JPWO2015072534A1 - Curable composition, method for producing cured film, cured film, and display device - Google Patents

Abstract

A curable composition capable of obtaining a cured film having excellent adhesion to the substrate, surface roughness of the film, and touch panel characteristics under high temperature and high humidity, a cured film obtained by curing the curable composition, and production thereof It is an object of the present invention to provide a method and an organic EL display device and a liquid crystal display device having the cured film. The curable composition of the present invention comprises, as Component A, a polymerizable compound having an ethylenically unsaturated bond, Component B as a polymerization initiator, Component C as a blocked isocyanate compound, and Component D as an organic solvent. And component A contains 6 or more functional urethane (meth) acrylate, the ratio of the 6 or more functional urethane (meth) acrylate in component A is 70 to 100% by mass, and component A and component B And the total amount of component C is 85% by mass or more based on the total organic solid content of the curable composition.

Description

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

Flat panel displays such as liquid crystal display devices and organic EL 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.
As a conventional curable composition, the composition described in patent document 1 or 2 is known.

JP 2011-126921 A JP 2010-39475 A

  Problems to be solved by the present invention include a curable composition capable of obtaining a cured film excellent in adhesion to a substrate, surface roughness of the film surface, and touch panel characteristics under high temperature and high humidity, and the above curable composition It is providing the cured film which hardened the thing, its manufacturing method, and the organic electroluminescent display device and liquid crystal display device which have the said cured film.

The above-mentioned problems of the present invention have been solved by means described in the following <1>, <7>, <9>, <11> or <12>. It is described below together with <2> to <6>, <8> and <10> which are preferred embodiments.
<1> Component A contains a polymerizable compound having an ethylenically unsaturated bond, Component B contains a polymerization initiator, Component C contains a blocked isocyanate compound, and Component D contains an organic solvent, , Containing 6 or more functional urethane (meth) acrylate, the ratio of the 6 or more functional urethane (meth) acrylate in Component A is 70 to 100% by mass, and the sum of Component A, Component B and Component C is A curable composition characterized in that the amount is 85% by mass or more based on the total organic solid content of the curable composition;
<2> The curable composition according to <1>, wherein Component B contains an oxime ester compound,
<3> 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> or <2 > Curable composition as described in>
<4> Component C is a compound in which a block structure is formed of any one 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 <3 > The curable composition according to any one of
<5> The curable composition according to any one of <1> to <4>, wherein the weight ratio of Component A to Component C is 100: 1 to 10: 1.
<6> The curable composition according to any one of <1> to <5>, further containing inorganic particles,
<7> Step 1 is the step of applying the curable composition according to any one of <1> to <6> on the substrate, and Step 2 is to remove the organic solvent from the applied curable composition. A process for removing the solvent, and a process for curing the curable composition from which the organic solvent has been removed as a process 3 by light and / or heat.
<8> The curing step is a step of curing the curable composition from which the organic solvent has been removed with light, and further includes a heat treatment step of heat-treating a cured film obtained by curing the curable composition with light after the curing step. A method for producing a cured film according to <7>,
<9> A cured film obtained by curing 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>.

  According to the present invention, a curable composition capable of obtaining a cured film having excellent adhesion to a substrate, surface roughness of the film surface, and touch panel characteristics under high temperature and high humidity, the curable composition is cured. The cured film, the manufacturing method thereof, and the organic EL display device and liquid crystal display device having the cured film can 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 description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what does not have a substituent and what has a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In 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, “polymerizable compound having an ethylenically unsaturated bond” 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.

In the present invention, (Component A) the molecular weight of the polymerizable compound having an ethylenically unsaturated bond is measured by ESI-MS (electrospray ionization mass spectrometry). Moreover, about a polymer component, it is the weight average molecular weight of polystyrene conversion measured by the gel permeation chromatography when tetrahydrofuran (THF) is used as a solvent.
Note that (A) a polymerizable compound having an ethylenically unsaturated bond is measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent for compounds having a molecular weight of 5,001 or more. Polystyrene equivalent weight average molecular weight.

(Curable composition)
The curable composition of the present invention (hereinafter also simply referred to as “composition”) includes (Component A) a polymerizable compound having an ethylenically unsaturated bond, (Component B) a polymerization initiator, and (Component C) a blocked isocyanate. A component and (Component D) an organic solvent, Component A contains a hexafunctional or higher urethane (meth) acrylate, and the ratio of the above hexafunctional or higher urethane (meth) acrylate in Component A is 70. The total amount of Component A, Component B and Component C is 85% by mass or more in the total organic solid content of the curable composition.
The curable composition of the present invention further comprises (Component E) an alkoxysilane compound, (Component F) inorganic particles, (Component G) (meth) acrylic copolymer, (Component H) mercapto compound, (Component W) interface. Other components such as an activator may be included.

  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 is a composition in which the strength of the cured product is further increased by heat-treating the obtained cured product after polymerization by light.

(Component A) Polymerizable compound having an ethylenically unsaturated bond The curable composition of the present invention contains (Component A) a polymerizable compound having an ethylenically unsaturated bond.
Component A only needs to have an ethylenically unsaturated bond, and may be a low molecular weight compound, an oligomer, or a polymer.
The content of component A is preferably 40% by mass or more, more preferably 50% by mass or more, and further preferably 60% by mass or more, based on the total solid content of the curable composition. It is preferably 70% by mass or more. The upper limit is not particularly defined, but is preferably 99% by mass or less, and more preferably 95% by mass or less, for example. Moreover, when mix | blending the inorganic particle mentioned later in a composition, it is preferable that it is 80 mass% or less, and it is more preferable that it is 75 mass% or less. In addition, "solid content" in a curable composition represents the component except volatile components, such as an organic solvent.

<6 or more urethane (meth) acrylate>
Component A contains 6 or more functional urethane (meth) acrylates, and the ratio of the 6 or more functional urethane (meth) acrylate in Component A is 70 to 100% by mass, and 75 to 100% by mass. Is more preferable, 90-100 mass% is more preferable, and 95-100 mass% is still more preferable. The effect of this invention is more effectively exhibited as it is the said aspect.
The content of hexafunctional or higher urethane (meth) acrylate is preferably 40% by mass or more, more preferably 50% by mass or more, and 65% by mass with respect to the total solid content of the curable composition. The upper limit is not particularly defined, but it is preferably 95% by mass or less.
Further, the content of hexafunctional or higher urethane (meth) acrylate is preferably 60% by mass or more, more preferably 70% by mass or more, based on the total organic solid content of the curable composition. More preferably, it is 80 mass% or more, and it is especially preferable that it is 80-95 mass%. The total organic solid content means a solid content obtained by removing inorganic substances (such as inorganic particles) from the total solid content of the curable composition.
Moreover, 60 mass% or more of the organic solid content of a curable composition is preferable, as for content of 6 or more functional urethane (meth) acrylate, 70 mass% or more is more preferable, and 80 mass% or more is the most preferable. The organic solid content here means the solid content of the organic material excluding organic particles such as polymer particles, inorganic particles such as metal oxide particles, and pigment components such as organic inorganic pigments from the solid content of the composition. Means.
The number of (meth) acryloxy groups in the hexafunctional or higher-functional urethane (meth) acrylate is preferably 8 or more, more preferably 10 or more, and still more preferably 12 or more. The effect of this invention is more effectively exhibited as it is the said aspect.
The upper limit of the number of the (meth) acryloxy groups is not particularly limited, but is preferably 50 or less, more preferably 30 or less, and still more preferably 20 or less.
The curable composition of the present invention may contain only one type of hexafunctional or higher urethane (meth) acrylate, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

  The molecular weight of the hexafunctional or higher urethane (meth) acrylate is preferably 500 to 20,000, more preferably 650 to 6,000, and still more preferably 800 to 3,000, from the viewpoint of cured film hardness. The effect of this invention is more effectively exhibited as it is the said aspect. In addition, the molecular weight of hexafunctional or higher urethane (meth) acrylate is the number average molecular weight in terms of polystyrene of GPC when the molecular weight is 1,000 or more.

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

The hexafunctional 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 represented by the following formula (Ae-1). It is more preferable that the compound has at least a group. Further, the hexafunctional 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). It is more preferable that
Moreover, it is preferable that the said terminal part in 6 or more functional urethane (meth) acrylate is group represented by a following formula (Ae-1) or a formula (Ae-2).

  In formula (Ae-1) and formula (Ae-2), R each independently represents an acryloyl group or a methacryloyl group, and a wavy line represents a bonding position with another structure.

Moreover, it is preferable that hexafunctional or more urethane (meth) acrylate is a compound which has at least group represented by a following formula (Ac-1) or a formula (Ac-2), and is a following formula (Ac-1). It is more preferable that the compound has at least the group represented.
Moreover, the said core part in urethane (meth) acrylate more than hexafunctional is a following formula (Ac-1) or a formula (Ac-2) from a viewpoint of hardness, low temperature curability, adhesiveness, solvent resistance, and applicability | paintability. It is preferable that it is group represented.

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 the bonding position with another structure. Represents.
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.
In addition, the hexafunctional or higher functional urethane (meth) acrylate is represented by the group represented by the formula (Ac-1) or the formula (Ac-2), the formula (Ae-1), and the formula (Ae-2). Particularly preferred are compounds in which two or three groups selected from the group consisting of groups are bonded.

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

  Further, examples of the urethane (meth) acrylate having 6 or more functional groups that can be used in the present invention include urethane addition polymerizable compounds produced by using an addition reaction between an isocyanate and a hydroxyl group, and JP-A-51-37193. Urethane acrylates such as those described in Japanese Patent Publications, JP-B-2-32293 and JP-B-2-16765 are exemplified, and these descriptions are incorporated in the present specification.

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

<Other polymerizable compounds having an ethylenically unsaturated bond>
The curable composition of the present invention is a polymerizable compound having an ethylenically unsaturated bond other than hexafunctional or higher urethane (meth) acrylate (also referred to as “other polymerizable compounds having an ethylenically unsaturated bond”). It may be included but is preferably not included.
The polymerizable compound having an ethylenically unsaturated bond other than the hexafunctional or higher urethane (meth) acrylate may be a polymer (for example, a molecular weight of 2,000 or more) or a monomer (for example, a molecular weight of 2,000). Less than that, preferably a molecular weight of 100 or more and less than 2,000), and a monomer is preferred.
As the polymerizable compound having another ethylenically unsaturated bond, a (meth) acrylate compound is preferable. 2-6 are preferable and, as for the number of the functional groups 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 polymerizable compound having an ethylenically unsaturated bond, pentafunctional or lower urethane (meth) acrylate may be included. Examples of the pentafunctional or lower urethane (meth) acrylate include the following compounds.

When the curable composition of the present invention contains a polymerizable compound having an ethylenically unsaturated bond other than a hexafunctional or higher urethane (meth) acrylate, 0.1 to 20% by mass of the total solid content of the curable composition. It is preferable to contain in the range of 0.5-10 mass%, and it is more preferable to contain in the range of 1-5 mass%.
The curable composition of the present invention may contain only one type of polymerizable compound having an ethylenically unsaturated bond other than hexafunctional or higher urethane (meth) acrylate, and 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 (Component B) a polymerization initiator.
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 polymerization of a hexafunctional or higher urethane (meth) acrylate 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, oxime ester compounds and hexaarylbiimidazole compounds are preferable from the viewpoint of sensitivity, and oxime ester compounds are more preferable.

Examples of the oxime ester compound include compounds described in JP-A No. 2000-80068, JP-A No. 2001-233842, JP-T No. 2004-534797, JP-A No. 2007-231000, and JP-A No. 2009-134289. Can be used.
The oxime ester compound is preferably a compound represented by the following formula (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, and R ² represents a hydrogen atom or an alkyl group. Further, R ² may be bonded to an Ar group to form a ring.

Ar represents an aromatic group or a heteroaromatic group, and is preferably a group obtained by removing one hydrogen atom 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 alkyloxy 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 Groups are more preferred.
R ² represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or a substituted alkyl group, and more preferably a hydrogen atom, a substituted alkyl group that forms a ring with Ar, or a toluenethioalkyl group.

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

In Formula (3) to Formula (5), R ¹ represents an alkyl group, an aromatic group or an alkoxy group, X represents —CH ₂ —, —C ₂ H ₄ —, —O— or —S—, R ³ independently represents a halogen atom, R ⁴ are each independently an alkyl group, a phenyl group, an alkyl-substituted amino group, an arylthio group, an alkylthio group, an alkoxy group, an aryloxy group or a halogen atom, R ⁵ Represents a hydrogen atom, an alkyl group or an aryl group, R ⁶ represents an alkyl group, n1 and n2 each independently represents an integer of 0 to 6, and n3 represents an integer of 0 to 5.

R ¹ represents an alkyl group, an aromatic group or an alkoxy group, and a group represented by R ¹¹ —X′-alkylene group— (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) compounds include monoacylphosphine oxide compounds and bisacylphosphine oxide compounds. Specific examples include Irgacure 819, Darocur 4265, Darocur TPO, etc. manufactured by Ciba Specialty Chemicals. Can be mentioned.

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, benzoflavin, 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 (Component C) a blocked isocyanate compound.
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 may be any as long as it has two isocyanate groups in one molecule, and may be aliphatic, alicyclic or aromatic. Polyisocyanate may be used. For example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,3-trimethylene diisocyanate, 1,4-tetrazine Methylene 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 , Isocyanation of hydrogenated 1,3-xylylene diisocyanate, hydrogenated 1,4-xylylene diisocyanate, etc. A compound, a multimer thereof, and a prepolymer type skeleton compound derived from these compounds can be preferably used. 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, oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, or pyrazole compounds are preferable, oxime compounds and lactam compounds are more preferable, oxime compounds are more preferable, and methyl ethyl ketone oxime is more preferable. Particularly preferred.
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 Preferably BL1100, BL1265 MPA / X, BL3575 / 1, BL3272MPA, BL3370MPA, BL3475BA / SN, BL5375MPA, VPLS2078 / 2, BL4265SN, PL340, PL350, Sumidur BL3175 (above, manufactured by 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 included 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. More preferably, it is contained in the range, and more preferably in the range of 1 to 5% by mass.
Moreover, it is preferable that content of the block isocyanate compound in the curable composition of this invention contains in the range of 0.1-20 mass% with respect to the total organic solid content of a curable composition, 0.5-10 More preferably, it is contained in the range of 1% by mass, and more preferably in the range of 1-5% by 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 50: 1 to 10: 1, and 20: 1 to More preferably, it is 10: 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. 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 concentration 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) Alkoxysilane Compound The curable composition of the present invention preferably contains (Component E) an alkoxysilane compound. When the alkoxysilane compound is contained, 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. A silane coupling agent having an ethylenically unsaturated bond is preferred.
Examples of the silane coupling agent include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrialkoxysilane, γ-glycidoxypropyl dialkoxysilane, and γ-methacryloxypropyl. Trialkoxysilane, γ-methacryloxypropyl dialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, vinyltrialkoxysilane It is done. Of these, γ-methacryloxypropyltrialkoxysilane, γ-acryloxypropyltrialkoxysilane, vinyltrialkoxysilane, or γ-glycidoxypropyltrialkoxysilane is more preferable. These can be used alone or in combination of two or more.
Examples of commercially available products include KBM-403 and KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd.

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 F) Inorganic particles The curable composition of the invention preferably contains inorganic particles. By containing the inorganic particles, the hardness (strength) of the cured film becomes more excellent. Moreover, the adhesiveness to a board | substrate can be improved by containing an inorganic particle.
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 most 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 maximum outer diameter is taken as the particle diameter of the particle.
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 inorganic particles, Be, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Gd, Tb, Dy, Yb, Lu, Ti, Zr, Hf, Nb, Mo, W, Zn, B, Al Metal oxide particles containing atoms such as Si, Ge, Sn, Pb, Sb, Bi, and Te are preferable. Silicon oxide, titanium oxide, titanium composite oxide, zinc oxide, zirconium oxide, indium / tin oxide, antimony / Tin oxide is more preferable, silicon oxide, titanium oxide, titanium composite oxide, zirconium oxide is more preferable, silicon oxide or titanium oxide is the stability of particles, availability, hardness of the cured film, transparency, This is particularly preferable from the viewpoint of adjusting the refractive index.

As a silicon oxide, a silica is mentioned preferably and a silica particle is mentioned more preferably.
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 the inorganic particles is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and still more preferably 10 parts by mass or more per 100 parts by mass of the total solid content of the curable composition. 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 G) (Meth) acrylic copolymer The curable composition of the present invention may comprise (Component G) (meth) acrylic copolymer.
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 Examples include copolymers obtained by copolymerizing monomers such as methylaminoethyl (meth) acrylate and N, N-dimethylaminoethylacrylamide. These monomers may be copolymerized alone with 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 (Component H) a mercapto compound. 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 represents a heterocycle together with N═C—X ^S. Represents an atomic group to be formed.

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 An imino group having 1 to 20 carbon atoms, an ammonio group having 3 to 20 carbon atoms, a carboxy group, a sulfo group, an oxy group, a mercapto group, an alkylsulfinyl group having 1 to 20 carbon atoms, an arylsulfinyl group having 6 to 20 carbon atoms, carbon C 1-20 alkylthio group, C 6-20 arylthio group, C 1-20 ureido group, C 2-20 hetero 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.

  In addition, 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 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.
As the alkoxy group and aryloxy group in the formulas (II) to (V), 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, allyloxyethoxyethoxy group, phenoxy group, tolyloxy group, xylyloxy group, mesityloxy group, cumyloxy group, methoxyphenyloxy group, ethoxyphenyloxy group, chloro Eniruokishi group, bromophenyl group, acetyloxy group, benzoyloxy group, naphthyloxy group and the like.
The alkyl group in Formula (II)-Formula (V) is synonymous with the alkyl group represented by ^RS of formula (I), and its preferable range 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 the substituent can be introduced into the alkyl group or aryl group represented by R ^S in formula (I). These are the same as those listed as examples of the substituent.

In the formulas (II) to (V), n and m are preferably 0 from the viewpoint of solubility in an organic solvent.
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), they are a linear, branched, and cyclic alkyl group, As a carbon number range, 1-16 are preferable 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 above 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 —, and L ^1S represents an nS-valent linking group. NS represents an 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.
L ^1S which is an nS-valent linking group in formula (S-2) is, for example, a divalent linking group such as — (CH ₂ ) _mS — (mS represents an integer of 2 to 6), trimethylol A trivalent linking group such as an isocyanuric ring having three propane residues, — (CH ₂ ) _pS — (pS represents an integer of 2 to 6), a tetravalent linking group such as a pentaerythritol residue, And hexavalent linking groups such as a divalent linking group and 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.
As the surfactant that can be used in the present invention, for example, commercially available products such as MegaFuck F142D, F172, F173, F176, F177, F183, F479, F482, F554, and F780 are commercially available. F781, F781-F, R30, R08, F-472SF, BL20, R-61, R-90 (manufactured by DIC Corporation), Florard FC-135, FC-170C, FC-430, FC-431, Novec FC-4430 (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.

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

In formula (W), R ^W1 and R ^W3 each independently represent a hydrogen atom or a methyl group, R ^W2 represents a linear alkylene group having 1 to 4 carbon atoms, and R ^W4 represents a hydrogen atom or 1 carbon atom. Represents an alkyl group having 4 or less, L ^W represents an alkylene group having 3 to 6 carbon atoms, p and q are mass percentages representing a polymerization ratio, and p is a numerical value of 10% by mass to 80% by mass. Q represents a numerical value of 20% by mass to 90% by mass, r represents an integer of 1 to 18, and s represents an integer of 1 to 10.

The L ^W is preferably a branched alkylene group represented by the following formula (W-2). R ^W5 in formula (W-2) represents an alkyl group having 1 to 4 carbon atoms, and is preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability with respect to the coated surface. Two or three alkyl groups are more preferred.
The sum (p + q) of p and q in the formula (W) is preferably p + q = 100, that is, 100% by mass.
The weight average molecular weight (Mw) of the copolymer is more preferably from 1,500 to 5,000.

When blended, the content of the surfactant in the curable composition of the present invention is preferably 0.001 to 5.0 parts by mass with respect to 100 parts by mass in the total solid content of the curable composition. 01-2.0 mass parts is more preferable.
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.

<< 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 30% by mass, and the content of component F is 0 to 50% 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.

<Other ingredients>
If necessary, other components such as a plasticizer, a thermal acid generator, and an acid proliferating agent can be added to the curable composition of the present invention. 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.

(Hardened product and manufacturing method thereof)
The cured product of the present invention is a cured product obtained by curing the curable composition of the present invention. 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.
As the process 1, as the application process 2 for applying the curable composition of the present invention on the substrate, as the solvent removal process 3 as the solvent removing process 3 for removing the solvent from the applied curable composition, the curable composition from which the organic solvent has been removed. Curing Step for Curing the Composition with Light and / or Heat The method for producing a cured product of the present invention more preferably includes the following steps 1 to 4.

As step 1, as the coating step 2 for applying the curable composition of the present invention on the substrate, as the solvent removing step 3 for removing the organic solvent from the applied curable composition, the curing with the organic solvent removed As a curing process step 4 for curing the curable composition with light, a heat treatment step for heat-treating the cured product cured with light Further, the method for producing a cured product of the present invention is preferably a method for producing a cured film.

In the application step (1), the curable composition of the present invention is preferably applied onto a substrate to form a wet film containing a solvent. Before applying the curable composition to the substrate, the substrate can be cleaned such as alkali cleaning or plasma cleaning. Furthermore, the substrate surface can be treated with hexamethyldisilazane or the like after cleaning the substrate. By performing this treatment, the adhesiveness of the curable composition to the substrate tends to be improved.
Examples of the substrate include inorganic substrates, resins, and resin composite materials.
Examples of the inorganic substrate include glass, quartz, silicon, silicon nitride, and a composite substrate in which molybdenum, titanium, aluminum, copper, or the like is vapor-deposited on such a substrate.
The 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 Substrate made of synthetic resin such as aromatic ether, maleimide-olefin, cellulose, episulfide resin It is below. These substrates are rarely used in the above-described form, and usually, a multilayer laminated structure such as a TFT element is formed depending on the form of the final product.

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

  The coating method on the substrate is not particularly limited. For example, a 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.

In the solvent removal step (2), it is preferable to remove the solvent from the coated 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.

In the curing step (3), a polymerization initiating species is generated from the polymerization initiator by light and / or heat, polymerization is performed, and the curable composition from which the organic solvent has been removed is cured. In the step (3), it is preferably a step of curing at least by light.
The light irradiation means that can be used in the step (3) is not particularly limited as long as it can be cured, but a mercury lamp, a metal halide lamp, a light emitting diode (LED), a laser diode (LD), a gas / solid laser, and the like can be used. Can be mentioned.
Moreover, there is no restriction | limiting in particular as the exposure amount in a process (3), However, It is preferable that it is 50-3,000 mJ / cm < ² >.
Furthermore, in the present invention, after the step of (2) removing the solvent and before the step of (3) thermosetting, a step of exposing the entire surface from the viewpoint of improving the film hardness may be included. 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 lamp.
For pattern formation, (3) pattern exposure can be performed in the curing step, and (3) development step can be performed after the curing step. 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 promoting curing that the light irradiation such as the entire surface exposure and pattern exposure in the step (3) is 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.

In the step (3), the heating temperature when curing by heat is preferably 180 ° C. or lower, more preferably 150 ° C. or lower, and further preferably 130 ° C. or lower. The lower limit is preferably 80 ° C. or higher, more preferably 90 ° C. or higher.
The heating method is not particularly limited, and a known method can be used. For example, a hot plate, an oven, an infrared heater, etc. are mentioned.
The heating time is preferably about 1 to 30 minutes in the case of a hot plate, and is preferably about 20 to 120 minutes in other cases. Within this range, the substrate and the device can be cured without damage. From the viewpoint of shape adjustment after heating, the heating can be performed at a lower temperature at the beginning and later at a higher temperature (addition of a middle baking step. For example, heating at 90 ° C. for 30 minutes first and then heating at 120 ° C. for 30 minutes later) .

It is preferable that the manufacturing method of the hardened | cured material of this invention includes the process (heat treatment process, post-baking process) of heat-processing hardened | cured material after the said hardening process, The process of heat-treating the hardened | cured material hardened | cured by said (4) light. More preferably. The cured product obtained by curing the curable composition of the present invention can obtain a cured product with higher strength by performing a heat treatment.
As temperature of the said heat processing, it is preferable that it is 100 to 180 degreeC, and it is more preferable that it is 110 to 150 degreeC.
Moreover, there is no restriction | limiting in particular as time of the said heat processing, However, 1 minute-360 minutes are preferable, 10 minutes-240 minutes are more preferable, 30 minutes-120 minutes are still more preferable.
Moreover, the said heat processing may be performed continuously by hardening with light and / or heat, and may be performed sequentially.

The cured film of the present invention can be suitably used as a protective film or an interlayer insulating film.
By the curable composition of the present invention, a cured film having sufficient hardness can be obtained, for example, a cured film having a pencil hardness of 2H or more can be obtained. Since the protective film formed by curing the curable composition of the present invention is excellent in cured film properties, it is useful for applications in organic EL display devices and liquid crystal display devices.

  Since the curable composition of the present invention is excellent in curability and cured film properties, a resist pattern formed using the curable composition of the present invention is used as a partition as a structural member of a MEMS device. Used as part of it. Examples of such MEMS devices include parts such as SAW filters, BAW filters, gyro sensors, display micro shutters, image sensors, electronic paper, inkjet heads, 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 TFT (Thin-Film Transistor) 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 organic material in which two electrodes are formed and sealed by bonding using a sealing glass plate and an ultraviolet curable epoxy resin, and each organic EL element is connected to a TFT 1 for driving it. An EL display device is obtained.

<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.
For example, specific examples of TFT (Thin-Film Transistor) included in the liquid crystal 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.
In addition, as a liquid crystal driving method that the liquid crystal display device of the present invention can take, a TN (Twisted Nematic) method, a VA (Virtual Alignment) method, an IPS (In-Placed Switching) method, an FFS (Fringe Field Switching) method, an OCB (OCB) (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 JP-A-2005-284291, or JP-A-2005 -346054 can be used as the organic insulating film (212). Specific examples of the alignment method of the liquid crystal alignment film that the liquid crystal display device of the present invention can take include a rubbing alignment method and a photo alignment method. Further, the polymer orientation may be supported by a PSA (Polymer Sustained Alignment) technique described in JP-A Nos. 2003-149647 and 2011-257734.
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, a white LED, a multicolor LED such as blue, red, and green, a fluorescent lamp (cold cathode tube), and an organic EL can be used.
Further, the liquid crystal display device can be a 3D (stereoscopic) type or a touch panel type. Further, a flexible type can also be used, and it is used as the second interlayer insulating film (48) described in JP2011-145686A or the interlayer insulating film (520) described in JP2009-258758A. Can do.

As the touch panel type, a so-called in-cell type (for example, FIG. 5, FIG. 6, FIG. 7 and FIG. 8 of JP 2012-517051 A), a so-called on-cell type (for example, FIG. 14 of JP 2012-43394 A). 2 (b) of International Publication No. 2012/141148), OGS type, TOL type, and other configurations (for example, FIG. 6 of JP2013-164871A).
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 a 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, it is preferable that they are silver, copper, aluminum, titanium, molybdenum, and these alloys.
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.

  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 a 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, the light shielding members 320 arranged in a matrix, the color filter 330 disposed on the second insulating substrate 310, and the color filter 330. And a common electrode 370 for applying a voltage to the liquid crystal layer 400 corresponding to the pixel electrode 290 of the lower display panel 200.

  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.

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

<Synthesis Example 1> Synthesis of A-8 Hexamethylene diisocyanate trimer (TPA-100 manufactured by Asahi Kasei Co., Ltd.) 50.4 g and dipentaerythritol pentaacrylate (obtained by column purification from Aldrich) 157.4 g Were mixed in a toluene solvent, 0.2 g of U-CAT SA 102 (manufactured by San Apro) was added as a curing catalyst, and the mixture was heated at 60 ° C. for 6 hours in a nitrogen atmosphere.
After allowing to cool, the reaction mixture was purified by silica gel column chromatography and fractionated to obtain 15-functional urethane acrylate A-8.

<Synthesis Example 2> Synthesis of A-9 A 10-functional urethane acrylate A-9 was obtained.

<(Component A) polymerizable compound having an ethylenically unsaturated bond>
[6 or more functional urethane (meth) acrylates]
A-1: NK oligo U-15HA (manufactured by Shin-Nakamura Chemical Co., Ltd., 15 functional groups)
A-2: UA-306H (Kyoeisha Chemical Co., Ltd., functional group number 6)
A-3: Laromer UA-9050 (manufactured by BASF, 8 functional groups)
A-4: NK oligo U-10HA (manufactured by Shin-Nakamura Chemical Co., Ltd., 10 functional groups)
A-5: NK oligo U-10PA (manufactured by Shin-Nakamura Chemical Co., Ltd., 10 functional groups)
A-6: NK oligo U-2PPA (manufactured by Shin-Nakamura Chemical Co., Ltd., functional group number 2)
A-8: Compound synthesized according to Synthesis Example 1 (Synthetic product, 15 functional groups)
A-9: Compound synthesized according to Synthesis Example 2 (Synthetic product, functional group number 10)

[Other polymerizable compounds having an ethylenically unsaturated bond]
A-7: A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd., dipentaerythritol hexaacrylate, functional group number 6)

<(Component B) radical polymerization initiator>
B-1: Compound B-1 below (Synthetic product, oxime ester compound)
B-2: Irgacure 379 (manufactured by BASF), acetophenone compound

<(Component C) blocked isocyanate compound>
C-1: Compound C-1 below (Synthetic product, methyl ethyl ketone oxime protecting compound of isophorone diisocyanate)
C-2: Compound C-2 below (Synthetic product, methyl ethyl ketone oxime protecting compound of hexamethylene diisocyanate trimer)
C-3: Compound C-3 below (Synthetic product, methyl ethyl ketone oxime protecting compound of diphenylmethane diisocyanate)
C-4: Compound C-4 below (Synthetic product, ε-caprolactam protecting compound of hexamethylene diisocyanate trimer)

<(Component D) Organic solvent>
D-1: Propylene glycol monomethyl ether acetate (manufactured by Daicel Corporation)
D-2: Methyl ethyl diglycol (manufactured by Daicel Corporation)

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

<(Component F) inorganic particles>
F-1: PMA-ST (manufactured by Nissan Chemical Co., Ltd., silica fine particles, average particle size of 10 to 15 nm)
F-2: MIBK-ST-L (Nissan Chemical Co., Ltd., silica fine particles, average particle size 40-50 nm)

<(Component G) (Meth) acrylic copolymer>
G-1: Joncryl 67 (manufactured by BASF, styrene-acrylic acid copolymer)

<(Component H) mercapto compound>
H-1: Karenz MT-PE1 (manufactured by Showa Denko KK)
H-2: Mercaptobenzothiazole (manufactured by Tokyo Chemical Industry Co., Ltd.)
<(Component I) Other additives>
I-1: Irganox 1035 (manufactured by BASF)
I-2: Hydroquinone monomethyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.)

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

<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 filtered with suction, 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 filtered with suction 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 1-41 and Comparative Examples 1-8)
<Preparation of curable composition>
Examples 1 to 41 and Comparative Example 1 were prepared by mixing and stirring each component as described in Tables 1 to 4 to obtain a solvent solution, and filtering through a polytetrafluoroethylene filter having a pore size of 0.3 μm. Each of -8 curable compositions was obtained. The unit of each component of the following Table 1-Table 4 is a mass part except the ratio of the component A + component B + component C in organic solid content. Moreover, the mass part of solid content conversion is shown except an organic solvent.

(Membrane property evaluation)
<Evaluation of adhesion>
Each composition prepared above was spin-coated on a copper-deposited substrate and pre-baked at 100 ° C. for 120 seconds to obtain a coating film having a thickness of 2.0 μm. Next, light irradiation of 500 mJ / cm ² (i-line conversion) was performed with a high-pressure mercury lamp, and a cured film was prepared by baking in an oven at 125 ° C. for 60 minutes. About the obtained cured film, the crosscut test of 100 squares was done by the method based on JISK5600, and adhesiveness was evaluated.
Each composition prepared above was spin-coated on a substrate on which ITO was vapor-deposited, and a cured film produced under the same conditions as above was also subjected to a cross cut of 100 squares by a method in accordance with JIS K5600. Tests were conducted to evaluate adhesion. In the following evaluation, Conditions 1, 2, and 3 are practical ranges. The evaluation results are shown in Tables 5-6.
1: No peeling at all.
2: Slightly peels off, but peels off less than 2%.
3: The peeling rate is 2% or more and less than 5%.
4: The peeling rate is 5% or more and less than 15%.
5: The peeling rate is 15% or more.

<Evaluation of surface roughness>
Each composition prepared above was spin-coated on a copper substrate and pre-baked at 100 ° C. for 120 seconds to obtain a coating film having a thickness of 2.0 μm. Next, light irradiation of 500 mJ / cm ² (i-line conversion) was performed with a high-pressure mercury lamp, and a cured film was prepared by baking in an oven at 125 ° C. for 60 minutes. The surface of the cured film was observed with an optical microscope (Olympus Co., Ltd.) 500 times, and the surface condition was evaluated. In the following evaluation, 1, 2, and 3 are practical ranges. The evaluation results are shown in Tables 5-6.
1: No surface roughness is seen at all.
2: Surface roughness is seen in a very small part.
3: Surface roughness is scattered.
4: Surface roughness can be seen throughout.
5: Surface roughness and wrinkles are seen throughout.

[Touch panel characteristics evaluation]
<Evaluation of touch detectability under high temperature and high humidity>
A liquid crystal display device schematically shown in FIG. 4 was prepared using the compositions of the examples and comparative examples as protective films. Specifically, the protective film (insulating film, 420) was ink-jet coated with the curable composition obtained in each example of the present invention, pre-baked at 100 ° C. for 120 seconds, and 500 mJ / cm with a high-pressure mercury lamp. ² (i-line conversion) light irradiation was performed, and further, baking was performed in an oven at 125 ° C. for 60 minutes. The other part of the display device was manufactured according to Japanese Patent Laid-Open No. 2013-168125. After lighting for 1,000 hours under conditions of 60 ° C. and 85%, each part of the screen was touched to evaluate touch detection ability. 1, 2, and 3 are practical ranges. The evaluation results are shown in Tables 5-6.
1: Sensitive and accurate detection is possible anywhere on the screen.
2: Very rarely detected only at the edge of the screen.
3: Very rarely detected at the edge of the screen and at portions other than the edge.
4: Sometimes it cannot be detected at the edge of the screen.
5: Sometimes it is not possible to detect the screen edge and other parts than the edge.

  As is apparent from Tables 1 to 6, the cured film obtained by curing the curable composition of the present invention has adhesion to the substrate, surface roughness of the film surface, and touch panel under high temperature and high humidity. It was excellent in characteristics.

  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, 370: common electrode, 400: liquid crystal layer, 410: sensing electrode, 420: insulating film, 430: drive electrode, 440: TFT

Claims (12)

As component A, a polymerizable compound having an ethylenically unsaturated bond,
As component B, a polymerization initiator,
As component C, a blocked isocyanate compound, and
Component D contains an organic solvent,
Component A contains a hexafunctional or higher urethane (meth) acrylate,
The ratio of the hexafunctional or higher urethane (meth) acrylate in component A is 70 to 100% by mass,
A curable composition, wherein the total amount of component A, component B, and component C is 85% by mass or more based on the total organic solid content of the curable composition.   The curable composition of Claim 1 in which the component B contains an oxime ester compound.   The curing according to claim 1 or 2, wherein 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. Sex composition.   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 1-4 whose weight ratio of the component A and the component C is 100: 1-10: 1.   The curable composition according to any one of claims 1 to 5, further comprising inorganic particles. As the process 1, the process of apply | coating the curable composition of any one of Claims 1-6 on a board | substrate,
As step 2, a solvent removal step of removing the organic solvent from the applied curable composition, and
Step 3 includes a curing step of curing the curable composition from which the organic solvent has been removed by light and / or heat. The curing step is a step of curing with light the curable composition from which the organic solvent has been removed,
The manufacturing method of the cured film of Claim 7 which further includes the heat processing process which heat-processes the cured film which hardened the curable composition with light after the said hardening process.   The cured film formed by hardening | curing 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.

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