIS K 2241 using a Dunui surface tension meter and the tension of the liquid surface and the platinum ring with the steel wire tension as the index.

The surface tension of Component C-1 is 30 mN / m or more and 41 mN / m or less. When the surface tension of Component C-1 exceeds 40 mN / m, the surface tension of the composition as a whole increases, causing repelling. On the other hand, if it is less than 30 mN / m, the surface tension is too low, so that wetting spreads too much and the back of the liquid on the substrate occurs.
The surface tension of component C is preferably 30 to 41 mN / m, and more preferably 32 to 36 mN / m.
The surface tension of the component C is a value measured at 20 ° C., specifically, a RE85L viscometer manufactured by Toki Sangyo Co., Ltd., using a cone of 1 ° 34 ′ × R24 and a liquid temperature of 20 Measured at ° C.
Component C-1 has a boiling point of preferably 100 ° C. to 300 ° C., more preferably 120 ° C. to 250 ° C., and still more preferably 200 ° C. to 250 ° C. from the viewpoint of applicability.

In the curable composition of this invention, content of component C-1 is 20-95 mass% with respect to the total mass of component C, content of component C-1 is with respect to the total mass of component C If it is less than 20% by mass, the desired viscosity as the curable composition cannot be obtained, and the printability is poor. Moreover, when content of the component C exceeds 95 mass%, a viscosity may become high too much.
The content of Component C-1 is preferably 20 to 95% by mass and more preferably 50 to 95% by mass with respect to the total mass of Component C.
In addition, component C-1 may be used individually by 1 type, and may use 2 or more types together. When using 2 or more types together as component C-1, it will suffice if the total content is reached.

Component C-1 is not particularly limited as long as it is a solvent having the above viscosity and surface tension, but is preferably a terpene compound having a hydroxy group and / or an acetoxy group, such as terpineol, dihydroterpineol, 4- (acetyl). Oxy) -α, α, 4-trimethylcyclohexanemethanol acetate and at least selected from the group consisting of 2- [1-methyl-1- (4-methyl-3-cyclohexen-1-yl) ethoxy] ethanol It is more preferable to contain one.
Terpineol has the following α-, β-, and γ- isomers, and is marketed by Nippon Fragrance Chemicals Co., Ltd. and Nippon Terpene Chemical Co., Ltd. (viscosity 54 mPa · s, surface tension 38 mN / m). ).

  In addition, dihydroterpineol has the following two compounds (1-hydroxy-p-menthane and 8-hydroxy-p-menthane), and dihydroterpineol (viscosity 83 mPa · s, surface) from Nippon Terpene Chemical Co., Ltd. (Tension 36 mN / m) and Tersolve DTO-210 (viscosity 72 mPa · s, surface tension 36 mN / m).

  4- (acetyloxy) -α, α, 4-trimethylcyclohexanemethanol acetate is a compound represented by the following formula C-3, but a compound represented by the formula C-1 and a formula C-2 As a mixture with a compound represented by, for example, Tersolve THA-90 (viscosity 144 mPa · s, surface tension 32.8 mN / m), Tersolve THA-70 (viscosity 144 mPa · s, surface tension) from Nippon Terpene Chemical Co., Ltd. 32.9 mN / m).

  2- [1-Methyl-1- (4-methyl-3-cyclohexen-1-yl) ethoxy] ethanol is a compound represented by the following formula. For example, Tersolve TOE-100 from Nippon Terpene Chemical Co., Ltd. (Viscosity 62 mPa · s, surface tension 40.6 mN / m).

  Among these, in the present invention, terpineol, dihydroterpineol, tersolve THA-90, tersolve THA-70 and tersolve TOE-100 are preferable, dihydroterpineol, tersolve THA-90 and tersolve THA-70 are more preferable, and tersolve THA-90. Tersolve THA-70 is more preferred.

Component C-2: Organic solvent having a viscosity at 20 ° C. of less than 50 mPa · s In the present invention, the component C-2 contains an organic solvent having a viscosity at 20 ° C. of less than 50 mPa · s. If the viscosity of Component C-2 exceeds 50 mPa · s, the viscosity of the composition as a whole will be too high, resulting in poor printability.
The viscosity of Component C-2 at 20 ° C. is preferably 10 mPa · s or less, more preferably 5 mPa · s or less, and still more preferably 3 mPa · s or less. Moreover, the lower limit is not particularly limited, but is preferably 0.5 mPa · s or more.

As the component C-2 used in the curable composition of the present invention, a known solvent can be used, and alcohols, ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates. , Propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, butylene glycol diacetates, dipropylene Glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates, esters, ketones Amides, lactones and the like. As other specific examples, reference can be made to paragraph 0062 of JP-A-2009-098616.
Among these solvents, preferred specific examples include butanol, tetrahydrofurfuryl alcohol, phenoxyethanol, 1,3-butylene glycol diacetate, diethylene glycol methyl ethyl ether, propylene glycol monomethyl ether acetate, acetylacetone, and ethyl lactate. , Butanol, 1,3-butylene glycol diacetate, diethylene glycol methyl ethyl ether, acetylacetone, and ethyl lactate are particularly preferred.
Component C-2 may be used alone or in combination of two or more.

  Component C-2 has a boiling point of preferably 100 ° C to 300 ° C, more preferably 120 ° C to 250 ° C, and still more preferably 120 ° C to 200 ° C, from the viewpoint of applicability.

  The content of the 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 8:92 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.

(Compound having a coordinating group)
In the present invention, when a1 and / or a2 is used as component A, it is preferable to contain a compound having a titanium and / or zirconium coordination group.
The “titanium and / or zirconium coordination group” in the present invention is a group capable of forming a coordination bond with a titanium atom and / or a zirconium atom, and is coordinated with only one of a titanium atom and a zirconium atom. A bond may be formed, or a coordinate bond may be formed with both a titanium atom and a zirconium atom.
The coordination formed by the titanium and / or zirconium coordination group is any of monodentate coordination (monodentate coordination), bidentate coordination, tridentate coordination, and tetradentate coordination or more. However, the coordination group is preferably a monodentate or bidentate coordination group, and more preferably a bidentate coordination group.
Furthermore, the titanium and / or zirconium coordinating group is preferably a group that coordinates to a titanium atom and / or a zirconium atom and becomes a neutral ligand on the titanium atom and / or the zirconium atom.
When a compound having at least a titanium and / or zirconium coordinating group is coordinated to a1 and / or a2, the energy level of the d orbital of the coordinated titanium atom or zirconium atom is split. Therefore, the presence or absence of coordination can be determined by observing the splitting of energy levels.
Examples of a method for confirming whether or not a titanium and / or zirconium coordination group include a method for observing the presence or absence of coordination. As a specific observation method for the presence or absence of coordination, a known observation method can be used, and examples thereof include spectroscopic techniques and electron spin resonance (ESR).

The titanium and / or zirconium coordinating group in the present invention is preferably a group having an oxygen atom, more preferably a group having two or more oxygen atoms, from the viewpoint of the stability of the composition and film physical properties. More preferably, the oxygen atom is more preferably a group having at least a structure in which two oxygen atoms are bonded to each other via 2 to 4 atoms, and the two oxygen atoms are the other atoms having 3 or 4 atoms. Particularly preferred is a group having at least a structure bonded therebetween. In addition, at least one of the oxygen atoms is preferably a carbonyl group or an oxygen atom of a carbonyl group in an ester structure.
In addition, the titanium and / or zirconium coordinating group in the present invention is preferably a group capable of coordinating with a titanium atom and / or a zirconium atom by an oxygen atom from the viewpoint of the stability of the composition and film properties.

  Examples of the titanium and / or zirconium coordinating group in the present invention include 1,2-diketone structure, 1,3-diketone structure, 1,4-diketone structure, α-hydroxyketone structure, α-hydroxyester structure, α- It is preferably a group having at least one structure selected from the group consisting of a ketoester structure, a β-ketoester structure, a malonic acid diester structure, a fumaric acid diester structure, and a phthalic acid diester structure, and a 1,2-diketone structure A group having at least one structure selected from the group consisting of 1,3-diketone structure, α-hydroxyketone structure, α-hydroxyester structure, α-ketoester structure, β-ketoester structure, and phthalic acid diester structure It is more preferable that 1,3-diketone structure, α-hydroxyketone structure, β More preferably, it is a group having at least one structure selected from the group consisting of a ketoester structure and a phthalic acid diester structure, and is based on a 1,3-diketone structure, an α-hydroxyketone structure, and a β-ketoester structure. A group having at least one structure selected from the group consisting of 1,3-diketone structure and a group having at least one structure selected from the group consisting of β-ketoester structures is particularly preferred. Is most preferred. It is excellent in the refractive index and storage stability of the cured film obtained as it is the said aspect.

  As the titanium or zirconium coordinating group in the present invention, a group having any of the structures represented by the following formulas b-1 to b-5 is preferable, and the following formula b-1, formula b-2, formula b -3 or a group having a structure represented by the formula b-5 is more preferable, a group having a structure represented by the following formula b-1, formula b-2 or formula b-3 is more preferable, and the following formula b- A group having a structure represented by 1 or formula b-2 is particularly preferred.

In Formula b-1 to Formula b-5, L ¹ and L ² each independently represent a single bond or an alkylene group having 1 or 2 carbon atoms, and R ′ each independently represents an alkyl group, an alkoxy group, or a halogen atom. Represents an acyl group or an alkoxycarbonyl group, nb represents an integer of 0 to 4, and the wavy line represents a bonding position with another structure.

L ¹ and L ² are preferably methylene groups.
The carbon number of R ′ is preferably 0-20. R ′ is preferably independently an alkyl group, an alkoxy group or a halogen atom.
nb is preferably 0 or 1, and more preferably 0.

  Specific examples of the titanium or zirconium coordinating group include the following groups. Note that the wavy line represents the coupling position with another structure.

In the present invention, the compound having titanium and / or zirconium coordinating group may be added as Component B, or may be added as Component C. Although not particularly limited, it may be added as Component C. The addition as component C-2 is particularly preferred.
When added as Component B, the ethylenically unsaturated group is not particularly limited, but (meth) acryloxy group, (meth) acrylamide group, allyl group, styryl group, and vinyloxy group are preferably exemplified. ) An acryloxy group and an allyl group are more preferable, and a (meth) acryloxy group is particularly preferable.
As a compound having a titanium and / or zirconium coordination group and an ethylenically unsaturated group, from the viewpoint of developability, a (meth) acrylate compound having a 1,3-diketone structure or a β-ketoester structure, or phthalic acid An ethylenically unsaturated compound having a diester structure is preferable, and a (meth) acrylate compound having a 1,3-diketone structure or a β-ketoester structure is more preferable.
Moreover, the compound which has a titanium and / or a zirconium coordination group, and an ethylenically unsaturated group may be used individually by 1 type, or may use 2 or more types together.
From the viewpoint of chemical resistance of the cured film, the compound having the titanium and / or zirconium coordinating group and the ethylenically unsaturated group is a (meth) acrylate compound having titanium and / or zirconium coordinating group. The monofunctional (meth) acrylate compound having a titanium and / or zirconium coordinating group is more preferable, and the following compounds are more preferable.
Moreover, as an ethylenically unsaturated compound which has the said phthalic acid diester structure, a diallyl phthalate can be illustrated preferably.

In addition, as the compound having titanium and / or zirconium coordinating group having no ethylenically unsaturated group, 1,2-diketone compound, 1,3-diketone compound, 1,4-diketone compound, α-hydroxyketone Compound, α-hydroxy ester compound, α-keto ester compound, β-keto ester compound, malonic acid diester compound, fumaric acid diester compound or phthalic acid diester compound are preferable, 1,2-diketone compound, 1,3-diketone compound An α-hydroxyketone compound, an α-ketoester compound, a β-ketoester compound, or a phthalic acid diester compound, more preferably a 1,3-diketone compound, an α-hydroxyketone compound, or a β-ketoester compound, 1,3-diketone compound or β-ketoe Ether compounds are particularly preferred.
Specific examples of the compound having titanium and / or zirconium coordinating group having no ethylenically unsaturated group include the following compounds.

  Among these, acetylacetone (2,4-pentadione), ethyl acetoacetate (ethyl 3-oxobutyrate), or ethyl lactate is preferable, and acetylacetone or ethyl acetoacetate is particularly preferable. These correspond to component C-2.

  It is preferable that content of the compound which has these coordinated groups is 15-140 mass parts with respect to 100 mass parts of total content of a1 and a2.

Component D: Photopolymerization Initiator The curable composition of the present invention preferably contains a photopolymerization initiator as Component D. When the curable composition of the present invention is a negative photosensitive composition, it is particularly preferable to contain a photopolymerization initiator.
The photopolymerization initiator preferably contains a photoradical polymerization initiator.
The photopolymerization initiator that can be used in the present invention is a compound that can initiate and accelerate the polymerization of a polymerizable compound such as a compound having an ethylenically unsaturated group by actinic rays.
“Actinic ray” is not particularly limited as long as it is an active energy ray that can give energy capable of generating a starting species from component D by irradiation, and is widely α-ray, γ-ray, X-ray, It includes 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 preferable, and an alkyl group or a halogen atom is more preferable. 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. Examples include compounds described in Hutt “Journal of Heterocyclic Chemistry” 1 (No. 3), (1970), and particularly, oxazole compounds substituted with a trihalomethyl group and s-triazine compounds.

  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, and 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 parts by mass, and 1 to 20 parts by mass with respect to 100 parts by mass of the total solid content in the composition. More preferably, it is 1-10 mass parts, More preferably, it is 2-5 mass parts.

-Sensitizer-
A sensitizer may 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 sensitizer in the excited state is capable of initiating / promoting polymerization due to the interaction with the component D such as electron transfer, energy transfer, and heat generation.
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.

Component F: 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.
Examples of the surfactant that can be used in the present invention include commercially available products, such as Megafac F142D, F172, F173, F176, F177, F183, F479, F482, F554, and F780. 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 (manufactured by Sumitomo 3M Limited), Asahi Guard AG7105, 70
00, 950, 7600, Surflon S-112, S-113, S-131, S-141, S-145, S-382, SC-101, SC-102, SC-103 SC-104, SC-105, SC-106 (manufactured by Asahi Glass Co., Ltd.), F-top EF351, 352, 801, 802 (manufactured by Mitsubishi Materials Electronics Chemical Co., Ltd.), Footage 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 parts by mass with respect to 100 parts by mass in the total solid content of the curable composition. 01-2.0 mass parts is more preferable.

Component E: Mercapto Compound It is preferable that the curable composition of the present invention further contains a mercapto compound as Component E. By containing a mercapto compound, the storage stability is excellent, a cured product having a higher refractive index is obtained, and the cured product has excellent chemical resistance.
The mercapto compound is a compound having at least one mercapto group (—SH) in the molecule.
Examples of the mercapto compound include a monofunctional mercapto compound and a polyfunctional mercapto compound, and among them, a polyfunctional mercapto compound is preferable from the viewpoint of sensitivity, storage stability, and film physical properties.
The mercapto group in the mercapto compound may be a primary mercapto group, a secondary mercapto group, or a tertiary mercapto group. From the viewpoint of sensitivity and chemical resistance, It is preferably a secondary or secondary mercapto group, more preferably a secondary mercapto group. Moreover, from the viewpoint of storage stability, a secondary or tertiary mercapto group is preferable, and a secondary mercapto group is more preferable.
The molecular weight of the mercapto compound that can be used in the present invention is preferably from 100 to 2,000, more preferably from 200 to 1,000.
The number of mercapto groups in the mercapto compound that can be used in the present invention is not particularly limited, but is preferably 1 to 20, more preferably 2 to 10, and still more preferably 2 to 6. .

-Monofunctional mercapto compound-
The mercapto compound is preferably a monofunctional mercapto compound from the viewpoint of stability over time and solubility in a solvent. As the monofunctional mercapto compound, a low molecular compound having a molecular weight of 100 or more is preferable, specifically, the molecular weight is preferably 80 to 1,000, and more preferably 100 to 800.
Moreover, it is preferable that a monofunctional mercapto compound has a heterocyclic ring from a viewpoint of a sensitivity, and it is more preferable to have a thiazole structure.

Examples of monofunctional mercapto compounds include monofunctional aliphatic mercapto compounds, monofunctional aromatic mercapto compounds, etc. Specific examples include mercaptoethanol, mercaptopropanol, mercaptobutanol, mercaptopropanediol, mercaptobutanediol, hydroxy Benzenethiol and its derivatives, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 1-phenyl-1H-benzimidazol-2-thiol, 2-mercapto-4 (3H) -quinazoline, β- Examples include mercapto compounds such as mercaptonaphthalene.
Other examples include compounds described in paragraphs 0097 to 0098 of JP2011-65087A and compounds described in paragraphs 0086 to 0088 of JP2008-299211.

-Multifunctional mercapto compound-
The mercapto compound is preferably a polyfunctional mercapto compound from the viewpoint of sensitivity, storage stability, and film properties. Examples of the polyfunctional mercapto compound include a polyfunctional aliphatic mercapto compound and a polyfunctional aromatic mercapto compound.
In the present invention, the “polyfunctional mercapto compound” means a compound having two or more mercapto groups in the molecule. The polyfunctional thiol compound is preferably a low molecular compound having a molecular weight of 100 or more, specifically, preferably having a molecular weight of 100 to 1,500, more preferably 150 to 1,000.
The polyfunctional mercapto compound preferably has 2 to 10 mercapto groups in the molecule, and more preferably 2 to 6 mercapto groups.
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 represents a hydrogen atom or an alkyl group, and A represents —CO— or —CH ₂ —.
As the polyfunctional mercapto compound, a compound having 2 to 6 groups represented by the formula e-1 is preferable, and a compound having 2 to 4 groups is more preferable.
The alkyl group in R in formula e-1 is a linear, branched or cyclic alkyl group, and the carbon number range is preferably 1 to 16, and more preferably 1 to 10. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an i-propyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, and a 2-ethylhexyl group. And a methyl group, an ethyl group, a propyl group or an i-propyl group is preferred.
R is preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, or an i-propyl group, and more preferably a methyl group or an ethyl group.

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

In formula e-2, R represents a hydrogen atom or an alkyl group, and A represents —CO— or —CH ₂ —. L represents an n-valent linking group, and n represents an integer of 2 to 6.

The alkyl group in R in Formula e-2 has the same meaning as R in Formula e-1, and the preferred range is also the same. n is preferably from 2 to 4.
L as the n-valent linking group in formula e-2 is a divalent linking group such as — (CH ₂ ) _m — (m represents an integer of 2 to 6), a trimethylolpropane residue, and the like. , — (CH ₂ ) _p — (p represents an integer of 2 to 6), a trivalent linking group such as an isocyanur ring, a tetravalent linking group such as a pentaerythritol residue, or a pentavalent linking group. Examples thereof include a linking group and a hexavalent linking group such as a dipentaerythritol residue.

Specific examples of the polyfunctional mercapto compound include, for example, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), Dipentaerythritol hexakis (3-mercaptopropionate), pentaerythritol tetrakis (thioglycolate), pentaerythritol tetrakis (3-mercaptobutyrate), butanediol bis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane, 1,4-bis (3-mercaptobutyloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2, 4, 6 (1H, 3H 5H) - trione, and the like Suitable polyfunctional thiol compound.
Examples of commercially available products of polyfunctional mercapto compounds include Karenz MT (registered trademark) BD1, NR1 or PE1 (manufactured by Showa Denko KK), TEMPIC (manufactured by SC Organic Chemical Co., Ltd.), and the like.

Other specific examples include the compounds described in paragraphs 0165 to 0167 of JP2012-14052A.
Examples of the aromatic mercapto compound include compounds described in paragraphs 0021 to 0022 of International Publication No. 2010/050580. Of these, 4,4′-thiobisbenzenethiol is preferred.

  Moreover, as an aromatic mercapto compound, the compound represented by Formula e-3 is mentioned preferably.

In the formula ^e-3, X e represents N or C atoms, Y ^e represents N or C, S, O atoms, L ^e represents a single bond or a divalent organic group, A ^e is, X ^e = C—Ye represents an atomic group that forms an aromatic ring together with ^e . The aromatic ring formed by A ^e may have a substituent such as a hydroxyl group, an ether group, an ester group, an amino group, an amide group, a nitro group, a cyano group, and the one drawn in the formula May have another mercapto group.

  As an aromatic mercapto compound, for example, benzenethiol, 4-acetamidobenzenethiol, 4-tert-butylbenzenethiol, 2-naphthalenethiol, 2-aminobenzenethiol, 4-aminobenzenethiol, 4- (dimethylamino) benzene Thiol, 2-mercaptothiazole, 2-mercaptobenzothiazole, triphenylmethanethiol, 5-mercapto-1-phenyl-1H-tetrazole, 2-mercaptopyridine, 2-mercapto-5-methyl-1,3,4-thiadiazole Monofunctional aromatic mercapto compounds such as 2-mercapto-1,3,4-thiadiazole, 2-amino-5-mercapto-1,3,4-thiadiazole,

  1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis (mercaptomethyl) benzene, 1,3-bis (mercaptomethyl) benzene, 1,4- Bis (mercaptomethyl) benzene, 1,3-bis (mercaptoethyl) benzene, 1,4-bis (mercaptoethyl) benzene, 1,2-bis (mercaptomethoxy) benzene, 1,3-bis (mercaptomethoxy) benzene 1,4-bis (mercaptomethoxy) benzene, 1,2-bis (mercaptoethoxy) benzene, 1,3-bis (mercaptoethoxy) benzene, 1,4-bis (mercaptoethoxy) benzene, 1,2,3 -Trimercaptobenzene, 1,2,4-trimercaptobenzene, 1,3,5-trimercaptoben 1,2,3-tris (mercaptomethyl) benzene, 1,2,4-tris (mercaptomethyl) benzene, 1,3,5-tris (mercaptomethyl) benzene, 1,2,3-tris (mercapto) Ethyl) benzene, 1,2,4-tris (mercaptoethyl) benzene, 1,3,5-tris (mercaptoethyl) benzene, 1,2,3-tris (mercaptomethoxy) benzene, 1,2,4-tris (Mercaptomethoxy) benzene, 1,3,5-tris (mercaptomethoxy) benzene, 1,2,3-tris (mercaptoethoxy) benzene, 1,2,4-tris (mercaptoethoxy) benzene, 1,3,5 -Tris (mercaptoethoxy) benzene, 1,2,3,4-tetramercaptobenzene, 1,2,3,5-tetramercap Benzene, 1,2,4,5-tetramercaptobenzene, 1,2,3,4-tetrakis (mercaptomethyl) benzene, 1,2,3,5-tetrakis (mercaptomethyl) benzene, 1,2,4 5-tetrakis (mercaptomethyl) benzene, 1,2,3,4-tetrakis (mercaptoethyl) benzene, 1,2,3,5-tetrakis (mercaptoethyl) benzene, 1,2,4,5-tetrakis (mercapto) Ethyl) benzene, 1,2,3,4-tetrakis (mercaptoethyl) benzene, 1,2,3,5-tetrakis (mercaptomethoxy) benzene, 1,2,4,5-tetrakis (mercaptomethoxy) benzene, 1 , 2,3,4-Tetrakis (mercaptoethoxy) benzene, 1,2,3,4-tetrakis (mercaptoethoxy) Benzene, 1,2,4,5-tetrakis (mercaptoethoxy) benzene, 2,2'-dimercaptobiphenyl, 4,4'-dimercaptobiphenyl, 4,4'-dimercaptobibenzyl, 2,5-toluene Dithiol, 3,4-toluenedithiol, 1,4-naphthalenedithiol, 1,5-naphthalenedithiol, 2,6-naphthalenedithiol, 2,7-naphthalenedithiol, 2,4-dimethylbenzene-1,3-dithiol, 4,5-dimethylbenzene-1,3-dithiol, 9,10-anthracene dimethanethiol, 1,3-di (p-methoxyphenyl) propane-2,2-dithiol, 1,3-diphenylpropane-2, 2-dithiol, phenylmethane-1,1-dithiol, 2,4-di (p-mercaptophenyl) pen 1,2-bis (mercaptomethylthio) benzene, 1,3-bis (mercaptomethylthio) benzene, 1,4-bis (mercaptomethylthio) benzene, 1,2-bis (mercaptoethylthio) benzene, 1,3 -Bis (mercaptoethylthio) benzene, 1,4-bis (mercaptoethylthio) benzene, 1,2,3-tris (mercaptomethylthio) benzene, 1,2,4-tris (mercaptomethylthio) benzene, 1,3 , 5-Tris (mercaptomethylthio) benzene, 1,2,3-tris (mercaptoethylthio) benzene, 1,2,4-tris (mercaptoethylthio) benzene, 1,3,5-tris (mercaptoethylthio) Benzene, 1,2,3,4-tetrakis (mercaptomethylthio) benzene, 1,2,3, Tetrakis (mercaptomethylthio) benzene, 1,2,4,5-tetrakis (mercaptomethylthio) benzene, 1,2,3,4-tetrakis (mercaptoethylthio) benzene, 1,2,3,5-tetrakis (mercapto) Ethylthio) benzene, 1,2,4,5-tetrakis (mercaptoethylthio) benzene, 4,4'-thiobisbenzenethiol, 2,5-dimercapto-1,3,4-thiadiazole, 2,6-di- Examples thereof include polyfunctional aromatic mercapto compounds such as mercaptopurine and 1,3,5-triazine-2,4,6-trithiol.

Only one type of mercapto compound may be used, or two or more types may be used in combination.
The mercapto compound is preferably a mercapto compound having an aromatic ring from the viewpoint of refractive index.
Furthermore, the mercapto compound preferably has a polar functional group such as an ester group, a thioester group, a hydroxyl group, an amide group, an ether group or a thioether group in the molecule from the viewpoint of developability.
The content of the mercapto compound is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass, and more preferably 1 to 10 parts by mass with respect to the total solid content of the curable composition from the viewpoint of film properties. Is more preferable.

Component G: Alkoxysilane Compound The composition of the present invention may contain an alkoxysilane compound as an adhesion improver. When an alkoxysilane compound is used, the adhesion between the film formed of the curable composition of the present invention and the substrate is improved, or the taper angle between the film formed of the curable composition of the present invention and the substrate is adjusted. can do.
The alkoxysilane compound that can be used in the composition of the present invention includes an inorganic material as a base material, for example, a silicon compound such as silicon, silicon oxide, or silicon nitride, a metal such as gold, copper, molybdenum, titanium, or aluminum, and an insulating film. It is preferable that it is a compound which improves adhesiveness. Specifically, a known silane coupling agent or the like is also effective.
Preferred examples of the silane coupling agent include alkoxysilane compounds having an epoxy group or a (meth) acryloxy group.
Examples of the silane coupling agent include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrialkoxysilane, and γ-glycidoxy. Propyl dialkoxysilane, γ-methacryloxypropyltrialkoxysilane, γ-methacryloxypropyl dialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyl Examples include trialkoxysilane, vinyltrialkoxysilane, and 3-acryloxypropyltrimethoxysilane. Of these, γ-glycidoxypropyltrialkoxysilane, γ-methacryloxypropyltrialkoxysilane, and 3-acryloxypropyltrimethoxysilane are more preferable.
The alkoxysilane compound that can be used in the curable composition of the present invention is not particularly limited, and known compounds can be used.

An alkoxysilane compound can be used individually by 1 type or in combination of 2 or more types.
When the curable composition of the present invention contains an alkoxysilane compound, the content of the alkoxysilane compound is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the total solid content in the curable composition, 0.5-20 mass parts is more preferable. Moreover, 0.1-20 mass parts is preferable with respect to 100 mass parts of component B, and 0.5-10 mass parts is more preferable.

Component H: 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.
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.

Component I: 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.

Component J: Other metal oxide particles The curable composition of the present invention contains other metal oxide particles that do not contain titanium atoms and zirconium atoms for the purpose of adjusting the refractive index and light transmittance. be able to. The metal of the metal oxide particles includes semimetals such as B, Si, Ge, As, Sb, and Te.
Preferred metal oxide particles include Be, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Gd, Tb, Dy, Yb, Lu, Hf, Nb, Mo, W, Zn, B, Al, Oxide particles containing atoms such as Si, Ge, Sn, Pb, Sb, Bi, and Te are preferable, and zinc oxide, indium / tin oxide, and antimony / tin oxide are more preferable.

  From the viewpoint of transparency of the curable composition, the average primary particle size of the other 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 longest side is the diameter.

Other metal oxide particles may be used alone or in combination of two or more.
The content of other 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, and the like. However, it is preferable to set it as 0-50 mass% with respect to the total solid of the curable composition of this invention, It is more preferable to set it as 1-40 mass%, It is still more preferable to set it as 2-30 mass%. preferable.

  In the present invention, the other metal oxide particles can be used as a dispersion prepared by mixing and dispersing in a suitable dispersant and solvent using a mixing device such as a ball mill or a rod mill.

-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 fluorene compound, a dispersant, 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.

<Polymer having a structural unit having a group in which an acid group is protected by an acid-decomposable group>
The curable composition of the present invention may contain a polymer having a structural unit having a group in which an acid group is protected with an acid-decomposable group.
In the present invention, the “structural unit having a group in which an acid group is protected by an acid-decomposable group” is also referred to as “(a1) a structural unit having a group in which an acid group is protected by an acid-decomposable group”.

The curable composition of the present invention may further contain a polymer other than a polymer having a structural unit having a group in which an acid group is protected with an acid-decomposable group.
It is preferable that the curable composition of this invention contains the polymer component containing the polymer which satisfy | fills at least one of following (1) and (2).
(1) (a1) a polymer having a structural unit having an acid group protected with an acid-decomposable group and (a2) a structural unit having a crosslinkable group (2) (a1) an acid group having an acid-decomposable group And a polymer having a structural unit having a group protected with (a2) a structural unit having a crosslinkable group The curable composition of the present invention further contains a polymer other than these. Also good.
It is preferable that the curable composition of this invention contains the component which satisfy | fills said (1) from a viewpoint of the transparency (haze) after hardening, and the remaining film rate of an unexposed part. In the present invention, a component satisfying the above (1) or a polymer having a structural unit having a crosslinkable group (a2) in the above (2) is treated as the above component B.

  As the “group in which the acid group is protected with an acid-decomposable group” in the present invention, those known as an acid group and an acid-decomposable group can be used, and are not particularly limited. Specific examples of the acid group preferably include a carboxyl group and a phenolic hydroxyl group. The acid-decomposable group is a group that is relatively easily decomposed by an acid (for example, an acetal such as an ester structure of a group represented by the formula a1-10 described later, a tetrahydropyranyl ester group, or a tetrahydrofuranyl ester group). A functional group) or a group that is relatively difficult to decompose by an acid (for example, a tertiary alkyl group such as a tert-butyl ester group or a tertiary alkyl carbonate group such as a tert-butyl carbonate group).

Among the groups in which the acid group is protected by an acid-decomposable group, the carboxyl group is a protected carboxyl group protected in the form of an acetal. From the viewpoint of storage stability of the curable composition. Furthermore, among the groups in which the acid group is protected with an acid-decomposable group, it is more preferable from the viewpoint of sensitivity that the carboxyl group is a protected carboxyl group protected in the form of an acetal represented by the following formula a1-10. In addition, when the carboxyl group is a protected carboxyl group protected in the form of an acetal represented by the following formula a1-10, the entire protected carboxyl group is-(C = O) -O-CR ¹⁰¹ R ¹⁰² ( OR ¹⁰³ ).

（式ａ１−１０中、Ｒ¹⁰¹及びＲ¹⁰²は、それぞれ独立に水素原子又はアルキル基を表し、ただし、Ｒ¹⁰¹とＲ¹⁰²とが共に水素原子の場合を除く。Ｒ¹⁰³は、アルキル基を表す。Ｒ¹⁰¹又はＲ¹⁰²と、Ｒ¹⁰³とが連結して環状エーテルを形成してもよい。）

(In formula a1-10, R ¹⁰¹ and R ¹⁰² each independently represent a hydrogen atom or an alkyl group, except that R ¹⁰¹ and R ¹⁰² are both hydrogen atoms. R ¹⁰³ represents an alkyl group. R ¹⁰¹ or R ¹⁰² and R ¹⁰³ may be linked to form a cyclic ether.)

In the formula a1-10, R ^{101 to} R ¹⁰³ each independently represent a hydrogen atom or an alkyl group, and the alkyl group may be linear, branched, or cyclic. Here, both R ¹⁰¹ and R ¹⁰² do not represent a hydrogen atom, and at least one of R ¹⁰¹ and R ¹⁰² represents an alkyl group.
The linear or branched alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms. Specifically, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, n Examples include -hexyl group, texyl group (2,3-dimethyl-2-butyl group), n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, and n-decyl group.

Among the above formulas A1-10, R ¹⁰¹ to R ¹⁰³ each independently represent a hydrogen atom or an alkyl group. The alkyl group may be linear, branched or cyclic. Here, both R ¹⁰¹ and R ¹⁰² do not represent a hydrogen atom, and at least one of R ¹⁰¹ and R ¹⁰² represents an alkyl group.
The linear or branched alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms. Specifically, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, n Examples include -hexyl group, texyl group (2,3-dimethyl-2-butyl group), n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, and n-decyl group.
The cyclic alkyl group preferably has 3 to 12 carbon atoms, more preferably 4 to 8 carbon atoms, and still more preferably 4 to 6 carbon atoms. Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, and an isobornyl group.

The alkyl group may have a substituent, and examples of the substituent include a halogen atom, an aryl group, and an alkoxy group. When it has a halogen atom as a substituent, R ¹⁰¹ , R ¹⁰² and R ¹⁰³ become a haloalkyl group, and when it has an aryl group as a substituent, R ¹⁰¹ , R ¹⁰² and R ¹⁰³ become an aralkyl group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among these, a fluorine atom or a chlorine atom is preferable.
Moreover, as said aryl group, a C6-C20 aryl group is preferable, More preferably, it is C6-C12, Specifically, a phenyl group, (alpha) -methylphenyl group, a naphthyl group etc. can be illustrated. Examples of the entire alkyl group substituted with an aryl group, that is, an aralkyl group, include a benzyl group, an α-methylbenzyl group, a phenethyl group, and a naphthylmethyl group.
As said alkoxy group, a C1-C6 alkoxy group is preferable, More preferably, it is C1-C4, and a methoxy group or an ethoxy group is still more preferable.
In the case where the alkyl group is a cycloalkyl group, the cycloalkyl group may have a linear or branched alkyl group having 1 to 10 carbon atoms as a substituent, and the alkyl group is directly In the case of a chain or branched alkyl group, it may have a cycloalkyl group having 3 to 12 carbon atoms as a substituent.
These substituents may be further substituted with the above substituents.

In Formula a1-10, when R ¹⁰¹ , R ^102, and R ¹⁰³ represent an aryl group, the aryl group preferably has 6 to 12 carbon atoms, and more preferably has 6 to 10 carbon atoms. The aryl group may have a substituent, and the substituent is preferably an alkyl group having 1 to 6 carbon atoms. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, a cumenyl group, and a 1-naphthyl group.
R ¹⁰¹ , R ¹⁰² and R ¹⁰³ can be bonded together to form a ring together with the carbon atom to which they are bonded. Examples of the ring structure when R ¹⁰¹ and R ¹⁰² , R ¹⁰¹ and R ¹⁰³ , or R ¹⁰² and R ¹⁰³ are bonded include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a tetrahydrofuranyl group, an adamantyl group, and the like. Examples thereof include a tetrahydropyranyl group.

In the above formula a1-10, it is preferable that any one of R ¹⁰¹ and R ¹⁰² is a hydrogen atom or a methyl group. For other polymers having a structural unit in which a specific acid group is protected with an acid-decomposable group, the acid group described in JP-A-2014-238438, paragraphs 0037 to 0101 is protected with an acid-decomposable group. A polymer having a structural unit having a group formed can also be preferably used.

<Photo acid generator>
The curable composition of the present invention may contain a photoacid generator. When the curable composition of the present invention is a positive photosensitive composition, it preferably contains a photoacid generator.
The photoacid generator used in the present invention is preferably a compound that reacts with actinic rays having a wavelength of 300 nm or more, preferably 300 to 450 nm, and generates an acid, but is not limited to its chemical structure. In addition, a photoacid generator that is not directly sensitive to an actinic ray having a wavelength of 300 nm or more can be used as a sensitizer as long as it is a compound that reacts with an actinic ray having a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. It can be preferably used in combination. The photoacid generator used in the present invention is preferably a photoacid generator that generates an acid having a pKa of 4 or less, more preferably a photoacid generator that generates an acid having a pKa of 3 or less, and an acid of 2 or less. Most preferred are photoacid generators that generate.

Examples of the photoacid generator include trichloromethyl-s-triazines, sulfonium salts and iodonium salts, quaternary ammonium salts, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. Among these, it is preferable to use an imide sulfonate compound or an oxime sulfonate compound from the viewpoint of sensitivity. These photoacid generators can be used singly or in combination of two or more. Specific examples of trichloromethyl-s-triazines, diaryliodonium salts, triarylsulfonium salts (for example, the following compounds), quaternary ammonium salts, and diazomethane derivatives include paragraph numbers 0083 to JP-A-2011-221494. The compounds described in 0088 and the compounds described in paragraph numbers 0013 to 0049 of JP 2011-105645 A can be exemplified, and the contents thereof are incorporated in the present specification. Specific examples of the imide sulfonate compound include compounds described in paragraph numbers 0065 to 0075 of WO2011 / 087011, and the contents thereof are incorporated in the present specification.
Specific examples of the oxime sulfonate compound include compounds described in paragraphs 0074 to 0102 of JP 2014-122972 A and paragraphs 0103 to 0133 of JP 2014-238438 A. Incorporated herein.

  In the curable composition of the present invention, the content of the photoacid generator is preferably 0.1 to 20 parts by mass, and 0.5 to 10 parts by mass with respect to 100 parts by mass of the total solid components in the curable composition. Part is more preferable, and 0.5 to 5 parts by mass is still more preferable. Only 1 type may be used for a photo-acid generator, and it can also use 2 or more types together.

<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 A curable composition can be prepared by dispersing. 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 with 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-process 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.

In the exposure step, when the curable composition is a negative photosensitive composition, a polymerization initiating species is generated from the photopolymerization initiator using actinic rays, and polymerization of a compound having an ethylenically unsaturated group is performed. It is preferable to perform the polymerization of the curable compound to cure at least a part of the curable composition from which the solvent has been removed.
In addition, when the curable composition is a positive photosensitive composition, it has a structural unit that has an acid group generated from a photoacid generator by actinic rays and the acid group is protected by an acid-decomposable group. By dissolving the protective group of the polymer to obtain a polymer having a structural unit having an acid group, the solubility in an aqueous developer is improved.
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 source, an excimer laser generator, and the like can be used, i-line (365 nm), h-line (405 nm). ) And actinic rays having a wavelength of 300 nm to 450 nm, such as 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, when a1 and / or a2 is used as component A, it is presumed that condensation of component A 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 is re-exposed (post-exposure) to the pattern-formed substrate with actinic rays, and then post-baked to cause condensation reaction between components A and / or photopolymerization remaining in the exposed portion. It is estimated that an initiator is generated from the initiator by thermal decomposition and functions as a catalyst for accelerating the cross-linking process, and film curing can be promoted. 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, a white LED, a multicolor LED such as blue, red, and green, a fluorescent lamp (cold cathode tube), and an organic EL can be used.
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, FIG. 2 (b) of International Publication No. 2012/141148, OGS type, TOL type, and other configurations (for example, FIG. 6 of JP 2013-164871 A).

  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.

(Measurement of surface tension)
The surface tension was measured at 20 ° C. with a Dunui surface tension meter according to JIS K2241.

(Measurement of viscosity)
Measured with a RE85L viscometer (rotor name; cone 1 °, 34 ′ × R24) manufactured by Toki Sangyo Co., Ltd. The liquid temperature was 20 ° C.

Various components used in Examples and Comparative Examples are as follows.
(Component A)
A-1: titanoxane, B-4, manufactured by Nippon Soda Co., Ltd., solid content 98% by mass
A-2: Titanium tetra n-butoxide, manufactured by Wako Pure Chemical Industries, Ltd. A-3: Zirconoxane, ZA-65, manufactured by Matsumoto Fine Chemical Co., Ltd., solid content 87% (butanol 13% by mass)
(Component B)
B-1: Urethane acrylate, 15 functional, U-15HA, manufactured by Shin-Nakamura Chemical Co., Ltd. B-2: Urethane acrylate, 15 functional, UA-32P, manufactured by Kowa Corporation B-3: Dipenta Erythritol hexaacrylate, DPHA, manufactured by Nippon Kayaku Co., Ltd. B-4: Pentaerythritol tetraacrylate, A-TMMT, manufactured by Shin-Nakamura Chemical Co., Ltd.

(Component C)
-C-1-1: Turpineol C (manufactured by Nippon Terpene Chemical Co., Ltd.)
C-1-2: dihydroterpineol (manufactured by Nippon Terpene Chemical Co., Ltd.)
C-1-3: Tersovrub DTO-210 (Nippon Terpene Chemical Co., Ltd.)
C-1-4: Tersolve THA-90 (manufactured by Nippon Terpene Chemical Co., Ltd.)
C-1-5: Tersolve THA-70 (manufactured by Nippon Terpene Chemical Co., Ltd.)
C-1-6: Tersolve TOE-100 (manufactured by Nippon Terpene Chemical Co., Ltd.)

(Comparative example)
C'-1-1: PGMEA (propylene glycol monomethyl ether acetate) (manufactured by Daicel Corporation)
C′-1-2: High Solve EDE (diethylene glycol diethyl ether) (manufactured by Toho Chemical Industry Co., Ltd.)
C′-1-3: MEDG (diethylene glycol ethyl methyl ether) (manufactured by Toho Chemical Industry Co., Ltd.)
C′-1-4: High Solve EPH (ethylene glycol monophenyl ether) (manufactured by Toho Chemical Industry Co., Ltd.)
C′-1-5: Tetrahydrofurfuryl alcohol (manufactured by Wako Pure Chemical Industries, Ltd.)
C′-1-6: dihydroterpinyl methyl ether (manufactured by Nippon Terpene Chemical Co., Ltd.)
C'-1-7: Tersolve MTPH (isobornyl cyclohexanol) (manufactured by Nippon Terpene Chemical Co., Ltd.)
C′-1-8: dihydroterpinyl acetate (manufactured by Nippon Terpene Chemical Co., Ltd.)
(Other)
C-2-1: High Solve EDE (diethylene glycol diethyl ether, viscosity at 20 ° C .: 1.47 mPa · s) (manufactured by Toho Chemical Industry Co., Ltd.)
C-2-2: Acetylacetone (viscosity at 20 ° C .: 0.6 mPa · s) (manufactured by Wako Pure Chemical Industries, Ltd.)

(Component D)
D-1: Irgacure CGI-242 (1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethane-1-one oxime-O-acetate, manufactured by Ciba Specialty Chemicals )
(Other)
KBM-5103: 3-acryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.

(Example 1)
<Preparation of curable composition>
Prepared as follows.
A-1: B-4 (Titanoxane, Nippon Soda Co., Ltd., solid content 98%): 2.60 parts B-1: Urethane acrylate (U-15HA, 15 functional, manufactured by Shin-Nakamura Chemical Co., Ltd.) ): 2.16 parts · B-2: urethane acrylate (UA-32P, 15-functional, manufactured by Kowa Co., Ltd.): 2.16 parts · C-1-1: terpineol C (manufactured by Nippon Terpene Chemical Co., Ltd.) : 80 parts · C-2-1: Hisolv EDE (manufactured by Toho Chemical Co., Ltd.): 10 parts · C-2-2: Acetylacetone (manufactured by Wako Pure Chemical Industries, Ltd.): 2.86 parts · D- 1: IRGACURE OXE-02 (manufactured by BASF): 0.30 part F-1: Megafac F-554 (perfluoroalkyl group-containing nonionic surfactant, manufactured by DIC Corporation): 0.004 part Ingredients with magnetic stirrer for 1 hour And 拌, filtered through a polytetrafluoroethylene filter with a pore size of 0.3 [mu] m, to obtain a curable composition of Example 1.

(Examples 2-6, Comparative Examples 1-9)
C-1-1 of Example 1 was changed into each solvent of Table 1, and the curable composition was obtained like Example 1 except having changed the addition amount according to Table 1.
(Example 7)
A curable composition was obtained in the same manner as in Example 2 except that B-1 and B-2 in Example 2 were each changed to B-3.

(Example 8)
A curable composition was obtained in the same manner as in Example 4 except that the amount of A-1 added was changed to 3.25 parts in Example 4.

Example 9
A curable composition was obtained in the same manner as in Example 4 except that the amount of Telsolve THA-90 added was changed to 60 parts.

(Example 10)
A curable composition was obtained in the same manner as in Example 4 except that A-1 was changed to A-2.

(Example 11)
A curable composition was obtained in the same manner as in Example 4 except that A-1 was changed to A-3 and the amounts of C-1 and C-2-1 added were changed as shown in Table 1.

Example 12
A curable composition was obtained in the same manner as in Example 4 except that C-2-2 was not used and the addition amount of Tersolve THA-90 was changed to 90 parts.

(Example 13)
A curable composition was obtained in the same manner as in Example 4 except that B-1 and B-2 in Example 4 were each changed to B-4.

(Example 14)
In Example 1, the curable composition was obtained like Example 1 except having changed the addition amount of the terpineol C into 32 parts, and also having changed the addition amount of the high solve EDE into 4 parts.

(Example 15)
In Example 4, the curable composition was obtained in the same manner as in Example 4 except that the addition amount of Telsolve THA-90 was changed to 100 parts and that the addition amount of Hisolv EDE was changed to 12.5 parts. .

(Example 16)
A curable composition was obtained in the same manner as in Example 4 except that 1% by mass of KBM-5103 was added to the total solid content of the composition.

(Example 17)
<Preparation of titanium oxide dispersion 1>
A dispersion having the following composition was prepared, mixed with 17,000 parts of zirconia beads (0.3 mmφ), and dispersed for 12 hours using a paint shaker. Zirconia beads (0.3 mmφ) were separated by filtration to obtain a dispersion.
-Titanium dioxide (Ishihara Sangyo Co., Ltd., trade name: TTO-51 (A), average primary particle size: 10-30 nm): 1,875 parts-Dispersant (DISPERBYK-111, 100% product): 660 parts Solvent (PGMEA, propylene glycol monomethyl ether acetate): 1,710 parts The components used are as follows.
TTO-51 (A): Titanium dioxide, manufactured by Ishihara Sangyo Co., Ltd., average primary particle size of 10 to 30 nm, surface treatment species: Al (OH) ₃
DISPERBYK-111: a polymeric dispersant having one or more phosphate ester structures, manufactured by Big Chemie

  A-1 was changed to the above titanium oxide dispersion so that the content of titanium dioxide was the same as the content of A-1, and the amount of C-2-1 added was changed to 6.47 parts. A curable composition was obtained in the same manner as in Example 4.

(Example 18)
A curable composition was prepared in the same manner as in Example 1 except that the amount of terpineol C in Example 1 was changed to 115 parts and that the amount of C-2-1 (Hisolv EDE) was changed to 115 parts. Obtained.

(Example 19)
A curable composition was prepared in the same manner as in Example 2, except that the amount of dihydroterpineol in Example 2 was changed to 115 parts and that the amount of C-2-1 (Hisolv EDE) was changed to 115 parts. Obtained.

(Example 20)
A curable composition was obtained in the same manner as in Example 3 except that the amount of Telsolve DTO-210 in Example 3 was changed to 115 parts and that the amount of C-2-1 (Hisolv EDE) was changed to 115 parts. I got a thing.

(Comparative Example 10)
In Example 4, a curable composition was obtained in the same manner as in Example 4 except that the addition amount of Telsolve THA-90 was changed to 15 parts, and further, the addition amount of High Soup EDE was changed to 65 parts.

(Comparative Example 11)
In Example 4, the curable composition was obtained in the same manner as in Example 4 except that the amount of Tersolve THA-90 added was changed to 90 parts, and Hisolv EDE was not added.

(Evaluation of curable composition)
The produced curable composition was evaluated as follows. The evaluation results are summarized in Table 2.
In the case of application by flexographic printing, a flexographic printing machine (model A45, manufactured by Nakan Co., Ltd.) was used as a printing machine. A curable composition was printed on a 300 mm × 400 mm glass substrate (trade name: XG, manufactured by Corning) using anilox roll # 400. In the case of application by a spin coater, a 10 cm × 10 cm glass substrate (trade name: XG, manufactured by Corning) was used.
In the case of inkjet printing, the curable composition was applied on a 10 cm × 10 cm glass substrate (trade name: XG, manufactured by Corning) using an inkjet printer (manufactured by Dimatix, DMP-281 printer).

<Substrate cloudiness>
The curable composition was spin-coated on a 10 cm × 10 cm glass substrate (trade name: XG, manufactured by Corning) so as to have a dry film thickness of 100 nm, and dried (prebaked) in an oven at 90 ° C. for 100 seconds. The film on the obtained substrate was visually observed and evaluated according to the following criteria. Less white turbidity means that a film with better transparency can be obtained. If the evaluation is 1 or 2, there is no practical problem and 1 is more preferable.
5: The dry film on the entire surface of the substrate is clouded. 4: The dry film on the entire surface of the substrate is slightly clouded. 3: The dry film of about half of the substrate is slightly clouded. 2: A portion of the substrate is dried. The film is slightly clouded 1: No dry film is clouded

<Repel failure>
The curable composition was spin-coated on a 10 cm × 10 cm glass substrate (trade name: XG, manufactured by Corning) so as to have a dry film thickness of 100 nm, and dried (prebaked) in an oven at 90 ° C. for 100 seconds. In the whole obtained substrate, the film on the substrate was visually observed and evaluated according to the following criteria. If the evaluation is 1 or 2, there is no practical problem and 1 is more preferable.
1: No repellency occurred 2: One or more repellent occurrences less than three 3: Three or more repellency occurrences less than ten 4: Four or more repellency occurrences

<In-plane film thickness uniformity>
On a glass substrate (trade name: XG, manufactured by Corning), the curable composition is applied by spin coating, flexographic printing, and ink jet printing so that the dry film thickness is 100 nm, and dried in an oven at 90 ° C. for 100 seconds ( Pre-baked). Thereafter, the entire surface was exposed to 150 mJ / cm ² using an ultrahigh pressure mercury lamp (illuminance was 24 mW / cm ² ), and then heated in an oven at 200 ° C. for 30 minutes.
The in-plane distribution of film thickness was measured at 64 points and evaluated as follows.
1: In-plane distribution is 100 nm ± 5 nm or less 2: In-plane distribution is over 100 nm ± 5 nm, 100 nm ± 10 nm or less 3: In-plane distribution is over 100 nm ± 10 nm, 100 nm ± 20 nm or less 4: In-plane distribution is 100 nm ± Over 20nm

<Chemical resistance evaluation>
The curable composition was spin-coated on a 10 cm × 10 cm glass substrate (trade name: XG, manufactured by Corning) so as to have a dry film thickness of 100 nm, and dried (prebaked) in an oven at 90 ° C. for 100 seconds. Thereafter, the entire surface was exposed to 150 mJ / cm ² using an ultrahigh pressure mercury lamp (illuminance was 24 mW / cm ² ), and then heated in an oven at 200 ° C. for 30 minutes.
Subsequently, it was immersed in N-methylpyrrolidone at 25 ° C. for 2 minutes, the film thickness before and after the immersion was measured, and the remaining ratio of the film was measured. The evaluation criteria are shown below.
1: Residual rate is less than 80% 2: Residual rate is 80% or more and less than 90% 3: Residual rate is 90% or more and less than 95% 4: Residual rate is 95% or more and less than 98% 5: Residual rate is 98% or more and 100% %Less than

<Pencil hardness evaluation>
The curable composition was spin-coated on a 10 cm × 10 cm glass substrate (trade name: XG, manufactured by Corning) so as to have a dry film thickness of 100 nm, and dried (prebaked) in an oven at 90 ° C. for 100 seconds. Thereafter, the entire surface was exposed to 150 mJ / cm ² using an ultrahigh pressure mercury lamp (illuminance was 24 mW / cm ² ), and then heated in an oven at 200 ° C. for 30 minutes. Based on JIS K5600-5-4: 1999, the pencil hardness of the obtained cured film was measured.

<Refractive index evaluation>
The curable composition was spin-coated on a 10 cm × 10 cm silicon wafer so as to have a dry film thickness of 500 nm, and dried (prebaked) in an oven at 90 ° C. for 100 seconds. Thereafter, the entire surface was exposed to 150 mJ / cm ² using an ultrahigh pressure mercury lamp (illuminance was 24 mW / cm ² ), and then heated in an oven at 200 ° C. for 30 minutes.
The refractive index of the cured film at 550 nm was measured using an ellipsometer VUV-VASE (manufactured by JA Woollam Japan Co., Ltd.).

(Example 21)
<Preparation of titanium oxide dispersion 2>
A dispersion having the following composition was prepared, mixed with 100.0 parts of zirconia beads (0.3 mmφ), and dispersed for 12 hours using a paint shaker. Zirconia beads (0.3 mmφ) were separated by filtration to obtain a dispersion.
Titanium dioxide (Ishihara Sangyo Co., Ltd., trade name: TTO-51 (C), average primary particle size: 10 to 30 nm): 25.0 parts Dispersant: 25.0 parts Solvent (PGMEA, propylene glycol) Monomethyl ether acetate): 50.0 parts In addition, the used component is as follows.
-TTO-51 (C): Titanium dioxide, manufactured by Ishihara Sangyo Co., Ltd., average primary particle size 10-30 nm, surface treatment type: Al (OH) ₃ , stearic acid treatment- Dispersant: Uses the following compound 1 (Molecular weight Mw = 13,800, solid content 30% PGMEA solution)

  In Compound 1, the sulfur atom bonded to the polymer chain may be bonded to the P1 monomer unit or may be bonded to the P2 monomer unit.

<Synthesis of polymer (polymer-1) having a group in which an acid group is protected by an acid-decomposable group>
In the following synthesis examples, the following abbreviations represent the following compounds, respectively.
V-601: Dityl-2,2′-azobis (2-methylpropionate)
GMA: Glycidyl methacrylate PGMEA: Propylene glycol monomethyl ether acetate

<Synthesis of Polymer-1 (K-1)>
Tetrahydrofuran-2-yl methacrylate (63.2 parts (0.405 molar equivalents)),
Methacrylic acid (8.2 parts (0.095 molar equivalent)),
(3-ethyloxetane-3-yl) methyl methacrylate (69 parts (0.375 molar equivalent)),
2-hydroxyethyl methacrylate (16.3 parts, (0.125 molar equivalent)), and
Propylene glycol monomethyl ether acetate (PGMEA) (120 parts)
The mixed solution was heated to 70 ° C. under a nitrogen stream. While stirring this mixed solution, radical polymerization initiator (V-601: dityl-2,2′-azobis (2-methylpropionate), manufactured by Wako Pure Chemical Industries, Ltd., 12.0 parts) and PGMEA (80 parts) of the mixed solution was added dropwise over 3.5 hours. After completion of the dropwise addition, a PGMEA solution of polymer-1 was obtained by reacting at 70 ° C. for 2 hours. Further, PGMEA was added to adjust the solid content concentration to 40% by mass.
The weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of the obtained polymer-1 was 15,000.

<Synthesis of Photoacid Generator 1>
Aluminum chloride (10.6 g) and 2-chloropropionyl chloride (10.1 g) were added to a suspension of 2-naphthol (10 g) and chlorobenzene (30 mL), and the mixture was heated to 40 ° C. for 2 hours. I let you. Under ice-cooling, 4N HCl aqueous solution (60 mL) was added dropwise to the reaction solution, and ethyl acetate (50 mL) was added for liquid separation. Potassium carbonate (19.2 g) was added to the organic layer, reacted at 40 ° C. for 1 hour, 2N HCl aqueous solution (60 mL) was added and separated, and the organic layer was concentrated, and the crystal was converted to diisopropyl ether (10 mL). Was reslurried, filtered and dried to obtain a ketone compound (6.5 g).
Acetic acid (7.3 g) and a 50 mass% aqueous hydroxylamine solution (8.0 g) were added to a suspension of the obtained ketone compound (3.0 g) and methanol (30 mL), and the mixture was heated to reflux. After allowing to cool, water (50 mL) was added, and the precipitated crystals were filtered, washed with cold methanol, and dried to obtain an oxime compound (2.4 g).
The obtained oxime compound (1.8 g) was dissolved in acetone (20 mL), triethylamine (1.5 g) and p-toluenesulfonyl chloride (2.4 g) were added under ice cooling, and the temperature was raised to room temperature. Reacted for hours. Water (50 mL) was added to the reaction solution, and the precipitated crystals were filtered, reslurried with methanol (20 mL), filtered and dried to obtain the compound of B-1 (the following structure) (2.3 g).
The ¹ H-NMR spectrum (300 MHz, CDCl ₃ ) of B-1 is δ = 8.3 (d, 1H), 8.0 (d, 2H), 7.9 (d, 1H), 7. 8 (d, 1H), 7.6 (dd, 1H), 7.4 (dd, 1H) 7.3 (d, 2H), 7.1 (d, 1H), 5.6 (q, 1H) , 2.4 (s, 3H), 1.7 (d, 3H).

<Preparation of curable composition>
Prepared as follows.
A-3: Titanium oxide dispersion 2: 3.0 parts K-1: Polymer 1 solution: 2.5 parts C-1: Turpineol C (manufactured by Nippon Terpene Chemical Co., Ltd.): 48. 5 parts C-2: propylene glycol monomethyl ether acetate (manufactured by Daicel Corporation): 45.0 parts L-1: the above-mentioned photoacid generator 1: 0.075 parts M-1: 1-cyclohexyl- 3- (2-monoforinoethyl) thiourea (DSP Gokyo Food & Chemical Co., Ltd.): 0.0007 parts O-1: Ogsol PG-100 (epoxy-fluorene derivative, manufactured by Osaka Gas Chemical Co., Ltd.) : 0.37 part O-2: Ogsol BPEF (9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene, fluorene monomer, manufactured by Osaka Gas Chemical Co., Ltd.): 0.29 part -1: Sylquest A-187SILANE (γ-glycidoxypropyltrimethoxysilane, manufactured by Momentive Performance Materials Co., Ltd.): 0.065 parts G-2: KBE-846 (bis (triethoxysilylpropyl) ) Tetrasulfide, manufactured by Shin-Etsu Chemical Co., Ltd.): 0.12 parts B-1: Celoxide 2021P (3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, manufactured by Daicel Corporation) : 0.022 parts P-1: 1,3-dimethylimidazolidin-2-one (manufactured by Wako Pure Chemical Industries, Ltd .: 0.056 parts)
F-1: Megafax F-554 (perfluoroalkyl group-containing nonionic surfactant, manufactured by DIC Corporation): 0.0032 parts The above ingredients were stirred with a magnetic stirrer for 1 hour, and the pore size was 0.3 μm. It filtered with the filter made from a polytetrafluoroethylene, and the curable composition of Example 21 was obtained.

(Examples 22-26, 29, 30, Comparative Examples 12-14)
C-1 and C-2 of Example 21 were changed to the solvents shown in Table 3, and the curable composition was obtained in the same manner as Example 21 except that the addition amount was changed according to Table 3. .

(Examples 27 and 28)
As in Example 21, except that C-1 and C-2 in Example 21 were changed to the solvents shown in Table 3 and the amount of addition of the solvent was changed so that the composition solid content in Table 3 was obtained. Thus, a curable composition was obtained.

(Example 31)
C-1 and C-2 of Example 21 were changed to the respective solvents shown in Table 3, and further, the addition amounts of C-1 and C-2-1 were changed so as to become the composition solid content of Table 3. Except for this, a curable composition was obtained in the same manner as in Example 21.

<Preparation of zirconia oxide dispersion>
The titanium oxide dispersion 2 described in Example 21 was treated in the same manner as the titanium oxide dispersion 2 except that the titanium oxide was changed to the following zirconia (UPE-100 (1st rare element)). To obtain a zirconia oxide dispersion.

The obtained curable composition was evaluated in the same manner as in Example 1 for repelling, substrate turbidity, in-plane film thickness uniformity, chemical resistance, refractive index, and pencil hardness.
In addition, about evaluation of in-plane film thickness uniformity, chemical resistance, and pencil hardness, it evaluated similarly to Example 1 except not performing exposure.

(Example 32)
3 to 5 except that an insulating layer W (hereinafter also referred to as “pedestal layer W”) surrounding the Y (102a) 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 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: The curable composition of Example 4 was applied on a substrate, pre-baked, then exposed using an ultra-high 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 4 was slit-coated on a substrate, pre-baked, exposed using an ultra-high 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, 111: substrate, 112: insulating film, 112a: contact hole, 113: protective film, W: pedestal layer, X, Y: electrode

Claims (17)

As component A, at least one selected from the group consisting of the following a1 to a3,
As component B, a curable compound;
Component C contains a solvent,
Component C, as Component C-1, has a viscosity at 20 ° C. of 50 mPa · s to 200 mPa · s, and a surface tension of 30 mN / m to 41 mN / m, and at least one organic solvent; Component C-2 contains at least one organic solvent having a viscosity at 20 ° C. of less than 50 mPa · s,
Content of the said component C-1 is 20-95 mass% with respect to the total mass of the component C,
A curable composition, wherein the curable composition has a viscosity at 20 ° C. of 1 mPa · s to 30 mPa · s.
a1: a titanium compound and / or a zirconium compound having an alkoxy group,
a2: titanoxane, zircoxane and / or titanoxane-zircoxane condensate having at least one alkoxy group directly bonded to a titanium atom or a zirconium atom,
a3: Metal oxide containing a titanium atom and / or a zirconium atom.   The curable composition of Claim 1 whose component B is a polymeric compound.   Component C-1 is terpineol, dihydroterpineol, 4- (acetyloxy) -α, α, 4-trimethylcyclohexanemethanol acetate, and 2- [1-methyl-1- (4-methyl-3-cyclohexene-1) The curable composition according to claim 1 or 2, comprising at least one selected from the group consisting of -yl) ethoxy] ethanol.   The curable composition of any one of Claims 1-3 whose total amount of the solid content in the said curable composition is 2-15 mass% with respect to the total mass of a curable composition.   The curable composition of any one of Claims 1-4 in which the component B contains the polymeric compound more than hexafunctional.   The a2 is at least one selected from the group consisting of a titanium compound having an alkoxy group, a zirconium compound having an alkoxy group, a titanium compound having a halogeno group, and a zirconium compound having a halogeno group. The titanoxane, zircoxane and / or titanoxane-zircoxane condensate obtained by hydrolytic condensation with 0.5 to 1.9 times molar equivalent of water with respect to a molar amount of 1.0 mol. The curable composition of any one of Claims.   The curable composition of any one of Claims 1-6 in which component A contains said a2.   The curable composition according to any one of claims 1 to 7, which contains a photopolymerization initiator as component D. 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 8 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 The manufacturing method of the cured film which contains at least process 1-process 5 in this order.
Process 1: Application | coating process which apply | coats the curable composition of any one of Claims 1-8 on a board | substrate Process 2: The solvent removal process which removes 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 1-8.   The cured film according to claim 11, which is an interlayer insulating film or an overcoat film.   The cured film of Claim 11 or 12 whose refractive index in wavelength 550nm is 1.6-1.9.   The liquid crystal display device which has a cured film of any one of Claims 11-13.   The organic electroluminescence display which has a cured film of any one of Claims 11-13.   The touch panel which has a cured film of any one of Claims 11-13.   A touch panel display device having the cured film according to claim 11.

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