JP6460900B2 - Curable composition, method for producing cured film, cured film, organic EL display device, liquid crystal display device, touch panel and touch panel display device - Google Patents

Description

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

Flat panel displays such as liquid crystal display devices and organic EL (Electroluminescence) display devices are widely used. Conventionally, in an electronic component such as a liquid crystal display element, an integrated circuit element, a solid-state imaging element, and an organic EL, generally, a flattening film for imparting flatness to the surface of the electronic component, and for preventing deterioration and damage of the electronic component A curable composition is used when forming a protective film or an interlayer insulating film for maintaining insulation. For example, in a TFT type liquid crystal display element, a polarizing plate is provided on a glass substrate, a transparent conductive circuit layer such as indium tin oxide (ITO) and a thin film transistor (TFT) are formed, and covered with an interlayer insulating film to form a back plate. On the other hand, a polarizing plate is provided on a glass substrate, a pattern of a black matrix layer and a color filter layer is formed as necessary, and a transparent conductive circuit layer and an interlayer insulating film are sequentially formed as a top plate, and this back plate and The liquid crystal is manufactured by enclosing the liquid crystal between the two plates with the upper plate facing the spacer.
In recent years, capacitive touch panels have attracted attention with the spread of smartphones and tablet terminals. The sensor substrate of the capacitive touch panel is made of transparent electrodes (ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), etc.), metal electrodes (silver, copper, molybdenum, titanium, aluminum, etc.) A structure in which a laminated body, an alloy, or the like) has a patterned wiring, and in addition, a structure having an insulating film, ITO, and a protective film for protecting a metal at a crossing portion of the wiring.
As a conventional curable composition used for such an insulating film and a protective film, the composition described in Patent Document 1 or 2 is known.

JP 2011-126921 A JP 2010-39475 A

Recently, in the manufacturing process of these display devices and the like, it is necessary to lower the heating temperature of various cured films in the manufacturing process from the viewpoint of reducing damage to substrates and circuits and saving energy.
In addition, the cured film produced by the conventional curable composition is caused by water such as a hydrolyzate of the components in the cured film in or around the cured film after being placed under high temperature and high humidity conditions. As a result, the relative dielectric constant of the cured film changes.
The problem to be solved by the present invention is that a cured film having high hardness and excellent suppression of change in relative permittivity after being exposed to high-temperature and high-humidity conditions can be obtained even when cured at a low temperature. It is providing the curable composition, the cured film which hardened the said curable composition, its manufacturing method, the organic electroluminescence display which has the said cured film, a liquid crystal display device, a touch panel, and a touch panel display device.

The above-mentioned problems of the present invention have been solved by means described in the following <1>, <7>, <9> or <11> to <14>. It is described below together with <2> to <6>, <8> and <10> which are preferred embodiments.
<1> Component A as an ethylenically unsaturated compound, Component B as a polymerization initiator, Component C as a blocked isocyanate compound, and Component D as an organic solvent, Component A is a pentafunctional or higher functional urethane The content of the pentafunctional or higher functional urethane (meth) acrylate is 20 to 100 parts by mass with respect to 100 parts by mass of the component A, and the pentafunctional or higher functional urethane (meth) is contained. A curable composition characterized in that the acrylate contains a urethane (meth) acrylate having a weight average molecular weight of 10,000 or more and a urethane (meth) acrylate having a molecular weight of 5,000 or less,
<2> The curable composition according to <1>, further containing inorganic particles as component E,
<3> The curable composition according to <1> or <2>, wherein component B comprises an oxime ester compound,
<4> Component C is a blocked isocyanate compound that protects a compound selected from the group consisting of tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and multimers thereof. <1> to <3 > The curable composition according to any one of
<5> Component C is a compound in which a block structure is formed by any of an oxime compound, a lactam compound, a phenol compound, an alcohol compound, an amine compound, an active methylene compound, or a pyrazole compound, <1> to <4 > The curable composition according to any one of
<6> The curable composition according to any one of <1> to <5>, wherein the weight ratio of component A to component C is 100: 1 to 10: 1.
<7> 1: a step of applying the curable composition according to any one of <1> to <6> on a substrate, 2: a step of removing an organic solvent from the applied curable composition, 3 : A method for producing a cured film comprising a step of thermosetting,
<8> Before the thermosetting step, 2 ′: The method for producing a cured film according to <7>, further including a step of curing the curable composition from which the organic solvent has been removed, with light,
<9> A cured film obtained by curing a film formed from the curable composition according to any one of <1> to <6>,
<10> The cured film according to <9>, which is a protective film,
<11> An organic EL display device having the cured film according to <9> or <10>,
<12> A liquid crystal 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>.

According to the present invention, even when cured at a low temperature, a curable composition capable of obtaining a cured film having high hardness and excellent suppression of a change in relative dielectric constant after being exposed to high temperature and high humidity conditions. Moreover, the cured film which hardened | cured the said curable composition, its manufacturing method, the organic electroluminescence display which has the said cured film, a liquid crystal display device, a touch panel, and the touch panel display device were able to be provided.

1 shows a conceptual diagram of a configuration of an example of an organic EL display device. A schematic cross-sectional view of a substrate in a bottom emission type organic EL display device is shown, and a planarizing film 4 is provided. 1 is a conceptual diagram of a configuration of an example of a liquid crystal display device. The schematic sectional drawing of the active matrix substrate in a liquid crystal display device is shown, and it has the cured film 17 which is an interlayer insulation film. 1 is a conceptual diagram illustrating a configuration of an example of a liquid crystal display device having a touch panel function. FIG. 5 shows a conceptual diagram of a configuration of another example of a liquid crystal display device having a touch panel function.

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

  Regarding the molecular weight of the compound in the present invention, the low molecular weight compound whose molecular weight can be specified is the molecular weight measured by ESI-MS (electrospray ionization mass spectrometry), and the compound having a molecular weight distribution is tetrahydrofuran (THF). The weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) when used as a solvent.

(Curable composition)
The curable composition of the present invention (hereinafter, also simply referred to as “composition”) includes, as Component A, an ethylenically unsaturated compound, Component B as a polymerization initiator, Component C as a blocked isocyanate compound, and Component D contains an organic solvent, Component A contains a pentafunctional or higher urethane (meth) acrylate, and the content of the pentafunctional or higher urethane (meth) acrylate is 100 parts by mass of Component A The urethane (meth) acrylate having a weight average molecular weight of 10,000 or more and a urethane (meth) acrylate having a molecular weight of 5,000 or less, which is 20 to 100 parts by mass. It is characterized by including.
By including these components, both the pencil hardness and the relative dielectric constant after the high temperature and high humidity test can be achieved. The mechanism is estimated as follows. By using two types of urethane (meth) acrylates having different molecular weights, compatibility with the blocked isocyanate compound in the film after coating is improved. By curing the coating film, the urethane-derived soft segment and (meth) acrylate-derived hard segment are uniformly present in the film, and further, the partially hydrolyzed portion is also crosslinked by the blocked isocyanate compound. By proceeding, it is considered that prevention of scratches at the time of measuring the pencil hardness and prevention of peeling by dispersing the load can be achieved. In addition, it is considered that deterioration during the high temperature and high humidity test can be prevented by the remaining blocked isocyanate sites trapping moisture and hydrolyzed portions. Therefore, the above-described problem can be solved by using the composition of the present invention.
The curable composition of the present invention is preferably a composition in which the strength of the cured product is increased by heat-treating the cured product such as the obtained cured film after polymerization or subsequent to polymerization, It is more preferable that the composition contains a photopolymerization initiator as Component B, and the resulting cured product is heat-treated after the polymerization by light, whereby the strength of the cured product is further increased.
The curable composition of the present invention preferably further contains inorganic particles as component E.
The curable composition of the present invention further contains other components such as component F: alkoxysilane compound, component G: (meth) acrylic copolymer, component H: mercapto compound, component W: surfactant. May be.

Component A: Ethylenically unsaturated compound The curable composition of the present invention contains an ethylenically unsaturated compound as Component A.
Moreover, the curable composition of this invention contains a urethane (meth) acrylate more than pentafunctional as an ethylenically unsaturated compound.
The ethylenically unsaturated compound in the present invention only needs to have an ethylenically unsaturated bond, and may be a low molecular weight compound, an oligomer, or a polymer.
The content of the ethylenically unsaturated compound is preferably 40% by mass or more, more preferably 50% by mass or more, and 60% by mass or more in the total organic solid content of the curable composition. Is more preferable, and it is especially preferable that it is 70 mass% or more. The upper limit is not particularly defined, but is preferably 98% by mass or less, and more preferably 95% by mass or less.
Moreover, when mix | blending the inorganic particle mentioned later, it is preferable that content of an ethylenically unsaturated compound is 80 mass% or less with respect to the total solid of a curable composition, and it is 75 mass% or less. Is more preferable. The “solid content” in the curable composition represents a component excluding volatile components such as an organic solvent, and the “organic solid content” in the curable composition refers to an inorganic component such as inorganic particles, and Represents components excluding volatile components such as organic solvents.
In the present invention, an ethylenically unsaturated compound that corresponds to an alkoxysilane compound described later, that is, a compound having an alkoxysilyl group and an ethylenically unsaturated group is an alkoxysilane compound.
In the present invention, urethane (meth) acrylate is a compound having one or more urethane bonds and one or more (meth) acryloxy groups.

[5 or more functional urethane (meth) acrylate]
In the curable composition of the present invention, the content of pentafunctional or higher urethane (meth) acrylate is 20 to 100 parts by mass and 20 to 69 parts by mass with respect to 100 parts by mass of component A. Is preferred. The effect of this invention is more effectively exhibited as it is the said range.
The number of (meth) acryloxy groups in the pentafunctional or higher urethane (meth) acrylate is preferably 6 or more, more preferably 10 or more, and particularly preferably 12 or more. By adopting such a configuration, the effect of the present invention is more effectively exhibited.
Further, the upper limit of the number of the (meth) acryloxy groups is not particularly limited, but when it is not a polymer structure, it is preferably 50 or less, more preferably 30 or less, and 20 or less. Further preferred.
The curable composition of the present invention may contain only one type of pentafunctional or higher functional urethane (meth) acrylate, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

  Examples of the urethane (meth) acrylate having 5 or more functional groups that can be used in the present invention include urethane addition polymerizable compounds produced by using an addition reaction between an isocyanate and a hydroxyl group, Japanese Patent Application Laid-Open No. 51-37193, The urethane acrylates described in JP-B-2-32293 and JP-B-2-16765 are exemplified, and these descriptions are incorporated in the present specification.

The (meth) acryloxy group in the penta- or higher functional urethane (meth) acrylate may be either an acryloxy group or a methacryloxy group, or both, but is preferably an acryloxy group.
The pentafunctional or higher urethane (meth) acrylate is preferably a pentafunctional or higher aliphatic urethane (meth) acrylate.
Moreover, it is preferable that pentafunctional or more urethane (meth) acrylate has an isocyanuric ring structure.
The pentafunctional or higher functional urethane (meth) acrylate is a compound comprising a core portion having one or more urethane bonds and a terminal portion bonded to the core portion and having one or more (meth) acryloxy groups. Preferably, the compound is a compound in which two or more of the terminal portions are bonded to the core portion.

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

  In formula Ae-1 and formula Ae-2, R represents an acrylic group or a methacryl group each independently, and a wavy line part represents a bonding position with another structure.

The curable composition of the present invention comprises a urethane (meth) acrylate having a weight average molecular weight of 10,000 or more and a urethane (meth) acrylate having a molecular weight of 5,000 or less as a pentafunctional or higher functional urethane (meth) acrylate. contains.
In the curable composition of the present invention, the content of urethane (meth) acrylate having a weight average molecular weight of 10,000 or more is 1 to 90 weights per 100 parts by mass of pentafunctional or more urethane (meth) acrylate. Part is preferable, 5 to 70 parts by weight is more preferable, and 10 to 60 parts by weight is particularly preferable.
In the curable composition of the present invention, the content of urethane (meth) acrylate having a molecular weight of 5,000 or less is 10 to 99 parts by weight with respect to 100 parts by mass of pentafunctional or higher urethane (meth) acrylate. Preferably, 15 to 95 parts by weight are more preferable, and 20 to 90 parts by weight are particularly preferable.

-Urethane (meth) acrylate having a weight average molecular weight of 10,000 or more-
The curable composition of the present invention contains urethane (meth) acrylate having a weight average molecular weight of 10,000 or more as pentafunctional or higher functional urethane (meth) acrylate.
That is, the urethane (meth) acrylate having a weight average molecular weight of 10,000 or more is a urethane (meth) acrylate having a weight average molecular weight of 10,000 or more and pentafunctional or more.
The weight average molecular weight of the urethane (meth) acrylate having a weight average molecular weight of 10,000 or more is preferably 10,000 to 100,000, and more preferably 10,000 to 50,000.
The urethane (meth) acrylate having a weight average molecular weight of 10,000 or more is preferably a polymer having a constitutional repeating unit represented by the following formula Aa-1 or Aa-2.

In Formula Aa-1 and Formula Aa-2, L ^{5 to} L ⁸ each independently represent a divalent linking group, A represents a group having a (meth) acryloyl group, and R ^a represents ^a hydrogen atom or a carbon number. 1 to 5 alkyl groups are represented.

L ^{5 to} L ⁸ are each independently preferably an alkylene group having 2 to 20 carbon atoms, more preferably an alkylene group having 2 to 10 carbon atoms, and an alkylene group having 4 to 8 carbon atoms. Is more preferable. The alkylene group may have a branched or ring structure, but is preferably a linear alkylene group.
A is preferably a group represented by the formula Ae-1 or Ae-2.
R ^a is preferably ^a hydrogen atom or a methyl group.

-Urethane (meth) acrylate having a molecular weight of 5,000 or less-
The curable composition of the present invention contains a urethane (meth) acrylate having a molecular weight of 5,000 or less as a pentafunctional or higher functional urethane (meth) acrylate.
That is, the urethane (meth) acrylate having a molecular weight of 5,000 or less is a urethane (meth) acrylate having a molecular weight of 5,000 or less and a pentafunctional or higher functionality.
When the urethane (meth) acrylate having a molecular weight of 5,000 or less is an oligomer or polymer having a distribution in molecular weight, the molecular weight may be a weight average molecular weight.
The number of urethane bonds in the urethane (meth) acrylate having a molecular weight of 5,000 or less is not particularly limited, but is preferably 1 to 30, more preferably 1 to 20, and more preferably 2 to 10. Is more preferable, and 2 to 5 is particularly preferable.
From the viewpoint of cured film hardness, the molecular weight of urethane (meth) acrylate having a molecular weight of 5,000 or less is preferably from 500 to 5,000, more preferably from 800 to 5,000, and particularly preferably from 800 to 3,000.
The pentafunctional or higher functional urethane (meth) acrylate preferably contains two or more urethane (meth) acrylates having a molecular weight of 5,000 or less, and the urethane (meth) acrylate having a molecular weight of 5,000 or less is 2 to 2. It is more preferable to include 4 types, and it is particularly preferable to include 2 or 3 types of urethane (meth) acrylate having a molecular weight of 5,000 or less. It is excellent in the hardness of the obtained cured film as it is the said aspect.
The number of (meth) acryloxy groups in the urethane (meth) acrylate having a molecular weight of 5,000 or less is preferably 5 to 30, more preferably 8 to 25, and 10 to 20. Is particularly preferred. It is excellent by the hardness of the cured film obtained as it is the said range.
Further, the urethane (meth) acrylate having a molecular weight of 5,000 or less is preferably a compound having at least a group represented by the following formula Ac-1 or formula Ac-2, and represented by the following formula Ac-1. It is more preferable that the compound has at least a group.
Moreover, it is preferable that the said core part in pentafunctional or more urethane (meth) acrylate is group represented by the following formula Ac-1 or formula Ac-2.

In Formula Ac-1 and Formula Ac-2, L ^{1 to} L ⁴ each independently represents a divalent hydrocarbon group having 2 to 20 carbon atoms, and the wavy line represents a bonding position with another structure.
L ^{1 to} L ⁴ are each independently preferably an alkylene group having 2 to 20 carbon atoms, more preferably an alkylene group having 2 to 10 carbon atoms, and an alkylene group having 4 to 8 carbon atoms. Is more preferable. The alkylene group may have a branched or ring structure, but is preferably a linear alkylene group.
The urethane (meth) acrylate having a molecular weight of 5,000 or less is a group represented by the formula Ac-1 or the formula Ac-2, a group represented by the formula Ae-1, and a formula Ae-2. Particularly preferred is a compound in which two or three groups selected from the group consisting of the groups represented are bonded.

  The urethane (meth) acrylate having a molecular weight of 5,000 or less, which is preferably used in the present invention, will be exemplified below, but it goes without saying that the present invention is not limited to these.

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

[Other ethylenically unsaturated compounds]
The curable composition of the present invention may contain, as Component A, an ethylenically unsaturated compound other than pentafunctional or higher urethane (meth) acrylate (also referred to as “other ethylenically unsaturated compounds”).
As an ethylenically unsaturated compound other than pentafunctional or higher urethane (meth) acrylate, even if it is a polymer (for example, a molecular weight of 2,000 or more), a monomer (for example, a molecular weight of less than 2,000, preferably The molecular weight may be 100 or more and less than 2,000), and the monomer is preferable.
The ethylenically unsaturated compound other than the pentafunctional or higher urethane (meth) acrylate is preferably a polyfunctional ethylenically unsaturated compound, and more preferably a 3-6 functional ethylenically unsaturated compound.
As the ethylenically unsaturated compound other than the pentafunctional or higher urethane (meth) acrylate, a (meth) acrylate compound is preferable. 2-15 are preferable and, as for the number of the (meth) acryloxy group of a (meth) acrylate compound, 3-6 are more preferable. By adopting such a configuration, the effect of the present invention is more effectively exhibited.
Specifically, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri ((meth) acryloyloxyethyl) isocyanurate , Trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate ethylene oxide (EO) modified product, dipentaerythritol hexa (meth) acrylate EO modified product, and the like.
Moreover, as another ethylenically unsaturated compound, tetrafunctional or less urethane (meth) acrylate may be included.
Examples of the tetrafunctional or lower urethane (meth) acrylate include the following compounds.

When the curable composition of the present invention contains an ethylenically unsaturated compound other than a pentafunctional or higher urethane (meth) acrylate, the content of the ethylenically unsaturated compound other than the pentafunctional or higher urethane (meth) acrylate is cured. Is preferably in the range of 0.1 to 50% by mass, more preferably in the range of 0.5 to 40% by mass, and in the range of 1 to 25% by mass with respect to the total solid content of the composition. More preferably.
The curable composition of the present invention may contain only one type of ethylenically unsaturated compound other than pentafunctional or higher urethane (meth) acrylate, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

Component B: Polymerization initiator The curable composition of the present invention contains a polymerization initiator as Component B.
The polymerization initiator preferably contains a radical polymerization initiator.
The radical polymerization initiator that can be used in the present invention is a compound that can initiate and accelerate the polymerization of an ethylenically unsaturated compound by light and / or heat. Among these, a photopolymerization initiator is preferable, and a photoradical polymerization initiator is more preferable.
The “light” is not particularly limited as long as it is an active energy ray capable of imparting energy capable of generating a starting species from the component B by the irradiation, and is widely limited to α rays, γ rays, X rays, ultraviolet rays. (UV), visible light, electron beam, and the like. Among these, light containing at least ultraviolet rays is preferable.

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

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

In Formula 1 or Formula 2, Ar represents an aromatic group or heteroaromatic group, R ¹ represents an alkyl group, an aromatic group or an alkyloxy group, R ² represents a hydrogen atom or an alkyl group, and R ² May combine with an Ar group to form a ring.

Ar represents an aromatic group or a heteroaromatic group, and is preferably a group obtained by removing one hydrogen atom from a benzene ring, naphthalene ring or carbazole ring, and a naphthalenyl group or carbazoyl group which forms a ring together with R ² More preferred.
R ¹ represents an alkyl group, an aromatic group or an alkoxy group, preferably a methyl group, an ethyl group, a benzyl group, a phenyl group, a naphthyl group, a methoxy group or an ethoxy group, and a methyl group, an ethyl group, a phenyl group or a methoxy group. Is more preferable.
R ² represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or a substituted alkyl group, more preferably a hydrogen atom, a substituted alkyl group that forms a ring with Ar, or a toluenethioalkyl group.

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

In formulas 3 to 5, R ¹ represents an alkyl group, an aromatic group or an alkoxy group, X represents —CH ₂ —, —C ₂ H ₄ —, —O— or —S—, and R ³ represents each. Independently represents a halogen atom, each R ⁴ 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 ⁵ represents a hydrogen atom, represents an alkyl group or an aryl group, R ⁶ represents an alkyl group, in each of n1 and n2 independently represents an integer of Less than six, n3 represents an integer of 0 to 5.

R ¹ represents an alkyl group, an aromatic group or an alkoxy group, and a group represented by R ¹¹ —X′-alkylene group— (R ¹¹ represents an alkyl group or an aryl group, and X ′ represents a sulfur atom or an oxygen atom. Are preferred). R ¹¹ is preferably an aryl group, more preferably a phenyl group. The alkyl group and aryl group as R ¹¹ may be substituted with a halogen atom (preferably a fluorine atom, a chlorine atom or a bromine atom) or an alkyl group.
X is preferably a sulfur atom.
R ³ and R ⁴ can be bonded at any position on the aromatic ring.
R ⁴ represents an alkyl group, a phenyl group, an alkyl-substituted amino group, an arylthio group, an alkylthio group, an alkoxy group, an aryloxy group or a halogen atom, preferably an alkyl group, a phenyl group, an arylthio group or a halogen atom, an alkyl group, an arylthio group A group or a halogen atom is more preferred, and an alkyl group or a halogen atom is still more preferred. As an alkyl group, a C1-C5 alkyl group is preferable and a methyl group or an ethyl group is more preferable. As a halogen atom, a chlorine atom, a bromine atom, or a fluorine atom is preferable.
The number of carbon atoms of R ⁴ is preferably 0 to 50, and more preferably from 0 to 20.
R ⁵ represents a hydrogen atom, an alkyl group or an aryl group, and an alkyl group is preferable. As an alkyl group, a C1-C5 alkyl group is preferable and a methyl group or an ethyl group is more preferable. As the aryl group, an aryl group having 6 to 10 carbon atoms is preferable.
R ⁶ represents an alkyl group, preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group or an ethyl group.
n1 and n2 each represent the number of substitutions of R ³ on the aromatic ring in Formula 3 or Formula 4, and n3 represents the number of substitutions of R ⁴ on the aromatic ring in Formula 5.
n1 to n3 are each independently preferably an integer of 0 to 2, and more preferably 0 or 1.

  Below, the example of the oxime ester compound preferably used by this invention is shown. However, it goes without saying that the oxime ester compounds used in the present invention are not limited to these. Me represents a methyl group and Ph represents a phenyl group.

  Specific examples of the organic halogenated compounds include Wakabayashi et al., “Bull Chem. Soc. Japan” 42, 2924 (1969), US Pat. No. 3,905,815, and Japanese Examined Patent Publication No. 46-4605. JP, 48-34881, JP 55-3070, JP 60-239736, JP 61-169835, JP 61-169837, JP 62-58241, JP-A 62-212401, JP-A 63-70243, JP-A 63-298339, M.S. P. Examples include compounds described in Hutt “Journal of Heterocyclic Chemistry” 1 (No. 3), (1970), and particularly, oxazole compounds substituted with a trihalomethyl group and s-triazine compounds.

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

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

A polymerization initiator can be used 1 type or in combination of 2 or more types.
The total amount of the polymerization initiator in the curable composition of the present invention is preferably 0.5 to 30% by mass and more preferably 1 to 20% by mass with respect to the total solid content in the composition. It is more preferable that it is 1-10 mass%, and it is especially preferable that it is 2-5 mass%.
Moreover, when a composition contains the inorganic particle mentioned later, the total amount of the polymerization initiator in the curable composition of this invention is 0.5-30 mass% with respect to the total solid in a composition. Is more preferable, 1 to 20% by mass is more preferable, 1 to 10% by mass is further preferable, and 2 to 5% by mass is particularly preferable.

[Sensitizer]
In addition to the polymerization initiator, a sensitizer can be added to the curable composition of the present invention.
Typical sensitizers that can be used in the present invention include those disclosed in Crivello (JV Crivello, Adv. In Polymer Sci., 62, 1 (1984)). Examples include pyrene, perylene, acridine orange, thioxanthone, 2-chlorothioxanthone, benzoflavine, N-vinylcarbazole, 9,10-dibutoxyanthracene, anthraquinone, coumarin, ketocoumarin, phenanthrene, camphorquinone, and phenothiazine derivatives. The sensitizer is preferably added at a ratio of 50 to 200% by mass with respect to the polymerization initiator.

Component C: Blocked isocyanate compound The curable composition of the present invention contains a blocked isocyanate compound as Component C.
By containing component C, the curable composition which can obtain the cured film excellent in the touch-panel characteristic under high temperature, high humidity is obtained.
The blocked isocyanate compound is not particularly limited as long as it is a compound having a blocked isocyanate group, but is preferably a compound having two or more blocked isocyanate groups in one molecule from the viewpoint of curability. The upper limit of the number of blocked isocyanate groups is not particularly defined, but is preferably 6 or less.
Further, the skeleton of the blocked isocyanate compound is not particularly limited, and any compound may be used as long as it is a compound obtained by blocking an isocyanate group of a compound having an isocyanate group in the molecule. The compound having an isocyanate group in the molecule may be an aliphatic, alicyclic or aromatic polyisocyanate. 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,3-trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, 2,2,4 -Trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,9-nonamethylene diisocyanate, 1,10-decamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 2,2'-diethyl ether diisocyanate, diphenylmethane -4,4'-diisocyanate, o-xylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, methylene bis (cyclohexyl isocyanate , Cyclohexane-1,3-dimethylene diisocyanate, cyclohexane-1,4-dimethylene diisocyanate, 1,5-naphthalene diisocyanate, p-phenylene diisocyanate, 3,3′-methylene ditolylene-4,4′-diisocyanate, 4, , 4'-diphenyl ether diisocyanate, tetrachlorophenylene diisocyanate, norbornane diisocyanate, hydrogenated 1,3-xylylene diisocyanate, hydrogenated 1,4-xylylene diisocyanate and the like, and multimers thereof are preferably used. Can do. Among these, blocked isocyanate compounds that protect a compound selected from the group consisting of tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), and multimers thereof. A blocked isocyanate compound in which a compound selected from the group consisting of hexamethylene diisocyanate, isophorone diisocyanate, and multimers thereof is protected is more preferable.
The isocyanate compound multimer is not particularly limited as long as it is a dimer or higher multimer, and examples thereof include biuret bodies, isocyanurate bodies, and adduct bodies, and biuret bodies are preferred.

Examples of the matrix structure of the blocked isocyanate compound in the curable composition of the present invention include biuret type, isocyanurate type, adduct type, and bifunctional prepolymer type.
Examples of the blocking agent that forms the block structure of the blocked isocyanate compound include oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, and imide compounds. be able to. Among these, a blocking agent selected from an oxime compound, a lactam compound, a phenol compound, an alcohol compound, an amine compound, an active methylene compound, or a pyrazole compound is preferable.
From the viewpoint of storage stability, a blocking agent selected from an oxime compound, a lactam compound, a phenol compound, and an alcohol compound is particularly preferable.
From the viewpoint of the transparency of the cured film, a blocking agent selected from an oxime compound, a lactam compound, an alcohol compound, an amine compound, an active methylene compound, or a pyrazole compound is particularly preferable.
From the viewpoint of film strength and substrate adhesion, a blocking agent selected from oxime compounds, lactam compounds, amine compounds, active methylene compounds, or pyrazole compounds is particularly preferable.
Therefore, as an overall performance, a blocking agent selected from an oxime compound or a lactam compound is more preferable.
Examples of the oxime compound include oxime and ketoxime, and specific examples include acetoxime, formaldoxime, cyclohexane oxime, methyl ethyl ketone oxime, cyclohexanone oxime, and benzophenone oxime.
Examples of the lactam compound include ε-caprolactam and γ-butyrolactam.
Examples of the phenol compound include phenol, naphthol, cresol, xylenol, and halogen-substituted phenol.
Examples of the alcohol compound include methanol, ethanol, propanol, butanol, cyclohexanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, and alkyl lactate.
Examples of the amine compound include primary amines and secondary amines, which may be aromatic amines, aliphatic amines, and alicyclic amines, and examples thereof include aniline, diphenylamine, ethyleneimine, and polyethyleneimine.
Examples of the active methylene compound include diethyl malonate, dimethyl malonate, ethyl acetoacetate, methyl acetoacetate and the like.
Examples of the pyrazole compound include pyrazole, methylpyrazole, dimethylpyrazole and the like.
Examples of the mercaptan compound include alkyl mercaptans and aryl mercaptans.

  The blocked isocyanate compound that can be used in the curable composition of the present invention is available as a commercial product. For example, Coronate AP Stable M, Coronate 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (above, Japan) Polyurethane Industry Co., Ltd.), Takenate B-830, B-815N, B-820NSU, B-842N, B-84N, B-870N, B-874N, B-882N (Mitsui Chemicals, Inc.) , Duranate 17B-60P, 17B-60PX, 17B-60P, TPA-B80X, TPA-B80E, MF-B60X, MF-B60B, MF-K60X, MF-K60B, E402-B80B, SBN-70D, SBB-70P, K6000 (above, manufactured by Asahi Kasei Chemicals Corporation), Desmo Preferred are BL1100, BL1265 MPA / X, BL3575 / 1, BL3272MPA, BL3370MPA, BL3475BA / SN, BL5375MPA, VPLS2078 / 2, BL4265SN, PL340, PL350, Sumidur BL3175 (above, Sumika Bayer Urethane Co., Ltd.) Can be used.

The content of the blocked isocyanate compound in the curable composition of the present invention is preferably in the range of 0.1 to 20% by mass, and preferably 0.5 to 10% by mass with respect to the total solid content of the curable composition. The range is more preferable, and the range of 1 to 5% by mass is further preferable.
Moreover, it is preferable that content of the block isocyanate compound in the curable composition of this invention is the range of 0.1-20 mass% with respect to the total organic solid of a curable composition, 0.5-10 The range is more preferably in the range of mass%, and still more preferably in the range of 1 to 5 mass%.
The weight ratio of Component A to Component C in the curable composition of the present invention is preferably 100: 1 to 10: 1, more preferably 80: 1 to 20: 1, and 60: 1 to More preferably, it is 30: 1.
The total amount of component A, component B, and component C is preferably 85% by mass or more, more preferably 90% by mass or more, and 95% by mass with respect to the total organic solid content of the curable composition. % Or more is more preferable.
The curable composition of the present invention may contain only one type of blocked isocyanate compound, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

Component D: Organic Solvent The curable composition of the present invention contains an organic solvent as Component D. It is preferable that the curable composition of this invention is prepared as a solution which melt | dissolved or disperse | distributed the component A, the component B, and the component C which are essential components, and the below-mentioned arbitrary component in the organic solvent.
As the organic solvent used in the curable composition of the present invention, known solvents can be used, such as 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, alcohols, esters, ketones, Bromide, lactones and the like. As specific examples of these solvents, reference can be made to paragraph 0062 of JP-A-2009-098616.

  Specifically, propylene glycol monomethyl ether acetate, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, 1,3-butylene glycol diacetate, cyclohexanol acetate, propylene glycol diacetate, and tetrahydrofurfuryl alcohol are preferable.

The boiling point of the solvent is preferably from 100 ° C to 300 ° C, more preferably from 120 ° C to 250 ° C, from the viewpoint of applicability.
The organic solvent which can be used for this invention can be used individually by 1 type or in combination of 2 or more types. It is also preferred to use solvents having different boiling points in combination.
The content of the organic solvent in the curable composition of the present invention is 100 to 3,000 parts by mass per 100 parts by mass of the total solid content of the curable composition from the viewpoint of adjusting to a viscosity suitable for coating. Is preferably 200 to 2,000 parts by mass, and more preferably 250 to 1,000 parts by mass.
As solid content in the curable composition of this invention, 3-50 mass% is preferable, and it is more preferable that it is 20-40 mass%.

  The viscosity of the curable composition of the present invention is preferably 1 to 200 mPa · s, more preferably 2 to 100 mPa · s, and most preferably 3 to 80 mPa · s. The viscosity is preferably measured at 25 ± 0.2 ° C. using, for example, a RE-80L rotational viscometer manufactured by Toki Sangyo Co., Ltd. The rotation speed during measurement is preferably 100 rpm for less than 5 mPa · s, 50 rpm for 5 mPa · s to less than 10 mPa · s, 20 rpm for 10 mPa · s to less than 30 mPa · s, and 10 rpm for 30 mPa · s or more.

Component E: Inorganic Particles It is preferable that the curable composition of the present invention contains inorganic particles as component E. By containing inorganic particles, the hardness of the cured film is excellent. In addition, adhesion to the substrate can be improved.
The average particle size of the inorganic particles used in the present invention is preferably 1 to 200 nm, more preferably 5 to 100 nm, and particularly preferably 5 to 50 nm. The average particle diameter is an arithmetic average obtained by measuring the particle diameter of 200 arbitrary particles with an electron microscope. When the particle shape is not spherical, the longest side is the diameter.
Moreover, from the viewpoint of the hardness of the cured film, the porosity of the inorganic particles is preferably less than 10%, more preferably less than 3%, and most preferably no void. The porosity of the particle is an arithmetic average of 200 of the area ratio between the void portion of the cross-sectional image obtained by an electron microscope and the entire particle.
As the inorganic particles, metal oxide particles are preferable.
Note that the metal of the metal oxide in the present invention includes metalloids such as B, Si, Ge, As, Sb, and Te.
As the metal oxide particles, Be, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Gd, Tb, Dy, Yb, Lu, Ti, Zr, Hf, Nb, Mo, W, Zn, B Metal oxide particles containing atoms such as Al, Si, Ge, Sn, Pb, Sb, Bi, and Te are preferable. Silicon oxide, titanium oxide, titanium composite oxide, zinc oxide, zirconium oxide, indium / tin oxide And more preferably metal oxide particles selected from the group consisting of antimony / tin oxide, and metal oxides selected from the group consisting of silicon oxide, titanium oxide, titanium composite oxide, and zirconium oxide. Particles are more preferable, and silicon oxide particles or titanium oxide particles are particularly preferable from the viewpoints of particle stability, availability, hardness of a cured film, transparency, and refractive index adjustment.

The silicon oxide particles are preferably silicon dioxide (silica) particles.
The silica particles are not particularly limited as long as they are inorganic oxide particles containing silicon dioxide, and particles containing silicon dioxide or a hydrate thereof as a main component (preferably 80% by mass or more) are preferable. The said particle | grains may contain the aluminate as a minor component (for example, less than 5 mass%). Examples of the aluminate that may be contained as a minor component include sodium aluminate and potassium aluminate. The silica particles may contain inorganic salts such as sodium hydroxide, potassium hydroxide, lithium hydroxide and ammonium hydroxide, and organic salts such as tetramethylammonium hydroxide. Colloidal silica is exemplified as an example of such a compound.
There is no restriction | limiting in particular as a dispersion medium of colloidal silica, Any of water, an organic solvent, and these mixtures may be sufficient. These may be used individually by 1 type and can also use 2 or more types together.
In the present invention, the particles can be used as a dispersion prepared by mixing and dispersing in a suitable dispersant and solvent using a mixing device such as a ball mill or a rod mill. In the curable composition of the present invention, it is not essential that the colloidal silica exists in a colloidal state.

From the viewpoint of hardness, the content of inorganic particles in the curable composition of the present invention is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and more preferably 10 parts by mass per 100 parts by mass of the total solid content of the curable composition. Part or more is more preferable. Moreover, 80 mass parts or less are preferable, 50 mass parts or less are more preferable, 40 mass parts or less are further more preferable, and 30 mass parts or less are especially preferable.
One type of inorganic particles may be included, or two or more types may be included. When two or more types are included, the total amount is preferably within the above range.

Component F: Alkoxysilane Compound The curable composition of the present invention preferably contains an alkoxysilane compound as Component F. When the alkoxysilane compound is contained, the coating property and the hardness of the resulting cured film are excellent, and the adhesion between the film formed from the curable composition of the present invention and the substrate can be further improved.
The alkoxysilane compound that can be used in the curable composition of the present invention includes a base material, for example, a silicon compound such as silicon, silicon oxide, and silicon nitride, a metal such as gold, copper, molybdenum, titanium, and aluminum, and an insulating film. It is preferable that it is a compound which improves the adhesiveness of. Specifically, a known silane coupling agent or the like is also effective. It is preferable to use a silane coupling agent having an ethylenically unsaturated group because it is particularly excellent in adhesion to ITO. Moreover, it is excellent in reliability when a silane coupling agent having an epoxy group is used.
Examples of the silane coupling agent include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltriacoxysilane, γ-glycidoxypropyl dialkoxysilane, and γ-methacryloxy. Propyltrialkoxysilane, γ-methacryloxypropyl dialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, vinyltrialkoxysilane Can be mentioned. Of these, γ-methacryloxypropyltrialkoxysilane, γ-acryloxypropyltrialkoxysilane, vinyltrialkoxysilane, or γ-glycidoxypropyltriacoxysilane is more preferable. These can be used alone or in combination of two or more.
Examples of commercially available products include Shin-Etsu Chemical Co., Ltd. KBM-403, KBM-5103, KBM-303, KBM-503, KBE-503, KBM-3103, and KBE-403.

The content of the alkoxysilane compound in the curable composition of the present invention is preferably 0.1 to 30 parts by mass and more preferably 2 to 20 parts by mass with respect to 100 parts by mass in total of the total solid content of the curable composition. 2 to 15 parts by mass is more preferable.
Only one type of alkoxysilane compound may be included, or two or more types may be included. When two or more types are included, the total amount is preferably within the above range.

Component G: (Meth) acrylic copolymer The curable composition of the present invention may contain a (meth) acrylic copolymer as the component G.
Component G shall not contain a compound corresponding to Component A.
(Meth) acrylic copolymer means a copolymer of (meth) acrylic acid and another monomer.
As a monomer to be copolymerized with (meth) acrylic acid, styrene, methyl (meth) acrylate, ethyl (meth) acrylate, which may be substituted with an alkyl group at the α-position such as styrene and α-methylstyrene, ( Meth) propyl acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, vinyl acetate, acrylonitrile, (meth) acrylamide, glycidyl (meth) acrylate, allyl glycidyl ether, glycidyl ethyl acrylate, crotonyl glycidyl ether, Crotonic acid glycidyl ether, (meth) acrylic acid chloride, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate, N-methylolacrylamide, N, N-dimethylacrylamide, N-methacryloylmorpholine, N, N-di And monomers such as methylaminoethyl (meth) acrylate and N, N-dimethylaminoethylacrylamide. These monomers may be copolymerized alone with (meth) acrylic acid, or two or more monomers may be used.
Further, a copolymer containing (meth) acrylic acid and styrene optionally substituted with an alkyl group at the α-position as a copolymerization component is preferable.
1-20 mass% is preferable, as for content of the component G of the curable composition of this invention, 1-15 mass% is more preferable, and 1-10 mass% is still more preferable.

Component H: Mercapto Compound The curable composition of the present invention preferably contains a mercapto compound as Component H. By containing a mercapto compound, the obtained cured film has excellent film strength.
As the mercapto compound, a monofunctional mercapto compound or a polyfunctional mercapto compound is preferably used.

As the monofunctional mercapto compound, either an aliphatic mercapto compound or an aromatic mercapto compound can be used. From the viewpoint of film strength, an aromatic mercapto compound is preferable.
Specific examples of the monofunctional aliphatic mercapto compound include 1-octanethiol, 1-dodecanethiol, β-mercaptopropionic acid, methyl-3-mercaptopropionate, 2-ethylhexyl-3-mercaptopropionate, Examples include n-octyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate, and stearyl-3-mercaptopropionate.

  As the monofunctional aromatic mercapto compound, those represented by the following formula I are preferable.

In formula I, X ^S represents an oxygen atom, a sulfur atom or N—R ^S , R ^S represents a hydrogen atom, an alkyl group or an aryl group, and A forms a heterocycle together with N═C—X ^S. Represents an atomic group.

In the formula I, R ^S represents a hydrogen atom, an alkyl group or an aryl group.
As said alkyl group, a C1-C20 linear, branched or cyclic alkyl group can be mentioned, C1-C12 linear, C3-C12 branched or carbon A cyclic alkyl group of 5 to 10 is more preferable. Specific examples thereof include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, hexadecyl group, octadecyl group. , Eicosyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group , 2-norbornyl group and the like.
Examples of the aryl group include, in addition to those having a single ring structure, those in which 1 to 3 benzene rings form a condensed ring, and those in which a benzene ring and a 5-membered unsaturated ring form a condensed ring. it can. Specific examples include phenyl group, naphthyl group, anthryl group, phenanthryl group, indenyl group, acenaphthenyl group, fluorenyl group and the like. In these, a phenyl group and a naphthyl group are more preferable.

  These alkyl groups and aryl groups may further have a substituent, and examples of the substituent that can be introduced include a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and 2 to 2 carbon atoms. 20 linear, branched or cyclic alkenyl groups, alkynyl groups having 2 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, acyloxy groups having 1 to 20 carbon atoms, alkoxycarbonyloxy having 2 to 20 carbon atoms Group, aryloxycarbonyloxy group having 7 to 20 carbon atoms, carbamoyloxy group having 1 to 20 carbon atoms, carbonamido group having 1 to 20 carbon atoms, sulfonamido group having 1 to 20 carbon atoms, and 1 to 20 carbon atoms A carbamoyl group, a sulfamoyl group, a substituted sulfamoyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and an aryl group having 7 to 20 carbon atoms. Sicarbonyl group, C2-C20 alkoxycarbonyl group, C1-C20 N-acylsulfamoyl group, C1-C20 N-sulfamoylcarbamoyl group, C1-C20 alkylsulfonyl Group, arylsulfonyl group having 6 to 20 carbon atoms, alkoxycarbonylamino group having 2 to 20 carbon atoms, aryloxycarbonylamino group having 7 to 20 carbon atoms, amino group, substituted amino group having 1 to 20 carbon atoms, carbon Number 1-20 imino group, number 3-20 ammonio group, carboxyl group, sulfo group, oxy group, mercapto group, number 1-20 alkylsulfinyl group, number 6-20 arylsulfinyl group, carbon C1-C20 alkylthio group, C6-C20 arylthio group, C1-C20 ureido group, C2-C20 hete A cyclic group, an acyl group having 1 to 20 carbon atoms, a sulfamoylamino group, a substituted sulfamoylamino group having 1 to 2 carbon atoms, a silyl group having 2 to 20 carbon atoms, an isocyanate group, an isocyanide group, a halogen atom (for example, , Fluorine atom, chlorine atom, bromine atom, etc.), cyano group, nitro group, onium group, hydroxyl group and the like.

In Formula I, A represents an atomic group that forms a heterocycle with N═C—X ^S.
Examples of atoms constituting this atomic group include a carbon atom, a nitrogen atom, a hydrogen atom, a sulfur atom, and a selenium atom.
The heterocycle formed by A and N═C—X ^S may further have a substituent, and the substituent that can be introduced is a substituent that can be introduced into the alkyl group or aryl group. The same thing is mentioned.

  The monofunctional aromatic mercapto compound is more preferably a compound represented by the following formula II to formula V.

In formulas II to V, R ^S1 represents a hydrogen atom or an aryl group, X ^S1 independently represents a hydroxyl group, a halogen atom, an alkoxy group, an aryloxy group, an alkyl group or an aryl group, and R ^S2 represents an alkyl group A group or an aryl group, n represents an integer of 0 to 4, and m represents an integer of 0 to 5.

As a halogen atom in Formula II-Formula V, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are preferable.
Examples of the alkoxy group and aryloxy group in the formulas II to V include methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butyloxy group, pentyloxy group, hexyloxy group, dodecyloxy group, benzyloxy group, allyloxy group, Phenethyloxy group, carboxyethyloxy group, methoxycarbonylethyloxy group, ethoxycarbonylethyloxy group, methoxyethoxy group, phenoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, morpholinoethoxy group, morpholinopropyloxy group, allyloxy Ethoxyethoxy group, phenoxy group, tolyloxy group, xylyloxy group, mesityloxy group, cumyloxy group, methoxyphenyloxy group, ethoxyphenyloxy group, chlorophene Aryloxy group, bromophenyl group, acetyloxy group, benzoyloxy group, naphthyloxy group and the like.
The alkyl group in formula II to formula V has the same meaning as the alkyl group represented by R ^S in formula I, and the preferred range thereof is also the same.
Moreover, the aryl group in Formula II-Formula V is synonymous with the aryl group represented by ^RS of Formula I, The preferable range is also the same.
Each group in Formula II to Formula V may further have a substituent, and examples of the substituent include substituents that can be introduced into the alkyl group or aryl group represented by R ^S in Formula I. It is the same as that.

In formulas II to V, n and m are preferably 0 from the viewpoint of solubility in organic solvents.
Of the compounds of formula II to formula V, the following compounds are more preferred. When these compounds are used, the film strength increases and the storage stability is also good.

Component H is preferably a polyfunctional mercapto compound from the viewpoint of adhesion to the substrate.
In the present invention, the polyfunctional mercapto compound means a compound having two or more mercapto groups (thiol groups) in the molecule. As the polyfunctional mercapto compound, a low molecular compound having a molecular weight of 100 or more is preferable, specifically, a molecular weight of 100 to 1,500 is more preferable, and 150 to 1,000 is still more preferable.
As the number of functional groups of the polyfunctional mercapto compound, 2 to 10 functions are preferable, 2 to 8 functions are more preferable, and 2 to 4 functions are still more preferable. When the number of functional groups is large, the film strength is excellent, while when the number of functional groups is small, the storage stability is excellent. In the case of the said range, these can be made compatible.

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

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

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

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

In formula S-2, R ^1S each independently represents a hydrogen atom or an alkyl group, A ^1S independently represents —CO— or —CH ₂ —, L ^1S represents an nS-valent linking group, nS represents the integer of 2-6. From the viewpoint of synthesis, it is preferred that all R ^1S are the same group, and all A ^1S are preferably the same group.

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

  Furthermore, as the polyfunctional mercapto compound, a secondary thiol is more preferable.

  Specific examples of the polyfunctional mercapto compound include ethylene glycol bisthiopropionate, butanediol bisthiopropionate, trimethylolpropane tris (3-mercaptopropionate), and tris [(3-mercaptopropionyloxy) ethyl]. Isocyanurate, pentaerythritol tetrakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate) Rate), 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H , 3H, 5H -Trione, 1,2-benzenedithiol, 1,3-benzenedithiol, 1,2-ethanedithiol, 1,3-propanedithiol, 1,6-hexamethylenedithiol, 2,2 '-(ethylenedithio) diethane Examples include thiol, meso-2,3-dimercaptosuccinic acid, p-xylene dithiol, m-xylene dithiol, di (mercaptoethyl) ether, and the like.

  As the polyfunctional mercapto compound, pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyryloxyethyl)- 1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione is preferred, and pentaerythritol tetrakis (3-mercaptobutyrate) is more preferred.

In this invention, a mercapto compound may be used individually by 1 type, or may use 2 or more types together.
In the present invention, the content of the mercapto compound is preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass, based on the total solid content of the curable composition. More preferably, it is 1-5 mass%. It is excellent in the point of coexistence with film | membrane intensity | strength and storage stability as it is the said range.

Component W: Surfactant The curable composition of the present invention may contain a surfactant.
As the surfactant, any of anionic, cationic, nonionic, or amphoteric surfactants can be used, but a preferred surfactant is a nonionic surfactant. The surfactant is preferably a nonionic surfactant, and more preferably a fluorosurfactant.
Examples of the surfactant that can be used in the present invention include commercially available products, such as Megafac F142D, F172, F173, F176, F177, F183, F479, F482, F554, and F780. F781, F781-F, R30, R08, F-472SF, BL20, R-61, R-90 (manufactured by DIC Corporation), Florard FC-135, FC-170C, FC-430, FC-431, Novec FC-4430 (manufactured by Sumitomo 3M Limited), Asahi Guard AG7105, 7000, 950, 7600, Surflon S-112, S-113, S-131, S -141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-1 05, the same SC-106 (Asahi Glass Co., Ltd.), F-top EF351, 352, 801, 802 (Mitsubishi Materials Electronics Chemical Co., Ltd.), and Footent 250 (Neos Co., Ltd.). . In addition to the above, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F-Top (manufactured by Mitsubishi Materials Denka Kasei Co., Ltd.), MegaFuck (manufactured by DIC Corporation) , FLORARD (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), PolyFox (manufactured by OMNOVA), and the like.

Moreover, as surfactant, the compound described in Paragraph 0119-0123 of Unexamined-Japanese-Patent No. 2014-238438 can also be mentioned as a preferable example.
When blended, the content of the surfactant in the curable composition of the present invention is preferably 0.001 to 5.0 mass% with respect to the total solid content of the curable composition, and 0.01 to 2. 0 mass% is more preferable.
Only one type of surfactant may be included, or two or more types of surfactants may be included. When two or more types are included, the total amount is preferably within the above range.

<Other ingredients>
If necessary, the curable composition of the present invention may contain other components such as a plasticizer, a polymerization inhibitor, a thermal acid generator, an acid multiplier, an antioxidant, an epoxy compound, and an oxetane compound. it can. As these components, for example, those described in JP2009-98616A, JP2009-244801A, and other known ones can be used. Further, various ultraviolet absorbers described in “New Development of Polymer Additives (Nikkan Kogyo Shimbun Co., Ltd.)”, metal deactivators, and the like may be added to the curable composition of the present invention. Moreover, it is preferable that the curable composition of the present invention does not contain polymer particles.

〔Antioxidant〕
The curable resin composition of the present invention may contain an antioxidant. As an antioxidant, a well-known antioxidant can be contained. By adding an antioxidant, there is an advantage that coloring of the cured film can be prevented, or a decrease in film thickness due to decomposition can be reduced, and heat resistant transparency is excellent.
Examples of such antioxidants include phosphorus antioxidants, amides, hydrazides, hindered amine antioxidants, sulfur antioxidants, phenol antioxidants, ascorbic acids, zinc sulfate, sugars, Examples thereof include nitrates, sulfites, thiosulfates, and hydroxylamine derivatives. Of these, phenolic antioxidants, hindered amine antioxidants, phosphorus antioxidants, and sulfur antioxidants are particularly preferable from the viewpoint of coloring the cured film and reducing the film thickness, with phenolic antioxidants being the most preferred. preferable. These may be used individually by 1 type and may mix 2 or more types.
Specific examples include the compounds described in paragraphs 0026 to 0031 of JP-A-2005-29515, and the compounds described in paragraphs 0106 to 0116 of JP-A-2011-227106. Embedded in the book.
As a preferable commercial item, ADK STAB AO-60, ADK STAB AO-80, ADK STAB AO-412S (above, manufactured by ADEKA Corporation), Irganox 1035, and Irganox 1098 (above, manufactured by BASF) can be exemplified.
Although there is no restriction | limiting in particular in content of antioxidant, It is preferable that it is 0.01-10 mass% with respect to the total solid of a curable composition, and it is 0.02-5 mass%. More preferably, it is 0.05-4 mass% further more preferable.

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

<Content of each component>
The total content of component A is preferably 40 to 99% by mass and the content of component B is 0.5 to 30% by mass with respect to the total solid content of the curable composition of the present invention. Preferably, the content of component C is preferably 0.1 to 20% by mass, the content of component E is preferably 0 to 50% by mass, and the content of component F is 0 to 30% by mass. Preferably, the content of component G is preferably 0 to 20% by mass, the content of component H is preferably 0 to 15% by mass, and the content of component W is 0 to 5% by mass. It is preferable that
Moreover, it is preferable that content of the component D is 100-3,000 mass parts per 100 mass parts of total solid of a curable composition.
Moreover, it is preferable that content of the component A is 40-80 mass% with respect to the total organic solid of the curable composition of this invention, and content of the component B is 0.5-30 mass%. The content of component C is preferably 0.1 to 20% by mass.
The total amount of component A, component B, and component C is preferably 85% by mass or more, more preferably 90% by mass or more, and 95% by mass with respect to the total organic solid content of the curable composition. % Or more is more preferable.

(Hardened product, cured film and production method thereof)
The cured product of the present invention is a cured product obtained by curing the curable composition of the present invention, and cures the film formed by removing at least a part of the organic solvent from the curable composition of the present invention. It is preferable that it is the cured film obtained by this. The cured product is preferably a cured film. Moreover, it is preferable that the hardened | cured material of this invention is the hardened | cured material obtained by the manufacturing method of the hardened | cured material of this 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, but preferably includes the following steps 1 to 3.
1: The process of apply | coating the curable composition of this invention on a board | substrate 2: The process of removing the organic solvent from the apply | coated curable composition 3: The process of thermosetting Moreover, the manufacturing method of the hardened | cured material of this invention is the following. More preferably, the following steps 1, 2, 2 ′ and 3 are included.
1: The process of apply | coating the curable composition of this invention on a board | substrate 2: The process of removing an organic solvent from the apply | coated curable composition 2 ': The curable composition from which the organic solvent was removed is hardened | cured with light. Process 3: The process of further hardening | curing the hardened | cured material hardened | cured with light Moreover, it is preferable that the manufacturing method of the said hardened | cured material of the said invention is a manufacturing method of a cured film.

1: In the step of applying, it is preferable to apply the curable composition of the present invention on a substrate to form a wet film containing an organic solvent. Before applying the curable composition to the substrate, the substrate can be cleaned such as alkali cleaning or plasma cleaning. Furthermore, the substrate surface can be treated with hexamethyldisilazane or the like after cleaning the substrate. By performing this treatment, the adhesiveness of the curable composition to the substrate tends to be improved.
Examples of the substrate include inorganic substrates, resins, and resin composite materials.
Examples of the inorganic substrate include glass, quartz, silicon, silicon nitride, and a composite substrate obtained by depositing molybdenum, titanium, aluminum, copper, or the like on such a substrate.
Resins include polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, polyethersulfone, polyarylate, allyl diglycol carbonate, polyamide, polyimide, polyamideimide, polyetherimide, poly Fluorine resins such as benzazole, polyphenylene sulfide, polycycloolefin, norbornene resin, polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, silicone resin, ionomer resin, cyanate resin, crosslinked fumaric acid diester, cyclic polyolefin, aromatic From synthetic resins such as aromatic ethers, maleimide-olefin copolymers, cellulose and episulfide resins. Board, and the like. These substrates are rarely used in the above-described form, and usually have a multilayer laminated structure such as a TFT (Thin-Film Transistor) element depending on the form of the final product.

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

  The coating method on the substrate is not particularly limited. For example, a method such as an inkjet method, a slit coating method, a spray method, a roll coating method, a spin coating method, a casting coating method, a slit and spin method, or a printing method may be used. it can.

  2: In the step of removing the organic solvent, it is preferable to remove the organic solvent from the applied film by vacuum (vacuum) and / or heating to form a dry coating film on the substrate. The heating conditions for the solvent removal step are preferably 70 to 130 ° C. and about 30 to 300 seconds. Moreover, in the said solvent removal process, it is not necessary to remove the organic solvent in a curable composition completely, and at least one part should just be removed.

Furthermore, in the present invention, a step of exposing the entire surface may be included from the viewpoint of improving the film hardness, 2: after the step of removing the organic solvent, and 3: before the step of thermosetting.
In addition, 2: after the step of removing the organic solvent, 3: before the step of thermosetting, from the viewpoint of improving the film hardness, 2 ′: including a step of curing the curable composition from which the organic solvent has been removed with light. It is preferable to include a step of curing the curable composition from which the solvent has been removed by overall exposure. Moreover, when it hardens | cures with light like the said aspect, it is preferable that the curable composition of this invention contains a photoinitiator.
In this case, it is preferable to perform energy exposure of about 50 to 3,000 mJ / cm ² with a mercury lamp or an LED (Light Emitting Diode) lamp.
Further, for pattern formation, pattern exposure and development processes can be performed after the process of 2: removing the organic solvent. The pattern exposure method is preferably a method using a mask or a direct drawing method using a laser or the like. It is preferable from the viewpoint of curing acceleration that the entire surface exposure and pattern exposure are performed in a state where oxygen is blocked. Examples of means for blocking oxygen include exposure in a nitrogen atmosphere and provision of an oxygen blocking film.
For pattern exposure and development, a known method or a known developer can be used. For example, the pattern exposure method and the development method described in JP 2011-186398 A and JP 2013-83937 A can be suitably used.

The cured film of the present invention is a cured film obtained by curing a film formed from the curable composition of the present invention, and is formed by removing at least a part of the organic solvent from the curable composition of the present invention. A cured film obtained by curing the film is preferred.
The cured film of the present invention can be suitably used as a protective film or an interlayer insulating film. Moreover, it is preferable that the cured film of this invention is a cured film obtained by the manufacturing method of the cured film of this invention.
The curable composition of the present invention provides a cured film having sufficient hardness even when cured at a low temperature. For example, a cured film having a pencil hardness of 3H or more at a load of 750 g measured according to JIS K5600: 1999 is obtained. It is done. Since the protective film formed by curing the curable composition of the present invention has excellent cured film properties, it is useful for applications of organic EL display devices, liquid crystal display devices, touch panels, and touch panel display devices.

  Since the curable composition of the present invention is excellent in curability and cured film properties, a cured product obtained by curing the curable composition of the present invention or a resist pattern is used as a partition as a structural member of a MEMS (Micro Electro Mechanical Systems) device. Or used as part of a mechanical drive component. Examples of such MEMS devices include SAW (Surface Acoustic Wave) filters, BAW (Bulk Acoustic Wave) filters, gyro sensors, micro shutters for displays, image sensors, electronic paper, inkjet heads, Examples include parts such as biochips and sealants. More specific examples are exemplified in JP-T-2007-522531, JP-A-2008-250200, JP-A-2009-263544, and the like.

  Since the curable composition of the present invention is excellent in flatness and transparency, for example, the bank layer (16) and the planarization film (57) described in FIG. 2 of JP2011-107476A, JP2010- The partition wall (12) and the planarization film (102) shown in FIG. 4A of 9793, and the bank layer (221) and the third interlayer insulating film (216b) shown in FIG. 10 of JP 2010-27591A. ), Second interlayer insulating film (125) and third interlayer insulating film (126) described in FIG. 4A of JP-A-2009-128577, and flatness described in FIG. 3 of JP-A-2010-182638. It can also be used to form a chemical film (12), a pixel isolation insulating film (14), and the like. In addition, spacers for keeping the thickness of the liquid crystal layer in the liquid crystal display device constant, color filters for the liquid crystal display device, color filter protective films, facsimiles, electronic copying machines, imaging of on-chip color filters such as solid-state image sensors It can also be suitably used for a microlens of an optical system or an optical fiber connector.

(Organic EL display device)
The organic EL display device of the present invention has the cured film of the present invention.
The organic EL display device of the present invention is not particularly limited except that it has a planarizing film and an interlayer insulating film formed using the curable composition of the present invention, and various known organic materials having various structures. An EL display device and a liquid crystal display device can be given.
For example, specific examples of the TFT included in the organic EL display device of the present invention include amorphous silicon-TFT, low-temperature polysilicon-TFT, oxide semiconductor TFT, and the like. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.
FIG. 1 is a conceptual diagram of an example of an organic EL display device. A schematic cross-sectional view of a substrate in a bottom emission type organic EL display device is shown, and a planarizing film 4 is provided.
A bottom gate type TFT 1 is formed on a glass substrate 6, and an insulating film 3 made of Si ₃ N ₄ is formed so as to cover the TFT 1. A contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height: 1.0 μm) connected to the TFT 1 through the contact hole is formed on the insulating film 3. The wiring 2 is used to connect the TFT 1 with an organic EL element formed between the TFTs 1 or in a later process.
Further, in order to flatten the unevenness due to the formation of the wiring 2, a planarizing film 4 is formed on the insulating film 3 in a state where the unevenness due to the wiring 2 is embedded.
On the planarizing film 4, a bottom emission type organic EL element is formed. That is, the first electrode 5 made of ITO is formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7. The first electrode 5 corresponds to the anode of the organic EL element.
An insulating film 8 having a shape covering the periphery of the first electrode 5 is formed. By providing the insulating film 8, a short circuit between the first electrode 5 and the second electrode formed in the subsequent process is prevented. can do.
Further, although not shown in FIG. 1, a hole transport layer, an organic light-emitting layer, and an electron transport layer are sequentially deposited through a desired pattern mask, and then a first layer made of Al is formed on the entire surface above the substrate. An active matrix type in which two electrodes are formed, sealed by bonding using a sealing glass plate and an ultraviolet curable epoxy resin, and TFTs 1 for driving the organic EL elements are connected. An organic EL display device is obtained.

(Liquid crystal display device)
The liquid crystal display device of the present invention has the cured film of the present invention.
The liquid crystal display device of the present invention is not particularly limited except that it has a protective film, a planarizing film, and an interlayer insulating film formed using the curable composition of the present invention, and is known in various structures. A liquid crystal display device can be mentioned.
Further, liquid crystal driving methods that can be taken by the liquid crystal display device of the present invention include TN (Twisted Nematic) method, VA (Vertical Alignment) method, IPS (In-Plane-Switching) method, FFS (Fringe Field Switching) method, OCB (OCB) method. Optically Compensated Bend) method.
In the panel configuration, the cured film of the present invention can also be used in a COA (Color Filter on Array) type liquid crystal display device. For example, the organic insulating film (115) of Japanese Patent Laid-Open No. 2005-284291, -346054 can be used as the organic insulating film (212). Specific examples of the alignment method of the liquid crystal alignment film that can be taken by the liquid crystal display device of the present invention include a rubbing alignment method and a photo alignment method. Further, the polymer alignment may be supported by the PSA (Polymer Sustained Alignment) technique described in JP2003-149647A or JP2011-257734A.
Moreover, the curable composition of this invention and the cured film of this invention are not limited to the said use, but can be used for various uses. For example, in addition to a planarization film and an interlayer insulating film, it is suitable for a protective film, a spacer for keeping the thickness of a liquid crystal layer in a liquid crystal display device constant, a microlens provided on a color filter in a solid-state imaging device, etc. Can be used.

FIG. 2 is a conceptual cross-sectional view showing an example of the 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 the liquid crystal panel includes all pixels disposed between two glass substrates 14 and 15 having a polarizing film attached thereto. The elements of the TFT 16 corresponding to are arranged. Each element formed on the glass substrate is wired with an ITO transparent electrode 19 that forms a pixel electrode through a contact hole 18 formed in the cured film 17. On the ITO transparent electrode 19, an RGB color filter 22 in which a liquid crystal 20 layer and a black matrix are arranged is provided.
The light source of the backlight is not particularly limited, and a known light source can be used. For example, white LED, multicolor LED such as blue, red, and green, fluorescent lamp (cold cathode tube), organic EL, and the like can be mentioned.
Further, the liquid crystal display device can be a 3D (stereoscopic) type or a touch panel type. Further, a flexible type can also be used, and it is used as the second interlayer insulating film (48) described in JP2011-145686A or the interlayer insulating film (520) described in JP2009-258758A. Can do.

(Touch panel and touch panel display device)
The touch panel of the present invention is a touch panel having the cured film of the present invention.
The touch panel display device of the present invention is a touch panel display device having the cured film of the present invention, and is preferably a touch panel display device having the touch panel of the present invention.
As the touch panel of the present invention, any of known methods such as a resistive film method, a capacitance method, an ultrasonic method, and an electromagnetic induction method may be used. Among these, the electrostatic capacity method is preferable.

  As the touch panel type, a so-called in-cell type (for example, those described in FIGS. 5, 6, 7 and 8 of JP-T-2012-517051), a so-called on-cell type (for example, JP 2013-168125 A). 19 of the gazette, those described in FIGS. 1 and 5 of JP 2012-89102 A, OGS (One Glass Solution) type and TOL (Touch on lens) type (for example, JP 2013-892 A). No. 54727 and FIG. 2, FIG. 3, FIG. 4 and FIG. 5 of JP-A-2015-15042, and other configurations (for example, JP-A-2013-164871) Various out-cell types (so-called GG, G1, G2, GFF, GF2, GF1, G1F, etc.) can be mentioned.

FIG. 3 is a conceptual diagram of an example of a liquid crystal display device having a touch panel function.
For example, the cured film of the present invention is preferably applied to the protective film between the layers in FIG. 3, and is also preferably applied to an interlayer insulating film that separates the detection electrodes of the touch panel. In addition, as a detection electrode of a touch panel, a transparent electrode (ITO (Indium Tin Oxide), IZO (Indium Tin Oxide, etc.)) or a metal electrode (silver, copper, molybdenum, titanium, aluminum, etc., or a laminate or alloy thereof) Or, it is preferable to be a laminate of these.
In FIG. 3, reference numeral 110 denotes a pixel substrate, 140 denotes a liquid crystal layer, 120 denotes a counter substrate, and 130 denotes a sensor unit. The pixel substrate 110 includes a polarizing plate 111, a transparent substrate 112, a common electrode 113, an insulating layer 114, a pixel electrode 115, and an alignment film 116 in order from the lower side of FIG. The counter substrate 120 includes an alignment film 121, a color filter 122, and a transparent substrate 123 in order from the lower side of FIG. The sensor unit 130 includes a retardation film 124, an adhesive layer 126, and a polarizing plate 127. In FIG. 3, reference numeral 125 denotes a sensor detection electrode. The cured film of the present invention includes an insulating layer (114) (also referred to as an interlayer insulating film) in the pixel substrate portion, various protective films (not shown), various protective films (not shown) in the pixel substrate portion, and a counter substrate portion. Can be used for various protective films (not shown), various protective films (not shown) for the sensor portion, and the like.

A known adhesive layer composition can be used for the adhesive layer 126 and the polarizing plate 127.
As specific examples of the polarizing plate and the adhesive layer, the polarizing plate with the adhesive layer described in Example 1, Example 7 and Example 13 of JP 2014-152319 A, Example 1 of JP 2014-191005 A, Polarizing plate with adhesive layer as described in Example 3 and Example 6, polarized light with adhesive layer as described in Example 1, Example 3, Example 6, Example 11 and Example 14 of JP2013-1000038 Examples thereof include the plate and the adhesive layers described in Example 1, Example 2, Example 3 and Example 4 of JP2013-163783A.
The adhesive layer preferably contains an antistatic agent for preventing static charge.
Known antistatic agents can be used. For example, metal particles, metal oxides, conductive polymers, and ionic compounds such as quaternary ammonium salts and lithium salts can be used.
Specific examples of the antistatic agent include those described in paragraphs 0107 to 0115 of JP 2014-191005 A, those described in paragraphs 0046 to 0054 of JP 2013-1003006 A, and special table 2014-515046. And those described in paragraphs 0027 to 0047 of the publication.

  In addition, a statically driven liquid crystal display device can display a pattern with high designability by applying the present invention. As an example, the present invention can be applied as an insulating film of a polymer network type liquid crystal as described in JP-A No. 2001-125086.

FIG. 4 is a conceptual diagram of the configuration of another example of a liquid crystal display device having a touch panel function.
A lower display panel 200 corresponding to a thin film transistor display panel provided with a thin film transistor (TFT) 440, and a color filter display panel provided with a plurality of color filters 330 on the surface facing the lower display panel 200 and facing the lower display panel 200. And the liquid crystal layer 400 formed between the lower display panel 200 and the upper display panel 300. The liquid crystal layer 400 includes liquid crystal molecules (not shown).

The lower display panel 200 is disposed on the first insulating substrate 210, the thin film transistor (TFT) disposed on the first insulating substrate 210, the insulating film 280 formed on the upper surface of the thin film transistor (TFT), and the insulating film 280. A pixel electrode 290 is included. The thin film transistor (TFT) may include a gate electrode 220, a gate insulating film 240 covering the gate electrode 220, a semiconductor layer 250, ohmic contact layers 260 and 262, a source electrode 270, and a drain electrode 272.
A contact hole 282 is formed in the insulating film 280 so that the drain electrode 272 of the thin film transistor (TFT) is exposed.

  The upper display panel 300 is disposed on one surface of the second insulating substrate 310, on the light shielding members 320 arranged in a matrix, the alignment film 350 disposed on the second insulating substrate 310, and the alignment film 350. A color filter 330 to be disposed, and a common electrode 370 disposed on the color filter 330 and corresponding to the pixel electrode 290 of the lower display panel 200 to apply a voltage to the liquid crystal layer 400 are included.

In the liquid crystal display device illustrated in FIG. 4, a sensing electrode 410, an insulating film 420, a driving electrode 430, and a protective film 280 are disposed on the other surface of the second insulating substrate 310. As described above, in the manufacture of the liquid crystal display device shown in FIG. 4, when the upper display panel 300 is formed, the sensing electrode 410, the insulating film 420, the drive electrode 430, and the like, which are constituent elements of the touch screen, are formed together. be able to. In particular, a cured film obtained by curing the curable composition of the present invention can be suitably used for the insulating film 420.
A polarizing plate with an adhesive layer or an adhesive layer exemplified for the adhesive layer 126 and the polarizing plate 127 can be attached to the protective film 280.

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

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

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

(Component A: ethylenically unsaturated compound)
<Synthesis Example 1: Synthesis of (a-1) -1>
50.4 parts of hexamethylene diisocyanate trimer (manufactured by Asahi Kasei Co., Ltd., TPA-100) was mixed in a toluene solvent, and U-CAT SA 102 (diazabicycloundecene (DBU) -octylate as a curing catalyst. 0.15 part of San Apro Co., Ltd.) was added and heated at 60 ° C. for 1 hour in a nitrogen atmosphere. A solution prepared by dissolving 157.4 parts of dipentaerythritol pentaacrylate (manufactured by Aldrich Co., Ltd.) in a toluene solvent was added dropwise and heated at 60 ° C. for 5 hours in a nitrogen atmosphere.
After allowing to cool, the reaction mixture was purified and separated by silica gel column chromatography to obtain (a-1) -1. The weight average molecular weight measured by gel permeation chromatography (GPC) of the obtained (a-1) -1 was 15,300.

<Synthesis Example 2: Synthesis of (a-1) -2>

A mixed solution of 2-isocyanatoethyl methacrylate (116.4 parts) and propylene glycol monomethyl ether acetate (PGMEA, 135.8 parts) was heated to 70 ° C. under a nitrogen stream. While stirring this mixed solution, radical polymerization initiator V-65 (trade name, 2,2′-azobis (2,4-dimethylvaleronitrile), manufactured by Wako Pure Chemical Industries, Ltd., 4 parts) and PGMEA ( 135.8 parts) was added dropwise over 2 hours. After completion of dropping, the reaction was carried out at 70 ° C. for 4 hours.
To the obtained polymer, 87.1 parts of 2-hydroxyethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and 0.3 part of p-methoxyphenol (manufactured by Wako Pure Chemical Industries, Ltd.), U-CAT 0.2 parts of SA 102 (manufactured by San Apro Co., Ltd.) was added and heated at 60 ° C. for 6 hours to obtain (a-1) -2.
The weight average molecular weight measured by gel permeation chromatography (GPC) of the obtained (a-1) -2 was 30,000.

<Synthesis Example 3: Synthesis of (a-1) '-3>

In Synthesis Example 2, the amount of the polymerization initiator V-65 was changed to 8 parts, and the amount of PGMEA was both 232.7 parts. 1) '-3 was obtained.
The weight average molecular weight measured by gel permeation chromatography (GPC) of the obtained (a-1) ′-3 was 8,000.

<Synthesis Example 4: Synthesis of (a-2) -1>

50.4 parts of hexamethylene diisocyanate trimer (Asahi Kasei Co., Ltd., TPA-100) and 157.4 parts of dipentaerythritol pentaacrylate (Aldrich manufactured by column purification) were used in a toluene solvent. After mixing, 0.2 part of U-CAT SA 102 (manufactured by San Apro) was added as a curing catalyst and heated at 60 ° C. for 6 hours in a nitrogen atmosphere.
After allowing to cool, the reaction mixture was purified and separated by silica gel column chromatography to obtain (a-2) -1.

<Synthesis Example 5: Synthesis of (a-2) -2>

  (A-2) -2 was obtained by synthesizing and purifying in the same manner as in Synthesis Example 4 except that the hexamethylene diisocyanate trimer in Synthesis Example 4 was changed to hexamethylene diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.). .

<Synthesis Example 6: Synthesis of (a-2) -3>

  (A-2)-The synthesis and purification were performed in the same manner as in Synthesis Example 5 except that dipentaerythritol pentaacrylate in Synthesis Example 5 was changed to pentaerythritol triacrylate (Aldrich was used after column purification). 3 was obtained.

<Synthesis Example 7: Synthesis of (a-2) '-4>

  (A-2) ′-4 was synthesized and purified in the same manner as in Synthesis Example 4 except that dipentaerythritol pentaacrylate in Synthesis Example 4 was changed to 2-hydroxyethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.). Obtained.

<Urethane (meth) acrylate>
(A-1) -1: Urethane acrylate prepared in Synthesis Example 1, Mw: 15,300, number of functional groups: many, having a constitutional repeating unit represented by the formula Aa-1.
(A-1) -2: The urethane acrylate produced in Synthesis Example 2, Mw: 30,000, the number of functional groups: many, and the structural repeating unit represented by the formula Aa-2.
(A-1) ′-3: Urethane acrylate prepared in Synthesis Example 3, Mw: 8,000, number of functional groups: many, having a constitutional repeating unit represented by the formula Aa-2.
(A-2) -1: Urethane acrylate produced in Synthesis Example 4, molecular weight: 2,078, number of functional groups: 15
(A-2) -2: Urethane acrylate produced in Synthesis Example 5, molecular weight: 1,218, number of functional groups: 10
(A-2) -3: Urethane acrylate produced in Synthesis Example 6, molecular weight: 764, number of functional groups: 6
(A-2) ′-4: Urethane acrylate produced in Synthesis Example 7, molecular weight: 853, number of functional groups: 3

<Ethylenically unsaturated compounds other than urethane (meth) acrylate>
A-1: Dipentaerythritol hexaacrylate A-2: Dipentaerythritol pentaacrylate A-3: Pentaerythritol tetraacrylate A-1 to A-3 are all used after purification by Aldrich. did.

(Component B: Polymerization initiator)
B-1: Compound represented by the following formula B-1, oxime ester compound

B-2: IRGACURE OXE01 (manufactured by BASF), oxime ester compound, following structure B-3: IRGACURE OXE02 (manufactured by BASF), oxime ester compound, following structure B-4: IRGACURE 907 (manufactured by BASF), aminoalkyl Phenone compound, 2-methyl-4 '-(methylthio) -2-morpholinopropiophenone

(Component C: Blocked isocyanate compound)
C-1: Takenate B870N (oxime block of isophorone diisocyanate, solid concentration 60%, manufactured by Mitsui Chemicals, Inc.)
C-2: Duranate 17B-60P (block isocyanate compound whose parent structure has biuret structure and block structure is oxime ester structure, solid concentration 60%, manufactured by Asahi Kasei Chemicals Corporation)
C-3: Duranate SBB-70P (block isocyanate compound having a base structure of biuret structure and a block structure of 1,3-dimethylpyrazole skeleton, solid content concentration 70%, manufactured by Asahi Kasei Chemicals Co., Ltd.) PGMEA Diluted to a solid content of 60%.
C-4: Desmodur VPLS2078 / 2 (block isocyanate compound whose block structure is ε-caprolactam structure, solid content concentration 60%, manufactured by Sumika Bayer Urethane Co., Ltd.)
C-5: Coronate AP stable M (block isocyanate compound whose block structure is a phenol structure, solid content concentration 100%, manufactured by Tosoh Corporation) is diluted with PGMEA to prepare a solid content concentration of 60%.
C-6: PGMEA solution having a solid content concentration of 60% of the compound represented by the following formula C-6 C-7: PGMEA solution having a solid content concentration of 60% of the compound having the structure represented by the following formula C-7

(Component D: Organic solvent)
D-1: Propylene glycol monomethyl ether acetate (manufactured by Daicel Corporation)
D-2: Methyl ethyl diglycol (manufactured by Nippon Emulsifier Co., Ltd.)
D-3: 1,3-butylene glycol diacetate D-4: Tetrahydrofurfuryl alcohol

(Component E: Inorganic particles)
E-1: PMA-ST (manufactured by Nissan Chemical Industries, Ltd.), silica particles, average particle size of 10-15 nm, solid content concentration of 30%)
E-2: MIBK-ST-L (manufactured by Nissan Chemical Industries, Ltd.), silica particles, average particle size of 40 to 50 nm, solid content concentration of 30%)
E-3: Nano-use OZ-S30K-AC (zirconium oxide particles, manufactured by Nissan Chemical Industries, Ltd., solid content concentration 30%)

(Component F: alkoxysilane compound)
S-1: KBM-403 (3-glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.)
S-2: KBM-5103 (3-acryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.)

(Component H: Mercapto compound)
S-3: Karenz MT-PE-1 (pentaerythritol tetrakis (3-mercaptobutyrate), manufactured by Showa Denko KK), functional group number 4
S-4: Karenz MT-BD-1 (1,4-bis (3-mercaptobutyryloxy) butane, manufactured by Showa Denko KK), functional group number 2

(Epoxy compound)
S-5: JER157S65 (manufactured by Mitsubishi Chemical Holdings Corporation)

(Component W: Surfactant)
W-1: Megafax F554 (manufactured by DIC Corporation), fluorine-based surfactant W-2: FTX-218 (manufactured by Neos Corporation), fluorine-based surfactant

(Sensitizer)
I-1: DBA (dibutoxyanthracene having the following structure) (manufactured by Kawasaki Kasei Kogyo Co., Ltd.)

(In the formula, Bu represents a butyl group.)

(Antioxidant)
J-1: ADK STAB AO-60 (hindered phenol-based antioxidant, manufactured by ADEKA Corporation)
J-2: ADK STAB LA-52 (hindered amine system, manufactured by ADEKA Corporation)

(Polymerization inhibitor)
K-1: Phenothiazine (manufactured by Tokyo Chemical Industry Co., Ltd.)

<Synthesis of Compound B-1>
[Synthesis of Compound A]
Ethylcarbazole (100.0 g, 0.512 mol) was dissolved in 260 ml of chlorobenzene, and after cooling to 0 ° C., aluminum chloride (70.3 g, 0.527 mol) was added. Subsequently, o-toluoyl chloride (81.5 g, 0.527 mol) was added dropwise over 40 minutes, the temperature was raised to room temperature (25 ° C., the same applies hereinafter), and the mixture was stirred for 3 hours. Next, after cooling to 0 ° C., aluminum chloride (75.1 g, 0.563 mol) was added. 4-Chlorobutyryl chloride (79.4 g, 0.563 mol) was added dropwise over 40 minutes, and the mixture was warmed to room temperature and stirred for 3 hours. A mixed solution of 156 ml of 35 mass% hydrochloric acid aqueous solution and 392 ml of distilled water was cooled to 0 ° C., and the reaction solution was added dropwise. The precipitated solid was subjected to suction filtration, washed with distilled water and methanol, and recrystallized from acetonitrile to obtain Compound A having the following structure (yield 164.4 g, yield 77%).

[Synthesis of Compound B]
Compound A (20.0 g, 47.9 mmol) obtained above was dissolved in 64 ml of tetrahydrofuran (THF), and 4-chlorobenzenethiol (7.27 g, 50.2 mmol) and sodium iodide (0.7 g, 4. 79 mmol). Subsequently, sodium hydroxide (2.0 g, 50.2 mmol) was added to the reaction solution, and the mixture was refluxed for 2 hours. Next, after cooling to 0 ° C., SM-28 (11.1 g, 57.4 mmol, sodium methoxide 28% methanol solution, manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise over 20 minutes, and the temperature was raised to room temperature. And stirred for 2 hours. Next, after cooling to 0 ° C., isopentyl nitrite (6.73 g, 57.4 mmol) was added dropwise over 20 minutes, and the mixture was warmed to room temperature and stirred for 3 hours. The reaction solution was diluted with 120 ml of acetone and added dropwise to a 0.1N hydrochloric acid aqueous solution cooled to 0 ° C. The precipitated solid was subjected to suction filtration and washed with distilled water. Subsequently, recrystallization was performed with acetonitrile to obtain a compound B having the following structure (yield: 17.0 g, yield: 64%).

[Synthesis of Compound B-1]
Compound B (18.0 g, 32.4 mmol) was dissolved in 90 ml N-methylpyrrolidone (NMP) and triethylamine (Et ₃ N, 3.94 g, 38.9 mmol) was added. Next, after cooling to 0 ° C., acetyl chloride (AcCl, 3.05 g, 38.9 mmol) was added dropwise over 20 minutes, and then the mixture was warmed to room temperature and stirred for 2 hours. The reaction solution was added dropwise to 150 ml of distilled water cooled to 0 ° C., and the precipitated solid was subjected to suction filtration, washed with 200 ml of isopropyl alcohol cooled to 0 ° C., dried, and then compound B-1 (yield 19.5 g, yield). 99%).

Moreover, the structure of obtained compound B-1 was identified by NMR.
¹ H-NMR (400 MHz, CDCl ₃ ) δ = 8.86 (s, 1H), 8.60 (s, 1H), 8.31 (d, 1H, J = 8.0 Hz), 8.81 (d , 1H, J = 8.0 Hz), 7.51-7.24 (m, 10H), 7.36 (q, 2H, 7.4 Hz), 3.24-3.13 (m, 4H), 2 .36 (s, 3H), 2.21 (s, 3H), 1.50 (t, 3H, 7.4 Hz).

(Examples 1 to 29 and Comparative Examples 1 to 5)
<Preparation of curable composition>
As shown in Tables 1 to 4 below, each component was mixed and stirred to form a solution and / or dispersion of an organic solvent, and filtered through a polytetrafluoroethylene filter having a pore size of 0.3 μm to cure the present invention. Sex composition was obtained. The unit of each numerical value described in the following Tables 1 to 4 is part by mass except for the ratio of component A in the total organic solid content and the ratio of component A to the total solid content. Moreover, mass parts of solid content conversion are shown except a block isocyanate compound, an inorganic particle, and an organic solvent. About a block isocyanate compound and an inorganic particle, the mass part of the solution of the said solid content concentration is shown. In addition, "-" in a table | surface has shown that the applicable compound is not contained.

<Evaluation of pencil hardness>
Each curable composition prepared above was spin-coated on a glass substrate on which ITO was formed, and prebaked at 90 ° C. for 120 seconds to obtain a coating film having a thickness of 3.0 μm. Next, irradiation with light of 500 mJ / cm ² (i-line conversion) was performed with a high-pressure mercury lamp, and further, baking was performed in an oven at 120 ° C. for 60 minutes to prepare a cured film.
The obtained cured film was subjected to a pencil hardness test by a method (load 750 g) based on JIS K5600: 1999 to evaluate the film strength and adhesion. A, B, and C are practical ranges.
A: 6H or more B: 5H
C: 3-4H
D: 2H or less or film was peeled off

<Evaluation of relative dielectric constant after high temperature and high humidity test>
Each photosensitive resin composition was spin-coated on a bare wafer substrate (N-type low resistance) (manufactured by SUMCO), then pre-baked on a hot plate at 90 ° C. for 120 seconds to volatilize the solvent, and the film thickness was 0.5 μm. A photosensitive resin composition layer was formed. Subsequently, exposure was performed using an ultra-high pressure mercury lamp so that the integrated irradiation amount was 500 mJ / cm ² (energy intensity: 20 mW / cm ² , i-line), and the substrate was heated in an oven at 120 ° C./60 minutes. With respect to this cured film, the relative dielectric constant was measured at a measurement frequency of 1 MHz using CVmap92A (made by Four Dimensions Inc.).
Thereafter, this cured film was placed in a thermostatic bath at a temperature of 60 ° C. and a humidity of 90% for 24 hours, and then taken out. Then, the relative dielectric constant was measured at a measurement frequency of 1 MHz using CVmap92A (made by Four Dimensions Inc.).
The smaller the change in the relative permittivity before and after the introduction of the thermostat, the better, and A and B are practical ranges.
A: Change in relative permittivity is less than 0.3 B: Change in relative permittivity is 0.3 or more and less than 0.5 C: Change in relative permittivity is 0.5 or more

  As is apparent from Tables 1 to 4 above, the curable composition of the present invention has high hardness even when cured at low temperature, and has a dielectric constant after being exposed to high temperature and high humidity conditions. It was excellent in suppressing rate change.

(Example 30)
<Production of display device>
In the display device shown in FIG. 4, the curable compositions obtained in Examples 1 to 29 were respectively used for forming the touch detection electrode protective film (insulating film, 420), and display devices were respectively produced. Specifically, the protective film (420) is obtained by applying the curable composition obtained in each example by inkjet, pre-baking at 90 ° C. for 120 seconds, and 500 mJ / cm ² (i-line conversion) with a high-pressure mercury lamp. It was formed by performing light irradiation of and further baking at 120 ° C. for 60 minutes in an oven. The other part of the display device was manufactured according to the manufacturing method described in FIG. 19 in JP 2013-168125 A. All of the manufactured display devices were excellent in display performance and touch detection performance.
Moreover, although the produced display apparatus was stored for 500 hours on the conditions of high temperature and humidity (temperature 60 degreeC, humidity 90%), all had no problem in subsequent display performance and touch detection performance.

  1: TFT (thin film transistor), 2: wiring, 3: insulating film, 4: flattening film, 5: first electrode, 6: glass substrate, 7: contact hole, 8: insulating film, 10: liquid crystal display device, 12 : Backlight unit, 14, 15: Glass substrate, 16: TFT, 17: Cured film, 18: Contact hole, 19: ITO transparent electrode, 20: Liquid crystal, 22: Color filter, 110: Pixel substrate, 111: Polarizing plate 112: transparent substrate, 113: common electrode, 114: insulating layer, 115: pixel electrode, 116: alignment film, 120: counter substrate, 121: alignment film, 122: color filter, 123: transparent substrate, 124: phase difference Film: 126: Adhesive layer, 127: Polarizing plate, 130: Sensor part, 140: Liquid crystal layer, 200: Lower display panel, 210: First insulating substrate, 220: Gate electrode, 240 Gate insulating film, 250: semiconductor layer, 260, 262: ohmic contact layer, 270: source electrode, 272: drain electrode, 280: insulating film, 282: contact hole, 290: image electrode, 300: upper display panel, 310: Second insulating substrate, 320: light shielding member, 330: color filter, 350: alignment film, 370: common electrode, 400: liquid crystal layer, 410: sensing electrode, 420: insulating film, 430: drive electrode, 440: TFT

Claims (14)

As component A, an ethylenically unsaturated compound,
As component B, a polymerization initiator,
As component C, a blocked isocyanate compound, and
Component D contains an organic solvent,
Component A contains a pentafunctional or higher urethane (meth) acrylate,
The content of the pentafunctional or higher urethane (meth) acrylate is 20 to 100 parts by mass with respect to 100 parts by mass of the component A,
The pentafunctional or higher functional urethane (meth) acrylate includes a urethane (meth) acrylate having a weight average molecular weight of 10,000 or more, and a urethane (meth) acrylate having a molecular weight of 5,000 or less,
The curable composition wherein the urethane (meth) acrylate having a weight average molecular weight of 10,000 or more is a polymer having a constitutional repeating unit represented by the following formula Aa-1.

In Formula Aa-1, L ^{5 to} L ⁷ each independently represents a divalent linking group, and A represents a group having a (meth) acryloyl group.   The curable composition according to claim 1, further comprising inorganic particles as component E.   The curable composition of Claim 1 or 2 in which the component B contains an oxime ester compound.   The component C is a blocked isocyanate compound in which a compound selected from the group consisting of tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and multimers thereof is protected. The curable composition according to item.   The component C is a compound in which a block structure is formed by any of an oxime compound, a lactam compound, a phenol compound, an alcohol compound, an amine compound, an active methylene compound, or a pyrazole compound. The curable composition according to item.   The curable composition of any one of Claims 1-5 whose weight ratio of the component A and the component C is 100: 1-10: 1. 1: The process of apply | coating the curable composition of any one of Claims 1-6 on a board | substrate 2: The process of removing the organic solvent from the apply | coated curable composition 3: The process of thermosetting is included. A method for producing a cured film.   8. The method for producing a cured film according to claim 7, further comprising 2 ′: a step of curing the curable composition from which the organic solvent has been removed with light before the thermal curing step.   The cured film obtained by hardening | curing the film | membrane formed from the curable composition of any one of Claims 1-6.   The cured film according to claim 9, which is a protective film.   An organic EL display device comprising the cured film according to claim 9.   A liquid crystal display device comprising the cured film according to claim 9.   A touch panel having the cured film according to claim 9.   A touch panel display device comprising the cured film according to claim 9.