CN105278246B

CN105278246B - Curable composition, method for producing cured film, touch panel, and display device

Info

Publication number: CN105278246B
Application number: CN201510382289.2A
Authority: CN
Inventors: 铃木成一; 河邉保雅; 伊藤寛晃; 柏木大助; 安藤豪
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2014-07-04
Filing date: 2015-07-02
Publication date: 2020-03-13
Anticipated expiration: 2035-07-02
Also published as: CN105278246A

Abstract

The invention aims to provide a curable composition, a method for manufacturing a cured film, the cured film, a touch panel and a display device. The curable composition of the present invention comprises: a hydrolysis-condensation titanium compound and/or zirconium compound as component A, a polyfunctional polymerizable component which can be a titanium coordinating component and/or zirconium coordinating component and the same compound as the coordinating component as component B, a photopolymerization initiator, and a solvent, wherein the content of component A is 40 to 90 mass%, the content of component B is 5 to 59 mass%, and the content of titanium coordinating component and/or zirconium coordinating component is 15 to 140 parts by mass with respect to 100 parts by mass of the content of component A, with respect to the total solid content of the curable composition. The curable composition of the present invention can combine the refractive index and developability of the cured film obtained and has excellent storage stability.

Description

Curable composition, method for producing cured film, touch panel, and display device

Technical Field

The present invention relates to a curable composition, a method for producing 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.

Background

Transparent materials are used as various partial structures of various display devices, imaging devices, solar cells, and the like in the form of insulating films, protective films, light extraction layers, spacers (spacers), microlenses (microlenses), and the like.

In addition, as applications of transparent materials, it is known to use them as materials for adjusting refractive index in order to improve device performance.

As a transparent material for refractive index adjustment, a composition using a metal alkoxide is known (for example, see International publication No. 2010/050580 and Japanese patent laid-open No. 2002-6104).

Further, as compositions using a metal alkoxide having patterning performance, compositions described in japanese patent laid-open nos. 2012 and 203061 and 2011 and 178587 are known.

Disclosure of Invention

[ problems to be solved by the invention ]

In recent years, high definition of display devices and imaging devices has been advanced, and high definition pattern forming performance has also been demanded for these transparent materials. The compositions described in International publication No. 2010/050580 and Japanese patent laid-open No. 2002-6104 do not satisfy the above-mentioned requirements because of their non-pattern-forming properties.

Further, the compositions disclosed in Japanese patent laid-open Nos. 2012 and 203061 and 2011 and 178587 are insufficient in developability.

As described above, conventional patterning materials using metal alkoxides do not satisfy the requirements of refractive index, patterning property (developability), and storage stability.

The present invention has been made to solve the problem of providing a curable composition which can combine the refractive index and developability of the obtained cured film and is excellent in storage stability, a cured film obtained by curing the curable composition, a method for producing the cured film, and an organic EL display device, a liquid crystal display device, a touch panel, and a touch panel display device each having the cured film.

[ means for solving problems ]

The problem of the present invention is solved by the means described in <1>, <8>, <9> and <11> - <14> below. Preferred embodiments of <2> to <7> and <10> are described below.

<1> a curable composition comprising: at least one component selected from the group consisting of a1 and a2, at least one component selected from the group consisting of B1 and B2, a photopolymerization initiator, and a solvent, wherein the component A is contained in an amount of 40 to 90% by mass based on the total solid content of the curable composition, the component B is contained in an amount of 5 to 59% by mass based on the total solid content of the curable composition, the total content of the compound having a titanium coordinating group and/or a zirconium coordinating group and an ethylenically unsaturated group, and the compound having a titanium coordinating group and/or a zirconium coordinating group is 15 to 140 parts by mass based on 100 parts by mass of the component A,

a 1: a titanium compound and/or a zirconium compound having an alkoxy group,

a 2: a titanoxane, zirconoalkane and/or a titanoxane-zirconoalkane condensate having at least one alkoxy group bonded directly to the titanium atom or the zirconium atom,

b 1: a compound having a titanium coordinating group and/or a zirconium coordinating group and an ethylenically unsaturated group,

b 2: a compound having a titanium coordinating group and/or a zirconium coordinating group, and a compound having an ethylenically unsaturated group.

<2> the curable composition according to <1>, wherein the a2 represents a titanoxane, a zirconane and/or a titanoxane-zirconane condensate obtained by hydrolytic condensation of at least one compound selected from the group consisting of a titanium compound having an alkoxy group, a zirconium compound having an alkoxy group, a titanium compound having a halogen group and a zirconium compound having a halogen group with water in an amount of 0.5 to 1.9 molar equivalents based on 1.0 mole of the total molar amount of titanium atoms and zirconium atoms.

<3> the curable composition according to <1> or <2>, wherein the component A comprises the above-mentioned a 2.

<4> the curable composition according to any one of <1> to <3>, which further comprises a mercapto compound (mercapto compound) as the component E.

<5> the curable composition according to any one of <1> to <4>, wherein when the component B contains B2, the mass ratio of the content BW1 of the compound having a titanium coordinating group and/or a zirconium coordinating group to the content BW2 of the compound having an ethylenically unsaturated group is BW 1: BW 2: 8: 2 to 2: 8.

<6> the curable composition according to any one of <1> to <5>, wherein the titanium coordinating group and/or the zirconium coordinating group is a group that can coordinate to the titanium atom and/or the zirconium atom through an oxygen atom.

<7> the curable composition according to any one of <1> to <6>, wherein the titanium coordinating group and/or the zirconium coordinating group is a group having at least one structure selected from the group consisting of a1, 2-diketone structure, a1, 3-diketone structure, a1, 4-diketone structure, an α -hydroxyketone structure, a α -hydroxyester structure, a α -ketoester structure, a β -ketoester structure, a malonic diester structure, a fumaric diester structure, and a phthalic diester structure.

<8> A method for producing a cured film, which comprises at least steps 1 to 5 in this order,

step 1: a coating step of coating the curable composition according to any one of the items <1> to <7> on a substrate;

and a step 2: a solvent removal step of removing the solvent from the applied curable composition;

step 3: an exposure step of exposing at least a part of the curable composition from which the solvent has been removed with actinic radiation;

and step 4: a developing step of developing the exposed curable composition with an aqueous developer;

step 5: a heat treatment step of heat-treating the developed curable composition.

<9> a cured film obtained by curing the curable composition according to any one of <1> to <7 >.

<10> the cured film according to <9>, which is an interlayer insulating film or an overcoat film.

<11> A liquid crystal display device having the cured film according to <9> or <10 >.

<12> an organic EL display device having the cured film according to <9> or <10 >.

<13> a touch panel having the cured film according to <9> or <10 >.

<14> A touch panel display device having the cured film according to <9> or <10 >.

[ Effect of the invention ]

According to the present invention, a curable composition which can combine the refractive index and developability of the obtained cured film and has excellent storage stability, a cured film obtained by curing the curable composition, a method for producing the cured film, and an organic EL display device, a liquid crystal display device, a touch panel, and a touch panel display device each having the cured film can be provided.

Drawings

Fig. 1 is a conceptual diagram showing a configuration of an example of a liquid crystal display device, and shows a schematic cross-sectional view of an active matrix substrate in the liquid crystal display device, and includes a cured film 17 as an interlayer insulating film.

Fig. 2 is a conceptual diagram showing a configuration of an example of an organic EL display device, and shows a schematic cross-sectional view of a substrate in a bottom emission type organic EL display device, and includes a planarization film 4.

Fig. 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 sectional view showing a sectional structure taken along line a-a' shown in fig. 3.

Fig. 5 is a sectional view showing a sectional structure taken along the line B-B' shown in fig. 3.

[ description of symbols ]

1: TFT (thin film transistor)

2: wiring harness

3: insulating film

4: planarizing film

5: a first electrode

6: glass substrate

7: contact hole

8: insulating film

10: liquid crystal display device having a plurality of pixel electrodes

12: backlight unit

14. 15: glass substrate

16：TFT

17: hardened film

18: contact hole

19: ITO transparent electrode

20: liquid crystal display device

22: color filter

101a, 102 a: intersection part

101b, 102 b: electrode part

101X: x-direction electrode

102: y-direction electrode

111: substrate

112: insulating layer

112 a: contact hole

113: protective layer

X: electrodes or X-direction

Y: electrodes or Y direction

W: insulating layer (pedestal layer)

Detailed Description

The present invention will be described in detail below. The following description of the constituent elements may be made in accordance with representative embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, "to" is used in a meaning including numerical values described before and after the "to" as a lower limit value and an upper limit value. The organic EL element of the present invention is an organic electroluminescent element.

In the expression of the group (atomic group) in the present specification, the expression that is not described as substituted or unsubstituted includes not only a group (atomic group) having no substituent but also a group (atomic group) having a substituent. For example, the term "alkyl" encompasses not only an unsubstituted alkyl group (unsubstituted alkyl group) but also an unsubstituted alkyl group (substituted alkyl group).

In addition, the chemical structural formula in the present specification may be described by a simplified structural formula in which a hydrogen atom is omitted.

In the present specification, "(meth) acrylate" represents acrylate and methacrylate, "(meth) acrylic acid" represents acrylic acid and methacrylic acid, and "(meth) acryloyl group" represents acryloyl group and methacryloyl group.

In the present invention, "at least one selected from the group consisting of a1 and a 2" and the like are also simply referred to as "component a" and the like.

In the present invention, "mass%" and "weight%" have the same meaning, and "part by mass" and "part by weight" have the same meaning.

In the present invention, a combination of preferred embodiments is a more preferred embodiment.

The weight average molecular weight and the number average molecular weight of the titanoxane, the zirconyl oxide, and the titanyl oxide-zirconyl oxide condensate of the present invention are measured by Gel Permeation Chromatography (GPC).

(curable composition)

The curable composition of the present invention (hereinafter also simply referred to as "composition") contains: the curable composition is characterized in that the curable composition comprises at least one component A selected from the group consisting of a1 and a2, at least one component B selected from the group consisting of B1 and B2, a photopolymerization initiator as a component C, and a solvent as a component D, wherein the content of the component A is 40 to 90 mass% relative to the total solid content of the curable composition, the content of the component B is 5 to 59 mass% relative to the total solid content of the curable composition, and the total content of the compound having a titanium coordinating group and/or a zirconium coordinating group and an ethylenically unsaturated group and the compound having a titanium coordinating group and/or a zirconium coordinating group is 15 to 140 parts by mass relative to 100 parts by mass of the content of the component A.

a 1: a titanium compound and/or a zirconium compound having an alkoxy group,

The present inventors have made extensive studies in view of the above-mentioned point of view, and as a result, have found that a curable composition containing the components a to D and having a specific content as described above can achieve both a refractive index and developability of the resulting cured product and has excellent storage stability, thereby completing the present invention.

It is presumed that, by coordinating the titanium coordinating group and/or the zirconium coordinating group in the component B to the titanium atom and/or the zirconium atom of the component a, the uniformity of the curable composition and the compatibility of the component a with other components are improved, and the refractive index and the developability of the obtained cured product can be both achieved and the storage stability is excellent, but the mechanism for expressing the detailed effects is not clear.

The curable composition of the present invention is preferably a composition in which the strength of a cured product such as a cured film obtained after polymerization with actinic rays is increased by heat treatment.

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 is preferably a curable composition in which the refractive index of the obtained cured product at a wavelength of 550nm is 1.78 or more, more preferably a curable composition in which the refractive index of the obtained cured product at a wavelength of 550nm is 1.80 or more, and still more preferably a curable composition in which the refractive index of the obtained cured product at a wavelength of 550nm is 1.83 or more. The refractive index of the resulting cured product at a wavelength of 550nm is preferably 2.40 or less, more preferably 2.30 or less, and still more preferably 2.20 or less.

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 selected from the group consisting of al and a2

The curable composition of the present invention contains at least one selected from the group consisting of a1 and a2 as the component a, and the content of the component a is 40 to 80% by mass relative to the total solid content of the curable composition.

a 1: a titanium compound and/or a zirconium compound having an alkoxy group,

a 2: a titanium-oxygen-alkane and/or a titanium-oxygen-alkane condensate having at least one alkoxy group bonded directly to a titanium atom or a zirconium atom.

It is obvious to those skilled in the art that a1 has the same meaning as "titanium compound having alkoxy group and/or zirconium compound having alkoxy group", and a2 has the same meaning as "titanium oxide having at least one alkoxy group directly bonded to titanium atom, zirconium oxide having at least one alkoxy group directly bonded to zirconium atom, or titanium oxide-zirconium oxide condensate having at least one alkoxy group directly bonded to titanium atom or zirconium atom".

The component a is not, of course, titanium particles or zirconium oxide (zirconia) particles of rutile (rutile) type or anatase (anatase) type.

The content of the component a is 40 to 90% by mass based on the total solid content of the curable composition, and from the viewpoint of refractive index adjustment, it is preferably 45 to 90% by mass, more preferably 50 to 85% by mass, and still more preferably 60 to 85% by mass. The "solid content" of the curable composition means a component obtained by removing volatile components such as a solvent, and the component B contains a part of compounds having a low boiling point and loses volatility by coordination with titanium or zirconium, and therefore the component B of the present invention is considered to be included in the solid content. The solid component may be a liquid component other than a solid component.

The component a may be any of a single a1, a single a2, a mixture of a1 and a2, and from the viewpoint of storage stability of the composition, a2 alone or a mixture of a1 and a2 is preferable, and a2 alone is more preferable.

In addition, a titanium compound and a zirconium compound may be used together as a 1.

From the viewpoint of refractive index and storage stability, the component a preferably contains at least a 2.

The component a is preferably a titanium compound and/or a titanoxane from the viewpoint of refractive index and developability, and is preferably a zirconium compound and/or a zirconyl oxide from the viewpoint of low-temperature hardenability, curing speed, and stability.

As a 1: examples of the titanium compound having an alkoxy group and the zirconium compound having an alkoxy group include: titanium monoalkoxy, titanium dialkoxide, titanium trialkoxide, titanium tetraalkoxide, zirconium monoalkoxy, zirconium dialkoxide, zirconium trialkoxide, and zirconium tetraalkoxide, and from the viewpoint of film physical properties, titanium tetraalkoxide and zirconium tetraalkoxide are preferable, and titanium tetraalkoxide is more preferable.

Further, a1 may have other groups such as a halogen group and an alkyl group as long as it has at least one alkoxy group.

The titanium tetraalkoxide is preferably titanium tetraalkoxide represented by the following formula a1-1 from the viewpoint of film physical properties.

In addition, the zirconium tetraalkoxide is preferably a zirconium tetraalkoxide represented by the following formula a1-2 from the viewpoint of film physical properties.

[ solution 1]

In the formulae a1-1 and a1-2, R¹～R⁴Each independently represents an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms or an aralkyl group having 7 to 18 carbon atoms.

From the viewpoint of the film physical properties, R in the formula a1-1 and the formula a1-2¹～R⁴Each independently preferably an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and particularly preferably an alkyl group having 1 to 5 carbon atoms.

The titanium tetraalkoxide represented by the formula a1-1 is not limited to the following specific examples, and examples thereof include: titanium tetramethoxide, titanium tetraethoxide, tetra-n-propoxide, titanium tetraisopropoxide, titanium tetra-n-butoxide, titanium tetraisobutoxide, titanium diisopropoxide, di-tert-butoxydiisopropoxide, titanium tetra-tert-butoxid, titanium tetraisooctanoxide, titanium tetrastearylalkoxyxide and the like.

The zirconium tetraalkoxide represented by the formula a1-2 is not limited to the following specific examples, and examples thereof include: zirconium tetramethoxide, zirconium tetraethoxide, tetra-n-propoxide, zirconium tetraisopropoxide, zirconium tetra-n-butoxide, zirconium tetraisobutoxide, zirconium diisopropoxide di-n-butoxide, zirconium di-tert-butoxydiisopropoxide, zirconium tetra-tert-butoxide, zirconium tetraisooctoxide, zirconium tetrastearylalkoxylate and the like.

These compounds may be used singly or in combination of two or more.

Titanoxanes, also known as polytitaxanes, are compounds having more than two Ti-O-Ti bonds. Examples of the production method include: a process for producing a titanoxane, which comprises subjecting titanium tetraalkoxide represented by the formula a1-1 to hydrolytic condensation with water. In addition, titanium halides such as titanium tetrachloride may be hydrolyzed and condensed. Among them, titanium alkoxide and titanium chloride are preferable, and titanium alkoxide is more preferable, from the viewpoint of ease of synthesis.

Zirconoxanes, also known as polyzirconias, are compounds having more than two Zr — O — Zr bonds. Further, examples of the production method include: the same method as the above-mentioned method for producing a titanoxane is used except that the raw material is changed to a zirconium compound such as zirconium alkoxide or zirconium halide.

The titanium oxide-zirconium oxide condensate is a condensate obtained by hydrolysis and condensation of both the titanium compound and the zirconium compound. Further, examples of the production method include: the same method as the above-mentioned production method is used except that a titanium compound and a zirconium compound are used in combination as raw materials.

The a2 is preferably a titanoxane, a zirconoalkane and/or a titanoxane-zirconoalkane condensate obtained by hydrolysis-condensing at least one selected from the group consisting of a titanium compound having an alkoxy group, a zirconium compound having an alkoxy group, a titanium compound having a halogen group and a zirconium compound having a halogen group with water in an amount of 0.5 to 1.9 molar equivalent to 1.0 molar amount based on the total molar amount of titanium atoms and zirconium atoms, and more preferably a titanoxane, a zirconoalkane and/or a titanoxane-zirconoalkane condensate obtained by hydrolysis-condensing at least one selected from the group consisting of a titanium compound having an alkoxy group and a zirconium compound having an alkoxy group with water in an amount of 0.5 to 1.9 molar equivalent to 1.0 molar amount based on the total molar amount of titanium atoms and zirconium atoms.

In the case of using a titanium compound having a halogen group and/or a zirconium compound having a halogen group, it is preferable to use a titanium compound having an alkoxy group and/or a zirconium compound having an alkoxy group in combination, or to use a titanium compound having a halogen group and a zirconium compound having a halogen group and having at least one or more alkoxy groups, or to add the compounds to water and add an alcohol compound to perform hydrolytic condensation.

Examples of the halogen-containing titanium compound and the halogen-containing zirconium compound include: titanium monohalide, titanium dihalide, titanium trihalide, titanium tetrahalide, zirconium monohalide, zirconium dihalide, zirconium trihalide and zirconium tetrahalide, and from the viewpoint of film physical properties, titanium tetrahalide and zirconium tetrahalide are preferable, and titanium tetrahalide is more preferable. These compounds may be used singly or in combination of two or more.

In the hydrolytic condensation, not only water but also a solvent and the like may be used, and an alcohol compound may be used as an additive. In addition, the solvent may suitably be an alcohol compound.

The amount of water used in the hydrolytic condensation is preferably 0.5 to 1.9 molar equivalents relative to the total molar amount of titanium atoms and zirconium atoms of the raw materials, from the viewpoint of mechanical strength of the obtained film, and the lower limit is preferably 0.9 molar equivalent or more, more preferably 1.2 molar equivalents or more, from the viewpoint of film strength, and the upper limit is preferably 1.8 molar equivalent or less, more preferably 1.7 molar equivalents or less, from the viewpoint of film flexibility.

From the viewpoint of storage stability of the composition and film physical properties, the component a preferably contains a titanium oxide having at least one alkoxy group directly bonded to a titanium atom (hereinafter also simply referred to as "titanium oxide"), a zirconium oxide having at least one alkoxy group directly bonded to a zirconium atom (hereinafter also simply referred to as "zirconium oxide"), or a titanium oxide-zirconium oxide condensate having at least one alkoxy group directly bonded to a titanium atom or a zirconium atom (hereinafter also simply referred to as "titanium oxide-zirconium oxide condensate"), more preferably contains a titanium oxide or a zirconium oxide, and still more preferably contains a titanium oxide.

The titanoxane, the zirconoxane, and the titanoxane-zirconoxane condensate may be in any polymer form such as a straight chain, a branched chain, a three-dimensional network, a cantilever, a ladder, and a cage, and the form thereof is not particularly limited, but a titanoxane or a zirconoxane that is compatible with the component B is preferable. The titanyl oxide and the zirconyl oxide may be solid or liquid at normal temperature (25 ℃).

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

The titanoxane is preferably represented by the following formula a2-1 from the viewpoint of film physical properties.

In addition, the zirconium siloxane is preferably a zirconium siloxane represented by the following formula a2-2 from the viewpoint of film physical properties.

Ti_αO_β(OR)_γ(a2-1)

Zr_αO_β(OR)_γ(a2-2)

In the formulas a2-1 and a2-2, R independently represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms or an aralkyl group having 7 to 18 carbon atoms, α, β and γ satisfy the following conditions a 'to c', α represent 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 titanium oxide, zirconium oxide and titanium oxide-zirconium oxide condensate of a2 may be a single component or a mixture of two or more components.

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

Component B: at least one selected from the group consisting of b1 and b2

The curable composition of the present invention contains at least one selected from the group consisting of B1 and B2 as a component B, wherein the content of the component B is 5 to 59 mass% relative to the total solid content of the curable composition, and the total content of the compound having a titanium coordinating group and/or a zirconium coordinating group and an ethylenically unsaturated group and the compound having a titanium coordinating group and/or a zirconium coordinating group is 15 to 140 parts by mass relative to 100 parts by mass of the content of the component A.

The curable composition of the present invention contains, as component B, at least a compound having a titanium coordinating group and/or a zirconium coordinating group and an ethylenically unsaturated group, or contains, as component B, at least both a compound having a titanium coordinating group and/or a zirconium coordinating group and a compound having an ethylenically unsaturated group.

In the present invention, the compound corresponding to component B is a compound having one or more titanium coordinating groups and/or zirconium coordinating groups, one or more ethylenically unsaturated groups, or both of them.

From the viewpoint of developability, component B preferably contains at least B2.

In addition, from the viewpoint of chemical resistance, the component B preferably contains at least a compound having an ethylenically unsaturated group, and more preferably contains at least a compound having no titanium coordinating group and/or zirconium coordinating group and having an ethylenically unsaturated group.

In the curable composition of the present invention, the content of the component B is 5 to 59 mass%, preferably 10 to 55 mass%, more preferably 15 to 50 mass%, and still more preferably 25 to 45 mass% with respect to the total solid content of the curable composition, from the viewpoint of achieving both the refractive index of the cured film and the developability.

In the curable composition of the present invention, the total content of the compound having a titanium coordinating group and/or a zirconium coordinating group and an ethylenically unsaturated group and the compound having a titanium coordinating group and/or a zirconium coordinating group is 15 to 140 parts by mass, preferably 15 to 80 parts by mass, more preferably 20 to 60 parts by mass, per 100 parts by mass of the content of the component a, from the viewpoint of the refractive index of the cured product, the developability, the storage stability, and the like.

The "titanium coordinating group and/or zirconium coordinating group" in the present invention means a group capable of forming a coordination bond with a titanium atom and/or a zirconium atom, and may form a coordination bond with either a titanium atom or a zirconium atom, or may form a coordination bond with both a titanium atom and a zirconium atom.

The coordination formed by the titanium coordinating group and/or the zirconium coordinating group may be any of monodentate coordination (monodentate coordination), bidentate coordination, tridentate coordination, and four or more dentate coordination, and the coordinating group is preferably a monodentate or bidentate coordinating group, and more preferably a bidentate coordinating group.

Further, the titanium coordinating group and/or the zirconium coordinating group are preferably groups which coordinate to a titanium atom and/or a zirconium atom to become neutral ligands on the titanium atom and/or the zirconium atom.

When a compound having at least a titanium coordinating group and/or a zirconium coordinating group is coordinated to the component a, the energy level of the d orbital of the coordinated titanium atom or zirconium atom in the component a is split. Therefore, the presence or absence of coordination is known by observing the division of the energy level.

The method for confirming whether or not the complex is a titanium coordinating group and/or a zirconium coordinating group includes a method for observing the presence or absence of coordination. Specific examples of the method for observing the presence or absence of coordination include a known observation method, such as a spectroscopic method or an Electron Spin Resonance (ESR) method.

From the viewpoint of the stability of the composition and the film physical properties, the titanium coordinating group and/or the zirconium coordinating group in the present invention is preferably a group having an oxygen atom, more preferably a group having two or more oxygen atoms, further preferably a group having a structure in which at least 2 oxygen atoms are bonded with another atom intervening between 2 atoms and 4 atoms, and particularly preferably a group having a structure in which at least 2 oxygen atoms are bonded with another atom intervening between 3 atoms or 4 atoms. In addition, at least one of the oxygen atoms is preferably an oxygen atom of a carbonyl group in a carbonyl group or an ester structure.

In addition, from the viewpoint of the stability of the composition and the film physical properties, the titanium coordinating group and/or the zirconium coordinating group of the present invention are preferably groups that can coordinate to a titanium atom and/or a zirconium atom through an oxygen atom.

The titanium coordinating group and/or the zirconium coordinating group of the present invention is preferably a group having at least one structure selected from the group consisting of a1, 2-diketone structure, a1, 3-diketone structure, a1, 4-diketone structure, a α -hydroxyketone structure, a α -hydroxyester structure, a α -keto ester structure, a α -keto ester structure, a malonic acid diester structure, a fumaric acid diester structure and a phthalic acid diester structure, more preferably a group having at least one structure selected from the group consisting of a1, 2-diketone structure, a1, 3-diketone structure, a α -hydroxyketone structure, a α -hydroxyester structure, a α -keto ester structure, an α -keto ester structure and a phthalic acid diester structure, further preferably a group having at least one structure selected from the group consisting of a1, 3-diketone structure, a α -hydroxyketone structure, a β -keto ester structure and a phthalic acid diester structure, and most preferably a group having at least one structure selected from the group consisting of a1, 3-diketone structure, a α -hydroxyketone structure, a β -keto ester structure and a β -keto ester structure.

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

[ solution 2]

In the formulae b-1 to b-5, L¹And L²Each independently represents a single bond or an alkylene group having 1 or 2 carbon atoms, R' independently represents an alkyl group, an alkoxy group, a halogen atom, an acyl group or an alkoxycarbonyl group, nb represents an integer of 0 to 4, and the wave line part represents a bonding position with another structure.

L¹And L²Preferably a single bond or a methylene group, more preferably a methylene group.

The carbon number of R' is preferably 0 to 20. In addition, each R' is 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 and the zirconium coordinating group include those shown below. In addition, the wave line part indicates a bonding position with another structure.

[ solution 3]

The ethylenically unsaturated group in the component B is not particularly limited, and may preferably include a (meth) acryloyl group, a (meth) acrylamide group, an allyl group, a styryl group, and a vinyloxy group, more preferably include a (meth) acryloyl group and an allyl group, and particularly preferably include a (meth) acryloyl group.

From the viewpoint of developability, the compound having a titanium coordinating group and/or a zirconium coordinating group and an ethylenically unsaturated group in b1 is preferably a (meth) acrylate compound having a1, 3-diketone structure or a β -keto ester structure or an ethylenically unsaturated compound having a phthalic diester structure, and more preferably a (meth) acrylate compound having a1, 3-diketone structure or a β -keto ester structure.

In addition, the compound having a titanium coordinating group and/or a zirconium coordinating group and an ethylenically unsaturated group may be used singly 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 coordinating group and an ethylenically unsaturated group is preferably a (meth) acrylate compound having a titanium coordinating group and/or a zirconium coordinating group, more preferably a monofunctional (meth) acrylate compound having a titanium coordinating group and/or a zirconium coordinating group, and further preferably a compound shown below.

The above-mentioned ethylenically unsaturated compound having a phthalic diester structure is preferably exemplified by diallyl phthalate.

[ solution 4]

The compound having a titanium coordinating group and/or a zirconium coordinating group in b2 is a compound having no ethylenically unsaturated group and having a titanium coordinating group and/or a zirconium coordinating group.

Further, one kind of the compound having a titanium coordinating group and/or a zirconium coordinating group may be used alone, or two or more kinds may be used in combination.

The compound having no ethylenically unsaturated group and having a titanium coordinating group and/or a zirconium coordinating group is preferably a1, 2-diketone compound, a1, 3-diketone compound, a1, 4-diketone compound, an α -hydroxyketone compound, a α -hydroxyester compound, a α -keto ester compound, a β -keto ester compound, a malonic acid diester compound, a fumaric acid diester compound or a phthalic acid diester compound, more preferably a1, 2-diketone compound, a1, 3-diketone compound, a α -hydroxyketone compound, a α -keto ester compound, a β -keto ester compound or a phthalic acid diester compound, still more preferably a1, 3-diketone compound, a α -hydroxyketone compound or a β -keto ester compound, and particularly preferably a1, 3-diketone compound or an β -keto ester compound.

Specific examples of the compound having no ethylenically unsaturated group and having a titanium coordinating group and/or a zirconium coordinating group include the compounds shown below.

[ solution 5]

Of these compounds, acetylacetone (2, 4-pentanedione), ethyl acetoacetate (ethyl 3-oxobutyrate), or ethyl lactate are preferable, and acetylacetone or ethyl acetoacetate are particularly preferable.

The compound having an ethylenically unsaturated group of b2 is not particularly limited as long as it is a compound having an ethylenically unsaturated group, and can be appropriately selected according to the purpose. Examples thereof include ester compounds, amide compounds, urethane compounds and other compounds.

The compound having an ethylenically unsaturated group may be either a monofunctional ethylenically unsaturated compound or a polyfunctional ethylenically unsaturated compound, and preferably contains a polyfunctional ethylenically unsaturated compound, and more preferably a polyfunctional ethylenically unsaturated compound.

Examples of the ester compound include: polyfunctional (meth) acrylates, itaconates, crotonates, methacrylates, maleates, other ester compounds, and the like. Among these, polyfunctional (meth) acrylates (polyfunctional (meth) acrylate compounds) and the like are preferred.

Examples of the polyfunctional (meth) acrylate compound include: polyethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1, 3-butanediol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol 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, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate are particularly preferable.

Other examples of the polyfunctional (meth) acrylate include: examples of the (meth) acrylic acid ester include compounds obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol such as glycerin, trimethylolethane or bisphenol A and then (meth) acrylating the resultant mixture, acrylic acid urethanes described in Japanese patent application publication No. 48-41708, Japanese patent application publication No. 50-6034 and Japanese patent application publication No. 51-37193, polyester acrylates described in Japanese patent application publication No. 48-64183, Japanese patent application publication No. 49-43191 and Japanese patent application publication No. 52-30490, epoxy acrylates which are reaction products of an epoxy resin and (meth) acrylic acid, and (meth) acrylic acid esters or (meth) acrylic acid urethanes or vinyl esters described in Japanese patent application publication No. 60-258539.

Examples of other polyfunctional ethylenically unsaturated compounds include: trimethylolpropane tris (acryloyloxypropyl) ether, isocyanuric acid tris (acryloyloxyethyl) ester, and photocurable monomers and oligomers described in journal of the subsequent society of Japan (Vol.20, No.7, pages 300 to 308).

The amide compound includes, for example, an amide (monomer) of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound, and specifically includes: methylene bis (meth) acrylamide, 1, 6-hexamethylene bis (meth) acrylamide, diethylenetriamine tri (meth) acrylamide, xylylene bis (meth) acrylamide, and the like, and further, there are mentioned (meth) acrylic acid amides described in Japanese patent laid-open No. Sho 60-258539, and the like.

The urethane compound may be exemplified by urethane chain polymerizable compounds produced by an addition reaction of isocyanate and hydroxyl groups, and examples thereof include: urethane compounds of pentaerythritol triacrylate and hexamethylene diisocyanate, urethane compounds of pentaerythritol triacrylate and toluene diisocyanate, urethane compounds of pentaerythritol triacrylate and isophorone diisocyanate, urethane compounds of dipentaerythritol pentaacrylate and hexamethylene diisocyanate, urethane compounds of dipentaerythritol pentaacrylate and toluene diisocyanate, and urethane compounds of dipentaerythritol pentaacrylate and isophorone diisocyanate.

Specific examples thereof include: acrylic urethanes such as those described in Japanese patent laid-open Nos. 2011-126921, 51-37193, 2-32293 and 2-16765 are incorporated in the present specification.

Further, other polyfunctional ethylenically unsaturated compounds include: an allyl group-containing compound or an alkenyl group-containing compound described in Japanese patent laid-open No. Sho 60-258539 and International publication No. 2010/050580.

Specific examples thereof include: 1, 2-divinylbenzene, 1, 4-divinylbenzene, 1, 2-diallylbenzene, 1, 3-diallylbenzene, 1, 4-diallylbenzene, 1,3, 5-trivinylbenzene, 1,3, 5-triallylbenzene, 1,2, 4, 5-tetraallylbenzene, hexaallylbenzene, divinyltoluene, bisphenol a diallyl ether, 1, 2-diallyloxybenzene, 1, 4-diallyloxybenzene, diallyl terephthalate, diallyl isophthalate, 1, 4-bis (dimethylvinylsilyl) benzene, divinylmethylphenylsilane, divinyldiphenylsilane, diallylbenzylsilane, and the like.

The number of ethylenically unsaturated groups in the polyfunctional ethylenically unsaturated compound is preferably 2 to 20, more preferably 2 to 16, and still more preferably 3 to 10.

Examples of monofunctional ethylenically unsaturated compounds include: unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, methacrylic acid and maleic acid, and salts thereof, and monofunctional ethylenically unsaturated compounds such as (meth) acrylates, (meth) acrylamides, (meth) acrylonitriles and styrenes.

In addition, addition reaction products of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl group, amino group, mercapto group, etc. with isocyanates or epoxies, and dehydration condensation reaction products with monofunctional or multifunctional carboxylic acids, etc. can also be suitably used.

Furthermore, the following reactants are also suitable: addition reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituent groups such as isocyanato groups (isocyanate groups) or epoxy groups with alcohols, amines and thiols, and substitution reaction products of unsaturated carboxylic acid esters or amides having dissociative substituent groups such as halogen groups or tosyloxy groups with alcohols, amines and thiols.

As another example, instead of the unsaturated carboxylic acid, a compound group substituted with an unsaturated phosphonic acid, styrene, vinyl ether, or the like may be used.

The monofunctional ethylenically unsaturated compound is not particularly limited, and various well-known compounds other than the above exemplified compounds can be used, and for example, compounds described in Japanese patent laid-open No. 2009-204962 and the like can be used.

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

One kind of the compound having an ethylenically unsaturated group may be used alone, or two or more kinds may be used in combination.

When the curable composition of the present invention contains b2, that is, a compound having a titanium coordinating group and/or a zirconium coordinating group and a compound having an ethylenically unsaturated group, the mass ratio of the content BW1 of the compound having a titanium coordinating group and/or a zirconium coordinating group to the content BW2 of the compound having an ethylenically unsaturated group in the curable composition of the present invention is preferably BW 1: BW2 of 1: 20 to 20: 1, more preferably 1: 10 to 10: 1, still more preferably 2: 8 to 8: 2, and particularly preferably 3: 7 to 7: 3.

The molecular weight of each compound corresponding to component B is preferably 80 to 2,000, more preferably 100 to 1,000.

The content of the compound having no titanium coordinating group and/or zirconium coordinating group and having an ethylenically unsaturated group is preferably 1 to 50% by mass, more preferably 5 to 40% by mass, based on the total solid content of the curable composition.

Component C: photopolymerization initiator

The curable composition of the present invention contains a photopolymerization initiator as component C.

The photopolymerization initiator preferably contains a photo radical polymerization initiator.

The photopolymerization initiator usable in the present invention is a compound which can be initiated by actinic rays and promotes polymerization of a polymerizable compound such as a compound having an ethylenically unsaturated group.

The "actinic rays" are not particularly limited as long as they are active energy rays capable of imparting energy capable of generating initiating species from the component C by irradiation with the actinic rays, and include α rays, γ rays, X rays, ultraviolet rays (UV), visible rays, electron beams, and the like widely.

Examples of the photopolymerization initiator include: oxime ester compounds, organohalogenated compounds, oxadiazole compounds, carbonyl compounds, ketal (ketal) compounds, benzoin compounds, acridine compounds, organoperoxy compounds, azo compounds, coumarin compounds, azide compounds, metallocene compounds, hexaarylbiimidazole compounds, organoboronic acid compounds, disulfonic acid compounds, onium salt compounds, acylphosphine (oxide) compounds. Among these compounds, oxime ester compounds and hexaarylbiimidazole compounds are preferable from the viewpoint of sensitivity, and oxime ester compounds are more preferable.

The oxime ester compound may be used: compounds described in Japanese patent laid-open Nos. 2000-80068, 2001-233842, 2004-534797, 2007-231000 and 2009-134289.

The oxime ester compound is preferably a compound represented by the following formula C-1 or formula C-2.

[ solution 6]

In the formula C-1 or C-2, Ar represents an aromatic group or a heteroaromatic group, R^C1Represents an alkyl group, an aromatic group or an alkoxy group, R^C2Represents a hydrogen atom or an alkyl group, and further R^C2May form a ring by bonding with the Ar group.

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, more preferably a group obtained by reacting with R^C2Naphthyl and carbazolyl groups which together form a ring. The heteroatom in the heteroaromatic group may preferably beExamples thereof include a nitrogen atom, an oxygen atom and a sulfur atom. Among them, nitrogen atoms are preferred.

R^C1Represents an alkyl, aromatic or alkoxy group, preferably a methyl, ethyl, benzyl, phenyl, naphthyl, methoxy or ethoxy group, more preferably a methyl, ethyl, phenyl or methoxy group.

R^C2Represents 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 which forms a ring together with Ar or a tosyl group.

Ar is preferably a group having 4 to 20 carbon atoms, R^C1Preferably C1-30 group, and R^C2Preferably a group having 1 to 50 carbon atoms.

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

[ solution 7]

In the formulae C-3 to C-5, R^C1Represents an alkyl group, an aromatic group or an alkoxy group, and X represents-CH₂-、-C₂H₄-, -O-or-S-, R^C3Each independently represents a halogen atom, R^C4Each independently represents an alkyl group, a phenyl group, an alkyl-substituted amino group, an arylthio group, an alkylthio group, an alkoxy group, an aryloxy group or a halogen atom, R^C5Represents a hydrogen atom, an alkyl group or an aryl group, R^C6N1 and n2 each independently represent an integer of 0 to 6, and n3 represents an integer of 0 to 5.

R^C1Represents an alkyl group, an aromatic group or an alkoxy group, preferably R^C11-X' -alkylene-represents a group. R^C11Represents an alkyl group or an aryl group, and X' represents a sulfur atom or an oxygen atom. R^C11Preferably aryl, more preferably phenyl. As R^C11The alkyl group and the aryl group of (b) may be substituted with a halogen atom (preferably a fluorine atom, a chlorine atom or a bromine atom) or an alkyl group.

X is preferably a sulfur atom.

R^C3And R^C4The bond may be at any position on the aromatic ring.

R^C4Represents an alkyl group, a phenyl group, an alkyl-substituted amino group, an arylthio group, an alkylthio group, an alkoxy group, an aryloxy group or a halogen atom, preferably an alkyl group, a phenyl group, an arylthio group or a halogen atom, more preferably an alkyl group, an arylthio group or a halogen atom, and further preferably an alkyl group or a halogen atom. The alkyl group is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group or an ethyl group. The halogen atom is preferably a chlorine atom, a bromine atom or a fluorine atom.

In addition, R^C4The carbon number of (b) is preferably 0 to 50, more preferably 0 to 20.

R^C5Represents 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, and more preferably a methyl group or an ethyl group. The aryl group is preferably an aryl group having 6 to 10 carbon atoms.

R^C6Represents 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 each represent R on an aromatic ring of the formula C-3 or C-4^C3N3 represents R on the aromatic ring of the formula C-5^C4The number of substitutions of (c).

n1 to n3 are each independently preferably an integer of 0 to 2, more preferably 0 or 1.

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

[ solution 8]

Specific examples of the organic halogenated compound include: examples of the halogen-substituted compound include compounds described in Japanese society of Chemistry (Bullchem. Soc. Japan) (42, 2924(1969)), U.S. Pat. No. 3,905,815, Japanese patent publication (Japanese Kokoku) No. 46-4605, Japanese patent application laid-open No. 48-36281, Japanese patent application laid-open No. 55-32070, Japanese patent application laid-open No. 60-239736, Japanese patent application laid-open No. 61-169835, Japanese patent application laid-open No. 61-169837, Japanese patent application laid-open No. 62-58241, Japanese patent application laid-open No. 62-212401, Japanese patent application laid-open No. 63-70243, Japanese patent laid-open No. 63-298339, Heterocyclic chemical (Journal of Heterocyclic Chemistry) (M.P.Hutt) (Journal of Heterocyclic Chemistry) No. 1 (3), and the like (Savoxazole compound described in JP-A-5, 1970, 19724, and the like), An s-triazine compound.

Examples of hexaarylbiimidazole compounds include: various compounds described in the specifications of Japanese patent publication No. 6-29285, U.S. Pat. No. 3,479,185, U.S. Pat. No. 4,311,783, and U.S. Pat. No. 4,622,286.

Examples of the acylphosphine (oxide) compound include monoacylphosphine oxide compounds and bisacylphosphine oxide compounds, and specifically include gazette (IRGACURE)819, Darocure (Darocure)4265, Darocure (Darocure) TPO, and the like, which are manufactured by BASF corporation.

An example of the acetophenone compound is Irgacure 127 manufactured by BASF corporation.

The photopolymerization initiator may be used singly or in combination of two or more. In addition, when a photopolymerization initiator having no absorption at the exposure wavelength is used, a sensitizer may also be used.

The total amount of the photopolymerization initiator in the curable composition of the present invention is preferably 0.5 to 30 parts by mass, more preferably 1 to 20 parts by mass, further preferably 1 to 10 parts by mass, and particularly preferably 2 to 5 parts by mass, based on 100 parts by mass of the total solid content in the composition.

In the present invention, when the photopolymerization initiator has a titanium coordinating group and/or a zirconium coordinating group, the compound having a titanium coordinating group and/or a zirconium coordinating group and an ethylenically unsaturated group in b1 or the compound having a titanium coordinating group and/or a zirconium coordinating group in b2 is not considered.

Sensitizers

In the curable composition of the present invention, a sensitizer may be added in addition to the photopolymerization initiator.

The sensitizer absorbs actinic rays or radiation to become an excited state. The sensitizer in an excited state interacts with the component C to cause the action of electron transfer, energy transfer, heat generation, etc., thereby initiating and accelerating polymerization.

Examples of preferred sensitizers include: a compound belonging to the following group and having an absorption wavelength in the range of 350nm to 450 nm. Polynuclear aromatic species (e.g., pyrene, perylene, triphenylene, anthracene, phenanthrene), xanthenes (e.g., fluorescein, eosin, erythrosine, rhodamine B, Bengal), xanthenones (e.g., xanthenone, thioxanthone, dimethylthioxanthone, diethylthioxanthone, isopropylthioxanthone, 2-chlorothioxanthone), cyanines (e.g., thiocyanine, oxycarbocyanine), merocyanines (e.g., merocyanine, carbocyanine), rhodanines, oxones, thiazines (e.g., thionine, methylene blue, toluidine blue), acridines (e.g., acridine orange, chlorotetracycline, acriflavine, benzoflavin), acridones (e.g., acridone, 10-butyl-2-chloroacridone), anthraquinones (e.g., anthraquinone, 9, 10-dibutoxyanthracene), squaric acid compounds (e.g., squaric acid compounds), styryl, xanthene, phenanthr, Basic styryls, coumarins (e.g., 7-diethylamino-4-methylcoumarin, ketocoumarins), carbazoles (e.g., N-vinylcarbazole), camphorquinones, and phenothiazines.

Further, typical examples of the sensitizer which can be used in the present invention include sensitizers disclosed in crivillo [ j.v. crivello, advanced Polymer science, 62, 1(1984) ].

Preferable specific examples of the sensitizer include: pyrene, flower, acridine orange, thioxanthone, 2-chlorothioxanthone, benzoflavin, N-vinylcarbazole, 9, 10-dibutoxyanthracene, anthraquinone, coumarin, ketocoumarin, phenanthrene, camphorquinone, phenothiazines, and the like. The sensitizer is preferably added in a proportion of 30 to 200 parts by mass with respect to 100 parts by mass of the polymerization initiator.

Component D: solvent(s)

The curable composition of the present invention contains a solvent as component D. In the present invention, the solvent is a compound other than the component B, and a compound corresponding to the component B is not considered to be included in the solvent.

The curable composition of the present invention is preferably prepared as a solution or dispersion in which essential components and optional components described later are dissolved or dispersed in a solvent.

The curable composition of the present invention can be prepared by using a known solvent, and examples thereof include: alcohols, ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, butylene glycol diacetates, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates, esters, ketones, amides, lactones, and the like. As another specific example, see paragraph 0062 of Japanese patent laid-open No. 2009-098616.

Among these solvents, preferable specific examples include: butanol, tetrahydrofurfuryl alcohol, phenoxyethanol, 1, 3-butanediol diacetate, diethylene glycol methyl ethyl ether, propylene glycol monomethyl ether acetate, more preferably: butanol, 1, 3-butanediol diacetate, diethylene glycol methyl ethyl ether.

The boiling point of the solvent is preferably 100 to 300 ℃ from the viewpoint of coatability, and more preferably 120 to 250 ℃.

The solvent usable in the present invention may be used singly or in combination of two or more. It is also preferable to use solvents having different boiling points in combination.

The content of the solvent in the curable composition of the present invention is preferably 100 to 3,000 parts by mass, more preferably 200 to 2,000 parts by mass, and still more preferably 250 to 1,000 parts by mass, based on 100 parts by mass of the total solid content of the curable composition, from the viewpoint of adjusting the viscosity suitable for application, and the like.

The viscosity of the curable composition of the present invention is preferably 1 mPas to 200 mPas, more preferably 2 mPas to 100 mPas, still more preferably 3 mPas to 50 mPas.

The viscosity is preferably measured at 25 ℃. + -. 0.2 ℃ using a RE-80L type rotary viscometer manufactured by Toyobo industries (Ltd.). The rotation speed at the time of measurement is preferably measured at 100rpm when the viscosity is less than 5 mPas, preferably at 50rpm when the viscosity is 5 mPas to less than 10 mPas, preferably at 20rpm when the viscosity is 10 mPas to less than 30 mPas, and preferably at 10rpm when the viscosity is 30 mPas or more.

Component E: mercapto compounds

The curable composition of the present invention preferably further contains a mercapto compound as component E. By containing the mercapto compound, a cured product having more excellent storage stability and a higher refractive index can be obtained, and the cured product has excellent chemical resistance.

The mercapto compound is a compound having at least one mercapto group (-SH) in the molecule.

The mercapto compound includes monofunctional mercapto compounds and polyfunctional mercapto compounds, and among them, polyfunctional mercapto compounds are preferable from the viewpoint 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 tertiary mercapto group, and from the viewpoint of sensitivity and chemical resistance, the primary mercapto group or the secondary mercapto group is preferable, and the secondary mercapto group is more preferable. In addition, from the viewpoint of storage stability, a secondary mercapto group or a tertiary mercapto group is preferable, and a secondary mercapto group is more preferable.

The molecular weight of the mercapto compound usable in the present invention is preferably 100 to 2,000, more preferably 200 to 1,000.

The number of mercapto groups in the mercapto compound usable in the present invention is not particularly limited, but is preferably 1 to 20, more preferably 2 to 10, and still more preferably 2 to 6.

Monofunctional mercapto compounds

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 weight compound having a molecular weight of 100 or more, specifically, a molecular weight of 80 to 1,000 is preferable, and 100 to 800 is more preferable.

In addition, the monofunctional mercapto compound preferably has a heterocyclic ring, and more preferably has a thiazole structure, from the viewpoint of sensitivity.

Examples of the monofunctional mercapto compound include monofunctional aliphatic mercapto compounds and monofunctional aromatic mercapto compounds, and specific examples thereof include mercapto compounds such as mercaptoethanol (mercapto ethanol), mercaptopropanol, mercaptobutanol, mercaptopropanediol, mercaptobutanediol, hydroxythiopheneitol (hydroxytoluenethiol) and derivatives thereof, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 1-phenyl-1H-benzimidazole-2-thiol, 2-mercapto-4 (3H) -quinazoline and β -mercaptonaphthalene.

In addition, compounds described in paragraphs 0097 to 0098 of Japanese patent laid-open publication No. 2011-65087 and compounds described in paragraphs 0086 to 0088 of Japanese patent laid-open publication No. 2008-299211 are mentioned.

Polyfunctional mercapto compounds

In addition, from the viewpoint of sensitivity, storage stability and film physical properties, the mercapto compound is preferably a polyfunctional mercapto compound. Examples of the polyfunctional mercapto compound include polyfunctional aliphatic mercapto compounds and polyfunctional aromatic mercapto compounds.

In the present invention, the "polyfunctional mercapto compound" refers to a compound having two or more mercapto groups in a molecule. The polyfunctional thiol compound is preferably a low-molecular weight compound having a molecular weight of 100 or more, specifically, a molecular weight of 100 to 1,500, more preferably 150 to 1,000.

The polyfunctional mercapto compound preferably has 2 to 10 mercapto groups, more preferably 2 to 6 mercapto groups in the molecule.

The aliphatic polyfunctional thiol compound is preferably a compound having two or more groups represented by the following formula e-1.

[ solution 9]

In the formula e-1, R represents a hydrogen atom or an alkyl group, and A represents-CO-or-CH₂-。

The polyfunctional mercapto compound is preferably a compound having 2 or more and 6 or less groups represented by formula e-1, and more preferably a compound having 2 or more and 4 or less groups.

The alkyl group of R in the formula e-1 is a linear, branched or cyclic alkyl group, and the carbon number is preferably 1 to 16, more preferably 1 to 10. Specific examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, and 2-ethylhexyl groups, with methyl, ethyl, propyl, and isopropyl being preferred.

R is preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group or an isopropyl group, and more preferably a methyl group or an ethyl group.

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

[ solution 10]

In the formula e-2, R represents a hydrogen atom or an alkyl group, and A represents-CO-or-CH₂-. 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 preferable range is also the same. n is preferably 2 to 4.

Examples of L as the n-valent linking group in the formula e-2 include: - (CH)₂)_mA divalent linking group such as- (m represents an integer of 2 to 6); a trimethylolpropane residue and having three- (CH)₂)_pA trivalent linking group such as an isocyanuric ring (isocyanuric ring) of- (p represents an integer of 2 to 6); a tetravalent linker or a pentavalent linker such as a pentaerythritol residue; and a hexavalent linking group such as a dipentaerythritol residue.

Specific examples of the polyfunctional thiol compound include the following compounds as preferable polyfunctional thiol compounds: trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), tetraethyleneglycol bis (3-mercaptopropionate), dipentaerythritol hexa (3-mercaptopropionate), pentaerythritol tetrakis (mercaptoacetate) (2-thioglycollate)), pentaerythritol tetrakis (3-mercaptobutyrate), butanediol bis (3-mercaptobutyrate), 1, 4-bis (3-mercaptobutyryloxy) butane, 1, 4-bis (3-mercaptobutyloxy) butane, 1,3, 5-tris (3-mercaptobutoxyethyl) -1, 3, 5-triazine-2, 4, 6(1H, 3H, 5H) -trione, and the like.

Commercially available examples of the polyfunctional mercapto compound include Carrenz MT (KarenzmT) (registered trademark) BD1, NR1 or PE1 (available from Showa Denko K.K.), Temppic (available from SC organic chemistry, Inc.), and the like.

[ solution 11]

Other specific examples include compounds described in paragraphs 0165 to 0167 of Japanese patent laid-open No. 2012-14052.

Examples of the aromatic mercapto compound include compounds described in paragraphs 0021 to 0022 of International publication No. 2010/050580. Among them, 4' -thiobisbenzenethiol is preferable.

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

[ solution 12]

In the formula e-3, X^eRepresents an N atom or a C atom, Y^eRepresents a N atom or a C atom, S atom, O atom, L^eRepresents a single bond or a divalent organic group A^eIs represented by the formula X^e＝C-Y^eTogether form an aromatic ring. Form A^eThe aromatic ring (b) may have a substituent such as a hydroxyl group, an ether group, an ester group, an amino group, an amide group, a nitro group, or a cyano group, and may further have a mercapto group different from those described in the formula.

Examples of the aromatic mercapto compound include: monofunctional aromatic mercapto compounds such as benzenethiol, 4-acetamibenzenethiol, 4-tert-butylbenzene thiol, 2-naphthalene thiol, 2-aminobenzenethiol, 4- (dimethylamino) benzenethiol, 2-mercaptothiazole, 2-mercaptobenzothiazole, triphenylmethanethiol (triphenylmethanethiol), 5-mercapto-1-phenyl-1H-tetrazole, 2-mercaptopyridine, 2-mercapto-5-methyl-1, 3, 4-thiadiazole, 2-mercapto-1, 3, 4-thiadiazole, and 2-amino-5-mercapto-1, 3, 4-thiadiazole, or

1, 2-dimercaptobenzene, 1, 3-dimercaptobenzene, 1, 4-dimercaptobenzene, 1, 2-bis (mercaptomethyl) benzene, 1, 3-bis (mercaptomethyl) benzene, 1, 4-bis (mercaptomethyl) benzene, 1, 3-bis (mercaptoethyl) benzene, 1, 4-bis (mercaptoethyl) benzene, 1, 2-bis (mercaptomethoxy) benzene, 1, 3-bis (mercaptomethoxy) benzene, 1, 4-bis (mercaptomethoxy) benzene, 1, 2-bis (mercaptoethoxy) benzene, 1, 3-bis (mercaptoethoxy) benzene, 1, 4-bis (mercaptoethoxy) benzene, 1,2, 3-trimercaptobenzene, 1,2, 4-trimercaptobenzene, 1,3, 5-trimercaptobenzene, 1,2, 3-tris (mercaptomethyl) benzene, 1,2, 3-trimercaptoethyl (mercaptoethoxy) benzene, 1, 3-trimercaptoethoxy) benzene, 1,2, 3-trimerca, 1,2, 4-tris (mercaptomethyl) benzene, 1,3, 5-tris (mercaptomethyl) benzene, 1,2, 3-tris (mercaptoethyl) benzene, 1,2, 4-tris (mercaptoethyl) benzene, 1,3, 5-tris (mercaptoethyl) benzene, 1,2, 3-tris (mercaptomethoxy) benzene, 1,2, 4-tris (mercaptomethoxy) benzene, 1,3, 5-tris (mercaptomethoxy) benzene, 1,2, 3-tris (mercaptoethoxy) benzene, 1,2, 4-tris (mercaptoethoxy) benzene, 1,3, 5-tris (mercaptoethoxy) benzene, 1,2, 3, 4-tetramercaptobenzene, 1,2, 3, 5-tetramercaptobenzene, 1,2, 4, 5-tetramercaptobenzene, 1,2, 3, 4-tetramercaptomethyl) benzene, 1,2, 3, 5-tetrakis (mercaptomethyl) benzene, 1,2, 4, 5-tetrakis (mercaptomethyl) benzene, 1,2, 3, 4-tetrakis (mercaptoethyl) benzene, 1,2, 3, 5-tetrakis (mercaptoethyl) benzene, 1,2, 4, 5-tetrakis (mercaptoethyl) benzene, 1,2, 3, 4-tetrakis (mercaptomethoxy) benzene, 1,2, 3, 5-tetrakis (mercaptomethoxy) benzene, 1,2, 4, 5-tetrakis (mercaptomethoxy) benzene, 1,2, 3, 4-tetrakis (mercaptoethoxy) benzene, 1,2, 3, 5-tetrakis (mercaptoethoxy) benzene, 1,2, 4, 5-tetrakis (mercaptoethoxy) benzene, 2 '-dimercaptobiphenyl, 4' -dimercaptobibenzyl, 2, 5-methanebenzenedithiol, 3, 4-methanedithiol, 1, 4-naphthalenedithiol, 1, 5-naphthalenedithiol, 2, 6-naphthalenedithiol, 2, 7-naphthalenedithiol, 2, 4-dimethylbenzene-1, 3-dithiol, 4, 5-dimethylbenzene-1, 3-dithiol, 9, 10-anthracenedithiol, 1, 3-bis (p-methoxyphenyl) propane-2, 2-dithiol, 1, 3-diphenylpropane-2, 2-dithiol, phenylmethane-1, 1-dithiol, 2, 4-bis (p-mercaptophenyl) pentane, 1, 2-bis (mercaptomethylthio) benzene, 1, 3-bis (mercaptomethylthio) benzene, 1, 4-bis (mercaptomethylthio) benzene, 1, 2-bis (mercaptoethylthio) benzene, 1, 3-bis (mercaptoethylthio) benzene, 1, 4-bis (mercaptoethylthio) benzene, 1,2, 3-tris (mercaptomethylthio) benzene, 1,2, 4-tris (mercaptomethylthio) benzene, 1,3, 5-tris (mercaptomethylthio) benzene, 1,2, 3-tris (mercaptoethylthio) benzene, 1,2, 4-tris (mercaptoethylthio) benzene, 1,3, 5-tris (mercaptoethylthio) benzene, 1,2, 3, 4-tetrakis (mercaptomethylthio) benzene, 1,2, 3, 5-tetrakis (mercaptomethylthio) benzene, 1,2, 4, 5-tetrakis (mercaptomethylthio) benzene, 1,2, 3, 4-tetrakis (mercaptoethylthio) benzene, 1,2, 4, 5-tetrakis (mercaptoethylthio) benzene, Polyfunctional aromatic mercapto compounds such as 4, 4 '-thiobisbenzenethiol (4, 4' -thiobisbenzenenethiol), 2, 5-dimercapto-1, 3, 4-thiadiazole, 2, 6-dimercaptopurine, and 1,3, 5-triazine-2, 4, 6-trithiol.

The mercapto compound may be used alone or in combination of two or more.

In addition, from the viewpoint of 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 (thioester group), a hydroxyl group, an amide group, an ether group, or a thioether group in the molecule.

From the viewpoint of film physical properties, the content of the mercapto compound is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass, and still more preferably 1 to 10 parts by mass, relative to the total solid content of the curable composition.

Component F: surface active agent

The curable composition of the present invention may contain a surfactant.

The surfactant may be any of anionic, cationic, nonionic and amphoteric, and a preferable surfactant is a nonionic surfactant. The surfactant is preferably a fluorine-based surfactant, and more preferably a fluorine-based nonionic surfactant.

Examples of the surfactant usable in the present invention include: commercially available Megafac (Megafac) F142D, Megafac (Megafac) F172, Megafac (Megafac) F173, Megafac (Megafac) F176, Megafac (Megafac) F177, Megafac (Megafac) F183, Megafac (Megafac) F479, Megafac (Megafac) F482, Megafac (Megafac) F554, Megafac (Megafac) F780, Megafac (Megafac) F781, Megafac (Megafac) F30, Megafac) R08, Megafac) F-472, Megafac (Megafac) BL20, Megafac R-R61, Megafac (Megafac) R4490, Megafac (Megafac) F170, Meifaac) F781 (Megafac) F781, Meifac (Megafac) F781F 170, Meifa) F170, Mei F-F170, Meigafac F23, Mei F, 7000. 950, 7600, Shafu Long (Surflon) S-112, Shafu Long (Surflon) S-113, Shafu Long (Surflon) S-131, Shafu Long (Surflon) S-141, Shafu Long (Surflon) S-145, Shafu Long (Surflon) S-382, Shafu Long (Surflon) SC-101, Shafu Long (Surflon) SC-102, Shafu Long (Surflon) SC-103, Shafu Long (Surflon) SC-104, Shafu Long (Surflon) SC-105, Shafu Long (Surflon) SC-106 (available from Asahi Kasei Corp.), Efu Tufu Tuo (Eftop) EF351, Efu Tufu (Eftop)352, Efu (Eftop 801), Efu Tufu (Eftop)802 (available from Sanshitsu corporation) for electronization into Neford (Osgen) (Oster Job) (250). In addition, in addition to the above, there may be mentioned: KP (manufactured by shin-Etsu chemical industries), treasurefloro (Polyflow) (manufactured by Cogrongy chemical industries), Avotu (Eftop) (manufactured by Mitsubishi Material electronics chemical industries), Meijia (Megafac) (manufactured by Di Aisheng (DIC)), (Fluorad) (manufactured by Sumitomo 3M (Inc.), Asahiguard (Asahiguard), Shafolon (Surflon) (manufactured by Asahi Nitro (Inc.), and other series.

The surfactant includes, as preferred examples, the following copolymers: a copolymer which contains a structural unit A and a structural unit B represented by the following formula F-1 and has a weight average molecular weight (Mw) of 1,000 to 10,000 in terms of polystyrene as measured by gel permeation chromatography using tetrahydrofuran as a solvent.

[ solution 13]

Structural unit A structural unit B

In the formula F-1, R⁴⁰¹And R⁴⁰³Each independently represents a hydrogen atom or a methyl group, R⁴⁰²Represents a C1-4 linear alkylene group, R⁴⁰⁴Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, L represents an alkylene group having 3 to 6 carbon atoms, p and q represent mass percentages representing a polymerization ratio, p represents a numerical value of 10 to 80 mass%, q represents a numerical value of 20 to 90 mass%, r represents an integer of 1 to 18, and s represents an integer of 1 to 10.

The L is preferably a branched alkylene group represented by the following formula F-2. R in the formula F-2⁴⁰⁵Represents an alkyl group having 1 to 4 carbon atoms, and is preferably an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 2 or 3 carbon atoms, from the viewpoint of compatibility and wettability to the surface to be coated.

The sum of p and q (p + q) in formula F-1 is preferably 100, i.e., 100 mass%.

[ solution 14]

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 singly or in combination of two or more.

When the surfactant is blended, the content of the surfactant in the curable composition of the present invention is preferably 0.001 to 5.0 parts by mass, more preferably 0.01 to 2.0 parts by mass, based on 100 parts by mass of the total solid content of the curable composition.

Component G: alkoxysilane compound

The composition of the present invention may also contain an alkoxysilane compound as the adhesion improver. When the alkoxysilane compound is used, the adhesion between the film formed from the curable composition of the present invention and the substrate can be improved, or the properties of the film formed from the curable composition of the present invention can be adjusted.

The alkoxysilane compound that can be used in the composition of the present invention is preferably a compound that improves the adhesion between an inorganic substance that becomes a base material, for example, a silicon compound such as silicon, silicon oxide, or silicon nitride, or a metal such as gold, copper, molybdenum, titanium, or aluminum, and an insulating film. Specifically, a known silane coupling agent and the like are also effective.

The silane coupling agent is preferably an alkoxysilane compound having an epoxy group or a (meth) acryloyl group.

Examples of the silane coupling agent include gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltrialkoxysilane, gamma-glycidoxypropyldialkoxysilane, gamma-methacryloxypropyltrialkoxysilane, gamma-methacryloxypropyldialkoxysilane, gamma-chloropropyltrialkoxysilane, gamma-mercaptopropyltrialkoxysilane, β - (3, 4-epoxycyclohexyl) ethyltrialkoxysilane, vinyltrialkoxysilane, 3-acryloxypropyltrialkoxysilane, among these, gamma-glycidoxypropyltrialkoxysilane, gamma-methacryloxypropyltrialkoxysilane, and 3-acryloxypropyltrialkoxysilane are more preferable.

The alkoxysilane compound that can be used in the curable composition of the present invention is not particularly limited to these compounds, and a known compound can be used.

The alkoxysilane compound may be used singly or in combination of two or more.

When the curable composition of the present invention contains an alkoxysilane compound, the content of the alkoxysilane compound is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, based on 100 parts by mass of the total solid content in the curable composition.

Component H: crosslinking agent

The curable composition of the present invention may optionally contain a crosslinking agent. By adding a crosslinking agent, a cured film obtained from the curable composition of the present invention can be made stronger.

The crosslinking agent is not limited as long as it causes a crosslinking reaction by heat (except for the above-mentioned components), 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 to 50 parts by mass, more preferably 0.1 to 30 parts by mass, and still more preferably 0.5 to 20 parts by mass, based on 100 parts by mass of the total solid content in the curable composition. By adding the amount within the above range, a cured film having excellent mechanical strength and solvent resistance can be obtained. It is also possible to combine different kinds of crosslinking agents in a plurality, in which case all crosslinking agents are added to calculate the content.

Component I: antioxidant agent

The curable composition of the present invention may also contain an antioxidant. The antioxidant may comprise a well-known antioxidant. The addition of the antioxidant has advantages such as prevention of coloring of the cured film, reduction in film thickness due to decomposition, and excellent heat resistance and transparency.

Examples of such antioxidants include: phosphorus antioxidants, amides, hydrazides, hindered amine antioxidants, sulfur antioxidants, phenol antioxidants, ascorbic acids, zinc sulfate, saccharides, nitrites, sulfites, thiosulfates, hydroxylamine derivatives, and the like. Among these, from the viewpoint of coloring of the cured film and thinning of the film thickness, a phenol-based antioxidant (hindered phenol), a hindered amine-based antioxidant, a phosphorus-based antioxidant (alkylphosphite), and a sulfur-based antioxidant (thioether) are particularly preferable, and a phenol-based antioxidant is most preferable. These antioxidants may be used singly or in combination of two or more.

Specific examples thereof include: the compounds described in paragraphs 0026 to 0031 of Japanese patent laid-open No. 2005-29515 and the compounds described in paragraphs 0106 to 0116 of Japanese patent laid-open No. 2011-227106 are incorporated into the present specification.

Preferred commercially available products include: adekastab AO-60, Adekastab AO-80 (manufactured by Adekata (Takara), Irganox 1035, Irganox 1098, Irganox 1726, and Irgafos 168 (manufactured by BASF).

When the curable composition of the present invention contains an antioxidant, the content of the antioxidant is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass, and still more preferably 0.5 to 4 parts by mass, based on 100 parts by mass of the total solid content in the curable composition.

Component J: metal oxide particles

The curable composition of the present invention may contain metal oxide particles for adjusting the refractive index or light transmittance. The metal of the metal oxide particles also includes semimetals such As boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), and tellurium (Te).

Preferred metal oxide particles are oxide particles containing atoms such as beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), gadolinium (Gd), terbium (Tb), dysprosium (Dy), ytterbium (Yb), lutetium (Lu), titanium (Ti), zirconium (Zr), hafnium (Hf), niobium (Nb), molybdenum (Mo), tungsten (W), zinc (Zn), boron (B), aluminum (a1), silicon (Si), germanium (Ge), tin (Sn), aluminum (Pb), antimony (Sb), bismuth (Bi), tellurium (Te), and the like, more preferred are titanium oxide, titanium composite oxide, zinc oxide, zirconium oxide, indium/tin oxide, antimony/tin oxide, and still more preferred are titanium oxide, titanium composite oxide, zirconium oxide, particularly preferred are titanium oxide, zirconium oxide, and most preferred is titanium oxide. Titanium oxide is particularly preferably a rutile type having a high refractive index. These metal oxide particles may be surface-treated with an organic material in order to impart dispersion stability.

The average primary particle diameter of the metal oxide particles is preferably 1nm to 200nm, more preferably 3nm to 80nm, and particularly preferably 5nm to 50nm, from the viewpoint of transparency of the curable composition. Here, the average primary particle size of the particles is an arithmetic average value of particle sizes of 200 arbitrary particles measured by an electron microscope. In addition, when the shape of the particles is not spherical, the longest side is regarded as the particle diameter.

One kind of the metal oxide particles may be used alone, or two or more kinds may be used in combination.

The content of the metal oxide particles in the curable composition of the present invention may be appropriately determined in consideration of the refractive index, light transmittance, and the like required for an optical member obtained from the curable composition, and is preferably 0 to 50% by mass, more preferably 1 to 40% by mass, and still more preferably 2 to 30% by mass, based on the total solid content of the curable composition of the present invention.

In the present invention, the metal oxide particles may be used in the form of a dispersion prepared by mixing and dispersing the metal oxide particles in an appropriate dispersant and solvent using a mixing device such as a ball mill or a rod mill.

Other ingredients-

The curable composition of the present invention may optionally contain other components such as a plasticizer, a polymerization inhibitor, a thermal acid generator, an acid amplifier, and a binder polymer. As these components, for example, the components described in Japanese patent laid-open Nos. 2009-98616 and 2009-244801, and other well-known components can be used. In addition, various ultraviolet absorbers and metal deactivators described in "new developments of polymer additives (journal industries, press), etc.", 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 is a substance that exerts the following actions: the polymerization initiating free radical component generated from the polymerization initiator is subjected to hydrogen supply (or hydrogen donation), energy supply (or energy donation), electron supply (or electron donation), or the like, to inactivate the polymerization initiating free radical and suppress polymerization initiation. For example, compounds described in paragraphs 0154 to 0173 of Japanese patent laid-open No. 2007 and 334322 can be used.

Preferred compounds include: phenothiazine, phenoxazine, hydroquinone and 3, 5-dibutyl-4-hydroxy toluene.

The content of the polymerization inhibitor is not particularly limited, and is preferably 0.0001 to 5% by mass based on the total solid content of the curable composition.

< method for producing curable composition >

The method for producing the curable composition of the present invention is not particularly limited, and the curable composition can be produced by a known method, for example, by mixing the respective components at a predetermined ratio by an arbitrary method, and dissolving and/or dispersing the mixture under stirring. For example, the curable composition can be prepared by dissolving each component in a solvent in advance and mixing the solutions at a predetermined ratio. The curable composition prepared as described above can be used after being filtered using, for example, a filter having a pore size of 0.2 μm.

(cured film and method for producing the same)

The cured film of the present invention is a cured film obtained by curing the curable composition of the present invention. 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 product of the present invention is not particularly limited as long as it is a method for producing a cured product by curing the curable composition of the present invention, and preferably includes the following steps 1 to 5 in this order.

Step 1: a coating step of coating the curable composition of the present invention on a substrate

And a step 2: solvent removal step for removing solvent from applied curable composition

Step 3: an exposure step of exposing at least a part of the curable composition from which the solvent has been removed with actinic rays

And step 4: developing step of developing the exposed curable composition with an aqueous developer

Step 5: heat treatment step for heat-treating developed curable composition

In the coating step, the curable composition of the present invention is preferably coated on a substrate to form a wet film containing a solvent. The substrate may be cleaned by alkali cleaning or plasma cleaning before applying the curable composition to the substrate. Further, the substrate surface may be treated with hexamethyldisilazane 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.

Examples of the substrate include an inorganic substrate, a resin, and a resin composite material.

Examples of the inorganic substrate include: glass, quartz, silicon nitride, and composite substrates on which molybdenum, titanium, aluminum, copper, or the like is vapor-deposited.

As the resin, the following resins can be mentioned: examples of the resin include a fluororesin such as polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, polyethersulfone, polyarylate, allyl diglycol carbonate resin, polyamide, polyimide, polyamideimide, polyetherimide, polybenzazole, polyphenylene sulfide, polycycloolefin, norbornene resin, polychlorotrifluoroethylene, a liquid crystal polymer, an acrylic resin, an epoxy resin, a silicone resin, an ionomer resin, a cyanate resin, a crosslinked fumarate diester, a cyclic polyolefin, an aromatic ether resin, a maleimide-olefin copolymer, cellulose, and an episulfide resin. These substrates are rarely used as they are, and a multilayer laminated structure such as a Thin Film Transistor (TFT) device is usually formed in accordance with the form of a final product.

The curable composition of the present invention is excellent in adhesion to a metal film or a metal oxide formed by sputtering, and therefore 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, neodymium, and oxides or alloys of these metals, more preferably molybdenum, titanium, aluminum, copper, and alloys of these metals. Further, the metal or metal oxide may be used alone or in combination.

The coating method for the substrate is not particularly limited, and examples thereof include slit coating, spraying, roll coating, spin coating, cast coating, slit and spin coating, inkjet, and printing (such as flexo, gravure, and screen). The ink jet method and the printing method are preferable because the composition can be provided in a desired portion and the composition can be reduced in volume.

The wet film thickness at the time of coating is not particularly limited, and can be applied to a film thickness corresponding to the application, and is preferably in the range of 0.05 μm to 10 μm.

Furthermore, a so-called wet pre-treatment method as described in Japanese patent laid-open No. 2009-145395 may be applied before the curable composition of the present invention is applied to a substrate.

In the solvent removal step, the solvent is removed from the applied film by, for example, reducing the pressure (vacuum) or heating, thereby forming a dry coating film on the substrate. The heating conditions in the solvent removal step are preferably 70 to 130 ℃ for about 30 to 300 seconds.

The coating step and the solvent removal step may be performed sequentially, simultaneously, or alternately. For example, the solvent removal step may be performed after all of the inkjet application in the application step is completed, or the solvent removal may be performed while the substrate is heated in advance and the curable composition of the inkjet application method is ejected in the application step.

The exposure step is a step of generating a polymerization initiating species by a photopolymerization initiator using actinic rays, polymerizing the compound having an ethylenically unsaturated group, and curing at least a part of the curable composition from which the solvent has been removed.

The exposure Light source used in the exposure step 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 generator, or the like, and preferably actinic rays having a wavelength of 300nm to 450nm, such as i-rays (365nm), h-rays (405nm), and g-rays (436nm), are used. The irradiation light may be adjusted by a spectral filter such as a long-wavelength cut filter, a short-wavelength cut filter, or a band-pass filter, if necessary.

The exposure apparatus may use: various types of exposure devices such as mirror projection alignment exposure machines, steppers, scanners, proximity exposure devices, contact exposure devices, microlens arrays, lens scanners, and laser exposure devices.

The exposure amount in the exposure step is not particularly limited, and is preferably 1mJ/cm²～3,000mJ/cm²More preferably 1mJ/cm²～500mJ/cm²。

From the viewpoint of accelerating the curing, the exposure in the exposure step is preferably performed in an oxygen-blocked state. Examples of the method of blocking oxygen include: exposure is performed in a nitrogen atmosphere, or an oxygen blocking film is provided.

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 may be, for example, a blanket exposure or a pattern exposure.

After the exposure step, a post-exposure heat treatment may be performed: post Exposure Bake (hereinafter also referred to as "PEB"). The temperature in the case of carrying out PEB is preferably 30 ℃ or higher and 130 ℃ or lower, more preferably 40 ℃ or higher and 120 ℃ or lower, and particularly preferably 50 ℃ or higher and 110 ℃ or lower.

The heating method is not particularly limited, and a known method can be used. Examples thereof include a hot plate, an oven, and an infrared heater.

The heating time is preferably about 1 minute to 30 minutes in the case of a hot plate, and about 20 minutes to 120 minutes in the other cases. Within the above range, the substrate and the device can be heated without damaging them.

The method for producing a cured film of the present invention preferably further comprises: and a developing step of developing the exposed curable composition with a developer.

In the developing step, the curable composition exposed in a pattern is developed with a solvent or an alkaline developer to form a pattern. The developer used in the developing step preferably contains an alkaline compound. The basic compound can be used, for example: alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal bicarbonates such as sodium bicarbonate and potassium bicarbonate; ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, and choline hydroxide; aqueous solutions of sodium silicate, sodium metasilicate, and the like. In addition, 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 alkali aqueous solution may be used as the developer.

A preferable developer is a 0.4 to 2.5 mass% aqueous solution of tetramethylammonium hydroxide.

The pH value of the developing solution is preferably 10.0-14.0. The developing time is preferably 30 seconds to 500 seconds, and the developing method may be any of a liquid filling method (puddle developing method), a shower method, a dipping method, and the like.

After development, a rinsing step may also be carried out. In the rinsing step, the developed substrate is washed with pure water or the like, and the adhering developer and the development residue are removed. The rinsing method may use a well-known method. Examples thereof include a spray rinsing and a dip rinsing.

For 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 Japanese patent laid-open Nos. 2011-186398 and 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 exposed curable composition after the exposure step. By performing heat treatment after exposing the curable composition of the present invention to light, a cured film having more excellent strength can be obtained.

The temperature of the heat treatment is preferably 80 to 300 ℃, more preferably 100 to 280 ℃, and particularly preferably 120 to 200 ℃. In the above embodiment, it is estimated that condensation of the component a occurs appropriately, and the cured film has more excellent physical properties.

The time of the heat treatment is not particularly limited, but is preferably 1 minute to 360 minutes, more preferably 5 minutes to 240 minutes, and further preferably 10 minutes to 120 minutes.

In the method for producing a cured film of the present invention, the curing by light and/or heat may be performed continuously or sequentially.

In addition, when the heat treatment is performed, the transparency can be further improved by performing the heat treatment in a nitrogen atmosphere.

Before the heat treatment step (post-baking), the heat treatment step (additional intermediate baking step) may be performed after baking at a relatively low temperature. In the intermediate baking, it is preferable to heat the sheet at 90 to 150 ℃ for 1 to 60 minutes and then post-bake the sheet at a high temperature of 200 ℃ or higher. The intermediate baking and the post baking may be divided into three or more stages to heat the material. By trying to perform such a middle bake and a post bake, the taper angle of the pattern can be adjusted. These heating methods may be a well-known heating method such as a hot plate, an oven, an infrared heater, or the like.

Further, before the post-baking, the substrate on which a pattern is formed may be subjected to a full-scale re-exposure (post-exposure) with actinic rays and then subjected to a post-baking, whereby it is presumed that the condensation reaction of the components a with each other and/or the generation of initiating species from the photopolymerization initiator remaining in the exposed portion due to thermal decomposition causes the initiating species to function as a catalyst for accelerating the crosslinking step, thereby accelerating the film hardening. The preferred exposure dose in the case of including the post-exposure step is preferably 100mJ/cm²～3,000mJ/cm²Particularly preferably 100mJ/cm²～500mJ/cm²。

(cured film)

The cured film or cured product (hereinafter, sometimes referred to as a cured film or the like) of the present invention is obtained by curing the curable composition of the present invention.

The cured film or the like of the present invention may be a cured film or the like developed as described above, or may be an undeveloped cured film, and a developed cured film or the like which can further exhibit the effects of the present invention is preferable.

The cured film of the present invention is not a crystalline film of a metal oxide, such as an organic-inorganic hybrid cured film formed from the component a, the component B, and the like. The metal oxide in the cured film or the like preferably has a crystal component of 30 vol% or less, more preferably 10 vol% or less, and further preferably contains no crystal component. With this embodiment, crack resistance is improved.

The cured film and the like of the present invention have a high refractive index and high transparency, and therefore can be suitably used as a microlens, an optical waveguide, an antireflection film, a light-taking in/out efficiency improving layer for a solar cell or an organic EL light-emitting element, an optical member such as a sealing material for LED and 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, and a protective film for a wiring electrode used in a touch panel.

The cured film of the present invention can be suitably used for a protective film of a color filter in a liquid crystal display device, an organic EL device, or the like, a spacer for holding a liquid crystal layer at a constant thickness in a liquid crystal display device, a structural member of a device for Micro Electro Mechanical Systems (MEMS), or the like.

The cured film and the like of the present invention can be used for a visibility reducing layer such as a wiring electrode used in a touch panel. The visibility reducing layer of the wiring electrode used in the touch panel is a layer that reduces the visibility of the wiring electrode used in the touch panel, that is, makes the wiring electrode difficult to see, and examples thereof include an interlayer insulating film between touch detection electrodes (made of, for example, Indium Tin Oxide (ITO)), and a protective film (overcoat film) of the electrode. In addition, the index matching layer (also referred to as an im (index matching) layer or a refractive index adjustment layer in some cases) is also suitable. The index matching layer is a layer for adjusting the reflectance or transmittance of light in the display device. Regarding the index matching layer, it is described in detail in japanese patent laid-open publication No. 2012-146217, which is incorporated in the present specification. By using the hardened film of the present invention for the visibility reducing layer, a touch panel excellent in visibility can be manufactured.

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 using the cured film for an interlayer insulating film or a protective film between touch detection electrodes, the refractive index of the cured film is preferably close to that of the electrodes, specifically, 1.70 to 2.40, more preferably 1.80 to 2.30, and still more preferably 1.90 to 2.20, from the viewpoint of improvement in visibility.

(liquid Crystal display device)

The liquid crystal display device of the present invention has the cured film of the present invention.

The liquid crystal display device of the present invention is not particularly limited except for having a planarizing film or an interlayer insulating film formed using the curable composition of the present invention, and known liquid crystal display devices having various structures can be exemplified.

For example, specific examples of the Thin-Film Transistor (TFT) included in the liquid crystal display device of the present invention include: amorphous silicon-TFTs, low-temperature polysilicon-TFTs, oxide semiconductor TFTs (e.g., indium gallium zinc oxide, so-called IGZO), and the like. The cured film of the present invention is excellent in electrical characteristics, and therefore can be preferably used in combination with these TFTs.

Further, examples of liquid crystal driving methods preferable for the liquid crystal display device of the present invention include: a Twisted Nematic (TN) system, a Vertical Alignment (VA) system, an In-Plane-Switching (IPS) system, a Fringe Field Switching (FFS) system, an Optically Compensated Bend (OCB) system, and the like.

In the panel structure, the cured film of the present invention can be used in a Color Filter on Array (COA) type liquid crystal display device, and can be used as an organic insulating film (115) in Japanese patent laid-open No. 2005-284291 or an organic insulating film (212) in Japanese patent laid-open No. 2005-346054, for example. Specific alignment methods of the liquid crystal alignment film preferable for the liquid crystal display device of the present invention include a rubbing alignment method, a photo-alignment method, and the like. Further, the Polymer orientation support can be also performed by the Polymer supported orientation (PSA) technique described in Japanese patent laid-open Nos. 2003-149647 and 2011-257734.

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 for various applications. For example, the film can be suitably used as a protective film for a color filter, a spacer for holding a liquid crystal layer at a constant thickness in a liquid crystal display device, a microlens provided on a color filter in a solid-state imaging element, or the like, in addition to a planarizing film or an interlayer insulating film.

Fig. 1 is a conceptual 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 elements of TFTs 16 are arranged in the liquid crystal panel, the elements of the TFTs 16 corresponding to all pixels arranged between 2

glass substrates

14 and 15 to which polarizing films are attached. For each element formed on the glass substrate, the ITO transparent electrode 19 of the pixel electrode is wired through the contact hole 18 formed in the cured film 17. On the ITO transparent electrode 19, a layer of liquid crystal 20 and a Red Green Blue (RGB) color filter 22 in which a black matrix is arranged are provided.

The light source of the backlight is not particularly limited, and a known light source can be used. Examples thereof include: white LEDs, multicolor LEDs such as blue, red, and green, fluorescent lamps (cold cathode tubes), and organic ELs.

In addition, the liquid crystal display device may be a Three-dimensional (3D) (stereoscopic view) type or a touch panel type. Further, the film can be made flexible and can be used as the 2 nd interlayer insulating film (48) described in Japanese patent laid-open No. 2011-145686 or the interlayer insulating film (520) described in Japanese patent laid-open No. 2009-258758.

(organic EL display device)

The organic EL display device of the present invention has the cured film of the present invention.

The organic EL display device of the present invention is not particularly limited except for having 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 crystal display devices having various structures can be exemplified.

For example, specific examples of the Thin-Film Transistor (TFT) included in the organic EL display device of the present invention include an amorphous silicon TFT, a low-temperature polysilicon TFT, and an oxide semiconductor TFT. The cured film of the present invention is excellent in electrical characteristics, and therefore can be preferably used in combination with these TFTs.

Fig. 2 is a conceptual diagram of the structure of an example of an organic EL display device, and shows 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 TFT1 is formed on a glass substrate 6, and an insulating film 3 containing Si3N4 is formed so as to cover the TFT 1. After forming a contact hole (not shown) in the insulating film 3, a wiring 2 (having a height of 1.0 μm) connected to the TFT1 through the contact hole is formed in the insulating film 3. The wiring 2 is a wiring for connecting the TFTs 1 to each other or connecting an organic EL element formed in a subsequent step to the TFT 1.

Further, in order to planarize the irregularities caused by the formation of the wiring 2, the planarization film 4 is formed on the insulating film 3 in a state where the irregularities caused by the wiring 2 are filled.

An organic EL element of bottom emission type is formed on the planarization film 4. That is, the first electrode 5 including ITO is formed on the planarization film 4 so as to be connected to the wiring 2 through the contact hole 7. The first electrode 5 corresponds to an anode of the organic EL element.

The insulating film 8 is formed in a shape covering the edge of the first electrode 5, and by providing the insulating film 8, short-circuiting between the first electrode 5 and the second electrode formed in the subsequent step can be prevented.

Further, although not shown in fig. 2, a hole transport layer, an organic light emitting layer, and an electron transport layer were sequentially vapor-deposited through a desired pattern mask, and then a second electrode including a1 was formed over the entire surface above the substrate, followed by bonding using a sealing glass plate and an ultraviolet-curable epoxy resin, thereby sealing the substrate, and an active matrix organic EL display device was obtained in which TFTs 1 for driving the organic EL elements were connected to the organic EL elements.

(touch Screen and touch Screen display device)

The touch panel of the present invention is a touch panel comprising a cured product of the curable composition of the present invention as a whole or a part of an insulating layer and/or a protective layer. The touch panel of the present invention preferably includes at least a transparent substrate, an electrode, and an insulating layer and/or a protective layer.

The touch panel display device of the present invention is preferably a touch panel display device having the touch panel of the present invention. The touch panel of the present invention may be any of known types such as a resistive film type, a capacitive type, an ultrasonic type, and an electromagnetic induction type. Among them, the electrostatic capacitance system is preferable.

Examples of the capacitive touch panel include a touch panel disclosed in japanese patent application laid-open No. 2010-28115 and a touch panel disclosed in international publication No. 2012/057165. Other touch panels include: the cell type is an in-cell type (e.g., FIG. 5, FIG. 6, FIG. 7, FIG. 8 of Japanese patent laid-open No. 2012 and 517051), an on-cell type (e.g., FIG. 14 of Japanese patent laid-open No. 2012 and 43394 and FIG. 2(b) of International publication No. 2012/141148), an OGS type, a TOL type, or other structures (e.g., FIG. 6 of Japanese patent laid-open No. 2013 and 164871).

[ examples ]

The present invention will be described in more detail with reference to examples. The materials, the amounts used, the ratios, the contents of the treatments, the treatment procedures and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "part" and "%" are based on mass.

< Synthesis example 1>

After 34.0g (0.10 mol) of titanium tetra-n-butoxide was dissolved in 12.0g of n-butanol, a mixture of 2.7g (0.15 mol) of water and 24.0g of n-butanol was added dropwise. After the completion of the dropwise addition, the mixture was stirred for 1 hour, and then heated under reflux for 1 hour to obtain titanoxane A-6. The solid content concentration was 20% by mass.

< Synthesis example 2>

After 34.0g (0.10 mol) of titanium tetra-n-butoxide was dissolved in 12.0g of n-butanol, a mixture of 1.8g (0.10 mol) of water and 24.0g of n-butanol was added dropwise. After the completion of the dropwise addition, the mixture was stirred for 1 hour, and then heated under reflux for 1 hour to obtain titanoxane A-7. The solid content concentration was 29 mass%.

< Synthesis example 3>

After 34.0g (0.10 mol) of titanium tetra-n-butoxide was dissolved in 12.0g of n-butanol, a mixture of 1.35g (0.075 mol) of water and 24.0g of n-butanol was added dropwise. After the completion of the dropwise addition, the mixture was stirred for 1 hour, and then heated under reflux for 1 hour to obtain titanoxane A-8. The solid content concentration was 34% by mass.

< Synthesis example 4>

After 34.0g (0.10 mol) of titanium tetra-t-butoxide was dissolved in 12.0g of t-butanol, a mixture of 1.8g (0.10 mol) of water and 24.0g of t-butanol was added dropwise. After the completion of the dropwise addition, the mixture was stirred for 1 hour, and then heated under reflux for 1 hour to obtain titanoxane A-9. The solid content concentration was 29 mass%.

< Synthesis example 5>

After 28.4g (0.10 mol) of titanium tetraisopropoxide was dissolved in 12.0g of isopropanol, a mixture of 1.8g (0.10 mol) of water and 24.0g of isopropanol was added dropwise. After the completion of the dropwise addition, the mixture was stirred for 1 hour, and then heated under reflux for 1 hour to obtain titanoxane A-10. The solid content concentration was 27 mass%.

< Synthesis example 6>

After 22.8g (0.10 mol) of titanium tetraethoxide was dissolved in 12.0g of ethanol, a mixture of 1.8g (0.10 mol) of water and 24.0g of ethanol was added dropwise. After the completion of the dropwise addition, the mixture was stirred for 1 hour and then heated under reflux for 1 hour to obtain titanoxane A-11. The solid content concentration was 25 mass%.

< Synthesis example 7>

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

(example 1)

< preparation of curable composition >

The preparation was carried out as described below.

With respect to each component described in table 1, the following components were mixed so that the solid content of each component was in the ratio described in table 1. Further, the mixture was diluted with the additive solvent shown in table 1 so as to have the solid content concentration shown in table 1, and stirred for 1 hour.

A-1: PC-200 (titanoxane, Matsumoto Fine Chemical) (Strand), solid content 31.0%)

B1-1: 2-Acetoacetoxyethyl methacrylate (2-acetoxyethyl methacrylate) (manufactured by Tokyo chemical industry Co., Ltd.)

C-1: yanjiacure (IRGACURE) CGI-124(1- [4- (phenylthio) phenyl ] -1, 2-octanedione-2- (O-benzoyl oxime), manufactured by Ciba Specialty Chemicals)

E-1: carrenz MT (KarenzMT) PE1 (the following compound, made by Showa Denko K.K.)

F-1: meijia method (Megafac) F-554 (made by Diesen (DIC) (Strand, a non-ionic surfactant containing perfluoroalkyl group)

Then, the mixture was filtered through a 0.45 μm membrane filter (membrane filter) to prepare a curable composition of example 1.

[ solution 15]

(examples 2 to 114 and comparative examples 1 to 28)

< preparation of curable composition >

Curable compositions of examples 2 to 114 and comparative examples 1 to 28 were prepared in the same manner as in the preparation of the curable composition of example 1, except that the components and their amounts of blending and the amount of solid matter were changed as shown in tables 1 to 5 below.

[ Table 1]

[ Table 2]

[ Table 3]

[ Table 4]

[ Table 5]

In tables 1 to 5, the amounts of the components other than the solid content of the compositions are parts by mass relative to 100 parts by mass of the total solid content, and "-" means that the components are not included.

The following shows the details of the abbreviations in tables 1 to 5 other than the above.

A-2: titanoxane (T-3072, manufactured by Matsumoto Fine Chemical Co., Ltd.)

A-3: titanoxanes (B-2, manufactured by Nippon Caoda)

A-4: titanoxanes (B-4, manufactured by Nippon Caoda)

A-5: zirconium Oxoxane (ZA-65, manufactured by Matsumoto Fine Chemical Co., Ltd.)

A-6 to A-12: titanoxanes produced in Synthesis examples 1 to 7

A-13: titanium tetra-n-butoxide (manufactured by Heguang pure chemical industry)

B1-2: the following compound (NK Ester) CB-1, manufactured by Newzhongcun chemical industry (Strand)

B2-1: acetylacetone (manufactured by Heguang pure chemical industry)

B2-2: ethyl lactate (manufactured by Tokyo chemical industry)

B2-3: the mass ratio of dipentaerythritol hexaacrylate to dipentaerythritol pentaacrylate is 70: 30 of a mixture of

B2-4: the mass ratio of the pentaerythritol tetraacrylate to the pentaerythritol triacrylate is 37-45: 63-55 of a mixture

B2-5: ethylene oxide-modified bisphenol A diacrylate (the following Compound)

C-2: brilliant beauty (IRGACURE) CGI-242(1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethane-1-oxime-O-acetate, manufactured by Ciba Specialty Chemicals)

C-3: brilliant good solid (IRGACURE)907 (2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropane-1, manufactured by Ciba Specialty Chemicals)

C-4: oxime ester photopolymerization initiator (the following compound is synthesized by referring to the method for synthesizing the specific compound 1 described in Japanese patent laid-open No. 2009-134289)

Adding a solvent 1: diethylene glycol methyl ethyl ether

Adding a solvent 2: mixed solution of diethylene glycol methyl ethyl ether/1, 3-butanediol diacetate 9/1 (mass ratio)

E-2: temmic (TEMPIC) (compound described below, manufactured by SC organic chemistry)

E-3: 4, 4' -Thiobibenzenethiol (Sigma Aldrich)

E-4: 1-phenyl-1H-benzimidazole-2-thiol (the following compound, manufactured by Chuanyou chemical industry)

E-5: carrenz MT (Karenzmt) (registered trademark) NR1 (the following compound, manufactured by Showa Denko K.K.)

E-6: 1, 5-glutaric mercaptan (manufactured by Tokyo chemical industry)

E-7: the following compounds (manufactured by Tokyo chemical industry)

E-8: the following compounds (manufactured by Tokyo chemical industry)

E-9: the following compounds (manufactured by Tokyo chemical industry)

E-10: the following compounds (manufactured by Tokyo chemical industry)

[ solution 16]

[ solution 17]

[ solution 18]

[ solution 19]

[ solution 20]

[ solution 21]

< evaluation of curable composition >

The obtained curable composition was evaluated as follows. The evaluation results are shown in tables 6 to 9. The unit of the content values in tables 6 to 9 is part by mass.

< evaluation of storage stability >

A curable composition was applied to a 300mm X400 mm glass substrate (trade name: XG, manufactured by corning corporation) to a film thickness of 1.0. mu.m, and the coated substrate was dried (prebaked) at 90 ℃ for 100 seconds. The film on the resulting substrate was visually observed and evaluated according to the following criteria.

1: white turbidity of the dry film on the entire surface of the substrate

2: the dried film on the entire surface of the substrate was slightly cloudy

3: the dried film of about half of the substrate was slightly cloudy

4: a part of the dried film of the substrate was slightly cloudy

5: the dried film has no white turbidity

< evaluation of refractive index >

The obtained curable composition was coated on a silicon wafer substrate using a spinner (spinner) and dried at 90 ℃ for 100 seconds, thereby forming a film having a thickness of 0.5 μm. Using an extra-high pressure mercury lamp at 150mJ/cm²The substrate was exposed to light (measured by i-ray), and thereafter, heated in an oven at 200 ℃ for 30 minutes.

The refractive index of the cured film at 550nm was measured using an ellipsometer (VUV-VASE) (manufactured by j.a. wolfland (j.a. woollam Japan) (stock)). The higher the refractive index is, the better is, more preferably, 1.78 or more. The evaluation criteria are shown below.

1: less than 1.75

2: 1.75 or more and less than 1.78

3: 1.78 or more and less than 1.80

4: 1.80 or more and less than 1.83

5: 1.83 or more

< evaluation of developability (resolution, margin (margin) and linearity) >

A curable composition was applied to a 300mm X400 mm glass substrate (trade name: XG, manufactured by corning corporation) to a film thickness of 1.0. mu.m, and the coated substrate was dried (prebaked) at 90 ℃ for 100 seconds. Thereafter, using a line and space (line and space) of 1: 1 with a line of 1 to 100 μm, and performing a process of 150mJ/cm²Exposure (illuminance of 24 mW/cm)²) Development was carried out at 25 ℃ using an alkaline developer (aqueous solution of 2.38 mass% tetramethylammonium hydroxide).

Analytical evaluation-

For the developed substrate, the thinnest dimension of the pattern formation was observed with a microscope. The evaluation criteria are shown below.

1: not resolved

2: can form a pattern of 20 μm or more

3: can form a pattern of 10 μm or more and less than 20 μm

4: can form a pattern of 2 μm or more and less than 10 μm

Evaluation of margins-

In the evaluation of developability, the time for immersion at 25 ℃ using an alkaline developer (aqueous solution of 2.38 mass% tetramethylammonium hydroxide) was changed, and the time for breaking a 50 μm pattern portion without leaving residue was evaluated. The longer the time, the wider the development margin is indicated. The evaluation criteria are shown below.

1: less than 10 seconds

2: 10 seconds or more and less than 20 seconds

3: over 20 seconds

Evaluation of straightness-

The linearity of the edge of the line was confirmed by an optical microscope for the developed substrate prepared with a line and gap of 50 μm. The evaluation criteria are shown below.

1: many voids exist in the plane of the line edge portion

2: with some clearance in the plane of the wire edge portion

3: almost no voids were observed at the edge portions of the wires

< evaluation of chemical resistance >

A curable composition was applied to a 300mm X400 mm glass substrate (trade name: XG, manufactured by Corning corporation) to a film thickness of 1.0. mu.m, and dried (prebaked) at 90 ℃ for 100 seconds. Thereafter, using an extra-high pressure mercury lamp, 150mJ/cm was applied to the entire surface²Exposure (illuminance of 24 mW/cm)²) And thereafter heated at 200 ℃ for 30 minutes using an oven.

Then, the film was immersed in N-methylpyrrolidone at 25 ℃ for 2 minutes, and the film thickness before and after the immersion was measured to measure the residual rate of the film. The evaluation criteria are shown below.

1: the survival rate is less than 80 percent

2: the survival rate is more than 80 percent and less than 90 percent

3: the survival rate is more than 90 percent and less than 95 percent

4: the survival rate is more than 95 percent and less than 98 percent

5: the residual rate is 98% to 100%

[ Table 6]

[ Table 7]

[ Table 8]

[ Table 9]

In comparative examples 1 to 24, the cured film had poor resolution, and the margin and linearity could not be evaluated.

In particular, the refractive index of the cured film of example 8 was 1.93.

Example 115

The touch panel of the present invention is obtained in the same manner as that described in japanese patent laid-open No. 2013-97692 except that an insulating layer W (hereinafter, also referred to as a "pedestal layer W") surrounding the Y (102a) electrode of fig. 4 together with the substrate 111 is formed as described below in the touch panel described in fig. 3 to 5. Further, a display device with a touch panel is obtained in accordance with japanese patent laid-open publication No. 2013-97692 using the touch panel.

In fig. 3 to 5, 101a and 102a denote intersecting portions, 101b and 102b denote electrode portions, 101X denotes an X-direction electrode, 102 denotes a Y-direction electrode, 112a denotes a contact hole, and X denotes an electrode or an X-direction.

Formation of the pedestal layer: the curable composition of example 69 was applied onto a substrate, prebaked, exposed to light using an ultrahigh pressure mercury lamp, developed with an alkaline aqueous solution to form a pattern, and subjected to a heat treatment at 200 ℃ for 30 minutes to form a pedestal layer W. Further, the pedestal layer functions as an interlayer insulating film between the touch detection electrodes.

When a driving voltage was applied to the obtained display device, the following results were obtained: the display device has good display characteristics and touch detection performance, and is a highly reliable device.

(example 116 to example 118)

A display device with a touch panel was produced in the same manner as in example 115, except that the curable composition of example 7, example 91, or example 92 was used instead of the curable composition of example 69.

When the drive voltages were applied to the obtained display devices, respectively, it was found that: the display device has good display characteristics and touch detection performance, and is a highly reliable device.

(example 119)

The touch panel described in fig. 3 to 5 is formed in the same manner as described in japanese patent laid-open No. 2013-97692, except that the insulating layer W (pedestal layer W), the insulating layer 112, and the protective layer 113 surrounding the Y (102a) electrode of fig. 4 together with the substrate 11 are formed as described below, and the touch panel of the present invention is obtained. Further, a display device with a touch panel is obtained in accordance with japanese patent laid-open publication No. 2013-97692 using the touch panel.

Formation of pedestal layer W, insulating layer 112, and protective layer 113: the curable composition of example 69 was slit-coated on a substrate, prebaked, exposed to light using an ultrahigh pressure mercury lamp, developed with an alkaline aqueous solution to form a pattern, and heat-treated at 200 ℃ for 30 minutes to form each layer.

(examples 120 to 122)

A display device with a touch panel was produced in the same manner as in example 119, except that the curable composition of example 7, example 91, or example 92 was used instead of the curable composition of example 69.

Claims

1. A curable composition characterized by comprising:

at least one component A selected from the group consisting of a1 and a2,

at least one component B selected from the group consisting of B1 and B2,

a photopolymerization initiator as component C, and

a solvent as component D; and is

Said component A comprising said a2 is,

the content of the component A is 40 to 90% by mass based on the total solid content of the curable composition,

the content of the component B is 5 to 59 mass% based on the total solid content of the curable composition,

the total content of the compound having a titanium coordinating group and/or a zirconium coordinating group and an ethylenically unsaturated group and the compound having a titanium coordinating group and/or a zirconium coordinating group is 15 to 140 parts by mass per 100 parts by mass of the component A;

a 1: a titanium compound and/or a zirconium compound having an alkoxy group,

2. The curable composition according to claim 1, wherein a2 is a titanoxane, a zirconane and/or a titanoxane-zirconane condensate obtained by hydrolytic condensation of at least one compound selected from the group consisting of a titanium compound having an alkoxy group, a zirconium compound having an alkoxy group, a titanium compound having a halogen group and a zirconium compound having a halogen group with 1.0 mol of 0.5 to 1.9 mol equivalent of water based on the total molar amount of titanium atoms and zirconium atoms.

3. The curable composition according to claim 1 or 2, further comprising a mercapto compound as component E.

4. The hardening composition according to claim 1 or 2, wherein in the case where the component B contains the B2, the mass ratio of the content BW1 of the compound having a titanium coordinating group and/or a zirconium coordinating group to the content BW2 of the compound having an ethylenically unsaturated group is BW 1: BW2 ═ 8: 2-2: 8.

5. the hardening composition according to claim 1 or 2, wherein the titanium coordinating group and/or the zirconium coordinating group are groups which can coordinate to a titanium atom and/or a zirconium atom through an oxygen atom.

6. The hardening composition according to claim 1 or 2, wherein the titanium coordinating group and/or the zirconium coordinating group is a group having at least one structure selected from the group consisting of a1, 2-diketone structure, a1, 3-diketone structure, a1, 4-diketone structure, an α -hydroxyketone structure, a α -hydroxyester structure, a α -ketoester structure, a β -ketoester structure, a malonic acid diester structure, a fumaric acid diester structure and a phthalic acid diester structure.

7. The curable composition according to claim 1 or 2, wherein the compound having an ethylenically unsaturated group is a (meth) acrylate compound having 2 to 20 ethylenically unsaturated groups.

8. The curable composition according to claim 1 or 2, wherein the compound having an ethylenically unsaturated group is a polyfunctional (meth) acrylate compound.

9. The hardenable composition of claim 3 wherein the mercapto compound is a multifunctional mercapto compound.

10. The hardening composition according to claim 3, wherein the mercapto compound is a compound represented by the formula e-2:

[ solution 1]

In the formula e-2, R represents a hydrogen atom or an alkyl group, and A represents-CO-or-CH₂-; l represents an n-valent linking group, and n represents an integer of 2 to 6.

11. The hardening composition according to claim 10, wherein L in said formula e-2 is a linking group selected from the group consisting of: - (CH)₂)_mA divalent linking group represented by the formula (I), m represents an integer of 2 to 6; as trimethylolpropane residue and having three- (CH)₂)_p-a trivalent linking group of an isocyanuric ring, p represents an integer of 2 to 6; a tetravalent linker or a pentavalent linker as a pentaerythritol residue; and a hexavalent linking group as a dipentaerythritol residue.

12. A method for producing a cured film, comprising at least steps 1 to 5 in this order,

step 1: a coating step of coating the curable composition according to claim 1 or 2 on a substrate;

step 3: an exposure step of exposing at least a part of the curable composition from which the solvent has been removed with actinic rays;

13. A cured film obtained by curing the curable composition according to claim 1 or 2.

14. The cured film according to claim 13, which is an interlayer insulating film or an overcoat film.

15. A liquid crystal display device having the cured film according to claim 13.

16. An organic electroluminescent display device having the cured film according to claim 13.

17. A touch screen having the hardened film of claim 13.

18. A touch screen display device having the hardened film of claim 13.