JP2016027154A - Curable composition, method for producing cured film, cured film, touch panel, and display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition that gives a cured film having both a desired refractive index and chemical resistance and has excellent storage stability, a cured film obtained by curing the above curable composition, a method for producing the cured film, as well as an organic EL display device, a liquid crystal display device, a touch panel, and a touch panel display device having the cured film.SOLUTION: The curable composition comprises: a specific amount of a hydrolytically condensable titanium and/or zirconium compound as a component A; a specific amount of a titanium and/or zirconium coordinating component and a polyfunctional polymerizable component that may be the same compound as the above coordinating component as a component B; a photopolymerization initiator as a component C; and a solvent as a component D. The content of the titanium and/or zirconium coordinating component is 15 to 140 pts. mass based on 100 pts. mass of the content of the component A.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.

The transparent material is used as an insulating film, a protective film, a light extraction layer, a spacer, a microlens and the like as many partial structures of various display devices, imaging devices, solar cells, and the like.
In addition, it is known that the transparent material is used as a material for adjusting the refractive index in order to improve the performance of the apparatus.
As a transparent material for adjusting the refractive index, a composition using a metal alkoxide is known (see, for example, Patent Documents 1 and 2).
Moreover, the composition described in patent document 3 and 4 is known as a composition using the metal alkoxide with patterning performance.

International Publication No. 2010/050580 JP 2002-6104 A JP 2012-203061 A JP 2011-178588 A

In recent years, high definition of display devices and imaging devices has progressed, and various chemicals are used in the manufacturing process. However, the compositions described in Patent Documents 1 and 2 have insufficient chemical resistance.
In addition, even the compositions described in Patent Documents 3 and 4 have insufficient chemical resistance.
Thus, the patterning material using the conventional metal alkoxide has not been able to satisfy the refractive index, the chemical resistance and the storage stability.
The problem to be solved by the present invention is to achieve both the refractive index and chemical resistance of the cured film obtained, and to cure the curable composition having excellent storage stability and the curable composition. It is to provide 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>, <7>, <8>, and <11> to <14>. It is described below together with <2> to <6>, <9>, and <10>, which are preferred embodiments.
<1> At least one selected from the group consisting of the following a1 and a2 as the component A, at least one selected from the group consisting of the following b1 and b2 as the component B, and a photopolymerization initiator as the component C, A solvent as component D, the content of component A is 40 to 90% by mass with respect to the total solid content of the curable composition, and the content of component B is the total solid content of the curable composition And a compound having the following titanium and / or zirconium coordinating group and two or more ethylenically unsaturated groups, and a compound having the following titanium and / or zirconium coordinating group. And a total content of 15 to 140 parts by mass with respect to 100 parts by mass of component A,
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,
b1: a compound having a titanium and / or zirconium coordinating group and two or more ethylenically unsaturated groups,
b2: A compound having a titanium and / or zirconium coordination group and a compound having two or more ethylenically unsaturated groups.

<2> The curable composition according to <1>, wherein the titanium and / or zirconium coordinating group is a group capable of coordinating with a titanium atom and / or a zirconium atom by an oxygen atom,
<3> The titanium and / or zirconium coordinating group is a 1,2-diketone structure, 1,3-diketone structure, 1,4-diketone structure, α-hydroxyketone structure, α-hydroxyester structure, α- <1> or <2>, which is 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 A curable composition of
<4> 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 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 1.0 mol of the total molar amount of zirconium atoms, The curable composition according to any one of 1> to <3>,
<5> The curable composition according to any one of <1> to <4>, wherein the component A includes the a2.
<6> When component B contains the above b2, the content of the compound having titanium and / or zirconium coordinating groups with respect to the total solid content of the curable composition is 1% by mass of BW, 2 or more ethylenically unsaturated The curable composition according to any one of <1> to <5>, in which BW1: BW2 is 2: 8 to 8: 2 when the content of the compound having a group is BW2% by mass;
<7> 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 the curable composition as described in any one of <1>-<6> on a board | substrate Process 2: The solvent removal process of removing a solvent from the apply | coated curable composition Process 3 : Exposure step of exposing at least a part of the curable composition from which the solvent has been removed with actinic rays Step 4: development step of developing the exposed curable composition with an aqueous developer Step 5: developed curable composition Heat treatment step for heat-treating the product <8> A cured film obtained by curing the curable composition according to any one of <1> to <6>,
<9> The cured film according to <8>, which is an interlayer insulating film or an overcoat film,
<10> The cured film according to <8> or <9>, wherein the refractive index at a wavelength of 550 nm is 1.78 to 2.40,
<11> A liquid crystal display device having the cured film according to any one of <8> to <10>,
<12> An organic EL display device having the cured film according to any one of <8> to <10>,
<13> A touch panel having the cured film according to any one of <8> to <10>,
<14> A touch panel display device having the cured film according to any one of <8> to <10>.

  According to the present invention, both the refractive index and the chemical resistance of the cured film obtained can be achieved, and the curable composition excellent in storage stability, the cured film obtained by curing the curable composition, and The production method, and the organic EL display device, the liquid crystal display device, the touch panel, and the touch panel display device having the cured film can be provided.

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 A-A ′ shown in FIG. 3. FIG. 4 is a cross-sectional view showing a cross-sectional structure along the line B-B ′ shown in FIG. 3.

Hereinafter, the contents of the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the specification of the present application, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value. The organic EL element in the present invention refers to an organic electroluminescence element.
In the notation of groups (atomic groups) in this specification, the notation that does not indicate substitution and non-substitution includes not only those having no substituent but also those having a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In 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 and a2” 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.
In the present invention, a combination of preferred embodiments is more preferred.

  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).

The curable composition of the present invention (hereinafter also simply referred to as “composition”) is at least one selected from the group consisting of the following a1 and a2 as component A, and the group consisting of b1 and b2 below as component B At least one selected from the above, a photopolymerization initiator as component C, and a solvent as component D, and the content of component A is 40 to 90 mass based on the total solid content of the curable composition %, The content of component B is 5 to 59% by mass with respect to the total solid content of the curable composition, and the following titanium and / or zirconium coordinating groups and two or more ethylenically unsaturated groups And the total content of the compound having the following titanium and / or zirconium coordination group is 15 to 140 parts by mass with respect to 100 parts by mass of component A.
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,
b1: a compound having a titanium and / or zirconium coordinating group and two or more ethylenically unsaturated groups,
b2: A compound having a titanium and / or zirconium coordination group and a compound having two or more ethylenically unsaturated groups.

As a result of intensive studies in view of the above-mentioned viewpoints, the inventors of the present invention have the components A to D and the curable composition having the specific content shown above. The present invention has been completed by finding that both the rate and the developability can be achieved and that the storage stability is excellent.
By coordinating the titanium and / or zirconium coordinating group in component B to the titanium atom and / or zirconium atom of component A, the uniformity of the curable composition and the compatibility with other components of component A are improved. However, it is estimated that both the refractive index and developability of the resulting cured product can be achieved, and that the storage stability is excellent, but the detailed mechanism of the effect is unclear.

The curable composition of the present invention is preferably a composition in which the strength of the cured product is increased by heat-treating the obtained cured product such as a cured film after polymerization by light.
In addition, 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 1.78 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 80 or more, and it is more preferable that the obtained cured product has a refractive index of 1.83 or more at a wavelength of 550 nm. The upper limit of the refractive index of the cured product is not particularly limited, but from the viewpoint of improving visibility, the refractive index at a wavelength of 550 nm is preferably 2.40 or less, more preferably 2.30 or less, and 2 More preferably, it is 20 or less.
Moreover, the curable composition of this invention can be used suitably as a curable composition for interlayer insulation films or overcoat films.

Component A: at least one selected from the group consisting of a1 and a2 The curable composition of the present invention contains, as Component A, at least one selected from the group consisting of the following a1 and a2, Content is 40-90 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: A titanoxane, zircoxane and / or titanoxane-zircoxane condensate having at least one alkoxy group directly linked to a titanium atom 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 an “alkoxy group directly bonded to a titanium atom”. It is synonymous with a titanoxane having at least one, a zircoxane having at least one alkoxy group directly bonded to a zirconium atom, or a titanoxane-zirconoxane condensate having at least one alkoxy group directly bonded to a titanium atom or a zirconium atom.
It goes without saying that Component A does not contain rutile or anatase titanium oxide particles or zirconia particles.

  The content of Component A is 40 to 90% by mass with respect to the total solid content of the curable composition, and is 50 to 90% by mass from the viewpoint of coexistence of refractive index and patternability (developability). It is preferably 55 to 85% by mass, and more preferably 60 to 85% by mass. The “solid content” in the curable composition represents a component excluding a volatile component such as a solvent, and the component B includes a compound having a low boiling point, but is coordinated to titanium or zirconium. In this case, since the volatility is lost, the component B in the present invention is included in the solid content. Needless to say, the solid content may be liquid instead of solid.

Component A may be any of a1 alone, a2 alone, or a mixture of a1 and a2, but from the viewpoint of the storage stability of the composition, it is preferably a2 alone or a mixture of a1 and a2. It is more preferable that a2 is single.
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 a titanium compound and / or titanoxane from the viewpoints of refractive index and developability, and is preferably a zirconium compound and / or zircoxane from the viewpoints of low-temperature curability, curing speed and stability.

Examples of a1 include titanium monoalkoxide, titanium dialkoxide, titanium trialkoxide, titanium tetraalkoxide, zirconium monoalkoxide, zirconium dialkoxide, zirconium trialkoxide, and zirconium tetraalkoxide. From the viewpoint of film properties, titanium tetraalkoxide Alkoxides and zirconium tetraalkoxides are preferred, and titanium tetraalkoxides are more preferred.
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 di n-butoxy diisopropoxide, titanium di t-butoxy diisopropoxide, 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 Tetra n-butoxide, zirconium tetraisobutoxide, zirconium di-n-butoxy diisopropoxide, zirconium di-t-butoxy diisopropoxide, zirconium tetra-t-butoxide, zirconium tetraisooctyloxide, zirconium tetrastearyl alkoxide, etc. It is done.
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 represents 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. It is preferably a 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 1.0 mol of the total molar amount of 0.5 to 1.9 times the molar equivalent of at least one selected from the group consisting of a titanium compound having a group and a zirconium compound having an alkoxy group with respect to 1.0 mol of the total molar amount of titanium atom and zirconium atom Titanoxane and zirco obtained by hydrolytic condensation with water More preferably Jirukonokisan condensate - hexane and / or Chitanokisan.
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 to have 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.
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: at least one selected from the group consisting of b1 and b2 The curable composition of the present invention contains, as Component B, at least one selected from the group consisting of b1 and b2 below. A compound having a content of 5 to 59% by mass with respect to the total solid content of the curable composition and having the following titanium and / or zirconium coordinating group and two or more ethylenically unsaturated groups, and the following titanium And / or the total content of the compound having a zirconium coordination group is 15 to 140 parts by mass with respect to 100 parts by mass of the component A.
b1: a compound having a titanium and / or zirconium coordinating group and two or more ethylenically unsaturated groups,
b2: A compound having a titanium and / or zirconium coordination group and a compound having two or more ethylenically unsaturated groups.

  The ratio of the number of titanium and / or zirconium coordinating groups to the total number of titanium atoms and zirconia atoms contained in Component A is preferably 20 to 500%, and preferably 40 to 400%. More preferred.

The curable composition of the present invention contains at least a compound having titanium and / or zirconium coordinating groups and two or more ethylenically unsaturated groups as component B, or titanium and / or zirconium coordinating groups. As well as compounds having two or more ethylenically unsaturated groups.
In the present invention, the compound corresponding to component B has one or more titanium and / or zirconium coordinating groups, two or more ethylenically unsaturated groups, or both. A compound.

In the curable composition of the present invention, the content of component B is 5 to 59% 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. It is preferably 10 to 55% by mass, more preferably 15 to 50% by mass, and still more preferably 25 to 45% by mass.
Further, in the curable composition of the present invention, the compound having the titanium and / or zirconium coordination group and two or more ethylenic unsaturated groups, and the compound having the titanium and / or zirconium coordination group, The total content of is 15 to 140 parts by mass with respect to 100 parts by mass of component A from the viewpoints of compatibility between the refractive index of the cured film and developability, and storage stability. It is preferable that it is a mass part, and it is more preferable that it is 20-60 mass parts.

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 component A, the energy level of the d orbital of the coordinated titanium atom or zirconium atom in component A 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 And more preferably a 1,3-diketone structure, a β-ketoester structure, and More preferably, it is a group having at least one structure selected from the group consisting of a tartrate diester structure, and has at least one structure selected from the group consisting of a 1,3-diketone structure and a β-ketoester structure. Particularly preferred is a group having It is excellent in the refractive index and crack resistance 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 or formula b is preferred. A group having a structure represented by -5 is more preferred, and a group having a structure represented by the following formula b-1 or formula b-2 is more 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 a 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.

  The ethylenically unsaturated group in Component B is not particularly limited, but (meth) acryloxy group, (meth) acrylamide group, allyl group, styryl group, and vinyloxy group are preferably exemplified, and (meth) acryloxy group, And an allyl group is more preferable, and a (meth) acryloxy group is particularly preferable.

b1: Compound having a titanium and / or zirconium coordinating group and two or more ethylenically unsaturated groups As b1, a polyfunctional compound having a 1,3-diketone structure or β-ketoester structure from the viewpoint of developability ( It is preferably a meth) acrylate compound or a polyfunctional ethylenically unsaturated compound having a phthalic acid diester structure, and more preferably a polyfunctional ethylenically unsaturated compound having a phthalic acid diester structure.
Moreover, the compound which has a titanium and / or a zirconium coordination group, and two or more ethylenically unsaturated groups may be used individually by 1 type, or may use 2 or more types together.
Examples of the compound having a titanium and / or zirconium coordinating group and two or more ethylenically unsaturated groups include compounds represented by the following formulae.

  From the viewpoint of chemical resistance of the cured film, a polyfunctional ethylenically unsaturated compound having a phthalic acid diester structure is preferable, and diallyl phthalate represented by the above formula (b1-1) is particularly preferable.

b2: Compound having titanium and / or zirconium coordinating group and compound having two or more ethylenically unsaturated groups The compound having titanium and / or zirconium coordinating group in b2 above has an ethylenically unsaturated group. It may be a compound having no titanium and / or zirconium coordinating group, or a compound having titanium and / or zirconium coordinating group having one ethylenically unsaturated group.
Moreover, the compound which has a titanium and / or a zirconium coordination group may be used individually by 1 type, or may use 2 or more types together.
Examples of the compound having titanium and / or zirconium coordinating group having no ethylenically unsaturated group include 1,2-diketone compound, 1,3-diketone compound, 1,4-diketone compound, α-hydroxyketone compound An α-hydroxyester compound, an α-ketoester compound, a β-ketoester compound, a malonic acid diester compound, a fumaric acid diester compound, or a phthalic acid diester compound, preferably a 1,2-diketone compound, a 1,3-diketone compound, An α-hydroxyketone compound, an α-ketoester compound, a β-ketoester compound, or a phthalic acid diester compound is more preferable, and a 1,3-diketone compound or β-ketoester compound is still more preferable.
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.

The compound having one titanium and / or zirconium coordinating group and one ethylenically unsaturated group is a monofunctional (meth) acrylate compound having a 1,3-diketone structure or β-ketoester structure from the viewpoint of developability. Preferably there is. The compound having one titanium and / or zirconium coordinating group and one ethylenically unsaturated group may be used alone or in combination of two or more.
The compound having one titanium and / or zirconium coordinating group and one ethylenically unsaturated group is monofunctional (meth) having titanium and / or zirconium coordinating group from the viewpoint of chemical resistance of the cured film. It is preferable that it is an acrylate compound, and it is more preferable that it is a compound shown below.

  In the above b2, the molecular weight of the compound having a titanium and / or zirconium coordinating group is preferably 550 to 5,000, and more preferably 550 to 2,000.

  In the above b2, the compound having a titanium and / or zirconium coordinating group is a compound having a titanium and / or zirconium coordinating group and having no ethylenically unsaturated group from the viewpoint of chemical resistance. It is preferable that the compound has a titanium and / or zirconium coordination group and one ethylenically unsaturated group from the viewpoint of refractive index.

  The compound having two or more ethylenically unsaturated groups in b2 is not particularly limited as long as it is a polyfunctional ethylenically unsaturated compound having two or more ethylenically unsaturated groups. You can choose. Examples include ester compounds, amide compounds, urethane compounds, and other compounds.

  Examples of the ester compound include polyfunctional (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, dipentaerythritol hexa (meth) acrylate, sorbi Rutori (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, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (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 the addition reaction of isocyanate and hydroxyl group. For example, urethanized products of pentaerythritol triacrylate and hexamethylene diisocyanate, pentaerythritol triacrylate. Urethanes of toluene and diisocyanates, Urethanes of pentaerythritol triacrylate and isophorone diisocyanate, Urethanes of dipentaerythritol pentaacrylate and hexamethylene diisocyanate, Urethanes of dipentaerythritol pentaacrylate and toluene diisocyanate, Dipentaerythritol Examples include urethanized products of pentaacrylate and isophorone diisocyanate.
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.

The number of ethylenically unsaturated groups in the polyfunctional ethylenically unsaturated compound is preferably 2-20, more preferably 2-16, and even more preferably 3-10.
The molecular weight of the polyfunctional ethylenically unsaturated compound (when having a molecular weight distribution, the weight average molecular weight) is preferably from 100 to 2,000, preferably from 200 to 1,000, from the viewpoint of applicability. Is more preferable.
The said polyfunctional ethylenically unsaturated compound may be used individually by 1 type, and may use 2 or more types together. The content of the compound having two or more ethylenically unsaturated groups not having titanium and / or zirconium coordinating groups is preferably 1 to 50% by mass with respect to the total solid content of the curable composition. -40 mass% is more preferable, and 5-25 mass% is still more preferable.

A compound having two or more ethylenically unsaturated groups may be used alone or in combination of two or more.
When the curable composition of the present invention contains b2, that is, a compound having a titanium and / or zirconium coordinating group and a compound having two or more ethylenically unsaturated groups, the curing of the present invention. The content of the compound having titanium and / or zirconium coordinating group with respect to the total solid content of the conductive composition is BM 1 W mass%, and the content of the compound having two or more ethylenically unsaturated groups is BW 2 mass% When BW1: BW2 is preferably 1:20 to 20: 1, more preferably 1:10 to 10: 1, still more preferably 2: 8 to 8: 2. It is particularly preferably 7 to 7: 3. It is preferable for BW1: BW2 to be in the above range because a cured product having excellent curability and a high refractive index can be obtained.

  When the curable composition of the present invention contains b1, that is, contains a compound having two or more titanium and / or zirconium coordinating groups and ethylenically unsaturated groups, in addition to b1, titanium and / or Alternatively, a compound having a zirconium coordinating group and not having an ethylenically unsaturated group (hereinafter, also simply referred to as a compound having titanium and / or a zirconium coordinating group) may be used in combination. A monofunctional or polyfunctional ethylenically unsaturated compound having no zirconium coordinating group (hereinafter also simply referred to as monofunctional or polyfunctional ethylenically unsaturated compound) may be used in combination, and titanium and / or zirconium A compound having one coordinating group and one ethylenically unsaturated group may be used in combination. Among these, it is preferable to use a compound having a titanium and / or zirconium coordinating group, or a compound having one titanium and / or zirconium coordinating group and one ethylenically unsaturated group.

Examples of the compound having a titanium and / or zirconium coordinating group include compounds having a titanium and / or zirconium coordinating group having no ethylenically unsaturated group described in b2, and the preferred range is also the same. .
Examples of the polyfunctional ethylenically unsaturated compound (compound having two or more ethylenically unsaturated groups) include compounds having two or more ethylenically unsaturated groups described in b2, and the preferred range is also the same. is there.
As the compound having one titanium and / or zirconium coordinating group and one ethylenically unsaturated group, the compound having one titanium and / or zirconium coordinating group and one ethylenically unsaturated group described in b2 is used. The preferred ranges are also the same.

The monofunctional ethylenically unsaturated compound is not particularly limited as long as it is a compound having one ethylenically unsaturated group not having titanium and / or zirconium coordinating groups, but acrylic acid, methacrylic acid, itaconic acid. Monofunctional ethylenically unsaturated compounds such as unsaturated carboxylic acids such as crotonic acid, isocrotonic acid and maleic acid and their salts, (meth) acrylates, (meth) acrylamides, (meth) acrylonitriles and styrenes Can be mentioned.
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 or the like is also preferably used.
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.

  In addition, when the curable composition of the present invention contains b2, that is, a compound having titanium and / or zirconium coordination group and a compound having two or more ethylenically unsaturated groups, b2 In addition, the above-described compound having one ethylenically unsaturated group, that is, a monofunctional ethylenically unsaturated compound may be contained.

  In the present invention, b1 is preferable in terms of chemical resistance, and b2 is preferable in terms of refractive index.

Component C: Photopolymerization initiator The curable composition of the present invention contains a photopolymerization initiator as Component C.
The photopolymerization initiator preferably contains a photoradical polymerization initiator.
The photopolymerization initiator that can be used in the present invention starts polymerization of a polymerizable compound such as a compound having two or more ethylenically unsaturated groups by actinic rays (hereinafter also simply referred to as “light”). It is a compound that can be promoted.
"Actinic light" 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 C 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, oxadiazole compounds, carbonyl compounds, alkylphenone compounds, benzoin compounds, acridine compounds, organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, Examples include metallocene compounds, hexaarylbiimidazole compounds, organic boric acid compounds, disulfonic acid compounds, onium salt compounds, and acylphosphine (oxide) compounds. Among these, from the viewpoint of sensitivity, an oxime ester compound, a hexaarylbiimidazole compound, and an alkylphenone compound are preferable, and an oxime ester compound is 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 C-1 or formula C-2.

In formula C-1 or formula C-2, Ar represents an aromatic group or a heteroaromatic group, R ¹ represents an alkyl group, an aromatic group or an alkoxy group, R ² represents a hydrogen atom or an alkyl group, Furthermore, R ² 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 on an aromatic ring from a benzene ring compound, a naphthalene ring compound or a carbazole ring compound, and forms a ring with R ² More preferred are a naphthalenyl group and a carbazoyl group. 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 ¹ 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 ² represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or a substituted alkyl group, and more preferably a hydrogen atom, a substituted alkyl group that forms a ring with Ar, or a toluenethioalkyl group.
Ar is preferably a group having 4 to 20 carbon atoms, R ¹ is preferably a group having 1 to 30 carbon atoms, and R ² 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 C-3, formula C-4 or formula C-5, and particularly preferably a compound represented by the following formula C-5.

In formula C-3 to formula C-5, R ¹ represents an alkyl group, an aromatic group or an alkoxy group, X represents —CH ₂ —, —C ₂ H ₄ —, —O— or —S—, R ³ independently represents a halogen atom, R ⁴ are each independently 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 ⁵ Represents a hydrogen atom, an alkyl group or an aryl group, R ⁶ 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 ¹ represents an alkyl group, an aromatic group or an alkoxy group, and a group represented by R ¹¹ —X′-alkylene group— is preferred. R ¹¹ represents an alkyl group or an aryl group, and X ′ represents a sulfur atom or an oxygen atom. R ¹¹ is preferably an aryl group, more preferably a phenyl group. The alkyl group and aryl group as R ¹¹ 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 ³ and R ⁴ can be bonded at any position on the aromatic ring.
R ⁴ represents an alkyl group, a phenyl group, an alkyl-substituted amino group, an arylthio group, an alkylthio group, an alkoxy group, an aryloxy group or a halogen atom, preferably an alkyl group, a phenyl group, an arylthio group or a halogen atom, an alkyl group, an arylthio group A group or a halogen atom is more preferred, and an alkyl group or a halogen atom is still more preferred. As an alkyl group, a C1-C5 alkyl group is preferable and a methyl group or an ethyl group is more preferable. As a halogen atom, a chlorine atom, a bromine atom, or a fluorine atom is preferable.
The number of carbon atoms of R ⁴ is preferably 0 to 50, and more preferably from 0 to 20.
R ⁵ represents a hydrogen atom, an alkyl group or an aryl group, and an alkyl group is preferable. 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 ⁶ 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 ³ on the aromatic ring in formula C-3 or formula C-4, and n3 represents the number of substitutions of R ⁴ on the aromatic ring in formula C-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 compounds used in the present invention are not limited to these. 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. Specific examples include IRGACURE 819, Darocur 4265, Darocur TPO, and the like manufactured by BASF.
Examples of the alkylphenone compounds include benzylmethyl ketal compounds, α-hydroxyalkylphenone compounds, and α-aminoalkylphenone compounds. Specific examples include IRGACURE 907 and 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.
In the present invention, even when the photopolymerization initiator has a titanium and / or zirconium coordination group, it has a titanium and / or zirconium coordination group in b1 and two or more ethylenically unsaturated groups. It is not treated as a compound or a compound having a titanium and / or zirconium coordinating group in b2.

Sensitizer In addition to the photopolymerization initiator, a sensitizer may be added to the curable composition of the present invention.
The sensitizer absorbs actinic rays or radiation and enters an excited state. The sensitizer that has been in an excited state is capable of initiating and promoting polymerization by causing an action such as electron transfer, energy transfer, and heat generation due to the interaction with the component C.
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), squaryliums (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 D: Solvent The curable composition of the present invention contains a solvent as Component D. Moreover, the solvent in this invention is a compound other than the component B, and the compound applicable to the component B shall not be included in a solvent.
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.
As the solvent used in the curable composition of the present invention, known solvents can be used, such as 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 ether Dipropylene glycol monoalkyl ether acetates, esters, ketones, amino acids S, 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, butanol, 1, More preferable examples include 3-butylene glycol diacetate and diethylene glycol methyl ethyl ether.
The boiling point of the solvent is preferably from 100 ° C to 300 ° C, more preferably from 120 ° C to 250 ° C, from the viewpoint of applicability.
The solvent which can be used for this invention can be used individually by 1 type or in combination of 2 or more types. It is also preferred to use solvents having different boiling points in combination.
The content of the solvent in the curable composition of the present invention is 100 to 3,000 parts by mass per 100 parts by mass of the total solid content of the curable composition from the viewpoint of adjusting to a viscosity suitable for coating. Preferably, it is 200 to 2,000 parts by mass, and more preferably 250 to 1,000 parts by mass.

The viscosity of the curable composition of the present invention is preferably 1 to 200 mPa · s, more preferably 2 to 100 mPa · s, and still more preferably 3 to 50 mPa · s.
The viscosity is preferably measured at 25 ± 0.2 ° C. using, for example, a RE-80L rotational viscometer manufactured by Toki Sangyo Co., Ltd. The rotation speed during measurement is preferably 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 30 mPa · s or more.

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

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

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

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

The weight average molecular weight (Mw) of the copolymer is more preferably from 1,500 to 5,000.
These surfactants can be used singly or in combination of two or more.
When blended, the content of the surfactant in the curable composition of the present invention is preferably 0.001 to 5.0 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 G: Alkoxysilane Compound The composition of the present invention may contain an alkoxysilane compound as an adhesion improver. When the alkoxysilane compound is used, the adhesion between the film formed from the composition of the present invention and the substrate can be improved, or the properties of the film formed from the composition of the present invention can be adjusted.
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.

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.
Preferable 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: Metal Oxide Particles The curable composition of the present invention can contain metal oxide particles for the purpose of adjusting the refractive index and light transmittance. 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, Ti, Zr, Hf, Nb, Mo, W, Zn, Oxide particles containing atoms such as B, Al, Si, Ge, Sn, Pb, Sb, Bi, and Te are preferable. Titanium oxide, titanium composite oxide, zinc oxide, zirconium oxide, indium / tin oxide, antimony / Tin oxide is more preferable, titanium oxide, titanium composite oxide, and zirconium oxide are more preferable, titanium oxide and zirconium oxide are particularly preferable, and titanium oxide is most 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.

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

Moreover, a metal oxide particle may be used individually by 1 type, and can also use 2 or more types together.
The content of the metal oxide particles in the curable composition of the present invention may be appropriately determined in consideration of the refractive index required for the optical member obtained from the curable composition, light transmittance, etc. It is preferable to set it as 0-40 mass% with respect to the total solid of the curable composition of this invention, It is more preferable to set it as 1-30 mass%, It is still more preferable to set it as 2-20 mass%.
The content of the metal oxide particles is preferably less than the content of component A. When the content of component A is 100 parts by mass, it is preferably 80 parts by mass or less, and 50 parts by mass or less. It is more preferable that it is 30 parts by mass or less.

  In the present invention, the 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)
If necessary, the curable composition of the present invention may contain other components such as a plasticizer, a polymerization inhibitor, a thermal acid generator, an acid multiplier, and a binder polymer. As these components, for example, those described in JP2009-98616A, JP2009-244801A, and other known ones can be used. Further, various ultraviolet absorbers described in “New Development of Polymer Additives (Nikkan Kogyo Shimbun Co., Ltd.)”, metal deactivators, and the like may be added to the curable composition of the present invention.

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

(Method for preparing curable composition)
There is no restriction | limiting in particular as a preparation method of the curable composition of this invention, It can prepare by a well-known method, For example, each component is mixed by a predetermined ratio and arbitrary methods, and stir-dissolves and / or 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 film of the present invention is a cured film obtained by curing the curable composition of the present invention. Moreover, it is preferable that the cured film of this invention is a cured film obtained by the manufacturing method of the cured film of this 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 1 to 5 in this order. preferable.
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 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.
As the resin, 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 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.
The wet film thickness when applied is not particularly limited and can be applied with a film thickness according to the application, but is preferably in the range of 0.05 to 10 μm.
Furthermore, before applying the curable composition of the present invention to the substrate, a so-called prewetting method as described in JP-A-2009-145395 can be applied.

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

The exposure step generates a polymerization initiation species from a photopolymerization initiator using an actinic ray, polymerizes a compound having an ethylenically unsaturated group, and cures at least a part of the curable composition from which the solvent is removed. It is a process to do.
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. ), 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; tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, choline hydroxide, and other ammonium hydroxides; sodium silicate, metasilicic acid Sodium or the like can be used. As the developer, an aqueous solution containing the basic compound is preferable, and 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 is used as the developer. You can also.
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 dipping 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 (post-baking) of heat-processing the developed curable composition after the said image development process. By performing heat treatment after developing the curable composition of the present invention, a cured film having higher strength can be obtained.
The temperature of the heat treatment is preferably 80 ° C to 300 ° C, more preferably 100 ° C to 280 ° C, and particularly preferably 120 ° C to 200 ° C. In the above embodiment, it is estimated that the 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 substrate on which the pattern is formed may be re-exposed (post-exposure) with actinic rays and then post-baked. Post-exposure can further accelerate the curing reaction of the film. As a preferable exposure amount when including a post-exposure step, 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. In addition, when it is a cured film etc. which are not developed, it can obtain by the same method except not having the said image development process.
The cured film of the present invention is an organic-inorganic hybrid cured film formed of component A, component B, etc., and is not a metal oxide crystal film. The crystal component of the metal oxide in the cured film or the like is preferably 30% by volume or less, more preferably 10% by volume or less, and still more preferably not contained. By setting it as such an aspect, crack tolerance improves. The content of the crystal component can be evaluated by X-ray diffraction of a cured film or the like.
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.
Further, the cured film of the present invention includes a protective film for a color filter in a liquid crystal display device or an organic EL device, a spacer for keeping the thickness of a liquid crystal layer in the liquid crystal display device constant, and a device for MEMS (Micro Electro Mechanical Systems). It can use suitably also for these structural members.

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 1.78 to 2.40 are preferable, 1.80 to 2.30 are more preferable, and 1.83 to 2.20 are still more preferable.

(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.

(Synthesis Example 1)
After dissolving 34.0 g (0.10 mol) of titanium tetranormal butoxide in 12.0 g of normal butyl alcohol, a mixture of 2.7 g (0.15 mol) of water and 24.0 g of normal butyl alcohol was brought to room temperature. And dripped. After completion of the dropwise addition, the mixture was stirred at room temperature for 1 hour and further heated to reflux at 110 ° C. for 1 hour to obtain titanoxane A-6. The solid content concentration was 20% by mass.

(Synthesis Example 2)
After dissolving 34.0 g (0.10 mol) of titanium tetranormal butoxide in 12.0 g of normal butyl alcohol, a mixture of 1.8 g (0.10 mol) of water and 24.0 g of normal butyl alcohol was brought to room temperature. And dripped. After completion of the dropwise addition, the mixture was stirred at room temperature for 1 hour and further heated to reflux at 110 ° C. for 1 hour to obtain titanoxane A-7. The solid content concentration was 29% by mass.

(Synthesis Example 3)
After dissolving 34.0 g (0.10 mol) of titanium tetranormal butoxide in 12.0 g of normal butyl alcohol, a mixture of 1.35 g (0.075 mol) of water and 24.0 g of normal butyl alcohol was brought to room temperature. And dripped. After completion of the dropwise addition, the mixture was stirred at room temperature for 1 hour and further heated to reflux at 110 ° C. for 1 hour to obtain titanoxane A-8. The solid content concentration was 34% by mass.

(Synthesis Example 4)
After dissolving 34.0 g (0.10 mol) of titanium tetratertiary butoxide in 12.0 g of tertiary butyl alcohol, a mixed solution of 1.8 g (0.10 mol) of water and 24.0 g of tertiary butyl alcohol. Was added dropwise at room temperature. After completion of the dropwise addition, the mixture was stirred at room temperature for 1 hour and further heated to reflux at 100 ° C. for 1 hour to obtain titanoxane A-9. The solid content concentration was 29% by mass.

(Synthesis Example 5)
After dissolving 28.4 g (0.10 mol) of titanium tetraisopropoxide in 12.0 g of isopropyl alcohol, a mixed solution of 1.8 g (0.10 mol) of water and 24.0 g of isopropyl alcohol was dissolved at room temperature. It was dripped. After completion of the dropwise addition, the mixture was stirred at room temperature for 1 hour and further heated to reflux at 85 ° C. for 1 hour to obtain titanoxane A-10. The solid content concentration was 27% by mass.

(Synthesis Example 6)
After dissolving 22.8 g (0.10 mol) of titanium tetraethoxide in 12.0 g of ethyl alcohol, a mixed solution of 1.8 g (0.10 mol) of water and 24.0 g of ethyl alcohol was added dropwise at room temperature. did. After completion of the dropwise addition, the mixture was stirred at room temperature for 1 hour, and further heated to reflux at 78 ° C. for 1 hour to obtain a titanoxane A-11 solution. The solid content concentration was 25% by mass.

(Synthesis Example 7)
After dissolving 5.0 g (0.026 mol) of titanium tetrachloride in 100 g of isopropyl alcohol with stirring, the mixture was stirred at room temperature (25 ° C.) for 2 hours. Ammonium chloride was precipitated by bubbling a mixed gas of ammonia gas and nitrogen (1/1 volume ratio). The mixture was filtered to remove ammonium chloride. Further, the solvent was distilled off under reduced pressure to obtain the target titanium isopropoxide. Thereafter, the same operation as in Synthesis Example 1 was performed to obtain titanoxane A-12. The solid content concentration was 19% by mass.

Example 1
<Preparation of curable composition>
Prepared as follows.
A-1: PC-200 (Titanoxane, manufactured by Matsumoto Fine Chemical Co., Ltd., solid content 31.0%)
R-1: Acetylacetone (manufactured by Wako Pure Chemical Industries, Ltd.)
M-1: polyfunctional ethylenically unsaturated compound C-1: IRGACURE CGI-124 (1- [4- (phenylthio) phenyl] -1,2-octanedione-2- (O-benzoyloxime), BASF (Made by company)
F-1: Megafac F-554 (perfluoroalkyl group-containing nonionic surfactant, manufactured by DIC Corporation)
Was adjusted with additive solvent 1 (diethylene glycol methyl ethyl ether) so as to have the addition amount and solid content shown in Table 1, and stirred with a magnetic stirrer for 1 hour.
Subsequently, it filtered with the 0.45 micrometer membrane filter, and produced the curable composition of Example 1. FIG.

(Examples 2-57 and Comparative Examples 1-21)
<Preparation of curable composition>
Examples 2 to 57 and Comparative Example 1 were carried out in the same manner as in the preparation of the curable composition of Example 1, except that the components described in Tables 1 to 4 below and the blending amounts thereof were changed to solid amounts. Each of -21 curable compositions was prepared.
In Tables 1 to 4, the added amount of each component other than the solid content of the composition represents parts by mass with respect to 100 parts by mass of the total solid content, and “-” means that the corresponding component is not contained. To do. Moreover, the addition amount of each component is described by the amount of solid content.
In Tables 1 to 4, “addition solvent” has the same meaning as “solvent”.

Details of abbreviations in Tables 1 to 4 other than those described above are shown below.
A-2: Titanoxane (T-3072, manufactured by Matsumoto Fine Chemical Co., Ltd.)
A-3: Titanoxane (B-2, manufactured by Nippon Soda Co., Ltd.)
A-4: Titanoxane (B-4, manufactured by Nippon Soda Co., Ltd.)
A-5: Zirconoxane (ZA-65, manufactured by Matsumoto Fine Chemical Co., Ltd.)
A-6 to A-12: Titanoxane prepared in Synthesis Examples 1 to 7 A-13: Titanium tetranormal butoxide (manufactured by Wako Pure Chemical Industries, Ltd.) diluted to 30% by mass with normal butyl alcohol R-2 : Methyl acetoacetate (Wako Pure Chemical Industries, Ltd.)
R-3: Ethyl lactate (manufactured by Tokyo Chemical Industry Co., Ltd.)
R-4: 2-acetoacetoxyethyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
M-1: Mixture of 70:30 mass ratio of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd.)
M-2: mixture of pentaerythritol tetraacrylate and pentaerythritol triacrylate in a mass ratio of 37 to 45:63 to 55 (manufactured by Toagosei Co., Ltd.)
M-3: Ethylene oxide modified bisphenol A diacrylate, the following compound (made by Shin-Nakamura Chemical Co., Ltd.)
M-4: Methyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
M-5: benzyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
M-6: diallyl phthalate (manufactured by Tokyo Chemical Industry Co., Ltd.)
C-2: IRGACURE CGI-242 (1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethane-1-one oxime-O-acetate, manufactured by BASF)
C-3: IRGACURE 907 (2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1, manufactured by BASF)
C-4: Oxime ester photopolymerization initiator (synthesized with reference to the synthesis method of the specific compound 1 described in the following compound, JP-A-2009-134289)
Addition solvent 2: Mixed solution of diethylene glycol methyl ethyl ether / 1,3-butylene glycol diacetate = 9/1 (mass ratio) C-5: 2,2′-bis (chlorophenyl) -4,4 ′, 5,5 '-Tetraphenyl-1,2'-biimidazole (Hodogaya Chemical Co., Ltd.)
C-6: Diethylaminobenzophenone (Hodogaya Chemical Co., Ltd.)

(Evaluation of curable composition)
The produced curable composition was evaluated as follows. The evaluation results are shown in Tables 1 to 4.

<Storage stability evaluation>
The curable composition was applied on a 100 mm × 100 mm glass substrate (trade name: XG, manufactured by Corning) so as to have a film thickness of 1.0 μm, and dried (prebaked) in an oven at 80 ° C. for 100 seconds. The film on the obtained substrate was visually observed and evaluated according to the following criteria.
1: After coating, the entire surface of the substrate is clouded 2: After coating, the entire surface of the substrate is slightly clouded 3: After coating, about half of the substrate is slightly clouded 4: After coating, Part is slightly cloudy 5: No cloudiness after pre-baking

<Refractive index evaluation>
The obtained curable composition was applied onto a silicon wafer substrate using a spinner, and dried at 80 ° C. for 100 seconds to form a film having a thickness of 0.5 μm. This substrate was exposed to 100 mJ / cm ² (measured by i-line) using an ultrahigh pressure mercury lamp, and then heated in an oven at 220 ° 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.). A higher refractive index is preferable, and 1.78 or more is more preferable. The evaluation criteria are as follows.
1: Less than 1.75 2: 1.75 or more and less than 1.78 3: 1.78 or more and less than 1.80 4: 1.80 or more and less than 1.83 5: 1.83 or more

<Developability evaluation (resolution, margin and linearity)>
The curable composition was applied on a 100 mm × 100 mm glass substrate (trade name: XG, manufactured by Corning) so as to have a film thickness of 1.0 μm, and dried (prebaked) in an oven at 80 ° C. for 100 seconds. Then, 100 mJ / cm ² exposure (illuminance is 24 mW / cm ² ) was performed with a mask having 1 μm to 100 μm lines of line and space 1: 1, and an alkali developer (tetramethylammonium hydroxide 2.38 mass% aqueous solution) And developed at 25 ° C.

-Resolution evaluation-
Whether or not the pattern was formed on the substrate after development was confirmed with an optical microscope. Evaluation criteria are shown below.
1: No resolution 2: A pattern of 20 μm or more can be formed 3: A pattern of 10 μm or more and less than 20 μm can be formed 4: A pattern of 5 μm or more but less than 10 μm can be formed 5: A pattern of 5 μm or less can be formed

-Margin evaluation-
In the evaluation of developability, the immersion time at 25 ° C. was changed using an alkali developer (tetramethylammonium hydroxide 2.38 mass% aqueous solution), and the time for the 50 μm pattern portion to be cut without residue was evaluated. The longer this time, the wider the development margin. Evaluation criteria are shown below.
1: Less than 10 seconds 2: More than 10 seconds but less than 20 seconds 3: More than 20 seconds

-Linearity evaluation-
The linearity of the line edge part was confirmed with an optical microscope for the developed substrate produced with a 50 μm line and space. Evaluation criteria are shown below.
1: There is a lot of rattling in the plane of the line edge part 2: There is a little rattling in the plane of the line edge part 3: Almost no rattling is seen in the line edge part

<Chemical resistance evaluation>
The curable composition was applied on a 100 mm × 100 mm glass substrate (trade name: XG, manufactured by Corning) so as to have a film thickness of 1.0 μm, and dried (prebaked) in an oven at 80 ° C. for 100 seconds. Thereafter, the entire surface was exposed to 100 mJ / cm ² using an ultrahigh pressure mercury lamp (illuminance was 24 mW / cm ² ), and then heated in an oven at 220 ° C. for 30 minutes.
Next, the film 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. 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

In Comparative Examples 1-21, the resolution of the cured film was poor, and the margin and linearity could not be evaluated.
In particular, the refractive index of the cured film in Example 21 at a wavelength of 550 nm was 1.94.

(Example 101)
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 11 was applied on a substrate, pre-baked, then exposed using an ultra-high pressure mercury lamp, and developed with an alkaline aqueous solution to form a pattern 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.

(Examples 102 and 103)
In Example 101, a display device with a touch panel was produced in the same manner as in Example 101 except that the composition of Example 11 was replaced with the composition of Example 45 and Example 48, respectively.
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 201)
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 11 was slit-coated on a substrate, pre-baked, exposed using an ultrahigh pressure mercury lamp, and developed with an alkaline aqueous solution. A pattern was formed, and heat treatment was performed at 200 ° C. for 30 minutes to form each layer.
When a driving voltage was applied to the obtained display device, it was found that the display device had good display characteristics and touch detection performance and was highly reliable.

(Examples 202 and 203)
A display device with a touch panel was produced in the same manner as in Example 201 except that the composition of Example 11 was replaced with the composition of Example 45 and Example 48 in Example 201, respectively.
When a driving voltage was applied to the obtained display device, it was found that the display device had good display characteristics and touch detection performance and was highly reliable.

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

Claims (14)

At least one selected from the group consisting of the following a1 and a2 as component A;
At least one selected from the group consisting of b1 and b2 below as component B;
A photopolymerization initiator as component C;
A solvent as component D,
The content of component A is 40 to 90% by mass with respect to the total solid content of the curable composition,
The content of Component B is 5 to 59% by mass with respect to the total solid content of the curable composition,
The total content of the compound having the following titanium and / or zirconium coordinating group and two or more ethylenically unsaturated groups and the compound having the following titanium and / or zirconium coordinating group is the content of component A It is 15-140 mass parts with respect to 100 mass parts, The curable composition 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,
b1: a compound having a titanium and / or zirconium coordinating group and two or more ethylenically unsaturated groups,
b2: A compound having a titanium and / or zirconium coordination group and a compound having two or more ethylenically unsaturated groups.   The curable composition according to claim 1, wherein the titanium and / or zirconium coordinating group is a group capable of coordinating with a titanium atom and / or a zirconium atom by an oxygen atom.   The titanium and / or zirconium coordinating group has a 1,2-diketone structure, 1,3-diketone structure, 1,4-diketone structure, α-hydroxyketone structure, α-hydroxyester structure, α-ketoester structure, The curable composition according to claim 1 or 2, which is a group having at least one structure selected from the group consisting of a β-ketoester structure, a malonic acid diester structure, a fumaric acid diester structure, and a phthalic acid diester structure. .   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. It is a 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 total molar amount of 1.0 mol. 4. The curable composition according to any one of 3.   The curable composition of any one of Claims 1-4 in which component A contains said a2.   When component B contains b2, the content of the compound having titanium and / or zirconium coordinating groups with respect to the total solid content of the curable composition is BW 1% by mass, and has two or more ethylenically unsaturated groups The curable composition according to any one of claims 1 to 5, wherein BW1: BW2 is from 2: 8 to 8: 2 when the content of the compound is BW2% by mass. A method for producing a cured film comprising at least Step 1 to Step 5 in this order.
Process 1: Application | coating process which apply | coats the curable composition of any one of Claims 1-6 on a board | substrate Process 2: The solvent removal process of removing a solvent from the apply | coated curable composition Process 3: Solvent An exposure step of exposing at least a part of the curable composition from which the polymer has been removed with actinic rays Step 4: a development step of developing the exposed curable composition with an aqueous developer Step 5: developing the developed curable composition Heat treatment process for heat treatment   The cured film formed by hardening | curing the curable composition of any one of Claims 1-6.   The cured film according to claim 8, which is an interlayer insulating film or an overcoat film.   The cured film of Claim 8 or 9 whose refractive index in wavelength 550nm is 1.78-2.40.   The liquid crystal display device which has a cured film of any one of Claims 8-10.   The organic electroluminescence display which has a cured film of any one of Claims 8-10.   The touch panel which has a cured film of any one of Claims 8-10.   A touch panel display device having the cured film according to claim 8.

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