TW201609902A - Curable composition, manufacturing method for a cured film, cured film, touch screen and display device - Google Patents

Abstract

The present invention provides a curable composition for a cured film, a cured film formed by curing the curable composition and manufacturing method thereof, a variety of display devices having the cured film, and a touch screen. The curable composition provided by the present invention is characterized by comprising: component A which is a specific titanium-containing compound and/or a zirconium-containing compound; component B, which is a curable compound; and component C, which is a solvent and includes component C-1 and component C-2, wherein component C-1 comprises at least one organic solvent whose viscosity at 20 DEG C is from 50 mPa.s to 200 mPa.s and surface tension is from 30 mN /m to 41 mN /m, and component C-2 comprises at least one organic solvent whose viscosity at 20 DEG C is less than 50 mPa.s. Relative to the total mass of the component C, the component C-1 is from 20 % to 95 % by mass. The viscosity of the curable composition at 20 DEG C is from 1 mPa.s to 30 mPa.s.

Description

Curing composition, method for producing cured film, cured film, touch screen and display device

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 electroluminescence (EL) display device, and a touch panel display device using the cured film. .

In recent years, a transparent curable composition has been used in order to form an interlayer insulating film, a protective film, a light extraction layer, a spacer member, a microlens member, or the like. The cured product obtained by using the transparent curable composition can be used as a member of various electronic devices such as a liquid crystal display device or an organic EL display device, and various electronic devices such as a touch panel, an image pickup device, and a solar cell. Further, it is known to adjust the refractive index of the transparent curable composition in order to further improve the light extraction efficiency of the organic EL display device or to prevent the touch detection electrode or the like from seeping to the touch panel. As the transparent curable composition having a refractive index adjusted, a composition using an oxidized metal or a metal alkoxide is known (for example, see Patent Document 1). Further, the composition described in Patent Document 2 is known as a transparent curable composition having a refractive index having a patterning property. [Prior Art Document] [Patent Literature]

[Patent Document 1] International Publication No. 2010/050580 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2012-203061

[Problems to be solved by the invention]

In recent years, from the viewpoint of liquid-saving property and application of various substrates, it is desired to apply a composition which can be applied to an electronic device such as a display device or a touch panel by a printing method. The compositions described in Patent Document 1 and Patent Document 2 have problems such as insufficient in-plane uniformity. The problem to be solved by the present invention is to provide a curable composition capable of obtaining a cured film having high transparency and high in-plane uniformity, a cured film obtained by curing the curable composition, a method for producing the same, and a method for producing the same. An organic EL display device, a liquid crystal display device, a touch panel, and a touch panel display device of the cured film. [Technical means to solve the problem]

The above problems of the present invention are solved by the means described in <1>, <9> to <11> or <14> to <17> below. <2> to <8>, <12>, and <13> which are preferred embodiments are described below. <1> A curable composition comprising, as component A, at least one selected from the group consisting of a1 to a3 described below, a curable compound as component B, and a solvent as component C; Further, the component C contains at least one organic solvent having a viscosity at 20 ° C of 50 mPa·s or more and 200 mPa·s or less and a surface tension of 30 mN/m or more and 41 mN/m or less as the component C-1, and The content of the component C-1 is 20% by mass to 95% by mass based on the total mass of the component C as at least one organic solvent having a viscosity at 20 ° C of 20 ° C as the component C-2, and the curable composition is The viscosity at 20 ° C is 1 mPa·s or more and 30 mPa·s or less; a1: a titanium compound having an alkoxy group and/or a zirconium compound, a2: having at least one alkane directly bonded to a titanium atom or a zirconium atom Alkoxy alkane, zirconium oxymethane and/or titanyl-zirconoxane condensate, a3: a metal oxide containing a titanium atom and/or a zirconium atom. The above described features and advantages of the invention will be apparent from the following description.

<2> The curable composition according to <1>, wherein the component B is a polymerizable compound. <3> The curable composition according to <1> or <2> wherein the component C-1 is selected from the group consisting of terpineol, dihydroterpineol, and 4-(ethylideneoxy). )-α,α,4-trimethylcyclohexanemethanol acetate, and 2-[1-methyl-1-(4-methyl-3-cyclohexen-1-yl)ethoxy] At least one of the groups consisting of ethanol. The curable composition according to any one of <1> to <3> wherein the total amount of solid components in the curable composition is 2 mass based on the total mass of the curable composition. % to 15% by mass. The curable composition according to any one of <1> to <4> wherein the component B contains a hexafunctional or higher functional polymerizable compound. The curable composition according to any one of <1> to <5> wherein the a2 is 0.5 to 1.9 times molar equivalent by 1.0 mol of the total molar amount with respect to the titanium atom and the zirconium atom. Titanium obtained by hydrolyzing and condensing at least one selected from the group consisting of a titanium compound having an alkoxy group, a zirconium compound having an alkoxy group, and a titanium compound having a halogen group and a zirconium compound having a halogen group Oxyalkane, zirconium oxide and/or titanyl-zirconoxane condensate. The curable composition according to any one of <1> to <6> wherein the component A contains the a2. <8> The curable composition according to any one of <1> to <7> which contains a photopolymerization initiator as component D.

<9> A method for producing a cured film, comprising at least a step a to a step d, and a step a: a coating step of applying the curable composition according to any one of <1> to <8> on a substrate Step b: solvent removal step, removing solvent from the applied curable composition; Step c: Exposure step, exposing at least a portion of the curable composition from which the solvent has been removed by actinic radiation; Step d: Heat treatment step The heat-treated composition is heat-treated.

<10> A method for producing a cured film, comprising at least a step 1 to a step 5, and a step 1: a coating step of applying the curable composition according to any one of <1> to <8> on a substrate Step 2: solvent removal step, removing solvent from the applied curable composition; Step 3: Exposure step, exposing at least a portion of the curable composition from which the solvent has been removed by actinic radiation; Step 4: Developing step The exposed curable composition is developed with an aqueous developing solution; Step 5: A heat treatment step of heat-treating the developed curable composition. <11> A cured film obtained by curing the curable composition according to any one of <1> to <8>. <12> The cured film according to <11>, which is an interlayer insulating film or an overcoat film. <13> The cured film according to <11> or <12> has a refractive index of 1.6 to 1.9 at a wavelength of 550 nm. <14> A liquid crystal display device having the cured film according to any one of <11> to <13>. <15> An organic EL display device having the cured film according to any one of <11> to <13>. <16> A touch panel having the cured film according to any one of <11> to <13>. <17> A touch panel display device having the cured film according to any one of <11> to <13>. [Effects of the Invention]

According to the present invention, it is possible to provide a curable composition capable of obtaining a cured film having high transparency and high in-plane uniformity, a cured film obtained by curing the curable composition, a method for producing the same, and the same An organic EL display device for a film, a liquid crystal display device, a touch panel, and a touch panel display device.

Hereinafter, the contents of the present invention will be described in detail. The description of the constituent elements described below may be performed according to a representative embodiment of the present invention, but the present invention is not limited to such an embodiment. In the present specification, the term "~" is used to mean that the numerical values described before and after are included as the lower limit and the upper limit. In addition, the organic EL element of the present invention means an organic electroluminescence element. In the expression of the group (atomic group) in the present specification, the unsubstituted and unsubstituted expression is not described to include not only a group having no substituent (atomic group) but also a group having a substituent (atomic group). 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). Further, the chemical structural formula in the present specification may be described in a simplified structural formula in which a hydrogen atom is omitted. Further, in the present specification, "(meth)acrylate" means acrylate and methacrylate, "(meth)acrylic" means acrylic acid and methacrylic acid, and "(meth)acrylylene group" means acrylonitrile group. And methacryl oxime. In the present invention, "at least one selected from the group consisting of a1 to a3" or the like is simply referred to as "component A" or the like. In the present invention, "% by mass" and "% by weight" have the same meaning, and "parts by mass" and "parts by weight" have the same meaning. Further, in the present invention, the combination of the preferred embodiments is a more preferred embodiment.

The weight average molecular weight and the number average molecular weight of the titanyl, zirconium and titanyl-zirconoxane condensate of the present invention are measured by a gel permeation chromatography (GPC) method.

(Curable composition) The curable composition of the present invention (hereinafter also referred to simply as "composition") is characterized by containing at least one selected from the group consisting of a1 to a3 described below as component A. The curable compound of the component B and the solvent of the component C; and the component C contains the viscosity at 20 ° C as the component C-1 of 50 mPa·s or more and 200 mPa·s or less and a surface tension of 30 mN/m. The content of the component C-1 is at least one organic solvent of 41 mN/m or less and at least one organic solvent having a viscosity of less than 50 mPa·s at 20 ° C as the component C-2, and the total mass of the component C. The viscosity of the curable composition at 20° C. is from 20% by mass to 95% by mass, and is from 1 mPa·s to 30 mPa·s. A1: a titanium compound having an alkoxy group and/or a zirconium compound, a2: a titanyl, zirconium and/or a titanyl-zirconium having at least one alkoxy group directly bonded to a titanium atom or a zirconium atom Oxyalkyl condensate, a3: a metal oxide containing a titanium atom and/or a zirconium atom. The curable composition of the present invention is suitably used in applications such as a refractive index adjusting layer (index matching layer) for improving visibility, or a refractive index adjusting insulating film or overcoat layer for preventing fluoroscopy.

In the field of touch screens, it has become a problem that polymer insulators are visible or wiring such as indium tin oxide (ITO) is visible (so-called perspective). In order to solve this problem, a refractive index adjusting layer (index matching layer) is used. In the past, as an index matching layer, a sputtering-type index matching layer, such as a sputtering vapor deposition layer of cerium oxide, has been used. However, due to the cost of materials or production, titanium oxide or zirconium oxide which imparts a high refractive index is being studied. A metal oxide, or a metal alkoxide such as a titanium alkoxide or a zirconium alkoxide, or a titanyl or zirconium oxide which is a condensate of these, is used as a coating liquid to form a coating form of a layer. As a result of intensive studies, the inventors of the present invention have found that the coating liquid using a usual solvent has a problem in that it becomes a cloudy surface state during drying, or the transparency is deteriorated, or a dishing failure occurs, or a flexo is used. In-plane distribution or the like occurs when printing or inkjet printing is performed. The present inventors have found that a curable composition capable of obtaining a cured film having high transparency and high in-plane uniformity can be obtained by using a specific solvent in combination, and completed the present invention. Further, the expression mechanism of the detailed effect is not clear, but if an alcohol-based high-viscosity solvent is used in order to obtain a viscosity suitable for flexographic printing or inkjet printing, there is a case where a high-viscosity solvent generally has a high surface tension and a depression occurs. The problem. Further, when a solvent having a high surface tension is used, there is a problem that pinholes are generated due to the phase property with the substrate during drying or drying. Further, there is a problem that compatibility with the component A and the component B is low, phase separation occurs during drying, white turbidity, and transparency is deteriorated. It is presumed that in the present invention, by using a specific solvent in combination as a solvent, the viscosity of the composition is improved, and the surface tension is lowered, thereby suppressing phase separation during drying and the occurrence of white turbidity, but the effect of detailed effects is exhibited. The mechanism is not clear.

The curable composition of the present invention is preferably a photosensitive composition, and may be a positive photosensitive composition or a negative photosensitive composition, and is preferably a negative photosensitive composition. When the curable composition of the present invention is a negative photosensitive composition, it is preferred that the component B is a polymerizable compound. In the case where the curable composition of the present invention is a positive photosensitive composition, it is preferred to contain a polymer containing a structural unit having a group in which an acid group is protected by an acid-decomposable group, and a photoacid generator. . Further, when the curable composition of the present invention is a positive photosensitive composition, a chemically amplified positive photosensitive composition (chemically amplified positive photosensitive composition) is preferably used, or 1 may be used. A 2-quinonediazide compound is a non-chemically amplified positive photosensitive composition which is a photoacid generator for inducing actinic rays. A chemically amplified positive photosensitive composition is preferred in terms of high sensitivity and excellent transparency.

Moreover, when the curable composition of the present invention is a negative photosensitive composition, it is preferable to heat-treat the cured product such as the obtained cured film after polymerization by actinic rays, and the strength of the cured product is preferably obtained. A composition that becomes higher. Further, when the curable composition of the present invention is a positive photosensitive composition, it is preferred that after the exposed portion is removed, the unexposed portion is heated to cause a crosslinking reaction and harden.

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. Further, the curable composition of the present invention preferably has a curable composition having a refractive index of 1.60 or more at a wavelength of 550 nm of the obtained cured product, and more preferably a refractive index of the obtained cured product at a wavelength of 550 nm. A curable composition of 1.62 or more. Further, the refractive index of the obtained cured product at a wavelength of 550 nm is preferably 1.90 or less, more preferably 1.85 or less. Further, the refractive index of the present invention is a refractive index of light having a wavelength of 550 nm at 25 ° C unless otherwise specified. Further, the curable composition of the present invention can be suitably used as a curable composition for an interlayer insulating film or an overcoat film. Further, the curable composition of the present invention can be suitably used as a curable composition for a refractive index adjusting layer.

Component A: At least one of the curable compositions of the present invention selected from the group consisting of a1 to a3 contains at least one selected from the group consisting of a1 to a3 described below as component A, and is relative to curability. The total solid content of the composition, the content of the component A is 40% by mass to 80% by mass. A1: a titanium compound having an alkoxy group and/or a zirconium compound, a2: a titanyl, zirconium and/or a titanyl-zirconium having at least one alkoxy group directly bonded to a titanium atom or a zirconium atom Oxyalkyl condensate, a3: a metal oxide containing a titanium atom and/or a zirconium atom. Further, it is of course understood by those skilled in the art that the a1 has the same meaning as "a titanium compound having an alkoxy group and/or a zirconium compound having an alkoxy group", and the a2 and "having at least one direct bond" a titanyl alkoxy group on a titanium atom, a zirconium oxide having at least one alkoxy group directly bonded to a zirconium atom, or an alkoxy group having at least one directly bonded to a titanium atom or a zirconium atom The aluminoxane-zirconoxane condensate has the same meaning, and the a3 has the same meaning as the "metal oxide containing a titanium atom and/or a metal oxide containing a zirconium atom".

The content of the component A is preferably 15% by mass to 90% by mass based on the total solid content of the curable composition. When the refractive index of the cured product (cured film) is 1.60 to 1.90, from the viewpoint of refractive index adjustment, it is more preferably 15% by mass to 60% by mass, still more preferably 17.5% by mass to 45% by mass, and particularly It is preferably 20% by mass to 35% by mass. Further, when used as a high refractive index material, from the viewpoint of refractive index adjustment, it is preferably 40% by mass to 90% by mass, more preferably 50% by mass to 85% by mass, still more preferably 60% by mass to 80% by mass. . In addition, the "solid component" of the curable composition means a component obtained by removing a volatile component such as a solvent. Further, the solid component may of course be a liquid component which is not solid.

Component A may be a single a1, a single a2, a single a3, a mixture of a1 and a2, a mixture of a1 and a3, a mixture of a2 and a3, a mixture of a1 and a2 and a3, from the storage stability of the composition. From the viewpoint, it is preferred to use a2 alone, a3 alone, or a mixture of a1 and a2, and more preferably a2 alone. Further, a titanium compound and a zirconium compound may be used in combination as a1. Further, from the viewpoint of refractive index and storage stability, the component A preferably contains at least a2. From the viewpoint of the refractive index and the developability, the component A is preferably selected from the group consisting of a titanium compound, a titanate, and a titanium oxide, and from the viewpoint of low-temperature curability, curing speed, and stability. Preferably, it is selected from the group consisting of zirconium compounds, zirconium oxides and zirconium oxides.

A1: a titanium compound having an alkoxy group and/or a zirconium compound, and a1: a titanium compound having an alkoxy group and a zirconium compound having an alkoxy group, examples thereof include monoalcobalt titanium oxide, dialkyl titanium oxide, and trioxane Titanium oxide, titanium tetraaloxide, zirconium monosilane, zirconium dialkylate, zirconium trioxide, and zirconium tetranitride are preferably tetraalkyltitanium oxide and tetraalkylzirconia, and more preferably four, from the viewpoint of film physical properties. Alkyl oxide. Further, a1 may have at least one alkoxy group, and may have another group such as a halogen group or an alkyl group. From the viewpoint of the physical properties of the film, the tetraalkyl titanium oxide is preferably a tetraalkyl titanium oxide represented by the following formula a1-1. Further, from the viewpoint of the physical properties of the film, the tetraalkyl zirconia is preferably a tetraalkyl zirconia represented by the following formula a1-2.

[Chemical 1]

In the formula a1-1 and the formula a1-2, R ¹ to R ⁴ each independently represent 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.

From the viewpoint of the physical properties of the film, R ¹ to R ⁴ in the formula a1-1 and the formula a1-2 are each independently preferably an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, particularly preferably. An alkyl group having 1 to 5 carbon atoms.

The tetraalkyl titanate represented by the formula a1-1 is not limited to the following specific examples, and examples thereof include tetratitanium oxide, tetra-titanium oxide, tetra-n-propoxide-titanium oxide, titanium tetraisopropoxide, and tetra-n-butoxide. Titanium, tetraisobutyl titanium oxide, diisopropoxy di-n-butoxide titanium oxide, di-tert-butoxy diisopropyl titanium oxide, tetra-tert-butyl titanium oxide, tetraisooctyl titanium oxide, tetrastearyl titanium oxide, etc. . The tetradecyl zirconia represented by the formula a1-2 is not limited to the following specific examples, and examples thereof include zirconium tetrachloride, zirconium tetraoxide, tetra-n-propoxide zirconia, zirconium tetraisopropoxide, and tetra-n-butoxide. Zirconium, tetraisobutyl zirconia, diisopropoxy bis-n-butoxide zirconia, di-tert-butoxy-zirconium diiso-zirconia, tetra-tert-butyl zirconia, tetraiso-octyl zirconia, tetra-stearyl alkoxy zirconium oxide, etc. . These compounds may be used alone or in combination of two or more.

The titanyl oxide, also called polytitanium oxide, is a compound having two or more Ti-O-Ti bonds. The production method is, for example, a method in which a titanium alkoxide represented by the formula a1-1 is hydrolyzed and condensed using water to obtain a titanyl oxide. In addition to this, it is also possible to carry out hydrolysis and condensation of a titanium halide such as titanium tetrachloride. Among them, from the viewpoint of easiness of synthesis, a titanium alkoxide or a titanium chloride is preferable, and a titanium alkoxide is more preferable. Zirconoxane, also known as polyzirconium oxide, is a compound having two or more Zr-O-Zr bonds. Further, the production method thereof is the same as the method for producing the titanal oxide, except that the raw material is changed to a zirconium compound such as zirconium azide or zirconium halide. The titanyl-zirconoxane condensate is a condensate obtained by hydrolysis-condensation using both the titanium compound and the zirconium compound. Further, the production method thereof is the same as the above-described production method except that a titanium compound and a zirconium compound are used in combination as a raw material.

A2: a titanyl, zirconium oxide and/or a titanyl-zirconoxane condensate having at least one alkoxy group directly bonded to a titanium atom or a zirconium atom. The a2 is preferably passed through a titanium atom. And a total molar amount of zirconium atom of 1.0 mol to 0.5 to 1.9 times molar equivalent of water, selected from a titanium compound having an alkoxy group, a zirconium compound having an alkoxy group, a titanium compound having a halogen group, and a halogen group. The titanate, zirconium oxide and/or titanyl-zirconoxane condensate obtained by hydrolytic condensation of at least one of the groups consisting of zirconium compounds, more preferably by total relative to titanium atoms and zirconium atoms a molar amount of 1.0 mole to 0.5 to 1.9 times molar equivalent of water, and a titanium oxyalkylene obtained by subjecting at least one selected from the group consisting of a titanium compound having an alkoxy group and a zirconium compound having an alkoxy group to undergo hydrolysis hydrolysis. Zirconoxane and/or titanyl-zirconoxane condensate. In the case of using a titanium compound having a halogen group and/or a zirconium compound having a halogen group, it is preferably used in combination with a titanium compound having an alkoxy group and/or a zirconium compound having an alkoxy group, or a halogen group. A titanium compound and a compound having a halogen group and a zirconium compound and having at least one alkoxy group are added to water and an alcohol compound is added to carry out hydrolysis condensation. The titanium compound having a halogen group and the zirconium compound having a halogen group may, for example, be a monohalogen halide, a titanium dihalide, a titanium trihalide, a titanium tetrahalide, a zirconium monohalide, a zirconium dihalide, a zirconium trihalide or a zirconium tetrahalide. From the viewpoint of film properties, titanium tetrahalide and zirconium tetrahalide are preferable, and titanium tetrahalide is more preferable. These compounds may be used alone or in combination of two or more.

Further, in the hydrolysis condensation, not only water but also a solvent or the like may be used, and an alcohol compound may be used as an additive. Further, the solvent may suitably be an alcohol compound. From the viewpoint of mechanical strength of the obtained film, the amount of water used in the hydrolysis condensation is preferably 0.5 molar equivalent to 1.9 molar equivalent, relative to the total molar amount of titanium atom and zirconium atom of the raw material of 1.0 mol, from the film strength. The lower limit is preferably 0.9 molar equivalent or more, more preferably 1.2 molar equivalent or more, and the upper limit is preferably 1.8 molar equivalent or less, and more preferably 1.7 molar equivalent or less, from the viewpoint of film flexibility. From the viewpoint of storage stability of the composition and film physical properties, the component A is preferably a titanyl oxide (hereinafter also simply referred to as "titanium oxide") having at least one alkoxy group directly bonded to a titanium atom. a zirconium oxide having at least one alkoxy group directly bonded to a zirconium atom (hereinafter also referred to simply as "zirconium oxyalkylene") or having at least one alkoxy group directly bonded to a titanium atom or a zirconium atom. The titanyl-zirconoxane condensate (hereinafter also referred to simply as "titanoxane-zirconoxane condensate") more preferably contains a titanyl or zirconium oxide, and more preferably contains a titanyl oxide.

The titanate, zirconium oxide and titanate-zirconoxane condensate may be in the form of a linear, branched, three-dimensional network, a cantilever, a ladder, a cage or the like, and the form thereof is not Particularly preferred is a titanyl or zirconium oxide which is compatible with the component B. Further, the titanol and the zirconium oxide may be solid or liquid at normal temperature (25 ° C).

The weight average molecular weight of the titanyl, zirconium and titanyl-zirconoxane condensate is not particularly limited, but is preferably 500 to 50,000, more preferably 1,000 to 20,000.

The titanyl oxide is preferably a titanyl oxide represented by the following formula a2-1 from the viewpoint of film physical properties. Further, the zirconium oxide is preferably a zirconium oxide represented by the following formula a2-2 from the viewpoint of film physical properties. Ti _α O _β (OR) _γ (a2-1) Zr _α O _β (OR) _γ (a2-2) In the formula a2-1 and the formula a2-2, R independently represents a hydrogen atom and has a carbon number of 1 to 18 The alkyl group, the aryl group having 6 to 18 carbon atoms or the 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 titanate, zirconium oxide and titanyl-zirconoxane condensate of a2 may be a single composition or a mixture of two or more kinds.

A3: Metal oxide containing a titanium atom and/or a zirconium atom Examples of a3 include titanium oxide, zirconium oxide, and a composite oxide containing a titanium atom and/or a zirconium atom. The composite oxide containing a titanium atom and/or a zirconium atom is preferably titanium oxide, a titanium composite oxide, a zirconium oxide or a zirconium composite oxide, more preferably titanium oxide, a titanium composite oxide, or zirconium oxide, and further preferably titanium oxide. Or zirconia, particularly preferably titanium oxide. Titanium oxide is particularly preferably a rutile type having a high refractive index. These metal oxide particles may also be treated with an organic material in order to impart dispersion stability. Examples of the composite oxide include tin oxide-titanium oxide composite particles, cerium oxide-titanium oxide composite particles, and tin oxide-zirconia composite particles. Titanium oxide is particularly preferably a rutile type having a high refractive index. These metal oxide particles may also be treated with an organic material in order to impart dispersion stability.

For example, a TTO series (TTO-51 (A), TTO-51 (C), etc.) manufactured by Ishihara Industries Co., Ltd., which is a titanium oxide particle, TTO-S, TTO, may be used. -V series (TTO-S-1, TTO-S-2, TTO-V-3, etc.), MT series (MT-01, MT-05, etc.) manufactured by Tayca (shares); as tin oxide - Optolake TR-502, Optolake TR-504 of titanium oxide composite particles; Optolake TR-503, Opp as yttrium oxide-titanium oxide composite particles Optolake TR-513, Optolake TR-520, Optolake TR-521, Optolake TR-527 (above is the Japanese catalyst catalyst industry) Manufactured); zirconia particles (manufactured by High Purity Chemical Research Institute); tin oxide-zirconia composite particles (produced by Nisshin Catalyst Chemical Co., Ltd.).

The average primary particle diameter of a3 is preferably from 1 nm to 200 nm, more preferably from 3 nm to 80 nm, and particularly preferably from 5 nm to 50 nm, from the viewpoint of transparency of the curable composition. Here, the average primary particle diameter of the particles means an arithmetic mean value obtained by measuring the particle diameter of an arbitrary 200 particles by an electron microscope. Further, in the case where the shape of the particles is not spherical, the longest side is regarded as the particle diameter. Further, a3 can also be used in the form of a dispersion which is prepared by mixing and dispersing a3 in a suitable dispersant and a solvent using a mixing device such as a ball mill or a rod mill.

Further, from the viewpoint of high refractive index and film physical properties, the total content of titanium atoms and zirconium atoms is preferably 5% by mass to 60% by mass, and more preferably 10% by mass based on the total solid content of the curable composition of the present invention. ～50% by mass, more preferably 15% by mass to 40% by mass.

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

<Compound having an epoxy group or oxetanyl group> When the curable composition of the present invention is a positive photosensitive composition, the curable compound preferably contains a compound having an epoxy group, and/or The compound having an oxetanyl group is more preferably a compound having two or more epoxy groups in the molecule and/or a compound having two or more oxetanyl groups in the molecule. Further, in the case where the curable composition of the present invention is a negative photosensitive composition and is cured by a cationic active species, the polymerizable compound preferably contains a compound having an epoxy group and/or has an oxetane. The compound of the group is more preferably a compound having two or more epoxy groups in the molecule and/or a compound having two or more oxetanyl groups in the molecule. By heating, an epoxy group or an oxetanyl group of a compound having an epoxy group or an oxetanyl group in the molecule reacts with each other or with an acid (carboxylic acid or the like) in the composition. Further, cationic polymerization is initiated by coexisting with a cationically active species. Specific examples of the compound having an epoxy group in the molecule include a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, and an aliphatic group. An epoxy resin or an acrylic resin having an epoxy group in a side chain. The acrylic resin means that 70% by mole or more of the structural unit is a polymer containing the following structural unit. The weight average molecular weight of the acrylic resin is preferably 3,000 to 300,000, more preferably 7,000 to 50,000.

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

In the formula, R ² represents a hydrogen atom or a monovalent organic group, and the monovalent organic group preferably contains any one of a hydrogen atom, a carbon atom, an oxygen atom, and a nitrogen atom. The carbon number of the organic group is preferably from 1 to 25, more preferably from 1 to 15.

These compounds are available as commercial products. For example, JER152, JER157S70, JER157S65, JER806, JER828, JER1007 (manufactured by Mitsubishi Chemical Holdings Co., Ltd.), and the like as described in paragraph 0189 of JP-A-2011-221494 And, in addition, Denacol EX-611, EX-612, EX-614, EX-614B, EX-622, EX-512, EX-521, EX-411, EX-421, EX-313, EX-314, EX-321, EX-211, EX-212, EX-810, EX-811, EX-850, EX-851, EX-821, EX-830, EX- 832, EX-841, EX-911, EX-941, EX-920, EX-931, EX-212L, EX-214L, EX-216L, EX-321L, EX-850L, DLC-201, DLC-203, DLC-204, DLC-205, DLC-206, DLC-301, DLC-402 (above is manufactured by Nagase ChemteX), YH-300, YH-301, YH-302, YH-315 YH-324, YH-325 (the above is manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.). These compounds may be used alone or in combination of two or more. Among these, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolak type epoxy resin, an acrylic resin having an epoxy group in a side chain, and an aliphatic epoxy resin are more preferable. Preferably, a bisphenol A type epoxy resin, an alicyclic epoxy resin, and an acrylic resin which has an epoxy group in a side chain are mentioned.

Specific examples of the compound having an oxetanyl group include: Aron Oxetane OXT-121, OXT-221, OX-SQ, PNOX (above, manufactured by Toagosei Co., Ltd.) An acrylic resin having an oxetanyl group in a side chain. Further, the oxetanyl group-containing compound is preferably used singly or in combination with an epoxy group-containing compound.

A preferred example of the acrylic resin having an epoxy group or an oxetanyl group in the side chain is exemplified by an acrylic resin having the following structural unit. Further, in the following structural unit, R represents a hydrogen atom or a methyl group.

[Chemical 3]

<Polymerizable Compound> The curable composition of the present invention preferably contains the following polymerizable compound as the component B. The polymerizable compound is not particularly limited, and any of a radical polymerizable compound and a cationically polymerizable compound can be used, and a radical polymerizable compound is preferred from the viewpoint of curability. A cationically polymerizable compound is preferred from the viewpoint of transparency. The radically polymerizable compound is not particularly limited as long as it has at least one ethylenically unsaturated group, and is preferably a terminal ethylenically unsaturated group, and can be appropriately selected from known ethylenically unsaturated compounds. Among these, component B preferably contains a hexafunctional or higher polymerizable compound, and more preferably contains component B-1: a hexafunctional or higher ethylenically unsaturated compound, and more preferably contains a hexafunctional or higher functional group (methyl). Acrylic urethane.

Component B-1: Hexafunctional or higher functional ethylenically unsaturated compound The curable composition of the present invention preferably contains Component B-1: a hexafunctional or higher ethylenically unsaturated compound as Component B. The hexafunctional or higher ethylenically unsaturated compound can be exemplified by the component B-1-1: a hexa-functional or higher (meth)acrylic acid urethane, and the component B-1-2: other hexa-functional or more ethylenically unsaturated compound. . Among these, it is preferable to contain the component B-1-1 as the component B. Hereinafter, the component B-1-1 and the component B-1-2 will be described.

Component B-1-1: Hexafunctional or higher (meth)acrylic acid urethane The curable composition of the present invention preferably contains the component B-1-1: a hexafunctional or higher (meth)acrylic acid carbamate The ester is used as component B. The number of (meth)acryloxy groups in the hexafunctional or higher (meth)acrylic urethane is preferably 8 or more, more preferably 10 or more, and most preferably 12 or more. By adopting such a configuration, the effects of the present invention can be exhibited more effectively. In addition, the upper limit of the number of the (meth) acryloxy group is not particularly limited, and when it is not a polymer structure, it is preferably 50 or less, more preferably 30 or less, still more preferably 20 or less. The curable composition of the present invention may contain only one type of hexafunctional or higher (meth)acrylic acid urethane, or may contain two or more types. In the case where two or more kinds are contained, the total amount is preferably the above range.

The hexa-functional or higher (meth)acrylic acid urethane which can be used in the present invention is exemplified by a urethane addition polymerizable compound produced by an addition reaction of an isocyanate and a hydroxyl group, and is exemplified by Japanese Patent Laid-Open No. 51. Acrylic urethanes as described in Japanese Laid-Open Patent Publication No. Hei. No. Hei.

The molecular weight of the hexa-functional or higher (meth)acrylic urethane is preferably from 500 to 20,000, more preferably from 650 to 6,000, still more preferably from 800 to 3,000, from the viewpoint of hardness of the cured film. By adopting such a configuration, the effects of the present invention can be exhibited more effectively.

The (meth) acryloxy group in the hexa-functional or higher (meth) acrylate urethane may be either propylene methoxy or methacryloxy, or may be two types, from curable. From the viewpoint, propylene methoxy group is preferred. The number of the urethane bonds in the hexafunctional or higher (meth)acrylic acid urethane is not particularly limited, but is preferably 1 to 30, more preferably 1 to 20, still more preferably 2 to 10, particularly preferably 2 to 5. Most preferably 2 or 3. The hexa-functional or higher (meth)acrylic urethane is preferably a hexa-functional or higher aliphatic (meth) acrylate urethane. Further, the hexa-functional or higher (meth)acrylic urethane preferably has an isocyanuric ring structure. Further, the hexa-functional or higher (meth)acrylic acid urethane preferably contains a core portion having one or more urethane bonds, and is bonded to the core portion and has one or more (meth) propylene oxides. The compound of the terminal portion of the group is more preferably a compound having two or more terminal moieties bonded to the core moiety, and it is further preferred that two to five of the core moiety are bonded to each other. The compound of the terminal moiety is particularly preferably a compound having 2 or 3 of the terminal moieties bonded to the core moiety.

The hexa-functional or higher (meth)acrylic acid urethane is preferably a compound having at least a group represented by the following formula Be-1 or formula Be-2, and more preferably at least having the following formula Be-1; The compound of the group indicated. Further, the hexa-functional or higher (meth)acrylic acid urethane is more preferably composed of two or more groups selected from the group represented by the following formula Be-1 and the group represented by the formula Be-2. A compound of a group in a group. Further, the terminal moiety in the hexa-functional or higher (meth)acrylic acid urethane is preferably a group represented by the following formula Be-1 or the formula Be-2.

[Chemical 4]

In the formulas Be-1 and Be-2, R independently represents an acryl group or a methacryl group, and the wave line portion indicates a bonding position with another structure.

Further, the hexa-functional or higher (meth)acrylic acid urethane is preferably a compound having at least a group represented by the following formula Bc-1 or formula Bc-2, and more preferably at least having the following formula Bc- A compound of the group represented by 1. Further, the core portion in the hexa-functional or higher (meth)acrylic acid urethane is preferably a group represented by the following formula Bc-1 or formula Bc-2.

[Chemical 5]

In the formula Bc-1 and the formula Bc-2, L ¹ to L ⁴ each independently represent a divalent hydrocarbon group having 2 to 20 carbon atoms, and the wave line portion indicates a bonding position with another structure. L ¹ to L ⁴ each independently represent an alkylene group having 2 to 20 carbon atoms, more preferably an alkylene group having 2 to 10 carbon atoms, and still more preferably an alkylene group having 4 to 8 carbon atoms. Further, the alkylene group may also be branched or have a ring structure, preferably a linear alkylene group. Further, a hexa-functional or higher (meth)acrylic acid urethane is particularly preferably a group represented by the formula Bc-1 or the formula Bc-2, and a group selected from the group consisting of the formula Be-1 and the formula Be-2. A compound in which two or three groups in a group consisting of groups are bonded.

Hereinafter, the hexa-functional or higher (meth)acrylic urethane which can be preferably used in the present invention is exemplified, but the present invention is of course not limited to these compounds.

[Chemical 6]

[Chemistry 7]

[化8]

A commercially available product of a hexa-functional or higher (meth)acrylic acid urethane can be exemplified by U-6HA, UA-1100H, U-6LPA, U-15HA, U-6H available from Shin-Nakamura Chemical Industry Co., Ltd. , U-10HA, U-10PA, UA-53H, UA-33H (all registered trademarks); or UA-306H, UA-306T, UA-306I, UA-510H available from Gongrongshe Chemical Co., Ltd. Laromer UA-9048, UA-9050, PR9052 available from BASF; EBCRYL 220 available from Daicel-Allnex (shares) , 5129, 8301, KRM8200, 8200AE, 8452, etc.

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

Component B-2: less than hexafunctional ethylenically unsaturated compound The curable composition of the present invention comprises not only the above-mentioned hexafunctional or higher ethylenically unsaturated compound but also less than hexafunctional ethylenically unsaturated compound. -2 is not particularly limited as long as it is a compound having less than 6 ethylenically unsaturated groups, and may be appropriately selected depending on the purpose. For example, an ester compound, a guanamine compound, a carbamate compound, and other compounds are mentioned. The compound having an ethylenically unsaturated group may be any of a monofunctional ethylenically unsaturated compound and a difunctional to pentafunctional polyfunctional ethylenically unsaturated compound, and preferably contains a difunctional to pentafunctional polyfunctional ethylenic group. A saturated compound is more preferably a difunctional to pentafunctional polyfunctional ethylenically unsaturated compound.

Examples of the ester compound include polyfunctional (meth) acrylate, itaconate, crotonate, methacrylate, maleate, and other ester compounds. Among these, a polyfunctional (meth) acrylate (polyfunctional (meth) acrylate compound), etc. are preferable.

Examples of the polyfunctional (meth) acrylate compound include polyethylene glycol di(meth) acrylate, ethylene glycol di(meth) acrylate, and 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, sorbus Sugar alcohol tri(meth)acrylate, sorbitol tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, hexanediol Di(meth)acrylate and the like. Among them, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol penta(meth)acrylate are particularly preferable.

Other examples of the polyfunctional (meth) acrylate include addition of ethylene oxide or propylene oxide to a polyfunctional alcohol such as glycerin, trimethylolethane or bisphenol A (methyl group). The acrylated compound, the urethane acrylate described in Japanese Patent Laid-Open Publication No. SHO-48-41708, the Japanese Patent Publication No. SHO-50-6034, and the Japanese Patent Publication No. Sho 51-37193, Japanese Patent Polyester acrylates described in JP-A-48-64183, JP-A-49-43191, and Japanese Patent Publication No. Sho 52-30490, as reaction products of an epoxy resin and (meth)acrylic acid (Ethylene acrylate) or (meth)acrylic acid urethane or vinyl ester described in JP-A-60-258539.

Examples of the other polyfunctional ethylenically unsaturated compound include trimethylolpropane tris(propylene methoxypropyl) ether, isocyanuric acid tris(propylene decyloxyethyl) ester, and the Journal of Japan Next Association. Photocurable monomers and oligomers described in (Vol. 20, No. 7, pages 300 to 308).

In addition, examples of the guanamine compound include decylamine (monomer) of an unsaturated carboxylic acid and an aliphatic polyamine compound, and specific examples thereof include methylene bis(meth) acrylamide and 1,6. - hexamethylene bis(meth) acrylamide, diethylene triamine tri (meth) acrylamide, xylene bis (meth) acrylamide, etc., and Japanese Patent Laid-Open No. 60 -Methyl methacrylate or the like described in JP-258539. Further, the urethane compound may be a urethane chain polymerizable compound produced by an addition reaction of an isocyanate and a hydroxyl group, and examples thereof include a carbamate of pentaerythritol triacrylate and hexamethylene diisocyanate. An acid ester, a carbamate of pentaerythritol triacrylate and toluene diisocyanate, a carbamate of pentaerythritol triacrylate and isophorone diisocyanate, dipentaerythritol pentaacrylate and hexamethylene diisocyanate A urethane compound, a carbamic acid ester of dipentaerythritol pentaacrylate and toluene diisocyanate, a pentoxide of dipentaerythritol pentaacrylate and isophorone diisocyanate, and the like. Specific examples of the acrylamide group include those described in JP-A-2011-126921, JP-A-53-37193, JP-A-2-332293, and JP-A No. 2-16765. These salts are incorporated into the specification of the present invention.

In addition, examples of the other polyfunctional ethylenically unsaturated compound include an allyl compound or an alkenyl group-containing compound described in JP-A-60-258539, and International Publication No. 2010/050580. Specific examples thereof include 1,2-divinylbenzene, 1,4-divinylbenzene, 1,2-diallylbenzene, 1,3-diallylbenzene, and 1,4-dienepropene. Benzobenzene, 1,3,5-trivinylbenzene, 1,3,5-triallylbenzene, 1,2,4,5-tetraallylbenzene, hexaallylbenzene, divinyltoluene , bisphenol A diallyl ether, 1,2-diallyloxybenzene, 1,4-diallyloxybenzene, diallyl terephthalate, diallyl isophthalate, 1,4-bis(dimethylvinyldecyl)benzene, divinylmethylphenylnonane, divinyldiphenylnonane, diallyldiphenyldecane, and the like.

Examples of the monofunctional ethylenically unsaturated compound include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, methacrylic acid, and maleic acid, and salts of these acids, (meth) acrylates, and the like. A monofunctional ethylenically unsaturated compound such as (meth)acrylamide, (meth)acrylonitrile or styrene.

Further, an unsaturated carboxylic acid ester having a nucleophilic substituent such as a hydroxyl group, an amino group or a fluorenyl group, or an addition reaction product of an isocyanate or an epoxy group, and a monofunctional or polyfunctional group may also be suitably used. a dehydration condensation reaction product of a carboxylic acid or the like. Further, the following reactants are also suitable: an unsaturated carboxylic acid ester having an electrophilic substituent such as an isocyanato group (isocyanate group) or an epoxy group, or an oxime amine and an alcohol, an amine or a thiol. The reactant is further substituted with an unsaturated carboxylic acid ester such as a halogen group or a toluenesulfonyloxy group or a substituted reactant of an oxime amine and an alcohol, an amine or a thiol. Further, as another example, a compound group substituted with an unsaturated phosphonic acid, styrene, vinyl ether or the like may be used instead of the unsaturated carboxylic acid. The monofunctional ethylenically unsaturated compound is not particularly limited, and various known compounds can be used in addition to the above-exemplified compounds. For example, a compound described in JP-A-2009-204962 or the like can be used.

Further, a monofunctional ethylenically unsaturated compound can be preferably used: methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. (meth)acrylic acid derivatives such as esters, carbitol (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, epoxy (meth) acrylate, N-vinyl N-vinyl compounds such as pyrrolidone and N-vinyl caprolactam, and derivatives of allyl compounds such as allyl glycidyl ether.

In the curable composition of the present invention, the content of the component B-1 is preferably 70 parts by mass to 100 parts by mass, more preferably 75 parts by mass to 100 parts by mass, per 100 parts by mass of the total mass of the component B. Further, it is preferably 90 parts by mass to 100 parts by mass, and particularly preferably 95 parts by mass to 100 parts by mass. According to the above embodiment, the effects of the present invention are more effectively exhibited. In the curable composition of the present invention, the content of the component B is preferably 5% by mass to 85% by mass based on the total solid content of the curable composition, from the viewpoint of the refractive index and the developability of the cured film. It is preferably 10% by mass to 82.5% by mass, and more preferably 15% by mass to 80% by mass.

Component C: Solvent The curable composition of the present invention contains a solvent as component C, and component C contains a viscosity at 20 ° C as component C-1 of 50 mPa·s or more and 200 mPa·s or less, and a surface tension of 30. At least one organic solvent having a mN/m or more and 41 mN/m or less; and at least one organic solvent having a viscosity at 20 ° C of 20 ° C as the component C-2, the component is relative to the total mass of the component C The content of C-1 is from 20% by mass to 95% by mass. The curable composition of the present invention is preferably a liquid prepared by dissolving and/or dispersing an essential component and any component described later in a solvent. Hereinafter, the component C-1 and the component C-2 will be described.

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

The viscosity of the component C-1 at 20 ° C is 50 mPa·s or more and 200 mPa·s or less. When the viscosity at 20 ° C is 50 mPa·s or less, the viscosity of the entire composition is low, and the in-plane uniformity is poor. Further, when the viscosity at 20 ° C exceeds 200 mPa·s, the viscosity of the entire composition is too high, and the in-plane uniformity or the dent failure inhibition property is inferior. The viscosity of the component C-1 at 20 ° C is preferably 80 mPa·s to 200 mPa·s. The viscosity of the component C-1 is a value measured at 20 ° C, specifically, a RE85L type viscometer manufactured by Toki Sangyo Co., Ltd., and a cone type: 1° 34' × R24 The measurement was carried out at a liquid temperature of 20 °C.

The surface tension of the component C-1 is 30 mN/m or more and 41 mN/m or less. When the surface tension of the component C-1 exceeds 41 mN/m, the surface tension of the entire composition becomes high, which causes dents. Further, when the surface tension is less than 30 mN/m, the surface tension is too low to be excessively wetted and diffused, so that liquid bleed out on the substrate. The surface tension of the component C-1 is preferably from 30 mN/m to 41 mN/m, more preferably from 32 mN/m to 36 mN/m. The surface tension of the component C-1 was measured according to the Japanese Industrial Standards (JIS) K 2241 at 20 ° C using the Duunou surface tension meter as the index of the steel wire. The tension of the platinum ring. The boiling point of the component C-1 is preferably from 100 ° C to 300 ° C, more preferably from 120 ° C to 250 ° C, even more preferably from 200 ° C to 250 ° C from the viewpoint of coatability.

In the curable composition of the present invention, the content of the component C-1 is 20% by mass to 95% by mass based on the total mass of the component C, and the content of the component C-1 is less than 20% with respect to the total mass of the component C. %, the viscosity required for the curable composition could not be obtained, and the printability was poor. In addition, when the content of the component C-1 exceeds 95% by mass, the viscosity may become too high. Further, in the curable composition of the present invention, the content of the component C-1 is preferably 30% by mass to 95% by mass, and more preferably 50% by mass to 95% by mass based on the total mass of the component C. Further, the component C-1 may be used alone or in combination of two or more. When two or more types are used together as the component C-1, the total content may be sufficient.

The component C-1 is not particularly limited as long as it has the above viscosity and surface tension, and is preferably a terpene compound having a hydroxyl group and/or an acetoxy group, and more preferably contains a selected from the group consisting of Terpineol, dihydroterpineol, 4-(ethoxycarbonyl)-α,α,4-trimethylcyclohexanemethanol acetate, and 2-[1-methyl-1-(4- At least one of the group consisting of methyl-3-cyclohexen-1-yl)ethoxy]ethanol. Terpineol has the following α-, β-, and γ-isomers, which are commercially available from Japanese perfume medicines and Japanese terpene chemicals (viscosity: 54 mPa·s, surface tension 38). mN/m).

[Chemistry 9] 萜-terpineol β-terpineol γ-terpineol

In addition, dihydroterpineol exists in the following two isomers (1-hydroxy-p-menthane, and 8-hydroxy-p-menthane), from the Japanese terpene chemistry (shares) Commercially available dihydroterpineol (viscosity 83 mPa·s, surface tension 36 mN/m), Terusolve DTO-210 (viscosity 72 mPa·s, surface tension 36 mN/m) ).

[化10]

4-(ethoxycarbonyl)-α,α,4-trimethylcyclohexanemethanol acetate is a compound represented by the following formula C-3, which is a compound represented by the formula C-1 and a formula C a mixture of the compounds represented by -2, for example, Terusolve THA-90 (viscosity: 144 mPa·s, surface tension: 32.8 mN/m), commercially available from Japan Terpinene Chemical Co., Ltd. Terusolve THA-70 (viscosity 144 mPa·s, surface tension 32.9 mN/m).

[11]

2-[1-methyl-1-(4-methyl-3-cyclohexen-1-yl)ethoxy]ethanol is a compound represented by the following formula, for example, from the Japanese terpene chemistry (shares) Commercially available Terusolve TOE-100 (viscosity 62 mPa·s, surface tension 40.6 mN/m).

[化12]

Among these, the component C-1 of the present invention preferably contains a compound selected from terpineol, dihydroterpineol, or any of the formulae C-1 to C-3, and 2-[1-methyl. a compound of the group consisting of -1-(4-methyl-3-cyclohexen-1-yl)ethoxy]ethanol, more preferably comprising dihydroterpineol and formula C-1~ The compound represented by any one of C-3 is more preferably a mixture of the compound represented by the formula C-1 and the compound represented by the formula C-2 and the compound represented by the formula C-3.

Component C-2: Organic solvent having a viscosity at 20 ° C of less than 50 mPa·s In the present invention, an organic solvent having a viscosity at 20 ° C of less than 50 mPa·s is contained as the component C-2. When the viscosity of the component C-2 exceeds 50 mPa·s, the viscosity of the entire composition is too high, and thus the in-plane uniformity is inferior. The viscosity of the component C-2 at 20 ° C is preferably 10 mPa·s or less, more preferably 5 mPa·s or less, still more preferably 3 mPa·s or less. Further, the lower limit thereof is not particularly limited, but is preferably 0.5 mPa·s or more.

As the component C-2 used in the curable composition of the present invention, a well-known solvent can be used, and examples thereof include alcohols, ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, and ethylene glycol monoalkyl groups. 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, butanediol diacetate, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates, esters, ketones, guanamines, lactones, and the like. For other specific examples, reference is made to paragraph 0062 of Japanese Patent Laid-Open Publication No. 2009-098616. Among these solvents, preferred examples thereof include butanol, tetrahydrofurfuryl alcohol, phenoxyethanol, 1,3-butylene glycol diacetate, diethylene glycol methyl ethyl ether, and propylene glycol monomethyl ether. Acetate, acetamidineacetone, ethyl lactate, particularly preferably exemplified by butanol, 1,3-butanediol diacetate, diethylene glycol methyl ethyl ether, acetamidine acetone, ethyl lactate . The component C-2 may be used alone or in combination of two or more.

The boiling point of the component C-2 is preferably from 100 ° C to 300 ° C, more preferably from 120 ° C to 250 ° C, even more preferably from 120 ° C to 200 ° C from the viewpoint of coatability.

The content of the solvent in the curable composition of the present invention is preferably such that the total solid content of the curable composition is from 3% by mass to 30% by mass, from the viewpoint of the viscosity to be applied. . It is more preferably 5% by mass to 20% by mass, still more preferably 8% by mass to 15% by mass. That is, it is preferred that the total solid content: total solvent (mass ratio) = 8: 92 to 30: 70, more preferably 5: 95 to 20: 80, still more preferably 8: 92 to 15: 85.

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

- Compound having a Coordinating Group - In the present invention, in the case of using a1 and/or a2, a compound having a titanium complex group and/or a zirconium complex group is preferably contained as the component A. The "titanium coordination group and/or zirconium coordination group" in the present invention means a group which can form a coordinate bond with a titanium atom and/or a zirconium atom, and can be used only for a titanium atom or a zirconium atom. One forms a coordinate bond, and can also form a coordinate bond with both a titanium atom and a zirconium atom. In addition, the coordination formed by the titanium coordination group and/or the zirconium coordination group may be a single tooth coordination (one tooth coordination), a second tooth coordination, a three tooth coordination, and a coordination of four teeth or more. Any one of the ligand groups is preferably a monodentate or a bidentate coordinating group, and more preferably a bidentate coordinating group. Further, the titanium ligand group and/or the zirconium ligand group are preferably a group which is coordinated to a titanium atom and/or a zirconium atom to form a neutral ligand on a titanium atom and/or a zirconium atom. In the case where a compound having at least a titanium coordinating group and/or a zirconium ligand group is coordinated to a1 and/or a2, the energy level of the d orbital of the coordinated titanium atom or zirconium atom is split. Therefore, the presence or absence of the coordination is known by observing the division of the energy level. A method of confirming whether or not it is a titanium complex group and/or a zirconium complex group includes a method of observing the presence or absence of coordination. A well-known observation method can be used for the specific observation method, and examples thereof include a spectroscopy method or an Electron Spin Resonance (ESR).

The titanium coordinating group and/or the zirconium complexing group in the present invention is preferably a group having an oxygen atom, and more preferably having two or more, from the viewpoint of stability of the composition or film properties. The group of the oxygen atom is more preferably a group having a structure in which at least two oxygen atoms are bonded via another atom of 2 to 4 atoms in the middle, and it is particularly preferred to have at least 2 oxygen atoms in the middle. A group of structures bonded by another atom of 3 atoms or 4 atoms. Further, at least one of the oxygen atoms is preferably an oxygen atom of a carbonyl group in a carbonyl or ester structure. Further, from the viewpoint of stability of the composition or film physical properties, the titanium coordinating group and/or the zirconium complexing group of the present invention preferably is coordinated to the titanium atom and/or the zirconium atom by an oxygen atom. The group on the top.

The titanium coordinating group and/or zirconium ligand group of the present invention preferably has a structure selected from the group consisting of a 1,2-diketone structure, a 1,3-diketone structure, a 1,4-diketone structure, and an α-hydroxyketone. In a group consisting of a structure, an α-hydroxyester structure, an α-ketoester structure, a β-ketoester structure, a malonic acid diester structure, a fumaric acid diester structure, and a phthalic acid diester structure More preferably, at least one structural group has a structure selected from the group consisting of a 1,2-diketone structure, a 1,3-diketone structure, an α-hydroxyketone structure, an α-hydroxyester structure, an α-ketoester structure, and β. a group having at least one structure in a group consisting of a ketoester structure and a phthalic acid diester structure, and further preferably having a structure selected from the group consisting of a 1,3-diketone structure, an α-hydroxyketone structure, and β- A group having at least one structure in a group consisting of a ketoester structure and a phthalic acid diester structure, particularly preferably having a structure selected from the group consisting of a 1,3-diketone structure, an α-hydroxyketone structure, and a β-ketone The group of at least one structure in the group consisting of the ester structure, most preferably having at least one selected from the group consisting of a 1,3-diketone structure and a β-ketoester structure Group structure. According to the embodiment, the cured film obtained is more excellent in refractive index and storage stability.

The titanium ligand group or the zirconium ligand group of the present invention is preferably a group having any one of the structures represented by the following formulas b-1 to b-5, and more preferably has the following formula b- 1. A group having a structure represented by the formula b-2, the formula b-3 or the formula b-5, and more preferably having a structure represented by the following formula b-1, formula b-2 or formula b-3 The group is particularly preferably a group having a structure represented by the following formula b-1 or formula b-2.

[Chemistry 13]

In the formulae b-1 to 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, a halogen atom or a hydrazine. The base or alkoxycarbonyl group, nb represents an integer of 0 to 4, and the wave line portion indicates a bonding position with another structure.

L ¹ and L ^{2 are} preferably methylene groups. The carbon number of R' is preferably 0 to 20. Further, R' is each independently preferably an alkyl group, an alkoxy group or a halogen atom. Nb is preferably 0 or 1, more preferably 0.

Specific examples of the titanium coordinating group or the zirconium complexing group are as shown below. In addition, the wave line portion indicates the bonding position with other structures.

[Chemistry 14]

In the present invention, the compound having a titanium complex group and/or a zirconium complex group may be added as the component B, or may be added as the component C, and is not particularly limited, and it is preferably added as the component C. It is especially preferable to add as component C-2. In the case of being added as the component B, the ethylenically unsaturated group is not particularly limited, and preferably (meth)acryloxy group, (meth)acrylamide group, allyl group, styryl group The vinyloxy group is more preferably a (meth) propylene decyloxy group and an allyl group, and a (meth) acryloxy group is particularly preferable. From the viewpoint of developability, a compound having a titanium coordinating group and/or a zirconium complex group and an ethylenically unsaturated group preferably has a 1,3-diketone structure or a β-ketoester structure ( a (meth) acrylate compound, or an ethylenically unsaturated compound having a phthalic acid diester structure, more preferably a (meth) acrylate compound having a 1,3-diketone structure or a β-ketoester structure . Further, the compound having a titanium complex group and/or a zirconium complex group and an ethylenically unsaturated group may be used alone or in combination of two or more. From the viewpoint of chemical resistance of the cured film, the compound having a titanium coordinating group and/or a zirconium complex group and an ethylenically unsaturated group preferably has a titanium coordinating group and/or zirconium. The (meth) acrylate compound having a ligand group is more preferably a monofunctional (meth) acrylate compound having a titanium coordinating group and/or a zirconium dentate group, and further preferably shown below. compound of. Further, the ethylenically unsaturated compound having a phthalic acid diester structure may preferably be exemplified by diallyl phthalate.

[化15]

Further, the compound having no ethylenically unsaturated group and having a titanium coordinating group and/or a zirconium complexing group is preferably a 1,2-diketone compound, a 1,3-diketone compound, or a 1,4-diketone compound. , an 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, 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 preferred, and 1,3 is further preferred. a diketone compound, an α-hydroxyketone compound or a β-ketoester compound, and a 1,3-diketone compound or a β-ketoester compound is particularly preferable. Specific examples of the compound having no ethylenically unsaturated group and having a titanium coordinating group and/or a zirconium ligand group include the compounds shown below.

[Chemistry 16]

Among these compounds, acetonitrile acetone (2,4-pentanedione), ethyl acetate (ethyl 3-oxobutanoate), or ethyl lactate is preferred, and ethyl acetate or ethyl acetate is particularly preferred. . These apply to ingredient C-2.

The content of these compounds having a coordinating group is preferably 15 parts by mass to 140 parts by mass based on 100 parts by mass of the total content of a1 and a2.

Component D: Photopolymerization Initiator The curable composition of the present invention preferably contains a photopolymerization initiator as component D. When the curable composition of the present invention is a negative photosensitive composition, it is particularly preferable to contain a photopolymerization initiator. The photopolymerization initiator preferably contains a photoradical polymerization initiator. The photopolymerization initiator which can be used in the present invention is a compound which can initiate polymerization of a polymerizable compound such as a compound having an ethylenically unsaturated group by irradiation with actinic rays. The "actinic ray" is not particularly limited as long as it is an active energy ray that can impart energy for inducing species to the component D by irradiation, and includes α rays, γ rays, X rays, and ultraviolet rays (UV) in a wide range. , visible light, electron beam, etc. Among these, light containing at least ultraviolet rays is preferred.

Examples of the photopolymerization initiator include an oxime ester compound, an organic halogenated compound, an oxydiazole compound, a carbonyl compound, a ketal compound, a benzoin compound, an acridine compound, an organic peroxidation compound, an azo compound, and a fragrance. A soy compound, an azide compound, a metallocene compound, a hexaarylbiimidazole compound, an organoboronic acid compound, a disulfonic acid compound, a phosphonium salt compound, a mercaptophosphine (oxide) compound. Among these compounds, an oxime ester compound and/or a hexaarylbiimidazole compound is preferable from the viewpoint of sensitivity, and an oxime ester compound is more preferable.

The oxime ester compound can be used, for example, in JP-A-2000-80068, JP-A-2001-233842, JP-A-2004-534797, JP-A-2007-231000, and JP-A-2009- The compound described in Japanese Patent Publication No. 134289. The oxime ester compound is preferably a compound represented by the following formula D-1 or formula D-2.

[化17]

In the formula D-1 or the formula D-2, Ar represents an aromatic group or a heteroaromatic group, R ^D1 represents an alkyl group, an aromatic group or an alkoxy group, and R ^D2 represents a hydrogen atom or an alkyl group, and further R ^D2 may be used. Bonded to the Ar group to form a ring.

Ar represents an aromatic group or a heteroaromatic group, preferably a group obtained by removing one hydrogen atom from a benzene ring, a naphthalene ring or a carbazole ring, and more preferably a naphthyl group or a carbazole which forms a ring together with R ^D2 . base. The hetero atom in the heteroaromatic group may preferably be a nitrogen atom, an oxygen atom or a sulfur atom. Among them, a nitrogen atom is preferred. R ^D1 represents an alkyl group, an aromatic group or an alkoxy group, preferably a methyl group, an ethyl group, a benzyl group, a phenyl group, a naphthyl group, a methoxy group or an ethoxy group, more preferably a methyl group, an ethyl group, a phenyl group or a methyl group. Oxygen. R ^D2 represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or a substituted alkyl group, more preferably a hydrogen atom, a substituted alkyl group or a toluenesulfanyl group which forms a ring together with Ar. Further, Ar is preferably a group having 4 to 20 carbon atoms, R ^D1 is preferably a group having 1 to 30 carbon atoms, and R ^D2 is preferably a group having 1 to 50 carbon atoms.

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

[化18]

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

R ^D1 represents an alkyl group, an aromatic group or an alkoxy group, and preferably a group represented by R ^D11 -X'-alkylene group. R ^D11 represents an alkyl group or an aryl group, and X' represents a sulfur atom or an oxygen atom. R ^D11 is preferably an aryl group, more preferably a phenyl group. The alkyl group and the aryl group as R ^D11 may be substituted by a halogen atom (preferably a fluorine atom, a chlorine atom or a bromine atom) or an alkyl group. X is preferably a sulfur atom. R ^D3 and R ^D4 can be bonded at any position on the aromatic ring. R ^D4 represents alkyl, phenyl, alkyl-substituted amino, arylthio, alkylthio, alkoxy, aryloxy or halogen atom, preferably alkyl, phenyl, arylthio or halogen atom, more An alkyl group, an arylthio group or a halogen atom is preferred, and an alkyl group or a halogen atom is further preferred. The alkyl group is preferably an alkyl group having 1 to 5 carbon atoms, more preferably a methyl group or an ethyl group. The halogen atom is preferably a chlorine atom, a bromine atom or a fluorine atom. Further, the carbon number of R ^D4 is preferably 0 to 50, and more preferably 0 to 20. R ^D5 represents a hydrogen atom, an alkyl group or an aryl group, preferably an alkyl group. The alkyl group is preferably an alkyl group having 1 to 5 carbon atoms, more preferably a methyl group or an ethyl group. The aryl group is preferably an aryl group having 6 to 10 carbon atoms. R ^D6 represents an alkyl group, preferably an alkyl group having 1 to 5 carbon atoms, more preferably a methyl group or an ethyl group. N1 and n2 respectively represent the substitution number of R ^D3 on the aromatic ring of the formula D-3 or the formula D-4, and n3 represents the substitution number of R ^D4 on the aromatic ring of the formula D-5. N1 to n3 are each independently preferably an integer of 0 to 2, and more preferably 0 or 1.

Examples of the oxime ester compound which can be preferably used in the present invention are shown below. However, the oxime ester compound used in the present invention is of course not limited to these compounds. Further, Me represents a methyl group, and Ph represents a phenyl group. Further, the cis-trans isomer of the double bond of fluorene in these compounds may be either EZ or a mixture of EZ.

[Chemistry 19]

Specific examples of the organic halogenated compound include: Bull Chem. Soc. Japan (42, 2924 (1969)), US Patent No. 3,905,815, and Japanese Patent Publication No. 46-- Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. JP-A-61-169837, JP-A-62-58241, JP-A-62-212401, JP-A-63-70243, and JP-A-63-298339 The compound described in "Journal of Heterocyclic Chemistry" (1 (No. 3), (1970)) of MP Hutt, and the like, in particular, is substituted by a trihalogenated methyl group. Oxazole compound, s-triazine compound.

Examples of the hexaarylbiimidazole compound include various compounds described in each specification, such as Japanese Patent Publication No. Hei. 6-29285, U.S. Patent No. 3,479,185, U.S. Patent No. 4,311,783, and U.S. Patent No. 4,622,286.

The mercaptophosphine (oxide) compound is exemplified by a monodecylphosphine oxide compound and a bis-fluorenylphosphine oxide compound, and specific examples thereof include IRGACURE 819 and Darooco (manufactured by BASF Corporation). Darocure) 4265, Darocure TPO, etc. The acetophenone compound can be exemplified by IRGACURE 127 manufactured by BASF Corporation.

The photopolymerization initiator may be used alone or in combination of two or more. Further, in the case of using a photopolymerization initiator which does not have absorption at 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 parts by mass to 30 parts by mass, more preferably 1 part by mass to 20 parts by mass, even more preferably 100 parts by mass of the total solid content in the composition. 1 part by mass to 10 parts by mass, particularly preferably 2 parts by mass to 5 parts by mass.

- Sensitizer - A sensitizer may be added to the curable composition of the present invention in addition to a photopolymerization initiator and a photoacid generator to be described later. The sensitizer absorbs actinic rays or radiation and becomes an excited state. The sensitizer which is in an excited state interacts with the component D, thereby generating an action of electron movement, energy movement, heat generation, etc., and can initiate and promote polymerization. Examples of preferred sensitizers include compounds belonging to the following compounds and having an absorption wavelength in the range of 350 nm to 450 nm. Polynuclear aromatics (such as lanthanum, cerium, triphenylene, anthracene, phenanthrene), xanthene (such as fluorescein, eosin, erythrosine, rhodamine B, bengal red), xanthone (such as xanthone) , thioxanthone, dimethyl thioxanthone, diethyl thioxanthone, isopropyl thioxanthone, 2-chlorothioxanthone), cyanines (eg, thiocarbocyanine, oxycarbocyanine), Cyanines (eg, merocyanine, carbonaceous cyanine), rhodamines, oxaphthalocyanines, thiazides (eg, thioindigo, methylene blue, toluidine blue), acridines (eg acridine orange, Chlorophyll, propylene flavin, benzoflavin), acridone (eg acridone, 10-butyl-2-chloroacridone), anthraquinones (eg hydrazine, 9,10-two Butyloxy), squaraine compounds (eg, squaraine compounds), styryls, basic styryls, coumarins (eg, 7-diethylamino-4-methylcoumarin, Ketocoumarins, carbazoles (eg N-vinylcarbazole), camphorquinones, phenothiazines. Further, as a typical sensitizer which can be used in the present invention, a sensitizer disclosed in JV Vrivello, Adv. in Polymer Sci., 62, 1 (1984) can be cited. . Preferable specific examples of the sensitizer include ruthenium, osmium, acridine orange, thioxanthone, 2-chlorothioxanthone, benzoflavin, N-vinylcarbazole, and 9,10-dibutoxy group.蒽, 蒽醌, coumarin, keto coumarin, phenanthrene, camphorquinone, phenothiazine and the like. The sensitizer is preferably added in a ratio of 30 parts by mass to 200 parts by mass based on 100 parts by mass of the polymerization initiator.

Component E: mercapto compound The curable composition of the present invention preferably further contains a mercapto compound as component E. By containing a mercapto compound, a cured product having more excellent storage stability and a higher refractive index can be obtained, and the cured product is excellent in chemical resistance. The mercapto compound is a compound having at least one mercapto group (-SH) in the molecule. The mercapto compound is a monofunctional mercapto compound and a polyfunctional mercapto compound. Among them, a polyfunctional mercapto compound is preferred from the viewpoints of sensitivity, storage stability, and film physical properties. The mercapto group of the mercapto compound may be a primary mercapto group, a secondary mercapto group, or a third-order mercapto group. From the viewpoint of sensitivity and chemical resistance, a primary mercapto group or a second mercapto group is preferred, and a divalent mercapto group is more preferred. Further, from the viewpoint of storage stability, a secondary fluorenyl group or a tertiary fluorenyl group is preferred, and a second fluorenyl group is more preferred. The molecular weight of the mercapto compound which can be used in the present invention is preferably from 100 to 2,000, more preferably from 200 to 1,000. The number of the fluorenyl group of the mercapto compound which can be used in the present invention is not particularly limited, but is preferably 1 to 20, more preferably 2 to 10, still more preferably 2 to 6.

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

The monofunctional thiol compound may, for example, be a monofunctional aliphatic mercapto compound or a monofunctional aromatic mercapto compound, and specific examples thereof include mercapto ethanol, mercaptopropanol, mercaptobutanol, mercaptopropanediol, and mercaptobutanediol. , hydroxybenzenethiol and its derivatives, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 1-phenyl-1H-benzimidazole-2-thiol a mercapto compound such as 2-mercapto-4(3H)-quinazoline or β-mercaptophthalene. In addition, the compound described in paragraph 0097 to paragraph 0098 of JP-A-2011-65087, and the compound described in paragraphs 0086 to 0,088 of JP-A-2008-299211.

- Polyfunctional mercapto compound - Further, the mercapto compound is preferably a polyfunctional mercapto compound from the viewpoints of sensitivity, storage stability, and film physical properties. The polyfunctional fluorenyl compound may, for example, be a polyfunctional aliphatic mercapto compound or a polyfunctional aromatic mercapto compound. In the present invention, the "polyfunctional thiol compound" means a compound having two or more fluorenyl groups in the molecule. The polyfunctional thiol compound is preferably a low molecular compound having a molecular weight of 100 or more. Specifically, it is preferably a molecular weight of from 100 to 1,500, more preferably from 150 to 1,000. The polyfunctional fluorenyl compound preferably has 2 to 10 fluorenyl groups in the molecule, and more preferably has 2 to 6 groups. The aliphatic polyfunctional thiol compound is preferably a compound having two or more groups represented by the following formula e-1.

[Chemistry 20]

In the formula e-1, R represents a hydrogen atom or an alkyl group, and A represents -CO- or -CH ₂ -. The polyfunctional fluorenyl compound is preferably a compound having two or more and six or less groups represented by the formula e-1, and more preferably having two or more and four or less compounds. The alkyl group of R in the formula e-1 is a linear, branched or cyclic alkyl group, and the carbon number is preferably in the range of 1 to 16, more preferably 1 to 10. Specific examples of the alkyl group are methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, 2-ethylhexyl and the like, preferably methyl, ethyl or propyl. Base or isopropyl. R is preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group or an isopropyl group, more preferably a methyl group or an ethyl group.

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

[Chem. 21]

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

The alkyl group of R in the formula e-2 has the same meaning as R in the formula e-1, and the preferred range is also the same. n is preferably 2 to 4. L which is an n-valent linking group in the formula e-2 includes, for example, a divalent linking group such as -(CH ₂ ) _m - (m represents an integer of 2 to 6); a trimethylolpropane residue; a trivalent linking group such as an isocyanuric ring of three -(CH ₂ ) _p - (p represents an integer of 2 to 6); a tetravalent linking group such as a pentaerythritol residue; or a pentavalent linking group; A hexavalent linking group such as a pentaerythritol residue.

Specific examples of the polyfunctional mercapto compound include, for example, the following compounds as a preferred polyfunctional thiol compound: trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), tetraethyl Diol bis(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), pentaerythritol tetrakis (2-thioglycollate), pentaerythritol tetrakis(3-mercaptobutyric acid) Ester), butanediol bis(3-mercaptobutyrate), 1,4-bis(3-mercaptobutoxy)butane, 1,4-bis(3-mercaptobutyloxy)butane, 1,3,5-tris(3-mercaptobutoxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione and the like. Commercial products of the polyfunctional mercapto compound include Karenz MT (registered trademark) BD1, NR1 or PE1 (manufactured by Showa Denko), and TEMPIC (SC organic chemistry) Manufacturing) and so on.

[化22]

Other specific examples include the compounds described in paragraphs 0165 to 0167 of JP-A-2012-14052. The aromatic mercapto compound is exemplified by the compounds described in paragraphs 0021 to 0022 of International Publication No. 2010/050580. Among them, 4,4'-thiobisbenzenethiol is preferred.

Further, the aromatic mercapto compound is preferably a compound represented by the formula e-3.

[化23]

E-3 in formula, X ^e represents a C atom or N atom, Y ^e represents a N atom, C atom, S atom or O atom, L ^e represents a single bond or a divalent organic group, A ^e represents X ^e = C- Y ^e together form an atomic group of an aromatic ring. The aromatic ring formed by A ^e may have a substituent such as a hydroxyl group, an ether group, an ester group, an amino group, a decylamino group, a nitro group, a cyano group or the like, and further may have a thiol group different from those described in the formula.

Examples of the aromatic mercapto compound include phenylthiol, 4-ethylguanamine thiol, 4-tert-butylbenzenethiol, 2-naphthylthiol, 2-aminobenzenethiol, and 4-aminobenzenethiol. , 4-(dimethylamino)benzenethiol, 2-mercaptothiazole, 2-mercaptobenzothiazole, triphenylmethanthiol, 5-mercapto-1-phenyl-1H-tetrazole, 2 - mercaptopyridine, 2-mercapto-5-methyl-1,3,4-thiadiazole, 2-mercapto-1,3,4-thiadiazole, 2-amino-5-mercapto-1,3,4 a monofunctional aromatic mercapto compound such as thiadiazole, or

1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis(decylmethyl)benzene, 1,3-bis(decylmethyl)benzene, 1, 4-bis(decylmethyl)benzene, 1,3-bis(decylethyl)benzene, 1,4-bis(decylethyl)benzene, 1,2-bis(decylmethoxy)benzene, 1,3 - bis(indenylmethoxy)benzene, 1,4-bis(decylmethoxy)benzene, 1,2-bis(decylethoxy)benzene, 1,3-bis(decylethoxy)benzene, 1 , 4-bis(decylethoxy)benzene, 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene, 1,3,5-trimethylbenzene, 1,2,3-tri Mercaptomethyl)benzene, 1,2,4-tris(decylmethyl)benzene, 1,3,5-tris(decylmethyl)benzene, 1,2,3-tris(decylethyl)benzene, 1, 2,4-tris(decylethyl)benzene, 1,3,5-tris(decylethyl)benzene, 1,2,3-tris(fluorenylmethoxy)benzene, 1,2,4-trisyl (fluorenyl) Methoxy)benzene, 1,3,5-tris(fluorenylmethoxy)benzene, 1,2,3-tris(decylethoxy)benzene, 1,2,4-tris(decylethoxy)benzene 1,3,5-tris(decylethoxy)benzene, 1,2,3,4-tetradecylbenzene, 1,2,3,5-tetradecylbenzene, 1,2,4,5-tetradecyl Benzene, 1,2,3,4-tetrakis(fluorenylmethyl)benzene, 1,2,3,5-tetrakis(fluorenylmethyl)benzene, 1,2,4,5-tetrakisylmethyl)benzene, 1,2,3,4-tetrakis(decylethyl)benzene, 1,2,3, 5-tetrakis(decylethyl)benzene, 1,2,4,5-tetrakis(fluorenylethyl)benzene, 1,2,3,4-tetrakis(fluorenylmethoxy)benzene, 1,2,3,5 -tetrakis(methoxymethyl)benzene, 1,2,4,5-tetrakis(fluorenylmethoxy)benzene, 1,2,3,4-tetrakis(decylethoxy)benzene, 1,2,3, 5-tetrakis(decylethoxy)benzene, 1,2,4,5-tetrakis(decylethoxy)benzene, 2,2'-dimercaptobiphenyl, 4,4'-dimercaptobiphenyl, 4, 4'-dimercaptobenzyl, 2,5-toluene dithiol, 3,4-toluene dithiol, 1,4-naphthalene dithiol, 1,5-naphthalene dithiol, 2,6-naphthalene Mercaptan, 2,7-naphthalene dithiol, 2,4-dimethylbenzene-1,3-dithiol, 4,5-dimethylbenzene-1,3-dithiol, 9,10- Dimethyl mercaptan, 1,3-bis(p-methoxyphenyl)propane-2,2-dithiol, 1,3-diphenylpropane-2,2-dithiol, phenylmethane- 1,1-dithiol, 2,4-di(p-nonylphenyl)pentane, 1,2-bis(mercaptomethylthio)benzene, 1,3-bis(decylmethylthio)benzene, 1, 4-bis(mercaptomethylthio)benzene, 1,2-bis(mercaptoethylthio)benzene, 1,3-bis(mercaptoethylthio)benzene, 1,4-bis(decylethylthio)benzene, 1,2,3-tris(mercaptomethylthio)benzene, 1,2,4-tris(mercaptomethylthio)benzene, 1,3,5-tris(decylmethylthio)benzene, 1,2,3 -Tris(decylethylthio)benzene, 1,2,4- Tris(mercaptoethylthio)benzene, 1,3,5-tris(mercaptoethylthio)benzene, 1,2,3,4-tetrakis(fluorenylmethylthio)benzene, 1,2,3,5-tetra (mercaptomethylthio)benzene, 1,2,4,5-tetrakis(fluorenylmethylthio)benzene, 1,2,3,4-tetrakis(mercaptoethylthio)benzene, 1,2,3,5- Tetrakis(mercaptoethylthio)benzene, 1,2,4,5-tetrakis(mercaptoethylthio)benzene, 4,4'-thiobisbenzenethiol, 2,5- A polyfunctional aromatic mercapto compound such as dimercapto-1,3,4-thiadiazole, 2,6-dimercaptopurine, 1,3,5-triazine-2,4,6-trithiol.

The mercapto compound may be used alone or in combination of two or more. Further, from the viewpoint of the refractive index, the mercapto compound is preferably a mercapto compound having an aromatic ring. Further, from the viewpoint of developability, the mercapto compound preferably has a polar functional group such as an ester group, a thioester group, a hydroxyl group, a guanamine group, an ether group, or a thioether group in the molecule. . The content of the mercapto compound is preferably 0.1 parts by mass to 20 parts by mass, more preferably 0.5 parts by mass to 15 parts by mass, even more preferably 1 part by mass to 10 parts by mass, based on the total solid content of the curable composition. Share.

Component F: Surfactant The curable composition of the present invention may also contain a surfactant. As the surfactant, any of an anionic, cationic, nonionic or amphoteric surfactant can be used, and a preferred surfactant is a nonionic surfactant. Further, the surfactant is preferably a fluorine-based surfactant, and more preferably a fluorine-based nonionic surfactant. Examples of the surfactant which can be used in the present invention include Megafac F142D, Megafac F172, Megafac F173, Megafac F176, and Megafa (commercially available). Megafac) F177, Megafac F183, Megafac F479, Megafac F482, Megafac F554, Megafac F780, Megafac F781, Megafac ) F781-F, Megafac R30, Megafac R08, Megafac F-472SF, Megafac BL20, Megafac R-61, Megafac R -90 (made by DiCai (DIC)), Fluorad FC-135, Fluorad FC-170C, Fluorad FC-430, Fluorad FC-431, Novec FC-4430 (made by Sumitomo 3M), Asahiguard AG7105, 7000, 950, 7600, Surflon S-112, Surflon S-113, Surflon S-131, Surflon S-141, Surflon S-145, Surflon S-382, Surflon SC-101, Surflon SC-102, Surflon SC-103, Sand Surflon SC-104, Surflon SC-105, Surflon SC-106 (made by Asahi Glass), Eftop EF351, Eftop 352, Eftop 801, Eftop 802 (Mitsubishi Materials Electronics Co., Ltd.), Ftergent 250 (manufactured by Neos). In addition, in addition to the above, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), and Eftop (Mitsubishi Materials) are also mentioned. Electronic manufacturing (share) manufacturing), Megafac (made by DiCai (DIC)), Fluorad (made by Sumitomo 3M), Asahiguard, Shafulong ( Surflon) (made by Asahi Glass Co., Ltd.), various series of PolyFox (manufactured by OMNOVA).

In addition, as a surfactant, the following copolymer is preferable, and the structural unit A and the structural unit B represented by the following formula F-1 are contained, and the polystyrene conversion by the gel permeation chromatography using tetrahydrofuran as a solvent is used. A copolymer having a weight average molecular weight (Mw) of 1,000 or more and 10,000 or less.

Structural unit A structural unit B

In the 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 or more and 4 or less carbon atoms, and R ⁴⁰⁴ represents a hydrogen atom or a carbon number of 1 or more and 4 In the following alkyl group, L represents an alkylene group having 3 or more and 6 or less carbon atoms, p and q are mass percentages indicating a polymerization ratio, p is a numerical value of 10% by mass or more and 80% by mass or less, and q is 20% by mass or more. And a numerical value of 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.

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

[化25]

The weight average molecular weight (Mw) of the copolymer is more preferably 1,500 or more and 5,000 or less. These surfactants may be used alone or in combination of two or more. In the case of formulating a surfactant, the content of the surfactant in the curable composition of the present invention is preferably 0.001 part by mass to 5.0 parts by mass, more preferably 0.01 mass, based on 100 parts by mass of the total solid content of the curable composition. Parts to 2.0 parts by mass.

Component G: alkoxydecane compound The composition of the present invention may also contain an alkoxydecane compound as a adhesion improving agent. When an alkoxydecane compound is used, the adhesion between the film formed of the curable composition of the present invention and the substrate can be improved, or the taper angle of the film formed by the curable composition of the present invention and the substrate can be adjusted (taper angle) ). The alkoxydecane compound which can be used in the composition of the present invention is preferably an inorganic material which is a substrate, an antimony compound such as cerium, cerium oxide or cerium nitride, or a metal such as gold, copper, molybdenum, titanium or aluminum. A compound having improved adhesion to a film. Specifically, a well-known decane coupling agent or the like is also effective. The decane coupling agent may preferably be an alkoxydecane compound having an epoxy group or a (meth) propylene fluorenyloxy group. Examples of the decane coupling agent include γ-aminopropyltrimethoxydecane, γ-aminopropyltriethoxydecane, γ-glycidoxypropyltrimethoxydecane, and γ-glycidoxypropyl group. Trialkoxy decane, γ-glycidoxypropyl dialkoxy decane, γ-methyl propylene methoxy propyl trialkoxy decane, γ-methyl propylene methoxy propyl dialkoxy Decane, γ-chloropropyltrialkoxydecane, γ-mercaptopropyltrialkoxydecane, β-(3,4-epoxycyclohexyl)ethyltrialkoxydecane, vinyltrialkoxy Decane, 3-propenyloxypropyltrimethoxydecane. Among these, γ-glycidoxypropyltrialkoxydecane or γ-methacryloxypropyltrialkoxydecane and 3-propenyloxypropyltrimethoxydecane are more preferable. The alkoxydecane compound which can be used in the curable composition of the present invention is not particularly limited to these compounds, and a well-known compound can be used.

The alkoxydecane compound may be used alone or in combination of two or more. When the curable composition of the present invention contains an alkoxydecane compound, the content of the alkoxydecane compound is preferably 0.1 parts by mass to 30 parts by mass, based on 100 parts by mass of the total solid content in the curable composition. It is preferably 0.5 parts by mass to 20 parts by mass. Moreover, it is preferably 0.1 parts by mass to 20 parts by mass, more preferably 0.5 parts by mass to 10 parts by mass, per 100 parts by mass of the component B.

Component H: Crosslinking agent The curable composition of the present invention may contain a crosslinking agent as needed. The cured film obtained from the curable composition of the present invention can be made into a stronger film by adding a crosslinking agent. The crosslinking agent is not limited as long as it causes a crosslinking reaction by heat (excluding each component described above), and a known crosslinking agent can be used. When the curable composition of the present invention contains a crosslinking agent, the content of the crosslinking agent is preferably 0.1 part by mass to 50 parts by mass, more preferably 0.1 part by mass, per 100 parts by mass of the total solid content of the curable composition. ～30 parts by mass, more preferably 0.5 parts by mass to 20 parts by mass. By adding in the said range, the hardening film which is excellent in mechanical strength and solvent resistance can be obtained. It is also possible to use a plurality of different kinds of crosslinking agents in combination, and at this time, all the crosslinking agents are added to calculate the content.

Ingredient I: Antioxidant The curable composition of the present invention may also contain an antioxidant. Antioxidants can contain well known antioxidants. By adding an antioxidant, it is possible to prevent the coloration of the cured film, or to reduce the thickness of the film due to decomposition, and to improve the heat-resistant transparency. Examples of such an antioxidant include phosphorus-based antioxidants, guanamines, guanidines, hindered amine-based antioxidants, sulfur-based antioxidants, phenolic antioxidants, ascorbic acid, zinc sulfate, saccharides, and nitrites. Sulfite, thiosulfate, hydroxylamine derivative, and the like. Among these, from the viewpoint of coloring of the cured film and thinning of the film thickness, phenol-based antioxidants (hindered phenols), hindered amine-based antioxidants, and phosphorus-based antioxidants (alkyl phosphites) are particularly preferable. A sulfur-based antioxidant (thioether) is most preferably a phenol-based antioxidant. These antioxidants may be used alone or in combination of two or more. 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. Enter the instructions in this case. Preferred commercially available products include: Adekastab AO-60, Adekastab AO-80 (above, manufactured by ADEKA), Yannos (Irganox) 1035, Irganox 1098, Irganox 1726, IRGAFOS 168 (above, BASF).

When the curable composition of the present invention contains an antioxidant, the content of the antioxidant is preferably 0.1 parts by mass to 10 parts by mass, more preferably 0.2 parts by mass to 5 parts by mass per 100 parts by mass of the total solid content of the curable composition. The part by mass is more preferably 0.5 parts by mass to 4 parts by mass.

Component J: Other metal oxide particles The curable composition of the present invention may contain other metal oxide particles in order to adjust the refractive index or light transmittance without containing titanium atoms and zirconium atoms. The metal of the other metal oxide particles also contains a semimetal such as boron (B), bismuth (Si), germanium (Ge), arsenic (As), antimony (Sb) or tellurium (Te). Preferred other metal oxide particles preferably include beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), strontium (Sc), strontium (Y), and lanthanum (La). , Ce (Ce), G (Gd), Tb (Tb), Dy, Yb, Lu, Hf, Nb, Mo (Mo), Tungsten (W) , zinc (Zn), boron (B), aluminum (Al), germanium (Si), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), antimony (Bi), antimony (Te) As the oxide particles of the equal atom, zinc oxide, indium/tin oxide, and antimony/tin oxide are more preferable.

The average primary particle diameter of the other metal oxide particles is preferably from 1 nm to 200 nm, more preferably from 3 nm to 80 nm, and particularly preferably from 5 nm to 50 nm from the viewpoint of transparency of the curable composition. Here, the average primary particle diameter of the particles means an arithmetic mean value obtained by measuring the particle diameter of an arbitrary 200 particles by an electron microscope. Further, in the case where the shape of the particles is not spherical, the longest side is regarded as the particle diameter.

Further, the other metal oxide particles may be used alone or in combination of two or more. The content of the other metal oxide particles in the curable composition of the present invention may be appropriately determined in consideration of the refractive index or light transmittance required for the optical member obtained from the curable composition, and the present invention. The total solid content of the curable composition is preferably from 0% by mass to 50% by mass, more preferably from 1% by mass to 40% by mass, even more preferably from 2% by mass to 30% by mass. .

In the present invention, other metal oxide particles can also be used in the form of a dispersion which mixes other metal oxide particles in a suitable dispersant and solvent by using a mixing device such as a ball mill or a rod mill. Prepared by dispersion.

-Other components - In the curable composition of the present invention, a plasticizer, a polymerization inhibitor, a thermal acid generator, an acid proliferator, a binder polymer, and an acid group-containing group having an acid group may be added as needed. Other components such as a polymer of a structural unit of a group, a photoacid generator, a fluorene compound, a dispersant, and a heterocyclic compound having two or more nitrogen atoms. For the components, for example, the components described in JP-A-2009-98616, JP-A-2009-244801, and the components described in paragraphs 0203 to 0298 of JP-A-2014-132292 can be used. The components described in paragraphs 0025 to 0050 of International Publication No. 2014/199967, and other well-known components. In addition, various ultraviolet absorbers, metal deactivators, and the like described in "New Development of Polymer Additives (Nikko Kogyo Co., Ltd.)" 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. The polymerization inhibitor refers to a substance that performs hydrogen supply (or hydrogen transfer), energy supply (or energy transfer), and electron supply (or electron donation) to a polymerization-initiated radical component generated by a polymerization initiator. Etc., the polymerization initiates the inactivation of free radicals and inhibits polymerization initiation. For example, the compound described in paragraphs 0154 to 0173 of JP-A-2007-334322 can be used. Preferred examples of the compound include phenothiazine, phenoxazine, hydroquinone, and 3,5-dibutyl-4-hydroxytoluene. The content of the polymerization inhibitor is not particularly limited, and is preferably 0.0001% by mass to 5% by mass based on the total solid content of the curable composition.

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

The curable composition of the present invention may further contain a polymer other than a polymer including a structural unit having a group in which an acid group is protected by an acid-decomposable group. The curable composition of the present invention preferably contains a polymer component containing a polymer satisfying at least one of the following (1) and (2). (1) A polymer (2) comprising (a1) a structural unit having a group having an acid group protected by an acid-decomposable group and (a2) a structural unit having a crosslinkable group (a1) having an acid group decomposed by an acid Polymer of a structural unit of a group which protects a group, and a polymer which comprises (a2) structural unit which has a bridge|crosslinking group The hardening composition of this invention can further contain the polymer other than these. The curable composition of the present invention preferably contains a component satisfying the above (1) from the viewpoints of transparency (haze) after curing and residual film ratio of the unexposed portion. Further, in the present invention, a polymer satisfying the component (1) or a structural unit containing (a2) a crosslinkable group in the above (2) is regarded as the component B.

In the present invention, the "group in which the acid group is protected by the acid-decomposable group" can be used as the acid group and the acid-decomposable group, and is not particularly limited. Specific acid groups are preferably exemplified by a carboxyl group and a phenolic hydroxyl group. Further, as the acid-decomposable group, a group which is relatively easily decomposed by an acid (for example, an ester structure of a group represented by the formula a1-10 or the like described later, a tetrahydropyranyl ester group, or an acetal system such as a tetrahydrofuran ester group) can be used. A functional group) or a group which is relatively difficult to be decomposed by an acid (for example, a tertiary alkyl group such as a tertiary alkyl group such as a tert-butyl ester group or a tertiary alkyl carbonate group such as a tert-butyl carbonate group).

Among the groups in which the acid group is protected by the acid-decomposable group, it is preferable from the viewpoint of the basic physical properties of the curable composition, particularly the sensitivity or pattern shape, the formation of contact pores, and the storage stability of the curable composition. It is a carboxyl group which is a protected carboxyl group protected by the form of an acetal. Further, in the group in which the acid group is protected by the acid-decomposable group, it is more preferable that the carboxyl group is a protected carboxyl group protected by the form of the acetal represented by the following formula a1-10 from the viewpoint of sensitivity. Further, in the case where the carboxyl group is a protected carboxyl group protected by the form of an acetal represented by the following formula a1-10, the entire protected carboxyl group becomes -(C=O)-O-CR ¹⁰¹ R ¹⁰² (OR ¹⁰³ ) structure.

[Chem. 26] (In the formula a1-10, R ¹⁰¹ and R ¹⁰² each independently represent a hydrogen atom or an alkyl group, wherein R ¹⁰¹ and R ¹⁰² are each a hydrogen atom. R ¹⁰³ represents an alkyl group. R ¹⁰¹ or R ¹⁰² and R ¹⁰³ can be linked to form a cyclic ether)

In the formula a1-10, R ¹⁰¹ to R ¹⁰³ each independently represent a hydrogen atom or an alkyl group, and the alkyl group may be any of a linear chain, a branched chain, and a cyclic group. Here, there is no case where both R ¹⁰¹ and R ¹⁰² represent a hydrogen atom, and at least one of R ¹⁰¹ and R ¹⁰² represents an alkyl group. The linear or branched alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 4 carbon atoms. Specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, 2,3- Dimethyl-2-butyl (thexyl), n-heptyl, n-octyl, 2-ethylhexyl, n-decyl, n-decyl, and the like.

The cyclic alkyl group preferably has 3 to 12 carbon atoms, more preferably 4 to 8 carbon atoms, still more preferably 4 to 6 carbon atoms. Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, an isobornyl group and the like.

The alkyl group may have a substituent, and the substituent may, for example, be a halogen atom, an aryl group or an alkoxy group. When a halogen atom is used as a substituent, R ¹⁰¹ , R ¹⁰² and R ^{103 are} a halogenated alkyl group, and when an aryl group is used as a substituent, R ¹⁰¹ , R ¹⁰² and R ^{103 are} an aralkyl group. The halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and among these, a fluorine atom or a chlorine atom is preferred. Further, the aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably a carbon number of 6 to 12, and specific examples thereof include a phenyl group, an α-methylphenyl group, a naphthyl group and the like, and an alkyl group substituted with an aryl group. The mono-, i.e., aralkyl group, may, for example, be a benzyl group, an α-methylbenzyl group, a phenethyl group or a naphthylmethyl group. The alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, still more preferably a methoxy group or an ethoxy group. Further, when the alkyl group is a cycloalkyl group, the cycloalkyl group may have a linear or branched alkyl group having 1 to 10 carbon atoms as a substituent, and the alkyl group may be linear or In the case of a branched alkyl group, a cycloalkyl group having 3 to 12 carbon atoms may be used as a substituent. These substituents may also be further substituted by the substituents.

In the formula a1-10, when R ¹⁰¹ , R ¹⁰² and R ¹⁰³ represent an aryl group, the aryl group preferably has 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms. The aryl group may have a substituent, and the substituent may preferably be an alkyl group having 1 to 6 carbon atoms. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, a cumenyl group, a 1-naphthyl group and the like. Further, R ¹⁰¹ , R ¹⁰² and R ¹⁰³ may be bonded to each other and form a ring together with these bonded carbon atoms. Examples of the ring structure when R ¹⁰¹ and R ¹⁰² , R ¹⁰¹ and R ¹⁰³ or R ¹⁰² and R ^{103 are} bonded include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a tetrahydrofuranyl group, and an adamantyl group. And tetrahydropyranyl and the like.

Further, in the formula a1-10, it is preferred that any of R ¹⁰¹ and R ¹⁰² is a hydrogen atom or a methyl group. With respect to other specific polymers including a structural unit having a group in which an acid group is protected by an acid-decomposable group, it is also preferred to use an acid group as described in paragraphs 0037 to 0101 of JP-A-2014-238438. A polymer of structural units of a group protected by an acid-decomposable group.

<Photoacid generator> The curable composition of the present invention may contain a photoacid generator. When the curable composition of the present invention is a positive photosensitive composition, it is preferred to contain a photoacid generator. The photoacid generator used in the present invention is preferably a compound which induces an acid by irradiation of an actinic ray having a wavelength of 300 nm or more, preferably 300 nm to 450 nm, but is not limited by its chemical structure. In addition, a photoacid generator that does not directly induce actinic rays having a wavelength of 300 nm or more can be sensitized if it is a compound that generates an acid by using an actinic ray with a sensitizer and a wavelength of 300 nm or more. The agents are preferably used after combination. The photoacid generator used in the present invention is preferably a photoacid generator which produces an acid having a pKa of 4 or less, more preferably a photoacid generator which produces an acid having a pKa of 3 or less, and most preferably is produced. A photoacid generator of an acid having a pKa of 2 or less.

Examples of the photoacid generator include trichloromethyl-s-triazine, sulfonium or phosphonium salt, quaternary ammonium salt, diazomethane compound, sulfhydryl sulfonate compound, and sulfonate. Compounds, etc. Among these, from the viewpoint of sensitivity, it is preferred to use a ruthenium sulfonate compound or an oxime sulfonate compound. These photoacid generators may be used alone or in combination of two or more. Specific examples of trichloromethyl-s-triazines, diarylsulfonium salts, triarylsulfonium salts (for example, the following compounds), quaternary ammonium salts, and diazomethane derivatives can be exemplified: Japanese Patent The compound described in paragraphs 0083 to 0888 of JP-A-2011-221494, or the compound described in paragraphs 0013 to 0049 of JP-A-2011-105645, the contents of which are incorporated herein by reference. Specific examples of the sulfhydryl sulfonate compound can be exemplified by the compounds described in paragraph 0063 to paragraph 0075 of International Publication No. 2011/087011, which is incorporated herein by reference. Specific examples of the oxime sulfonate compound include those described in paragraphs 0074 to 0 203 of JP-A-2014-122972, and paragraphs 0103 to 0133 of JP-A-2014-238438. The content is incorporated into the specification of the present application.

In the curable composition of the present invention, the content of the photoacid generator is preferably 0.1 parts by mass to 20 parts by mass, more preferably 0.5 parts by mass to 10 parts by mass, per 100 parts by mass of the total solid content in the curable composition. Further, it is preferably 0.5 parts by mass to 5 parts by mass. The photoacid generator may be used singly or in combination of two or more.

<Method for Producing Curable Composition> The method for producing the curable composition of the present invention is not particularly limited, and it can be produced by a known method. For example, the components can be mixed at a predetermined ratio and by any method, and stirred and dissolved. And/or dispersed to prepare a curable composition. Further, for example, each component may be prepared as a solution each dissolved in a solvent in advance, and these solutions may be mixed at a predetermined ratio to prepare a curable composition. The curable composition prepared as described above can be used, for example, by filtration using a filter having a pore size of 0.2 μm or the like.

(Cured film and method for producing the same) The cured product of the present invention is a cured product obtained by curing the curable composition of the present invention. Further, the cured product of the present invention is preferably a cured film. The cured film of the present invention is preferably a cured film obtained by the method for producing a cured film of the present invention. The method for producing a cured film of the present invention is not particularly limited as long as it is a method for producing a cured film by curing the curable composition of the present invention, and it is preferable to include the following steps a to d in order. Step a: Coating step b of applying the curable composition of the present invention on a substrate: solvent removal step for removing a solvent from the applied curable composition Step c: Curing property of the solvent removed by actinic radiation Exposure step d at least a part of the composition is exposed. Heat treatment step of heat-treating the curable composition. The method for producing a cured film of the present invention preferably includes the following steps 1 to 5 in this order. Step 1: Coating step of applying the curable composition of the present invention on a substrate Step 2: Solvent removal step for removing a solvent from the applied curable composition Step 3: Curing property of the solvent removed by actinic radiation Exposure step of exposing at least a part of the composition Step 4: Developing step of developing the exposed curable composition by an aqueous developing solution Step 5: Heat treatment step of heat-treating the developed curable composition

In the method of producing a cured film including the step a to the step d, the development step is an arbitrary step, and a case where the refractive index adjusting layer is provided on one surface of the substrate or the like is not required, and the pattern formation is not required.

In the coating step, it is preferred that the curable composition of the present invention is applied onto a substrate to form a wet film containing a solvent. The substrate may be cleaned such as a ruthenium cleaning or a plasma cleaning before the curable composition is applied onto the substrate. Further, the surface of the substrate can be treated with hexamethyldiazane or the like after the substrate is cleaned. By performing the above treatment, the adhesion of the curable composition to the substrate tends to be improved. The substrate may, for example, be an inorganic substrate, a resin, a resin composite material or the like. Examples of the inorganic substrate include glass, quartz, tantalum, tantalum nitride, and a composite substrate on which molybdenum, titanium, aluminum, copper, or the like is vapor-deposited. The resin includes the following synthetic resins: polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, Polycarbonate, polyfluorene, polyether oxime, polyarylate, allyl diglycol carbonate resin, polyamine, polyimine, polyamidimide, polyether quinone, polyfluorene , polyphenylene sulfide, polycycloolefin, norbornene resin, fluororesin such as polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, fluorenone resin, ionic polymer resin, cyanate resin, Cross-linked fumaric acid diester, cyclic polyolefin, aromatic ether resin, maleic imine-olefin copolymer, cellulose, episulfide resin, and the like. These substrates are rarely used as they are in the above-described form, and a multilayer laminated structure such as a thin film transistor (TFT) element is usually 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 a metal oxide formed by sputtering, the substrate preferably contains a metal film formed by sputtering. The metal is preferably titanium, copper, aluminum, indium, tin, manganese, nickel, cobalt, molybdenum, tungsten, chromium, silver, lanthanum and oxides or alloys of these metals, more preferably molybdenum, titanium, aluminum, copper and alloys of these metals. . Further, the metal or the metal oxide may be used singly or in combination of two or more.

The method of applying the substrate is not particularly limited, and for example, a slit coating method, a spray method, a roll coating method, a spin coating method, a cast coating method, a slit and a spin method, and a printing method (inkjet, flexo, gravure) can be used. , screen, etc.). The printing method is preferable because it concentrates on a necessary portion to provide a composition, and it is possible to achieve a liquid-saving composition. Among these, the curable composition of the present invention is suitable for use in a printing method, and is particularly suitable for a flexographic printing method and an inkjet printing method. The wet film thickness at the time of application is not particularly limited, and it can be applied in a film thickness corresponding to the application, and is preferably in the range of 0.05 μm to 10 μm. Further, a so-called pre-wet method as described in JP-A-2009-145395 may be applied before the curable composition of the present invention is applied onto a substrate.

In the solvent removal step, a solvent is removed from the applied film by pressure reduction (vacuum) and/or heating to form a dried coating film on the substrate. The heating conditions in the solvent removal step are preferably from 70 ° C to 130 ° C and from about 30 seconds to 300 seconds. Further, the coating step and the solvent removal step may be sequentially performed, or may be carried out simultaneously or alternately. For example, after the inkjet coating in the coating step is completed, the solvent removal step may be performed, and the substrate may be heated in advance to perform the discharge of the curable composition by the inkjet coating method in the coating step. The solvent was removed.

In the case where the curable composition is a negative photosensitive composition, it is preferable to use an actinic ray to generate a polymerization initiating species from a photopolymerization initiator, and to carry out polymerization of a compound having an ethylenically unsaturated group. The polymerization of the compound to cure at least a part of the curable composition from which the solvent has been removed. Further, in the case where the curable composition is a positive photosensitive composition, an acid is generated from the photoacid generator by actinic rays, thereby polymerizing a structural unit containing a group having an acid group protected by an acid-decomposable group. The protective group of the substance is decomposed to become a polymer containing a structural unit having an acid group, whereby the solubility in the aqueous developing solution is improved. The exposure light source usable in the exposure process may be a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a chemical lamp, a light emitting diode (LED) light source, an excimer laser generating device, or the like, and may preferably be used. Actinic rays having a wavelength of 300 nm or more and 450 nm or less, such as rays (365 nm), h rays (405 nm), and g rays (436 nm). Further, the irradiation light may be adjusted by a long-wavelength cut filter, a short-wavelength cut filter, or a spectral filter such as a band pass filter as needed. The exposure apparatus can use various types of exposure apparatuses such as a mirror projection alignment machine, a stepper, a scanner, a proximity exposure apparatus, a contact exposure apparatus, a microlens array, a lens scanner, and a laser exposure. Further, the amount of exposure in the exposure step is not particularly limited, but is preferably 1 mJ/cm ² to 3,000 mJ/cm ² , and more preferably 1 mJ/cm ² to 500 mJ/cm ² . From the viewpoint of promoting hardening, the exposure in the exposure step is preferably carried out in a state of being blocked by oxygen. The method of blocking oxygen can be exemplified by exposure under a nitrogen atmosphere or by setting an oxygen blocking membrane. Further, the exposure in the exposure step may be performed on at least a part of the curable composition from which the solvent has been removed, and for example, it may be a full exposure or a pattern exposure. Further, after the exposure step, post-exposure heat treatment: Post Exposure Bake (hereinafter also referred to as "PEB") may be performed. The temperature in the case of 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 method of heating is not particularly limited, and a well-known method can be used. For example, a hot plate, an oven, an infrared heater, etc. are mentioned. Further, in the case of the heating time, the hot plate is preferably about 1 minute to 30 minutes, and in other cases, it is preferably about 20 minutes to 120 minutes. Within the above range, heating can be performed without causing damage to the substrate or the device.

The method for producing a cured film of the present invention preferably further comprises a developing step of developing the exposed curable composition with a developing solution. In the developing step, the curable composition exposed to the pattern is developed with a solvent or an alkali developing solution to form a pattern. It is preferable that the developing solution used in the developing step contains a basic compound. As the basic compound, for example, an alkali metal hydroxide such as lithium hydroxide, sodium hydroxide or potassium hydroxide; an alkali metal carbonate such as sodium carbonate or potassium carbonate; or an alkali metal bicarbonate such as sodium bicarbonate or potassium bicarbonate; a salt; tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, choline hydroxide, etc.; An aqueous solution of sodium citrate or sodium metasilicate. Further, 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 aqueous solution of the hydrazine may be used as the developing solution. A preferred developer is a 0.4% by mass to 2.5% by mass aqueous solution of tetramethylammonium hydroxide. The pH of the developer is preferably from 10.0 to 14.0. The development time is preferably from 30 seconds to 500 seconds, and the development method may be any one of a liquid coating method (a puddle development method), a shower method, and a dipping method. After the development, the rinsing process can also be performed. In the rinsing step, the developed substrate is washed with pure water or the like, and the adhered developing solution is removed and the developing residue is removed. A well-known method can be used for the rinsing method. For example, spray rinsing, immersion rinsing, etc. are mentioned. As the pattern exposure and development, a well-known method or a well-known developer can be used. For example, the pattern exposure method and the development method described in JP-A-2011-186398 and JP-A-2013-83937 can be suitably used.

The method for producing a cured film of the present invention preferably includes a step of heat-treating the curable composition after the exposure step. By performing heat treatment after exposing the curable composition of the present invention, a cured film having more excellent strength can be obtained. The temperature of the heat treatment is preferably from 80 ° C to 300 ° C, more preferably from 100 ° C to 280 ° C, particularly preferably from 120 ° C to 250 ° C. In the case of the above-described embodiment, it is estimated that when a1 and/or a2 are used as the component A, the condensation of the component A is appropriately caused, and the physical properties of the cured film are more excellent. Further, the time of the heat treatment is not particularly limited, but is preferably from 1 minute to 360 minutes, more preferably from 5 minutes to 240 minutes, still more preferably from 10 minutes to 120 minutes. Further, the curing by light and/or heat in the method for producing a cured film of the present invention may be carried out continuously or sequentially. Further, when the heat treatment is performed, the transparency can be further improved by performing in a nitrogen atmosphere. Before the heat treatment step (post-baking), the heat treatment step (additional baking step) may be performed after baking at a relatively low temperature. In the case of the baking in progress, it is preferred to carry out post-baking at a high temperature of 200 ° C or higher after heating at 90 ° C to 150 ° C for 1 minute to 60 minutes. In addition, the middle baking and the post baking may be divided into three stages or more in multiple stages for heating. By attempting to perform such a middle baking and post baking, the taper angle of the pattern can be adjusted. These heating can be carried out using a well-known heating method such as a hot plate, an oven, or an infrared heater. Further, before the post-baking, the substrate on which the pattern is formed may be subjected to post-baking by full re-exposure (post-exposure) using actinic rays, thereby presuming condensation reaction of the components A by thermal decomposition. The photopolymerization initiator remaining in the exposed portion generates an initiating species and functions as a catalyst for promoting the crosslinking step, thereby promoting film hardening. The preferable exposure amount in the case of including the post-exposure step is preferably 100 mJ/cm ² to 3,000 mJ/cm ² , and particularly preferably 100 mJ/cm ² to 500 mJ/cm ² .

(Cured film) The cured film or cured product of the present invention (hereinafter sometimes referred to as a cured film or the like) 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 which is developed as described above, or may be an undeveloped cured film or the like, and is preferably a developed cured film or the like which can further exhibit the effects of the present invention. Since the cured film of the present invention has a high refractive index and high transparency, it can be suitably used as a light extraction/extraction efficiency improving layer of a microlens, an optical waveguide, an antireflection film, a solar cell or an organic EL light-emitting element, and an LED. An optical member such as a sealing material or a chip coating material for LED, 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, or a protective film for a wiring electrode used in a touch panel. Further, the cured film of the present invention can also be suitably used for a protective film of a color filter in a liquid crystal display device or an organic EL display device, or a spacer for holding a liquid crystal layer at a certain thickness in a liquid crystal display device, Structural members of devices for Micro Electro Mechanical Systems (MEMS), etc.

Further, the cured film of the present invention or the like can be used for a visibility reducing layer such as a wiring electrode used in a touch panel. In addition, the visibility reduction layer of the wiring electrode used in the touch panel refers to a layer that reduces visibility of a wiring electrode or the like used in the touch panel, that is, a wiring electrode or the like is not easily seen, and for example, a touch detection electrode (for example, An interlayer insulating film between indium tin oxide (ITO), a protective film for an electrode (overcoat film), and the like. In addition, it is also suitable for an index matching layer (sometimes referred to as an IM (Index Matching) layer or a refractive index adjusting layer). The index matching layer refers to a layer that adjusts the reflectance or transmittance of light of the display device. The content of the index matching layer is described in detail in Japanese Patent Laid-Open No. 2012-146217, the entire contents of which are incorporated herein. By using the cured film of the present invention for the visibility reducing layer, a touch panel excellent in visibility can be produced. Among them, 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. In the case of an interlayer insulating film or a protective film for use between the touch detecting electrodes, the refractive index of the cured film is preferably close to the refractive index of the electrode from the viewpoint of visibility improvement, and specifically, the wavelength is preferably 550. The refractive index at nm is from 1.60 to 1.90, more preferably from 1.62 to 1.85.

(Liquid Crystal Display Device) The liquid crystal display device of the present invention is characterized by having the cured film of the present invention. The liquid crystal display device of the present invention is not particularly limited as long as it has a planarizing film or an interlayer insulating film formed using the curable composition of the present invention, and a known liquid crystal display device having various structures can be cited. Specific examples of the thin film transistor (TFT) included in the liquid crystal display device of the present invention include amorphous germanium-TFT, low-temperature polysilicon-TFT, and oxide semiconductor TFT (for example, indium gallium zinc oxide, So-called IGZO). Since the cured film of the present invention is excellent in electrical characteristics, it can be used in combination with these TFTs. Further, the liquid crystal driving method which can be obtained by the liquid crystal display device of the present invention includes a twisted nematic (TN) method, a vertical alignment (VA) method, and an in-plane switching (In-Plane-Switching, IPS). Mode, Fringe Field Switching (FFS) mode, Optically Compensated Bend (OCB) mode, etc. In the panel configuration, the cured film of the present invention can also be used in a liquid crystal display device of a color filter on Array (COA) type, for example, as an organic insulating film of JP-A-2005-284291. (115) or an organic insulating film (212) of JP-A-2005-346054. In addition, a specific orientation of the liquid crystal aligning film which can be obtained by the liquid crystal display device of the present invention is a rubbing alignment method, a photo-alignment method, or the like. In addition, the polymer orientation support can also be carried out by the Polymer Sustained Alignment (PSA) technique described in JP-A-2003-149647 or JP-A-2011-257734. Further, the curable composition of the present invention and the cured film of the present invention are not limited to the above applications, and can be used in various applications. For example, in addition to the planarization film or the interlayer insulating film, it can be suitably used as a protective film for a color filter, or a spacer for holding a liquid crystal layer at a certain thickness in a liquid crystal display device, or a solid-state image sensor. Microlenses and the like on a color filter.

FIG. 1 is a conceptual cross-sectional view showing an example of an active matrix type 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 an element of the TFT 16 is disposed in the liquid crystal panel, and the elements of the TFT 16 and the two glass substrates 14 to which the polarizing film is attached are All the pixels arranged between the glass substrates 15 correspond. The wiring of the ITO transparent electrode 19 forming the pixel electrode is formed by the contact holes 18 formed in the cured film 17 for each element formed on the glass substrate. On the ITO transparent electrode 19, a layer of the liquid crystal 20 and a red green blue (RGB) color filter 22 in which a black matrix is disposed are provided. The light source of the backlight is not particularly limited, and a well-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), an organic EL, or the like can be given. In addition, the liquid crystal display device can be made into a three-dimensional (3D) (stereoscopic) type, or can be made into a touch screen type. Further, it can be made into a flexible type, and it can be used as the second interlayer insulating film (48) described in Japanese Laid-Open Patent Publication No. 2011-145686, or the interlayer insulating film (520) disclosed in Japanese Laid-Open Patent Publication No. 2009-258758. ).

(Organic EL display device) The organic EL display device of the present invention is characterized by having the cured film of the present invention. The organic EL display device of the present invention is not particularly limited as long as it has a planarizing film or an interlayer insulating film formed using the curable composition of the present invention, and various well-known organic EL display devices or liquid crystals having various configurations are exemplified. Display device. Specific examples of the thin film transistor (TFT) included in the organic EL display device of the present invention include an amorphous germanium-TFT, a low-temperature polysilicon-TFT, an oxide semiconductor TFT, and the like. Since the cured film of the present invention is excellent in electrical characteristics, it can be used in combination with these TFTs.

2 is a conceptual view showing an example of an organic EL display device, and is a schematic cross-sectional view of a substrate in a bottom emission type organic EL display device, and has a planarizing film 4. A bottom gate type TFT 1 is formed on the glass substrate 6 to cover the state of the TFT 1 to form an insulating film 3 containing Si ₃ N ₄ . After the contact hole (not shown) is formed in the insulating film 3, the wiring 2 (having a height of 1.0 μm) connected to the TFT 1 through the contact hole is formed on the insulating film 3. The wiring 2 is a wiring for connecting the TFTs 1 or connecting the organic EL elements formed in the subsequent steps to the TFT 1. Further, in order to flatten the unevenness due to the formation of the wiring 2, the planarizing film 4 is formed on the insulating film 3 in a state in which the unevenness due to the wiring 2 is filled. A bottom emission type organic EL element is formed on the planarization film 4. That is, the first electrode 5 including ITO is formed on the planarizing film 4 by being connected to the wiring 2 via the contact hole 7. Further, the first electrode 5 corresponds to the anode of the organic EL element. The insulating film 8 having a shape covering the edge of the first electrode 5 is formed, and by providing the insulating film 8, a short circuit between the first electrode 5 and the second electrode formed in the subsequent process can be prevented. Further, although not shown in FIG. 2, a hole transport layer, an organic light-emitting layer, and an electron transport layer are sequentially deposited by vapor deposition through a desired pattern mask, and then a second layer containing Al is formed on the entire upper surface of the substrate. The electrode is bonded by using a glass plate for sealing and an ultraviolet curable epoxy resin, and sealed to obtain an active matrix type in which the TFTs 1 for driving the respective organic EL elements are connected to the respective organic EL elements. Organic EL display device.

(Touch Screen and Touch Screen Display Device) The touch panel of the present invention is a touch panel in which all or a part of the insulating layer and/or the protective layer contains a cured product of the curable composition of the present invention. Further, the touch panel of the present invention preferably has at least a transparent substrate, an electrode, and an insulating layer and/or a protective layer. The touch screen display device of the present invention is preferably a touch screen display device having the touch screen of the present invention. The touch panel of the present invention may be any one of well-known methods such as a resistive film method, a capacitive method, an ultrasonic method, and an electromagnetic induction method. Among them, a capacitive method is preferred. The touch panel disclosed in Japanese Laid-Open Patent Publication No. 2010-28115 or the touch panel disclosed in Japanese Laid-Open Patent Publication No. 2012/057165. Other touch panels include an in-cell type (for example, FIG. 5, FIG. 6, FIG. 7, and FIG. 8 of Japanese Patent Laid-Open Publication No. 2012-517051), so-called on-cell. (for example, FIG. 14 of Japanese Laid-Open Patent Publication No. 2012-43394, FIG. 2(b) of International Publication No. 2012/141148), OGS type, TOL type, and other configurations (for example, Japanese Patent Laid-Open Publication No. 2013-164871) Figure 6). [Examples]

The invention will now be described more specifically by way of examples. The materials, the amounts used, the ratios, the processing contents, the processing order, and the like shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. In addition, “parts” and “%” are quality standards unless otherwise specified.

(Measurement of Surface Tension) The surface tension was measured at 20 ° C using a Dunouy surface tension meter in accordance with JIS K2241.

(Measurement of Viscosity) The RE85L type viscometer manufactured by Toki Sangyo Co., Ltd. (rotor name: cone type 1°34'×R24 was used for measurement. The liquid temperature was set to 20 °C.

The various components used in the examples and comparative examples are as follows. (Component A) · A-1: manufactured by titanate, B-4, and Japan's Soda Co., Ltd., solid content: 98% by mass · A-2: tetra-n-butyl titanium oxide, and Wako Pure Chemical Industries Co., Ltd. A-3: zirconium oxymethane, ZA-65, Matsumoto Fine Chemical (manufactured by Matsumoto Fine Chemical Co., Ltd.), solid content: 87% by mass (butanol: 13% by mass) (ingredient B) · B-1: acrylic acid amino group Formate, 15-functional, U-15HA, manufactured by Shin-Nakamura Chemical Industry Co., Ltd. · B-2: Acrylic urethane, 15-functional, UA-32P, Kowa (manufactured), B-3: Manufacture of dipentaerythritol hexaacrylate, DPHA, Nippon Kayaku Co., Ltd. · B-4: pentaerythritol tetraacrylate, A-TMMT, manufacturing of Shin-Nakamura Chemical Industry Co., Ltd.

(Component C) · C-1-1: Terpineol C (manufactured by Japan Terpinene Chemical Co., Ltd., a mixture of the following three types) · C-1-2: Dihydroterpineol (Japanese terpene chemistry) (Stock) Manufacture, a mixture of the following two types) C-1-3: Terusolve DTO-210 (manufactured by Japan Terpinene Chemical Co., Ltd., dihydroterpineol (1-hydroxy-pair) a mixture of menthane and 8-hydroxy-p-menthan)) C-1-4: Terusolve THA-90 (manufactured by Nippon Terpinol Chemical Co., Ltd., a mixture of the following three types) · C- 1-5: Terusolve THA-70 (manufactured by Japan Terpinene Chemical Co., Ltd., a mixture of the following three types) · C-1-6: Terusolve TOE-100 (Japanese product) Alkene chemical (manufacturing), the following compounds)

[化27]

(Comparative Example) · C'-1-1: PGMEA (propylene glycol monomethyl ether acetate) (made by Daicel (share)) · C'-1-2: Hisolve EDE (two Ethylene glycol diethyl ether) (Manufactured by Toho Chemical Industry Co., Ltd.) · C'-1-3: MEDG (diethylene glycol ethyl methyl ether) (manufactured by Toho Chemical Industry Co., Ltd.) · C'-1-4 : Hisolve EPH (ethylene glycol monophenyl ether) (manufactured by Toho Chemical Industry Co., Ltd.) · C'-1-5: tetrahydrofurfuryl alcohol (manufactured by Wako Pure Chemical Industries, Ltd.) · C'- 1-6: Dihydrofurfuryl methyl ether (manufactured by Japanese terpene chemistry (stock), a mixture of the following two) · C'-1-7: Terusolve MTPH (isolated base ring) Hexanol) (manufactured by Japan Terpinene Chemical Co., Ltd.) (Others) · C-2-1: Hisolve EDE (diethylene glycol diethyl ether, viscosity at 20 ° C: 1.47 mPa·s, Manufactured by Toho Chemical Industry Co., Ltd.) ·C-2-2: Acetylacetone (viscosity at 20 ° C: 0.6 mPa·s, manufactured by Wako Pure Chemical Industries Co., Ltd.)

[化28]

(Component D) · D-1: IRGACURE CGI-242 (1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]B Alkan-1-one oxime-O-acetate, manufactured by Ciba Specialty Chemicals Co., Ltd. (Others) · KBM-5103: 3-propenyloxypropyltrimethoxydecane, Shin-Etsu Chemical Industry ( Manufacturing

(Example 1) <Preparation of curable composition> Preparation was carried out as follows. · A-1: B-4 (titanium oxide, Japan's Soda (stock), solid content: 98% by mass): 2.60 parts · B-1: Acrylic urethane (U-15HA, 15-functional, Shin-Nakamura Chemical Industrial (manufactured by the company): 2.16 parts · B-2: Acrylic urethane (manufactured by UA-32P, 15-functional, Kowa): 2.16 parts · C-1-1: Terpineol C (Manufactured by Japanese terpene chemistry (stock)): 80 parts · C-2-1: Hisolve EDE (manufactured by Toho Chemical Industry Co., Ltd.): 10 parts · C-2-2: Acetylacetone (Manufactured by Wako Pure Chemical Industries Co., Ltd.): 2.86 parts·D-1: IRGACURE OXE-02 (manufactured by BASF Corporation): 0.30 parts·F-1: Megafac F-554 (including Perfluoroalkyl nonionic surfactant, manufactured by Diane (DIC): 0.004 parts of the component was stirred for 1 hour using a magnetic stirrer, and made of polytetrafluoroethylene having a pore diameter of 0.3 μm. The filter was filtered to obtain the curable composition of Example 1.

(Examples 2 to 6 and Comparative Examples 1 to 8) The C-1-1 of Example 1 was changed to each solvent described in Table 1, and the amount of addition was changed according to Table 1, and The curable composition was obtained in the same manner as in Example 1. (Example 7) A curable composition was obtained in the same manner as in Example 2 except that B-1 and B-2 of Example 2 were changed to B-3, respectively.

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

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

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

(Example 11) A hardening was carried out in the same manner as in Example 4 except that A-1 was changed to A-3, and the amounts of C-1 and C-2-1 added were changed as shown in Table 1. Composition.

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

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

(Example 14) In the same manner as in Example 1, except that the amount of the terpineol C added in Example 1 was changed to 32 parts, and the amount of the addition of the Hisolve EDE was changed to 4 parts. The hardening composition is obtained by carrying out.

(Example 15) The amount of addition of Terusolve THA-90 in Example 4 was changed to 100 parts, and the amount of addition of Hisolve EDE was changed to 12.5 parts, and Example 4 was carried out in the same manner to obtain a curable composition.

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

(Example 17) <Preparation of titanium oxide dispersion liquid 1> A dispersion liquid of the following composition was prepared, mixed with 17,000 parts of zirconia beads (0.3 mmf), and dispersed for 12 hours using a paint shaker (paint shaker). . The zirconia beads (0.3 mmf) were separated by filtration to obtain a dispersion. · Titanium dioxide (Ishihara Industry Co., Ltd., trade name: TTO-51 (A), average primary particle size: 10 nm to 30 nm): 1,875 parts · Dispersant (DISPERBYK-111, 100) % grade): 660 parts·solvent (PGMEA, propylene glycol monomethyl ether acetate): 1,710 parts Further, the components used were as follows. TTO-51(A): Manufactured by Titanium Dioxide and Ishihara Industries, with an average primary particle size of 10 nm to 30 nm, surface treatment type: Al(OH) ₃ DISPERBYK-111: with more than one Phosphate structure polymer dispersant, manufactured by BYK-Chemie

In the same ratio as the content of the titanium oxide and the content of A-1, A-1 was changed to the titanium oxide dispersion liquid, and the amount of C-2-1 added was changed to 6.47 parts, and Example 4 was carried out in the same manner to obtain a curable composition.

(Example 18) The amount of terpineol C in Example 1 was changed to 115 parts, and the amount of C-2-1 (Hisolve EDE) was changed to 115 parts, and Example 1 was carried out in the same manner to obtain a curable composition.

(Example 19) The amount of dihydroterpineol in Example 2 was changed to 115 parts, and the amount of C-2-1 (Hisolve EDE) was changed to 115 parts, and The curable composition was obtained in the same manner as in Example 2.

(Example 20) The amount of Terusolve DTO-210 in Example 3 was changed to 115 parts, and the amount of C-2-1 (Hisolve EDE) was changed to 115 parts. Otherwise in the same manner as in Example 3, a curable composition was obtained.

(Comparative Example 9) In Example 4, the amount of addition of Terusolve THA-90 was changed to 15 parts, and the amount of addition of Hisolve EDE was changed to 65 parts. The curable composition was obtained in the same manner as in Example 4.

(Comparative Example 10) In the same manner as in Example 4, the amount of the addition of Terusolve THA-90 was changed to 90 parts in the fourth embodiment, and further, without the addition of Hisolve EDE. The curing is carried out to obtain a curable composition.

[Table 1]

(Evaluation of Curable Composition) The produced curable composition was evaluated as follows. The evaluation results are summarized in Table 2. Further, in the case of coating by flexographic printing, a flexographic printing machine (Model A45, manufactured by NAKAN Co., Ltd.) was used as a printing machine. The curable composition was printed on an 300 mm × 400 mm glass substrate (trade name: XG, manufactured by Corning) using an anilox roll #400. Further, in the case of coating by a spin coater, a glass substrate (trade name: XG, manufactured by Corning Incorporated) of 10 cm × 10 cm was used. In the case of inkjet printing, an inkjet printer (manufactured by Dimatix Co., Ltd., DMP-281 printer) is used, and a glass substrate of 10 cm × 10 cm (trade name: XG, The hardening composition is coated on the Corning Company.

<Substrate turbidity> On a glass substrate (trade name: XG, manufactured by Corning Incorporated) of 10 cm × 10 cm, the curable composition was spin-coated so that the dry film thickness became 100 nm, and dried at 90 ° C in an oven (prebaking) Bake) 100 seconds. The film on the obtained substrate was visually observed and evaluated according to the following criteria. If the white turbidity is less, it means that a film which is more excellent in transparency can be obtained. If the evaluation is 1 or 2, there is no problem in practical use, and 1 is more preferable. 5: The dry film on the entire surface of the substrate is white turbid. 4: The dried film on the entire surface of the substrate is slightly turbid. 3: The dried film of about half of the substrate is slightly cloudy. 2: The dried film of a part of the substrate is slightly cloudy. 1: The dry film is not turbid.

<Concave failure> On a glass substrate of 10 cm × 10 cm (trade name: XG, manufactured by Corning Incorporated), the curable composition was spin-coated at a dry film thickness of 100 nm, and dried at 90 ° C in an oven (prebaking) Bake) 100 seconds. The film on the substrate in the entire substrate obtained was visually observed and evaluated according to the following criteria. If the evaluation is 1 or 2, there is no problem in practical use, and 1 is more preferable. 1: no depression is generated 2: one or more and less than 3 depressions are generated 3: 3 or more and less than 10 depressions are produced 4: 10 or more depressions are generated

<In-plane film thickness uniformity> The curable composition was applied by spin coating, flexographic printing, or inkjet printing so as to have a dry film thickness of 100 nm on a glass substrate (trade name: XG, manufactured by Corning Incorporated). It was dried (prebaked) in an oven at 90 ° C for 100 seconds. Thereafter, the entire surface was exposed to 150 mJ/cm ² (illuminance of 24 mW/cm ² ) using an ultrahigh pressure mercury lamp, and then heated at 200 ° C for 30 minutes in an oven. The in-plane distribution measurement of the film thickness at 64 places was evaluated as described below. 1: In-plane distribution is below 100 nm ± 5 nm 2: In-plane distribution exceeds 100 nm ± 5 nm and is below 100 nm ± 10 nm 3: In-plane distribution exceeds 100 nm ± 10 nm and is below 100 nm ± 20 nm 4: In-plane distribution exceeds 100 nm ± 20 nm 5: There is no need to measure in-plane distribution, and there are coated and uncoated portions on the substrate.

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

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

<Refractive Index Evaluation> The curable composition was spin-coated on a 10 cm × 10 cm ruthenium wafer so that the dry film thickness was 500 nm, and dried (prebaked) in an oven at 90 ° C for 100 seconds. Thereafter, the entire surface was exposed to 150 mJ/cm ² (illuminance of 24 mW/cm ² ) using an ultrahigh pressure mercury lamp, and then heated at 200 ° C for 30 minutes in an oven. The refractive index of the cured film at 550 nm was measured at 25 ° C using an ellipsometer VUV-VASE (manufactured by JA Woollam Japan Co., Ltd.).

[Table 2]

(Example 21) <Preparation of titanium oxide dispersion liquid 2> A dispersion liquid having the following composition was prepared, mixed with 100.0 parts of zirconia beads (0.3 mmf), and dispersed for 12 hours using a paint shaker. The zirconia beads (0.3 mmf) were separated by filtration to obtain a dispersion. · Titanium dioxide (Ishihara industry (stock) manufacturing, trade name: TTO-51 (C), average primary particle size: 10 nm ~ 30 nm): 25.0 parts · Dispersant: 25.0 parts · Solvent (PGMEA, propylene glycol monomethyl ether B Acid ester): 50.0 parts Further, the components used were as follows. ·TTO-51(C): Manufactured by Titanium Dioxide and Ishihara Industries, with an average primary particle size of 10 nm to 30 nm, surface treatment type: Al(OH) ₃ , and stearic acid treatment and dispersant: Compound 1 (PGMEA solution with molecular weight Mw = 13,800 and solid content of 30%)

[化29]

Further, in the compound 1, the sulfur atom bonded to the polymer chain may be bonded to the monomer unit of P1 or may be bonded to the monomer unit of P2.

<Synthesis of a polymer (Polymer-1) having a group in which an acid group is protected by an acid-decomposable group> In the following synthesis examples, the following compounds are respectively indicated below. V-601: dimethyl-2,2'-azobis(2-methylpropionate) GMA: glycidyl methacrylate PGMEA: propylene glycol monomethyl ether acetate

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

<Synthesis of Photoacid Generator 1> To a suspension solution of 2-naphthol (10 g) and chlorobenzene (30 mL), aluminum chloride (10.6 g) and 2-chloropropionyl chloride (10.1 g) were added. The mixture was heated to 40 ° C and reacted for 2 hours. Under ice cooling, a 4N aqueous HCl solution (60 mL) was added dropwise, and then ethyl acetate (50 mL) was added to carry out liquid separation. Potassium carbonate (19.2 g) was added to the organic layer, and the mixture was reacted at 40 ° C for 1 hour, and then a 2N aqueous HCl solution (60 mL) was added to carry out liquid separation, and the organic layer was concentrated, and then diisopropyl ether (10 mL) was used. The crystals were reslurryed, then filtered and dried to obtain a ketone compound (6.5 g). To a suspension solution of the obtained ketone compound (3.0 g) and methanol (30 mL), acetic acid (7.3 g) and a 50% by mass aqueous hydroxylamine solution (8.0 g) were added, and the mixture was heated under reflux. After standing to cool, water (50 mL) was added, and the precipitated crystals were filtered, washed with cold methanol, and dried to obtain a hydrazine compound (2.4 g). The obtained hydrazine compound (1.8 g) was dissolved in acetone (20 mL), and triethylamine (1.5 g) and p-toluenesulfonyl chloride (2.4 g) were added under ice-cooling, and the mixture was warmed to room temperature. hour. Water (50 mL) was added to the reaction liquid, and the precipitated crystals were filtered, and then re-slurryed with methanol (20 mL), and then filtered and dried to obtain a compound of B-1 (the following structure) (2.3) g). Further, the ¹ H-NMR spectrum of B-1 (300 MHz, CDCl ₃ ) was δ = 8.3 (d, 1H), 8.0 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1H), 7.6 (dd, 1H), 7.4 (dd, 1H), 7.3 (d, 2H), 7.1 (d, 1H), 5.6 (q, 1H), 2.4 (s, 3H), 1.7 (d, 3H).

[化30]

<Preparation of Curable Composition> Preparation was carried out as follows. A-3: The titanium oxide dispersion 2: 3.0 parts·K-1: The polymer-1 solution: 2.5 parts·C-1: Terpineol C (manufactured by Japan Terpinene Chemical Co., Ltd.) : 48.5 parts·C-2: propylene glycol monomethyl ether acetate (manufactured by Daicel): 45.0 parts·L-1: the photoacid generator 1: 0.075 parts·M-1:1-cyclohexyl -3-(2-morpholinoethyl)thiourea (DSP GOKYO FOOD & CHEMICAL): 0.0007 parts·O-1: OGSOL PG-100 (epoxy-anthracene derivative, manufactured by Osaka Gas Chemical Co., Ltd.): 0.37 parts·O-2: OGSOL BPEF (9,9-bis[4-(2-hydroxyethoxy)benzene) Base] 芴, 芴 monomer, manufactured by Osaka Gas Chemical Co., Ltd.): 0.29 parts G-1: Silquest A-187 SILANE (γ-glycidoxypropyl trimethyl) Oxydecane, manufactured by Momentive Performance Materials (stock): 0.065 parts G-2: KBE-846 (bis(triethoxydecylpropyl) tetrasulfide, Shin-Etsu Chemical Industry Co., Ltd. ))): 0.12 parts · B-1: Celloxide 2021P 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, manufactured by Daicelin): 0.022 parts·P-1: 1,3-dimethylimidazolidine -2-ketone (manufactured by Wako Pure Chemical Industries, Ltd.): 0.056 parts·F-1: Megafac F-554 (perfluoroalkyl-containing nonionic surfactant, Di Aisheng (DIC) (manufacturing): 0.0032 parts of the components were stirred for 1 hour by a magnetic stirrer, and filtered using a filter made of polytetrafluoroethylene having a pore diameter of 0.3 μm to obtain a curable composition of Example 21.

(Examples 22 to 26, Example 29, Example 30, and Comparative Example 11 to Comparative Example 13) C-1 and C-2 of Example 21 were changed to the respective solvents described in Table 3, and The curable composition was obtained in the same manner as in Example 21 except that the amount of addition was changed in accordance with Table 3.

(Example 27 and Example 28) C-1 and C-2 of Example 21 were changed to the respective solvents described in Table 3, and the amount of the solvent added was changed so as to become the solid content of the composition of Table 3. A curable composition was obtained in the same manner as in Example 21 except for the above.

(Example 31) C-1 and C-2 of Example 21 were changed to the respective solvents described in Table 3, and the titanium oxide dispersion liquid 2 was changed to the following zirconia dispersion liquid, and Example 21 was carried out in the same manner to obtain a curable composition.

<Preparation of the zirconia dispersion liquid> The titanium oxide of the titanium oxide dispersion liquid 2 described in the example 21 was changed to the following zirconia (UPE-100, manufactured by the first rare element chemical industry), and The dispersion treatment was carried out in the same manner as in the titanium oxide dispersion 2 to obtain a zirconia dispersion.

With respect to the obtained curable composition, in the same manner as in Example 1, evaluation of the depression, the substrate turbidity, the in-plane film thickness uniformity, the chemical resistance, the refractive index, and the pencil hardness were performed. In addition, the evaluation of the in-plane film thickness uniformity, the chemical resistance, and the pencil hardness was evaluated in the same manner as in Example 1 except that the exposure was not performed.

[table 3]

[Table 4]

(Embodiment 32) In the touch panel shown in Figs. 3 to 5, an insulating layer W (hereinafter also referred to as "a pedestal" which surrounds the Y (102a) electrode of Fig. 4 together with the substrate 111 is formed as follows. The layer W") is formed in the same manner as the method described in Japanese Laid-Open Patent Publication No. 2013-97692, and the touch panel of the present invention is obtained. Further, using the touch panel, a display device with a touch panel is obtained in accordance with Japanese Laid-Open Patent Publication No. 2013-97692. Formation of a pedestal layer: The curable composition of Example 4 was applied onto a substrate, prebaked, exposed to light using an ultrahigh pressure mercury lamp, developed by an aqueous alkaline solution to form a pattern, and subjected to a pattern at 200 ° C for 30 minutes. Heat treatment to form a pedestal layer W. Further, the pedestal layer has a function 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 characteristics and the touch detection performance were excellent, and the device was highly reliable.

(Example 33) In the touch panel shown in Figs. 3 to 5, an insulating layer W (a pedestal layer W) which surrounds the Y (102a) electrode of Fig. 4 together with the substrate 11 and insulation is formed as follows. The layer 112 and the protective layer 113 are formed in the same manner as the method described in Japanese Laid-Open Patent Publication No. 2013-97692, and the touch panel of the present invention is obtained. Further, using the touch panel, a display device with a touch panel is obtained in accordance with Japanese Laid-Open Patent Publication No. 2013-97692. Formation of the pedestal layer W, the insulating layer 112, and the protective layer 113: The sclerosing composition of Example 4 is slit-coated on a substrate, pre-baked, exposed to 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 characteristics and the touch detection performance were excellent, and the device was highly reliable.

1‧‧‧TFT (thin film transistor)
2‧‧‧Wiring
3‧‧‧Insulation film
4‧‧‧Flat film
5‧‧‧First electrode
6‧‧‧ glass substrate
7‧‧‧Contact hole
8‧‧‧Insulation film
10‧‧‧Liquid crystal display device
12‧‧‧Backlight unit
14, 15‧‧‧ glass substrate
16‧‧‧TFT
17‧‧‧ hardened film
18‧‧‧Contact hole
19‧‧‧ITO transparent electrode
20‧‧‧LCD
22‧‧‧Color filters
102a‧‧‧electrode
111‧‧‧Substrate
112‧‧‧Insulation
113‧‧‧Protective layer
W‧‧‧Insulation (seat floor)
Y‧‧‧electrode

1 is a conceptual view showing an example of a liquid crystal display device, and is a schematic cross-sectional view showing an active matrix substrate in a liquid crystal display device, and has a cured film 17 as an interlayer insulating film. 2 is a conceptual view showing an example of an organic EL display device, and is a schematic cross-sectional view of a substrate in a bottom emission type organic EL display device, and has a planarizing film 4. 3 is a plan view showing an electrode pattern of a touch panel in an example of a display device with a touch panel. Fig. 4 is a cross-sectional view showing a cross-sectional structure taken along line A1-A2 shown in Fig. 3. Fig. 5 is a cross-sectional view showing a cross-sectional structure taken along the line B1-B2 shown in Fig. 3.

Claims (17)

A curable composition comprising: at least one selected from the group consisting of a1 to a3 described below as a component A, a curable compound as component B, and a solvent as component C; and component C Containing at least one organic solvent having a viscosity at 20° C. of 20° C. as component C-1 of 50 mPa·s or more and 200 mPa·s or less and a surface tension of 30 mN/m or more and 41 mN/m or less, and as component C -2 at least one organic solvent having a viscosity at 20 ° C of less than 50 mPa·s, and the content of the component C-1 is 20% by mass to 95% by mass based on the total mass of the component C, at 20 ° C of the curable composition The viscosity is 1 mPa·s or more and 30 mPa·s or less; a1: a titanium compound having an alkoxy group and/or a zirconium compound, a2: having at least one alkoxy group directly bonded to a titanium atom or a zirconium atom. A titanate, a zirconium oxide and/or a titanyl-zirconoxane condensate, a3: a metal oxide containing a titanium atom and/or a zirconium atom. The curable composition according to claim 1, wherein the component B is a polymerizable compound. The sclerosing composition according to claim 1 or 2, wherein the component C-1 is selected from the group consisting of terpineol, dihydroterpineol, 4-(ethyloxy)-α, α, a group consisting of 4-trimethylcyclohexane methanol acetate and 2-[1-methyl-1-(4-methyl-3-cyclohexen-1-yl)ethoxy]ethanol At least one of them. The curable composition according to claim 1 or 2, wherein the total amount of the solid components in the curable composition is from 2% by mass to 15% by mass based on the total mass of the curable composition. %. The curable composition according to claim 1 or 2, wherein the component B contains a hexafunctional or higher polymerizable compound. The curable composition according to claim 1 or 2, wherein the a2 is 0.5 to 1.9 times molar equivalent of water per 1.0 mol of the total of the titanium atom and the zirconium atom. a titanate or zirconium obtained by hydrolysis-condensation of at least one selected from the group consisting of a titanium compound having an alkoxy group, a zirconium compound having an alkoxy group, and a titanium compound having a halogen group and a zirconium compound having a halogen group Oxyalkane and/or titanyl-zirconoxane condensate. The sclerosing composition according to claim 1 or 2, wherein the component A comprises the a2. The curable composition according to claim 1 or 2, which contains a photopolymerization initiator as component D. A method for producing a cured film, comprising at least a step a to a step d, a step a: a coating step, and applying the curable composition according to the first or second aspect of the patent application to a substrate; The solvent removal step removes the solvent from the applied curable composition; Step c: Exposure step, exposing at least a portion of the curable composition from which the solvent has been removed by actinic rays; and step d: heat treatment step to hardening The composition is subjected to heat treatment. A method for producing a cured film, comprising at least a step 1 to a step 5, a step 1: a coating step, and applying the curable composition according to the first or second aspect of the patent application to a substrate; The solvent removal step removes the solvent from the applied curable composition; Step 3: Exposure step exposes at least a portion of the curable composition from which the solvent has been removed by actinic radiation; Step 4: Development step, using aqueous development The liquid is subjected to development of the exposed curable composition; and in the step 5: heat treatment step, the developed curable composition is subjected to heat treatment. A cured film obtained by curing the curable composition according to the first or second aspect of the invention. The cured film according to claim 11, which is an interlayer insulating film or an overcoat film. The cured film according to claim 11, wherein the refractive index at a wavelength of 550 nm is from 1.6 to 1.9. A liquid crystal display device having the cured film as described in claim 11 of the patent application. An organic electroluminescence display device comprising the cured film according to claim 11 of the patent application. A touch screen having a cured film as described in claim 11 of the patent application. A touch screen display device having the cured film according to claim 11 of the patent application.