JP6517077B2 - Curable composition, cured film, organic EL display device, liquid crystal display device, touch panel and touch panel display device - Google Patents

Description

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

BACKGROUND Flat panel displays such as liquid crystal display devices and organic EL (Electroluminescence) display devices are widely used. Also, in recent years, with the spread of smartphones and tablet terminals, electrostatic capacitive touch panels have attracted attention. The sensor substrate of the capacitive touch panel includes a transparent electrode (ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), etc.) and a metal electrode (silver, copper, molybdenum, titanium, aluminum, etc.) on glass or film, and It is common to have a wiring in which the laminates and alloys thereof are patterned, and to have an insulating film, an ITO, and a protective film for protecting metal at intersections of the wirings.
As a curable composition used for such an insulating film or protective film, for example, Patent Document 1 discloses unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride, an epoxy group-containing radically polymerizable compound, and mono A thermosetting resin composition is disclosed, which is characterized in that a copolymer with an olefinically unsaturated compound is dissolved in an organic solvent.

Japanese Patent Application Laid-Open No. 6-157716

Recently, in the manufacturing process of these displays and the like, it is necessary to lower the heating temperature of various cured films in the manufacturing process from the viewpoint of reducing damage to substrates, circuits and the like, saving energy and the like.
However, the curable composition described in Patent Document 1 requires a heating temperature of 200 ° C. or more, and when cured at a low temperature (eg, 180 ° C. or less, further 150 ° C. or less), sufficient hardness is not obtained. .
The problem to be solved by the present invention is to provide a curable composition which is excellent in coatability and can obtain high hardness even when cured at low temperature.
In addition, another problem to be solved by the present invention is to provide a cured film obtained by curing the curable composition, and a liquid crystal display device, an organic EL display device, a touch panel and a touch panel display device having the cured film. It is.

The said subject of this invention was solved by the means as described in following <1>, <8> or <11>-<14>. It describes below with <2>-<7>, <9> and <10> which are preferable embodiment.
Component A includes an ethylenically unsaturated compound, a component B, a polymerization initiator, a component C, an alkoxysilane compound, a component D, an organic solvent, and a component E, inorganic particles; The content of the pentafunctional or higher urethane (meth) acrylate is 20 to 100 parts by mass with respect to 100 parts by mass of the component A, A curable composition characterized in that the functional or higher urethane (meth) acrylate comprises a urethane (meth) acrylate having a weight average molecular weight of 10,000 or more and a urethane (meth) acrylate having a molecular weight of 5,000 or less. ,
The curable composition as described in <1> in which <2> component B contains an oxime ester compound,
The curable composition as described in <1> or <2> in which <3> component A contains ethylenically unsaturated compounds other than the said urethane (meth) acrylate of 5 or more functions,
<4> The curable composition according to <3>, wherein the ethylenically unsaturated compound other than the pentafunctional or higher functional urethane (meth) acrylate is a polyfunctional ethylenically unsaturated compound,
The curable composition as described in any one of <1>-<4> whose content of <5> component A is 70 mass% or more with respect to the total organic solid content of a curable composition,
<6> The curing according to any one of <1> to <5>, wherein the pentafunctional or higher urethane (meth) acrylate contains two or more urethane (meth) acrylates having the molecular weight of 5,000 or less. Sex composition,
Any one of <1> to <6>, further including at least one selected from the group consisting of a compound having an epoxy group, a compound having an oxetanyl group, a blocked isocyanate compound, and a polyfunctional mercapto compound The curable composition according to
A cured film obtained by curing a film formed from the curable composition according to any one of <8><1> to <7>,
<9> The cured film according to <8>, which is a protective film
The cured film as described in <8> or <9> whose pencil hardness in load 750g measured according to <10> JIS K 5600: 1999 is 3H or more,
The organic electroluminescence display which has a cured film as described in any one of <11><8>-<10>,
The liquid crystal display device which has a cured film as described in any one of <12><8>-<10>,
The touch panel which has a cured film as described in any one of <13><8>-<10>,
The touch panel display device which has a cured film as described in any one of <14><8>-<10>.

ADVANTAGE OF THE INVENTION According to this invention, the curable composition which is excellent in applicability | paintability and can obtain high hardness even if it harden | cures at low temperature can be provided.
Moreover, according to the present invention, it is possible to provide a cured film obtained by curing the curable composition, and a liquid crystal display device, an organic EL display device, a touch panel and a touch panel display device having the cured film.

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

Hereinafter, the contents of the present invention will be described in detail. Although the description of the configuration requirements described below may be made based on the representative embodiments of the present invention, the present invention is not limited to such embodiments. In the specification of the present application, "-" is used in the meaning including the numerical values described before and after it as the lower limit value and the upper limit value. Moreover, the organic EL element in this invention means the thing of an organic electroluminescent element.
In the notation of groups (atomic groups) in the present specification, notations not describing substitution and non-substitution include those having no substituent as well as those having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present specification, “(meth) acrylate” represents acrylate and methacrylate, “(meth) acrylic” represents acrylic and methacrylic, and “(meth) acryloyl” represents acryloyl and methacryloyl.
In the present invention, "ethylenically unsaturated compound" and the like are also simply referred to as "component A" and the like.
Moreover, in the present invention, “mass%” and “weight%” are synonymous, and “mass part” and “part by weight” are synonymous.
In the present invention, a combination of two or more preferred embodiments is a more preferred embodiment.

  With regard to the molecular weight of the compound in the present invention, the low molecular weight compound capable of specifying the molecular weight is the molecular weight measured by ESI-MS (electrospray ionization mass spectrometry), and the compound having a molecular weight distribution is tetrahydrofuran (THF) It shall be a weight average molecular weight of polystyrene conversion measured by gel permeation chromatography (GPC) when using it as a solvent.

(Curable composition)
The curable composition of the present invention (hereinafter, also simply referred to as "composition") is, as component A, an ethylenically unsaturated compound, as component B, a polymerization initiator, as component C, an alkoxysilane compound, as component D , Organic solvent, and component E, which contains inorganic particles, component A contains urethane (meth) acrylate having five or more functional groups, and the content of urethane (meth) acrylate having five or more functional groups is the component A 20 to 100 parts by mass relative to 100 parts by mass of the urethane (meth) acrylate having a weight average molecular weight of 10,000 or more, and a molecular weight of 5,000 or less And urethane (meth) acrylate.
By including these components, it is possible to achieve both pencil hardness and coatability. The mechanism is presumed as follows. By using two kinds of urethane (meth) acrylates having different molecular weights, the compatibility with the alkoxysilane compound in the film after coating is improved. By curing the coating film, soft segments derived from urethane and hard segments derived from (meth) acrylate and alkoxysilane are uniformly present in the film, and damage prevention and load dispersion at pencil hardness measurement are performed. It is considered that the prevention of possible peeling can be achieved. In addition, when a composition comprising only a component having a high molecular weight is used when applied to a substrate having irregularities such as electrodes on the base, thickness unevenness of the coating film may occur along the irregularities, or the coated end In some cases, problems such as nonuniform liquid spreading may occur. On the other hand, even in the case where only the component having a low molecular weight is used, the spread of the solution at the coated end may become too large. Also, the hardness of the film may be degraded. It is estimated that it will become possible to solve the said subject by using the composition of this invention.
The curable composition of the present invention may further contain other components such as ethylenically unsaturated compounds other than pentafunctional or higher urethane (meth) acrylates, polyfunctional mercapto compounds, and / or blocked isocyanate compounds. Good.

Component A: Ethylenically Unsaturated Compound The curable composition of the present invention contains an ethylenically unsaturated compound as component A.
Moreover, the curable composition of this invention contains the urethane (meth) acrylate of 5 or more functions as an ethylenically unsaturated compound.
The ethylenically unsaturated compound in the present invention may have an ethylenically unsaturated bond, and may be a low molecular compound, an oligomer or a polymer.
The content of the ethylenically unsaturated compound is preferably 40% by mass or more, more preferably 50% by mass or more, and more preferably 60% by mass or more in the total organic solid content of the curable composition. Is more preferable, and 70% by mass or more is particularly preferable. The upper limit is not particularly limited, but is preferably 100% by mass or less, more preferably 99% by mass or less, still more preferably 98% by mass or less, particularly preferably 95% by mass or less preferable.
Moreover, when mix | blending the inorganic particle mentioned later, it is preferable that it is 80 mass% or less in the total solid of a curable composition, and, as for content of an ethylenically unsaturated compound, it is 75 mass% or less preferable. The lower limit value is preferably 20% by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, and particularly preferably 50% by mass or more. In addition, "solid content" in the curable composition represents a component excluding volatile components such as an organic solvent, and "organic solid content" in the curable composition represents an inorganic component such as inorganic particles, and It represents a component excluding volatile components such as an organic solvent.
In the present invention, an ethylenically unsaturated compound that corresponds to an alkoxysilane compound described later, that is, a compound having an alkoxysilyl group and an ethylenically unsaturated group is referred to as an alkoxysilane compound.
In the present invention, urethane (meth) acrylate is a compound having one or more urethane bonds and one or more (meth) acryloyloxy groups.

<Urethane (Meth) Acrylate with 5 or More Functionalities>
In the curable composition of the present invention, the content of the pentafunctional or higher urethane (meth) acrylate is 20 to 100 parts by mass and 20 to 69 parts by mass with respect to 100 parts by mass of the component A. Is preferred. The effect of the present invention is exhibited more effectively as it is the above-mentioned range.
The number of (meth) acryloyloxy groups in the pentafunctional or higher urethane (meth) acrylate is preferably 6 or more, more preferably 10 or more, and particularly preferably 12 or more. With such a configuration, the effects of the present invention are more effectively exhibited.
Further, the upper limit of the number of (meth) acryloyloxy groups is not particularly limited, but in the case of not having a polymer structure, it is preferably 50 or less, more preferably 30 or less, and 20 or less. Is more preferred.
The curable composition of the present invention may contain only one type of urethane (meth) acrylate having five or more functional groups, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.

  Examples of the pentafunctional or higher urethane (meth) acrylate that can be used in the present invention include urethane addition polymerizable compounds produced by using an addition reaction of an isocyanate and a hydroxyl group, as described in JP-A-51-37193. The urethane acrylates as described in JP-B-2-32293 and JP-B-2-16765 are exemplified, and these descriptions are incorporated in the present specification.

The (meth) acryloyloxy group in the urethane (meth) acrylate having five or more functional groups may be either an acryloyloxy group or a methacryloyloxy group, or both of them, but an acryloyloxy group is preferable.
The pentafunctional or higher urethane (meth) acrylate is preferably a pentafunctional or higher aliphatic urethane (meth) acrylate.
Moreover, it is preferable that the urethane (meth) acrylate having five or more functions has an isocyanuric ring structure.
Further, the urethane (meth) acrylate having five or more functional groups is a compound comprising a core portion having one or more urethane bonds and an end portion bonded to the core portion and having one or more (meth) acryloyloxy groups. It is more preferable that it is a compound which two or more said terminal parts couple | bonded with the said core part.

The pentafunctional or higher urethane (meth) acrylate is preferably a compound having at least a group represented by the following formula Ae-1 or Ae-2, and a compound having at least a group represented by the following formula Ae-1 It is more preferable that In addition, the urethane (meth) acrylate having five or more functional groups 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 following formula Ae-2 More preferable.
Moreover, it is preferable that the said terminal part in urethane (meth) acrylate of 5 or more functions is group represented by following formula Ae-1 or 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 portion represents a bonding position to another structure.

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

<< Urethane (Meth) Acrylate with a Weight Average Molecular Weight of 10,000 or More >>
The curable composition of the present invention contains, as a pentafunctional or higher functional urethane (meth) acrylate, a urethane (meth) acrylate having a weight average molecular weight of 10,000 or higher.
That is, the urethane (meth) acrylate having a weight average molecular weight of 10,000 or more is a urethane (meth) acrylate having a weight average molecular weight of 10,000 or more and having five or more functions.
10,000-100,000 are preferable and, as for the weight average molecular weight of urethane (meth) acrylate which is the said weight average molecular weight 10,000 or more, 10,000-50,000 are more preferable.
The urethane (meth) acrylate having a weight average molecular weight of 10,000 or more is preferably a polymer having a structural repeating unit represented by the following formula Aa-1 or Aa-2.

In formulas Aa-1 and Aa-2, L ^{5 to} L ⁸ each independently represent a divalent linking group, A represents a group having a (meth) acryloyl group, and R ^a is a hydrogen atom or carbon number Represents an alkyl group of 1 to 5;

L ^{5 to} L ⁸ are preferably each independently 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 preferred. The alkylene group may have a branch or ring structure, but is preferably a linear alkylene group.
It is preferable that A is a group represented by said Formula Ae-1 or Formula Ae-2.
R ^a is preferably ^a hydrogen atom or a methyl group.

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

L < ¹ > -L < ⁴ > respectively independently represents a C2-C20 bivalent hydrocarbon group in Formula Ac-1 and Formula Ac-2, and a wavy line part represents a coupling | bonding position with another structure.
L ^{1 to} L ⁴ are preferably each independently 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 preferred. The alkylene group may have a branch or ring structure, but is preferably a linear alkylene group.
The urethane (meth) acrylate having a molecular weight of 5,000 or less is represented by the group represented by Formula Ac-1 or Formula Ac-2, the group represented by Formula Ae-1, and Formula Ae-2. It is particularly preferable that it is a compound in which 2 or 3 groups selected from the group consisting of the represented groups are bonded.

  Although the urethane (meth) acrylate which is the said molecular weight 5,000 or less preferably used by this invention below is illustrated, it can not be overemphasized that this invention is not limited to these.

  Commercially available urethane (meth) acrylates having 5 or more functional groups include U-6HA, UA-1100H, U-6LPA, U-15HA, U-6H, U-10HA, available from Shin-Nakamura Chemical Co., Ltd. U-10PA, UA-53H, UA-33H (all are registered trademarks), UA-306H available from Kyoeisha Chemical Co., Ltd., UA-306T, UA-306I, UA-510H, available from BASF Examples include Laromer UA-9048, UA-9050, PR9052, EBECRYL 220, 5129, 8301 available from Daicel Ornex Co., KRM 8200, 8200 AE, 8452 and the like.

<Other Ethylenically Unsaturated Compounds>
The curable composition of the present invention may contain, as Component A, an ethylenically unsaturated compound (also referred to as “other ethylenically unsaturated compound”) other than a urethane (meth) acrylate having 5 or more functional groups.
As the ethylenically unsaturated compound other than the pentafunctional or higher urethane (meth) acrylate, even if it is a polymer (for example, a molecular weight of 2,000 or more), a monomer (for example, a molecular weight of less than 2,000, preferably The molecular weight may be 100 or more and less than 2,000, and a monomer is preferable.
The ethylenically unsaturated compound other than the pentafunctional or higher urethane (meth) acrylate is preferably a polyfunctional ethylenically unsaturated compound, and more preferably a 3 to 6 functional ethylenically unsaturated compound.
As the ethylenically unsaturated compound other than the pentafunctional or higher urethane (meth) acrylate, a (meth) acrylate compound is preferable. 2-15 are preferable and, as for the number of (meth) acryloyloxy groups of a (meth) acrylate compound, 3-6 are more preferable. With such a configuration, the effects of the present invention are more effectively exhibited.
Specifically, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri ((meth) acryloyloxyethyl) isocyanurate And trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate ethylene oxide (EO) modified product, and dipentaerythritol hexa (meth) acrylate EO modified product.
Moreover, as another ethylenic unsaturated compound, the urethane (meth) acrylate of tetrafunctional or less may be included.
The following compounds are illustrated as urethane (meth) acrylate of tetrafunctional or less.

When the curable composition of the present invention contains an ethylenically unsaturated compound other than a pentafunctional or higher urethane (meth) acrylate, the content of the ethylenically unsaturated compound other than the pentafunctional or higher urethane (meth) acrylate is cured Content is preferably in the range of 0.1 to 50% by mass, more preferably in the range of 0.5 to 40% by mass, and in the range of 1 to 25% by mass with respect to the total organic solid content of the composition It is further preferred that
The curable composition of the present invention may contain only one type of ethylenically unsaturated compound other than the urethane (meth) acrylate having five or more functional groups, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.

Component B: Polymerization Initiator The curable composition of the present invention contains a polymerization initiator as component B.
As a polymerization initiator, it is preferable to contain a radical polymerization initiator.
The radical polymerization initiator that can be used in the present invention is a compound capable of initiating and promoting the polymerization of the ethylenically unsaturated compound by light and / or heat. Among them, a photopolymerization initiator is preferable, and a photo radical polymerization initiator is more preferable.
The "light" is not particularly limited as long as it is an active energy ray capable of giving energy capable of generating a starting species from the component B by the irradiation, and a broad range of alpha rays, gamma rays, X rays, ultraviolet rays (UV), visible light, electron beam and the like. Among these, light containing at least ultraviolet light 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, and metallocenes. A compound, a hexaaryl biimidazole compound, an organic boric acid compound, a disulfonic acid compound, an onium salt compound, and an acyl phosphine (oxide) compound are mentioned. Among these, from the viewpoint of sensitivity, an oxime ester compound and / or a hexaarylbiimidazole compound are preferable, and an oxime ester compound is more preferable.

  As oxime ester compounds, JP-A-2000-80068, JP-A-2001-233842, JP-A-2004-534797, JP-A-2007-231000, JP-A-2009-134289, and International Publication The compounds described in paragraphs 0046 to 0059 of JP 2012/057165 can be used.

  As examples of organic halogenated compounds, specifically, Wakabayashi et al., "Bull Chem. Soc. Japan" 42, 2924 (1969), U.S. Pat. No. 3,905,815, Japanese Patent Publication No. 46-4605. JP-A-48-36281, JP-A-55-32070, JP-A-60-239736, JP-A-61-169835, JP-A-61-169837, JP-A 62-58241, JP-A-62-212401, JP-A-63-70243, JP-A-63-298339, M.I. P. The compounds described in Hutt “Journal of Heterocyclic Chemistry” 1 (No 3), (1970) and the like can be mentioned, and in particular, oxazole compounds and s-triazine compounds substituted with a trihalomethyl group can be mentioned.

  Examples of hexaarylbiimidazole compounds include, for example, each of Japanese Patent Publication No. 6-29285, US Patent Nos. 3,479,185, 4,311,783, and 4,622,286. It includes various compounds described in the specification.

  Examples of the acyl phosphine (oxide) compound include monoacyl phosphine oxide compounds and bisacyl phosphine oxide compounds, and specific examples thereof include IRGACURE 819, DAROCURE 4265, DAROCURE TPO and the like manufactured by BASF.

The polymerization initiator can be used alone or in combination of two or more.
It is preferable that it is 0.5-30 mass% with respect to the total solid in a curable composition, and, as for the total amount of the photoinitiator in the curable composition of this invention, it is 1-20 mass%. Is more preferable, 1 to 10% by mass is further preferable, and 2 to 5% by mass is particularly preferable.

<Sensitizer>
A sensitizer may be added to the curable composition of the present invention in addition to the polymerization initiator.
Typical sensitizers that can be used in the present invention include Crivero [J. V. Crivello, Adv. in Polymer Sci. , 62, 1 (1984)], and specifically, pyrene, perylene, acridine orange, thioxanthone, 2-chlorothioxanthone, benzoflavin, N-vinylcarbazole, 9, 10-di Examples include butoxyanthracene, anthraquinone, coumarin, ketocoumarin, phenanthrene, camphorquinone, and phenothiazine derivatives. The sensitizer is preferably added in a proportion of 50 to 200 parts by mass with respect to 100 parts by mass of the content of the polymerization initiator.

Component C: Alkoxysilane Compound The curable composition of the present invention contains an alkoxysilane compound as Component C. When the alkoxysilane compound is used, the coating property and the hardness of the obtained cured film are excellent, and the adhesion between the film formed of the curable composition of the present invention and the substrate can be improved.
The alkoxysilane compound is not particularly limited as long as it is a compound having at least a group in which an alkoxy group is directly bonded to a silicon atom, but a compound having a dialkoxysilyl group and / or a trialkoxysilyl group is preferable. It is more preferable that it is a compound having a trialkoxysilyl group.
Moreover, as an alkoxysilane compound, the alkoxysilane compound which has an ethylenically unsaturated group and / or an epoxy group like the silane coupling agent mentioned later is preferable.
The alkoxysilane compound which can be used for the curable composition of the present invention is a base material, for example, silicon compounds such as silicon compounds such as silicon oxide and silicon nitride, metals such as gold, copper, molybdenum, titanium and aluminum, and insulating films It is preferable that it is a compound which improves the adhesiveness of the above. Specifically, known silane coupling agents are also effective. It is preferable to use a silane coupling agent having an ethylenically unsaturated group, because it is particularly excellent in adhesion to ITO. In addition, when a silane coupling agent having an epoxy group is used, the reliability is excellent.
As a silane coupling agent, for example, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrialkoxysilane, γ-glycidoxypropyl dialkoxysilane, γ-methacryloxypropyl Trialkoxysilane, γ-methacryloxypropyl dialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, vinyltrialkoxysilane Be Among these, γ-methacryloxypropyltrialkoxysilane, γ-acryloxypropyltrialkoxysilane, vinyltrialkoxysilane, and γ-glycidoxypropyltriaxoxysilane are more preferable. These can be used singly or in combination of two or more.
As a commercial item, Shin-Etsu Chemical Co., Ltd. product, KBM-403, KBM-5103, KBM-303, KBM-503, KBE-503, KBM-3103, and KBE-403 grade | etc., Are illustrated.

  0.1-30 mass% is preferable with respect to the total solid of a curable composition, as for content of the alkoxysilane compound in the curable composition of this invention, 0.5-15 mass% is more preferable, and 2-2 10 mass% is more preferable. The alkoxysilane compound may be only one kind or two or more kinds. When two or more types are contained, the total amount is preferably in the above range.

Component D: Organic Solvent The curable composition of the present invention contains an organic solvent as Component D. The curable composition of the present invention is preferably prepared as a solution obtained by dissolving or dispersing the essential components Component A, Component B, Component C, and Component E, and the optional components described below in an organic solvent. .
As the organic solvent used in the curable composition of the present invention, known solvents can be used, and 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 mono alkyl ether acetates, dipropylene glycol monoalkyl ethers, butylene glycol diacetates, dipropylene glycol dialkyl ethers, Dipropylene glycol monoalkyl ether acetates, alcohols, esters, ketones, Bromide and lactones like. As a specific example of these organic solvents, paragraph 0062 of JP-A-2009-098616 can be referred to.

  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 / or tetrahydrofurfuryl Alcohol is preferred.

The boiling point of the organic solvent is preferably 100 ° C. to 300 ° C., and more preferably 120 ° C. to 250 ° C., from the viewpoint of coatability.
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 preferable 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 with respect to 100 parts by mass of the total solid content of the curable composition from the viewpoint of adjusting the viscosity suitable for coating. Is preferable, 200 to 2,000 parts by mass is more preferable, and 250 to 1,000 parts by mass is even more preferable.
The solid content of the curable composition of the present invention is preferably 3 to 50% by mass, and more preferably 20 to 40% by mass.

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

Component E: Inorganic Particles The curable composition of the present invention contains inorganic particles as component E. By containing the inorganic particles, the hardness of the cured film becomes excellent. In addition, the adhesion to the substrate can be improved.
1-200 nm is preferable, as for the average particle diameter of the inorganic particle used by this invention, 5-100 nm is more preferable, and 5-50 nm is especially preferable. The average particle size is a particle size of an arbitrary particle of 200 measured by an electron microscope, and the arithmetic mean thereof. Also, when the shape of the particles is not spherical, the longest side is taken as the diameter.
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 voids. The porosity of the particles is an arithmetic mean of 200 area ratios of void portions of the cross-sectional image by the electron microscope to the whole particles.
As the inorganic particles, metal oxide particles are preferable.
The metal of the metal oxide in the present invention also includes semimetals such as B, Si, Ge, As, Sb, and Te.
As metal oxide particles, Be, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Gd, Tb, Dy, Yb, Lu, Ti, Zr, Hf, Nb, Mo, W, Zn, B Preferred are metal oxide particles containing atoms such as Al, Si, Ge, Sn, Pb, Sb, Bi and Te, and silicon oxide, titanium oxide, titanium complex oxide, zinc oxide, zirconium oxide, indium / tin oxide And particles of a metal oxide selected from the group consisting of antimony / tin oxide are more preferable, and metal oxides selected from the group consisting of silicon oxide, titanium oxide, titanium composite oxide, and zirconium oxide Particles are more preferable, and silicon oxide particles or titanium oxide particles are particularly preferable in view of particle stability, availability, hardness of cured film, transparency, refractive index adjustment, and the like.

As a silicon oxide particle, a silicon dioxide (silica) particle is mentioned preferably.
The silica particles are not particularly limited as long as they are particles of inorganic oxide containing silicon dioxide, and particles containing silicon dioxide or its hydrate as a main component (preferably 80% by mass or more) are preferable. The particles may contain an aluminate as a minor component (e.g. less than 5% by weight). As the aluminate which may be contained as a minor component, sodium aluminate, potassium aluminate and the like can be mentioned. The silica particles may contain inorganic salts such as sodium hydroxide, potassium hydroxide, lithium hydroxide and ammonium hydroxide, and organic salts such as tetramethyl ammonium hydroxide. Colloidal silica is illustrated 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 alone or in combination of two or more.
In the present invention, the particles can also be used as a dispersion prepared by mixing and dispersing in a suitable dispersing agent and solvent using a mixing apparatus such as a ball mill and a rod mill. In the curable composition of the present invention, the presence of colloidal silica in a colloidal state is not essential.

From the viewpoint of hardness, the content of the inorganic particles in the curable composition of the present invention is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and 100 parts by mass with respect to 100 parts by mass of the total solid of the curable composition. More than part is more preferable. Moreover, 80 mass parts or less are preferable, 50 mass parts or less are more preferable, 40 mass parts or less are still more preferable, and 30 mass parts or less are especially preferable.
The inorganic particles may contain only one type, or two or more types. When it contains two or more types, it is preferable that the total amount becomes the said range.

<Curable compounds other than Component A to Component C, such as a compound having an epoxy group, a compound having an oxetanyl group, a blocked isocyanate compound, a polyfunctional mercapto compound, etc.
The curable composition of the present invention preferably contains a curable compound which is a component curable by heat or light other than Component A to Component C, a compound having an epoxy group, a compound having an oxetanyl group, a blocked isocyanate compound, And, it is more preferable to include at least one selected from the group consisting of polyfunctional mercapto compounds. It is excellent by the hardness of the hardened | cured material obtained as it is the said aspect.

<< Compound Having an Epoxy Group >>
The curable composition of the present invention may contain a compound having an epoxy group. The compound having an epoxy group may have one epoxy group in the molecule, but preferably two or more.

  Specific examples of the compound having two or more epoxy groups in the molecule include bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, aliphatic epoxy resin and the like. Can.

These are commercially available. For example, as bisphenol A type epoxy resin, JER 827, JER 828, JER 834, JER 1001, JER 1002, JER 1003, JER 1005, JER 1007, JER 1009, JER 1010 (above, made by Japan Epoxy Resins Co., Ltd.), EPICLON 860, EPICLON 1050, EPICLON 1051, EPICLON 1055 (more than , DIC Corporation) and the like, and as bisphenol F type epoxy resin, JER 806, JER 807, JER 4004, JER 4005, JER 4007, JER 4010 (above, Japan Epoxy Resins Co., Ltd.), EPICLON 830, EPICLON 835 (above, DIC (from above) Products), LCE-21, RE-602S (above, Nippon Kayaku Co., Ltd.) As phenol novolac type epoxy resin, JER152, JER154, JER157S70, JER157S65 (above, made by Japan Epoxy Resins Co., Ltd.), EPICLON N-740, EPICLON N-740, EPICLON N-770, EPICLON N-775 (above , DIC Corporation) and the like, and as cresol novolac type epoxy resin, EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON. N-695 (above, DIC Corporation), EOCN-1020 (above, Nippon Kayaku Co., Ltd.) and the like, and as aliphatic epoxy resin, ADEKA RESIN EP-408 S, the same EP-4085S, the same EP-4088S (more, product made by ADEKA), celoxide 2021P, celoxide 2081, celoxide 2083, celoxide 2085, EHPE 3150, EPOLEAD PB 3600, same PB 4700 (above, Daicel Chemical Industries ( And so on. In addition, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4011S (all, manufactured by ADEKA), NC-2000, NC-3000, NC-7300, XD-1000, and the like. EPPN-501, EPPN-502 (above, manufactured by ADEKA Co., Ltd.) and the like can be mentioned.
In addition, urethane compounds having an ethylene oxide skeleton described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, or JP-B-62-39418 are also suitably used. The contents of which are incorporated herein.

When the curable composition of the present invention contains a compound having an epoxy group, the content of the compound having an epoxy group is in the range of 0.1 to 20% by mass based on the total solid content of the curable composition. Is preferably, the range of 0.5 to 10% by mass is more preferable, and the range of 1 to 5% by mass is even more preferable.
The curable composition of the present invention may contain only one type of compound having an epoxy group, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.

<< Compound Having Oxetanyl Group >>
The curable composition of the present invention may contain a compound having an oxetanyl group. The compound having an oxetanyl group may have one oxetanyl group in the molecule, but preferably two or more.
As a specific example of the compound which has oxetanyl group, aron oxetane OXT-121, OXT-221, OX-SQ, PNOX (above, Toagosei Co., Ltd. product) can be used.
Moreover, it is preferable to use the compound containing an oxetanyl group individually or in mixture with the compound containing an epoxy group.

When the curable composition of the present invention contains a compound having an oxetanyl group, the content of the compound having an oxetanyl group is in the range of 0.1 to 20% by mass based on the total solid content of the curable composition. Is preferably, the range of 0.5 to 10% by mass is more preferable, and the range of 1 to 5% by mass is even more preferable.
The curable composition of the present invention may contain only one type of compound having an oxetanyl group, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.

<< block isocyanate compound >>
The curable composition of the present invention may contain a blocked isocyanate compound.
The blocked isocyanate compound is not particularly limited as long as it is a compound having a blocked isocyanate group, but from the viewpoint of curability, a compound having two or more blocked isocyanate groups in one molecule is preferable. The upper limit of the number of blocked isocyanate groups is not particularly limited, but is preferably 6 or less.
The skeleton of the blocked isocyanate compound is not particularly limited, and may be any one having two isocyanate groups in one molecule, and it may be aliphatic, alicyclic or aromatic. It may be a polyisocyanate. For example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,3-trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, 2,2,4- Trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,9-nonamethylene diisocyanate, 1,10-decamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 2,2'-diethyl ether diisocyanate, diphenylmethane 4,4'-diisocyanate, o-xylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, methylene bis (cyclohexyl isocyanate Cyclohexane-1,3-dimethylene diisocyanate, cyclohexane-1,4-dimethylene diisocyanate, 1,5-naphthalene diisocyanate, p-phenylene diisocyanate, 3,3′-methyleneditrilene-4,4′-diisocyanate Isocyanate compounds such as 4,4'-diphenylether diisocyanate, tetrachlorophenylene diisocyanate, norbornane diisocyanate, hydrogenated 1,3-xylylene diisocyanate, hydrogenated 1,4-xylylene diisocyanate, and prepolymers derived from these compounds The compound of can be suitably used. Among these, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI) and isophorone diisocyanate (IPDI) are particularly preferable.

As a matrix structure of the block isocyanate compound in the curable composition of this invention, a biuret type, an isocyanurate type, an adduct type, a bifunctional prepolymer type etc. can be mentioned.
Examples of the blocking agent that forms the block structure of the blocked isocyanate compound include an oxime compound, a lactam compound, a phenol compound, an alcohol compound, an amine compound, an active methylene compound, a pyrazole compound, a mercaptan compound, an imidazole compound, an imide compound and the like. be able to. Among these, blocking agents selected from oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds and pyrazole compounds are particularly preferable.

  Blocked isocyanate compounds that can be used for the curable composition of the present invention are commercially available products, for example, Coronate AP table M, Coronate 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (all, Japan Polyurethane Industry Co., Ltd.), Takenate B-830, B-815N, B-820NSU, B-842N, B-846N, B-870N, B-874N, B-882N (all manufactured by 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, Asahi Kasei Chemicals Corporation), Desmo Urle BL1100, BL1265 MPA / X, BL3575 / 1, BL3272 MPA, BL3370 MPA, BL3475 BA / SN, BL5375 MPA, VPLS2078 / 2, BL4265 SN, PL340, PL350, Semidur BL3175 (manufactured by Sumika Bayer Urethane Co., Ltd.), etc. are preferable. It can be used.

When the curable composition of the present invention contains a blocked isocyanate compound, the content of the blocked isocyanate compound is preferably in the range of 0.1 to 20% by mass with respect to the total solid content of the curable composition, 0 The content is more preferably in the range of 0.5 to 10% by mass, and still more preferably in the range of 1 to 5% by mass.
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 contained, the total amount is preferably in the above range.

<< Multifunctional Mercapto Compound >>
The curable composition of the present invention may contain a polyfunctional mercapto compound.
The polyfunctional mercapto compound is not particularly limited as long as it is a compound having two or more mercapto groups, but a compound having 2 to 6 mercapto groups is preferable, and a compound having 2 to 4 mercapto groups is more preferable. As a polyfunctional mercapto compound, an aliphatic polyfunctional mercapto compound is preferable. Preferred examples of the aliphatic polyfunctional mercapto compounds are compounds comprising a combination of an aliphatic hydrocarbon group and -O- or -C (= O)-, and at least 2 of the hydrogen atoms of the aliphatic hydrocarbon group. Examples are compounds in which one is substituted with a mercapto group.

  Examples of aliphatic polyfunctional mercapto compounds include pentaerythritol tetrakis (3-mercaptobutyrate) and 1,4-bis (3-mercaptobutyryloxy) butane. As a commercial item, Kalens MT-PE-1, Kalens MT-BD-1, lenses MT-NR-1 (made by Showa Denko KK) etc. are mentioned, for example.

When the curable composition of the present invention contains a polyfunctional mercapto compound, the content of the polyfunctional mercapto compound is preferably in the range of 0.1 to 20% by mass of the total solid content of the curable composition, 0 The content is more preferably in the range of 5 to 10% by mass, and still more preferably in the range of 1 to 5% by mass.
The curable composition of the present invention may contain only one type of polyfunctional mercapto compound, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.

<< Polysulfide compound >>
The curable composition of the present invention may also contain a polysulfide compound. By containing a polysulfide compound, the cured film which is excellent in base material adhesiveness and moisture resistance is obtained.
The polysulfide compound is not particularly limited as long as it has a polysulfide bond, but it is preferably a compound having a disulfide bond, trisulfide bond, tetrasulfide bond, pentasulfide bond, hexasulfide bond, disulfide bond, trisulfide bond The compound is more preferably a compound having a tetrasulfide bond, and more preferably a compound having a disulfide bond or a tetrasulfide bond. Use of a compound having a disulfide bond or a tetrasulfide bond is more excellent in moisture resistance.
The polysulfide bond may be linear, branched or cyclic, but is preferably a linear polysulfide bond.
Further, as the polysulfide compound, a compound in which an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic group, or a monovalent group combining two or more of them is bonded to both sides of a polysulfide bond is preferable, and a polysulfide bond is preferable. Compounds in which an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a monovalent group in which two or more of these are combined are bonded to both sides of the group are more preferable. The aliphatic hydrocarbon group, aromatic hydrocarbon group or heterocyclic group may have a substituent. The substituent is not particularly limited, and examples thereof include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic group, a halogen atom, a carboxy group, an amido group, an alkoxy group, an alkoxycarbonyl group and a silyl group. Among them, it is particularly preferable to have a trialkoxysilyl group as a substituent. That is, as the polysulfide compound, a compound in which an aliphatic hydrocarbon group having a trialkoxysilyl group is bonded to both sides of a polysulfide bond is particularly preferable.

  Although the specific example of a polysulfide compound is shown below, this invention is not limited to the following specific example. In the following formulas, Ph represents a phenyl group, Me represents a methyl group, and Et represents an ethyl group.

In the present invention, the polysulfide compounds may be used alone or in combination of two or more.
In the present invention, the content of the polysulfide compound is preferably 0.01 to 20% by mass, and more preferably 0.1 to 10% by mass, with respect to the total solid content of the curable composition. It is further more preferable that it is 0.5-5 mass%. The cured film which is excellent in base-material adhesiveness and moisture resistance as it is the said range is obtained.

The curable composition of the present invention may contain other compounds (for example, an alkoxymethyl group-containing compound, etc.) other than the above without departing from the scope of the present invention.
As an alkoxy methyl group containing compound, the thing as described in stage 0192-0194 of Unexamined-Japanese-Patent No. 2011-221494 can be mentioned.

In the present invention, the total content of the ethylenically unsaturated compound, the compound having an epoxy group, the compound having an oxetanyl group, the blocked isocyanate compound and the polyfunctional mercapto compound is cured by the heat or light contained in the curable composition. It is preferable to occupy 90% by mass or more (more preferably, 95% by mass or more) of the total amount of the components, and the total content of the ethylenically unsaturated compound and the blocked isocyanate compound is contained in the curable composition It is more preferable to occupy 90% by mass or more (more preferably 95% by mass or more) of the total amount of components cured by light.
Moreover, when it contains at least one of a compound having an epoxy group, a compound having an oxetanyl group, a blocked isocyanate compound and a polyfunctional mercapto compound, a component which is cured by heat or light contained in the curable composition in total. It is preferable to occupy 0.1-20 mass% of the total amount of, and it is still more preferable to occupy 1-10 mass%. With such a configuration, the effects of the present invention are more effectively exhibited.

<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 preferred surfactants are nonionic surfactants. The surfactant is preferably a nonionic surfactant, and more preferably a fluorinated surfactant.
As surfactants which can be used in the present invention, for example, Megafac F142D, F172, F173, F176, F177, F183, F479, F482, F554, F780, which are commercially available products, can be used. F781, F781-F, R30, R08, F-472SF, BL20, R-61, R-90 (manufactured by DIC Corporation), Florard FC-135, FC-170C, FC-430, FC-431, Novec FC-4430 (Sumitomo 3M Co., Ltd. product), Asahi Guard AG7105, 7000, 950, 7600, Surfron S-112, S-113, S-131, S-131 -141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-1 05, SC-106 (Asahi Glass Co., Ltd.), F-top EF 351, 352, 801, 802 (Mitsubishi Materials Electronics Kasei Co., Ltd.), Futargent 250 (Neos Co., Ltd.) . In addition to the above, KP (Shin-Etsu Chemical Co., Ltd.), Polyflow (Kyoeisha Chemical Co., Ltd.), F-Top (Mitsubishi Materials Electronic Chemicals Co., Ltd.), Megafac (manufactured by DIC Corporation) And each series such as Florard (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard, Surfron (manufactured by Asahi Glass Co., Ltd.), PolyFox (manufactured by OMNOVA) and the like.

Moreover, as surfactant, the compound described in stage 0119-0123 of Unexamined-Japanese-Patent No. 2014-238438 can also be mentioned as a preferable example.
When it mix | blends, 0.001-5.0 mass% is preferable with respect to the total solid of a curable composition, and, as for content of surfactant in the curable composition of this invention, 0.01-2. 0 mass% is more preferable.
The surfactant may contain only one type, or two or more types. When it contains two or more types, it is preferable that the total amount becomes the said range.

<Antioxidant>
The curable composition of the present invention may contain an antioxidant. As an antioxidant, a well-known antioxidant can be contained. By adding an antioxidant, it is possible to prevent coloring of the cured film, or to reduce a decrease in film thickness due to decomposition, and there is an advantage of being excellent in heat-resistant transparency.
Examples of such an antioxidant include phosphorus-based antioxidants, amides, hydrazides, hindered amine-based antioxidants, sulfur-based antioxidants, phenolic antioxidants, ascorbic acids, zinc sulfate, saccharides, Nitrate, sulfite, thiosulfate, hydroxylamine derivative and the like can be mentioned. Among them, phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants and sulfur-based antioxidants are particularly preferable from the viewpoint of coloring of the cured film and reduction in film thickness, and phenol-based antioxidants are the most preferable. preferable. These may be used singly or in combination of two or more.
Specific examples thereof include compounds described in paragraphs 0026 to 0031 of JP-A-2005-29515, and compounds described in paragraphs 0106 to 0116 of JP-A-2011-227106, and the contents of these compounds are as described in the present specification. Incorporated into the book.
As preferable commercial products, Adekastab AO-60, Adekastab AO-80, Adekastab AO-412S (all, manufactured by ADEKA Co., Ltd.), Irganox 1035, Irganox 1098 (All, manufactured by BASF Corporation) can be mentioned.
The content of the antioxidant is not particularly limited, but is preferably 0.1 to 10% by mass, and more preferably 0.2 to 5% by mass with respect to the total solid content of the curable composition. More preferably, it is further preferably 0.5 to 4% by mass.

<Polymerization inhibitor>
The curable composition of the present invention may contain a polymerization inhibitor. A polymerization inhibitor is hydrogen donating (or giving hydrogen), energy donating (or giving energy), electron donating (or giving electron) etc. to a polymerization initiating radical component generated from a polymerization initiator by exposure or heat. To deactivate the polymerization initiation radical and to inhibit the polymerization initiation. For example, the compounds described in paragraphs [0154] to [0173] of JP-A-2007-334322 can be used.
As preferable compounds, phenothiazine, phenoxazine, hydroquinone, 3,5-dibutyl-4-hydroxytoluene can be mentioned.
The content of the polymerization inhibitor is not particularly limited, but is preferably 0.0001 to 5% by mass with respect to the total solid content of the curable composition.

<Binder polymer>
The curable composition of the present invention may contain a binder polymer from the viewpoint of improving resolution and film properties.
There is no restriction | limiting in particular as a binder polymer, Although although a well-known thing can be used, it is preferable to use a linear organic polymer. As such a linear organic polymer, known ones can be optionally used. Preferably, a linear organic polymer which is soluble or swellable in water or weakly alkaline water is selected to enable water development or weakly alkaline water development. The linear organic polymer is selected and used not only as a film-forming agent but also according to the use as a water, weak alkaline water or organic solvent developer. For example, water development is possible with water-soluble organic polymers. As such a linear organic polymer, a radical polymer having a carboxylic acid group in a side chain, for example, JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B No. 54-25957, JP-A-54-92723, JP-A-59-53836, JP-A-59-71048, that is, a monomer having a carboxyl group alone or A copolymerized resin, a monomer having an acid anhydride mono- or copolymerized to hydrolyze or half-esterify or half-amidate an acid anhydride unit, an epoxy resin with unsaturated monocarboxylic acid and acid anhydride The modified epoxy acrylate etc. are mentioned. Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 4-carboxystyrene, and the like. Examples of the acid anhydride-containing monomer include maleic anhydride and the like. Be
There are also acid cellulose derivatives having a carboxylic acid group in the side chain. In addition to this, a polymer having a hydroxyl group to which a cyclic acid anhydride is added is useful.
As a binder polymer, the acrylic resin which copolymerized (meth) acrylic acid and other (meth) acrylic acid ester is preferable.
The content of the binder polymer in the curable composition of the present invention is not particularly limited, but is preferably 1 to 40% by mass, and preferably 3 to 30% by mass, with respect to the total solid content of the curable composition. Is more preferably 4 to 20% by mass.

<Other ingredients>
If necessary, other components such as a plasticizer, a thermal acid generator, an acid multiplier and the like can be added to the curable composition of the present invention in addition to those described above. As these components, for example, those described in JP-A-2009-98616 or JP-A-2009-244801 and other known ones can be used. In addition, various ultraviolet light absorbers described in “New development of polymer additive (Nippon Kogyo Shimbun Co., Ltd.)”, metal deactivator and the like may be added to the curable composition of the present invention.

(Cured product, cured film and method for producing them)
The cured product of the present invention is a cured product obtained by curing the curable composition of the present invention, and the cured product obtained by removing and curing at least a part of the organic solvent in the curable composition of the present invention It is preferable that it is a thing. It is. The cured product is preferably a cured film. Moreover, it is preferable that the hardened | cured material of this invention is a hardened | cured material obtained by the manufacturing method of the hardened | cured material of this invention.
The method for producing the cured product of the present invention is not particularly limited as long as it is a method of curing the curable composition of the present invention to produce a cured product, but includes the following steps (1) to (3) Is preferred.
(1) Step of applying the curable composition of the present invention onto a substrate (2) Step of removing a solvent from the applied curable composition (3) Step of heat curing Also, a method of producing a cured product of the present invention It is more preferable to include the following steps (1), (2), (2 ′) and (3).
(1) A step of applying the curable composition of the present invention on a substrate (2) A step of removing an organic solvent from the applied curable composition (2 ′) A light of the curable composition from which the organic solvent has been removed Step of curing by (3) step of further curing by heat the cured product cured by light The method of producing a cured product of the present invention is preferably a method of 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 a substrate, the substrate may be cleaned by alkaline cleaning or plasma cleaning. Furthermore, after cleaning the substrate, the substrate surface can be treated with hexamethyldisilazane or the like. By performing this treatment, the adhesion of the curable composition to the substrate tends to be improved.
Examples of the above-mentioned 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 a substrate such as them.
As the resin, polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, polyether sulfone, polyarylate, allyl diglycol carbonate, polyamide, polyimide, polyamide imide, polyether imide, poly Benzazole, polyphenylene sulfide, polycycloolefin, norbornene resin, fluorocarbon resin such as polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, epoxy resin, silicone resin, ionomer resin, cyanate resin, crosslinked fumaric acid diester, cyclic polyolefin, aroma Synthetic resins such as aliphatic ether, maleimide-olefin copolymer, cellulose and episulfide resin Board, and the like. These substrates are rarely used as they are in the above-mentioned form, and usually, a multilayer laminate structure such as a TFT (Thin-Film Transistor) element is formed depending on the form of the final product.

  The curable composition of the present invention preferably adheres to a metal film or metal oxide formed by sputtering, and therefore, preferably includes a metal film formed by sputtering as a substrate. The metal is preferably titanium, copper, aluminum, indium, tin, manganese, nickel, cobalt, molybdenum, tungsten, chromium, silver, neodymium, and oxides or alloys thereof, and molybdenum, titanium, aluminum, copper And it is further preferable that they are these alloys. The metal and the metal oxide may be used alone or in combination of two or more.

  There is no particular limitation on the method of coating on a substrate, and for example, methods such as inkjet method, slit coating method, spray method, roll coating method, spin coating method, cast coating method, slit and spin method, printing method, etc. may be used. it can.

  In the step of removing the solvent in (2), it is preferable to remove the solvent from the applied film by reducing pressure (vacuum) and / or heating or the like to form a dried coating on the substrate. The heating conditions of the solvent removal step are preferably about 70 to 130 ° C. and about 30 to 300 seconds. In the solvent removal step, it is not necessary to completely remove the organic solvent in the curable composition, and at least a portion of the organic solvent may be removed.

Furthermore, the present invention may include the step of exposing the entire surface from the viewpoint of improving the film hardness before the step of (2) removing the solvent and (3) thermally curing.
In addition, after the step of removing the solvent and (3) before the step of curing by heat, the step of curing the curable composition from which the organic solvent has been removed by light from the viewpoint of improving the film hardness It is preferable to include, and it is more preferable to include the process of hardening the curable composition from which the organic solvent was removed by whole surface exposure. Moreover, when it hardens | cures by light like the said aspect, it is preferable that the curable composition of this invention contains a photoinitiator.
In this case, it is preferable to perform energy exposure of about 50 to 3,000 mJ / cm ² with a mercury lamp or an LED lamp.
Moreover, the process of pattern exposure and development can also be performed after the solvent removal process of (2) for pattern formation. The method of pattern exposure is preferably a method using a mask or a method such as direct drawing using a laser or the like. It is preferable from the viewpoint of curing acceleration to carry out the entire surface exposure and the pattern exposure in a state of being oxygen-blocked. As means for blocking oxygen, exposure under a nitrogen atmosphere or provision of an oxygen blocking film is exemplified.
For pattern exposure and development, known methods and known developers 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.

(3) In the step of heat curing, the ethylenically unsaturated compound etc. may be polymerized by heating to form a cured film, or the cured cured product may be further cured. When polymerization is carried out by heating, the curable composition of the present invention preferably contains a thermal polymerization initiator.
As heating temperature, 180 degrees C or less is preferable, 150 degrees C or less is more preferable, 130 degrees C or less is still more preferable. 80 degreeC or more is preferable and, as for a lower limit, 90 degreeC or more is more preferable. The method of heating is not particularly limited, and known methods can be used. For example, a hot plate, an oven, an infrared heater, etc. may be mentioned.
Moreover, as heating time, in the case of a hot plate, about 1 minute-30 minutes are preferable, and about 20 minutes-120 minutes are preferable in other cases. Within this range, curing can be performed without damage to the substrate and the device. From the viewpoint of shape control after heating, heating can also be performed initially at a lower temperature and later at a higher temperature (addition of a middle bake step, eg, first heating at 90 ° C. for 30 minutes and then heating at 120 ° C. for 30 minutes).

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

  Since the curable composition of the present invention is excellent in curability and cured film properties, a cured product obtained by curing the curable composition of the present invention or a resist pattern is used as a partition as a structural member of a MEMS (Micro Electro Mechanical Systems) device. Or used as part of machine drive parts. Such MEMS devices include, for example, SAW (Surface Acoustic Wave, surface acoustic wave) filter, BAW (Bulk Acoustic Wave, bulk wave) filter, gyro sensor, micro shutter for display, image sensor, electronic paper, inkjet head, Examples include parts such as biochips and sealants. More specific examples are illustrated in JP-A-2007-522531, JP-A-2008-250200, and JP-A-2009-263544.

  Since the curable composition of the present invention is excellent in flatness and transparency, for example, the bank layer (16) and the flattening film (57) described in FIG. 2 of JP-A-2011-107476, JP-A 2010- The barrier rib (12) and the flattening film (102) described in FIG. 4 (a) of 9793, and the bank layer (221) and the third interlayer insulating film (216b) described in FIG. 10 of JP-A-2010-27591. A second interlayer insulating film (125) and a third interlayer insulating film (126) described in FIG. 4 (a) of JP-A-2009-128577, and a flat surface described in FIG. 3 of JP-A-2010-182638. It can also be used to form a chemical conversion film (12) and a pixel isolation insulating film (14). In addition, spacers for maintaining the thickness of the liquid crystal layer in liquid crystal display devices constant, color filters for liquid crystal display devices, protective films for color filters, on-chip color filters such as facsimiles, electronic copiers, solid-state imaging devices, etc. It can also be suitably used as a microlens of an optical system or an optical fiber connector.

(Organic EL display device)
The organic EL display device of the present invention is characterized by having the cured film of the present invention.
The organic EL display device of the present invention is not particularly limited 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 compounds having various structures are used. An EL display device or a liquid crystal display device can be mentioned.
For example, as a specific example of the TFT included in the organic EL display device of the present invention, an amorphous silicon-TFT, a low temperature polysilicon-TFT, an oxide semiconductor TFT and the like can be mentioned. 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 structural conceptual view of an example of the 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 planarization 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 in a state of covering the TFT 1. After forming a contact hole (not shown) in the insulating film 3, a wire 2 (height 1.0 μm) connected to the TFT 1 via the contact hole is formed on the insulating film 3. The wiring 2 is for connecting the TFT 1 to an organic EL element formed between the TFTs 1 or in a later step.
Furthermore, in order to planarize the unevenness due to the formation of the wiring 2, a planarizing film 4 is formed on the insulating film 3 in a state in which the unevenness due to the wiring 2 is embedded.
A bottom emission type organic EL element is formed on the planarization film 4. That is, the first electrode 5 made of ITO is formed on the planarization film 4 so as to be connected to the wiring 2 through the contact hole 7. The first electrode 5 corresponds to the anode of the organic EL element.
An insulating film 8 having a shape covering the periphery of the first electrode 5 is formed, and the provision of the insulating film 8 prevents a short circuit between the first electrode 5 and a second electrode to be formed in a later step. can do.
Furthermore, 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 the entire surface of the substrate is made of Al. An active matrix type 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 with a TFT 1 for driving the same. An organic EL display device is obtained.

(Liquid crystal display device)
The liquid crystal display device of the present invention is characterized by having the cured film of the present invention.
The liquid crystal display device of the present invention is not particularly limited except that it has a protective film, a planarization film and an interlayer insulating film formed using the curable composition of the present invention, and various known structures A liquid crystal display can be mentioned.
In addition, as a liquid crystal driving method that can be used for the liquid crystal display device of the present invention, a TN (Twisted Nematic) method, a VA (Vertical Alignment) method, an IPS (In-Plane-Switching) method, an FFS (Fringe Field Switching) method, an OCB Optically Compensated Bend) and the like.
In the panel configuration, the cured film of the present invention can also be used in a liquid crystal display device of a COA (Color Filter on Array) system, and, for example, the organic insulating film (115) of JP-A-2005-284291 It can be used as the organic insulating film (212) of Japanese Unexamined Patent Publication No. 346054. Moreover, as a specific orientation system of the liquid crystal aligning film which the liquid crystal display device of this invention can take, a rubbing orientation method, an optical orientation method, etc. are mentioned. Moreover, polymer orientation support may be carried out by the PSA (Polymer Sustained Alignment) technology described in Japanese Patent Application Laid-Open 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, It can be used for various uses. For example, in addition to a planarizing film and an interlayer insulating film, a protective film, a spacer for keeping the thickness of a liquid crystal layer in a liquid crystal display device constant, a microlens suitably provided on a color filter in a solid-state imaging device, etc. It can be used.

FIG. 2 is a conceptual cross-sectional view showing an example of the active matrix liquid crystal display device 10. As shown in FIG. 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 is all pixels disposed between two glass substrates 14 and 15 to which a polarizing film is attached. Elements of the TFT 16 corresponding to In each element formed on the glass substrate, an ITO transparent electrode 19 for forming a pixel electrode is wired 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 layer of liquid crystal 20 and a black matrix are arranged is provided.
The light source for the backlight is not particularly limited, and any known light source can be used. For example, white LEDs, multicolor LEDs such as blue, red and green, fluorescent lamps (cold cathode tubes), organic EL and the like can be mentioned.
In addition, the liquid crystal display device may be a 3D (stereoscopic) type or a touch panel type. Furthermore, it is possible to use a flexible type, and use as the second interlayer insulating film (48) described in JP-A-2011-145686 or the interlayer insulating film (520) described in JP-A-2009-2558758. Can.

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

  As a touch panel type, a so-called in-cell type (for example, those shown in FIGS. 5, 6, 7 and 8 of JP-A-2012-517051), a so-called on-cell type (for example, JP-A-2013-168125) The thing of FIG. 19 of gazette, the thing of FIG. 1 and FIG. 5 of Unexamined-Japanese-Patent No. 2012-89102, OGS type | mold and TOL type | mold (For example, the thing of FIG. 2 of Unexamined-Japanese-Patent No. 2013-54727 , And those shown in FIG. 2, FIG. 3, FIG. 4 and FIG. 5 of JP-A-2015-15042, and other configurations (for example, those described in FIG. 6 of JP-A-2013-164871) There may be mentioned out-cell types (so-called GG, G1 · G2, GFF, GF2, GF1, G1 F, etc.).

Moreover, FIG. 3 shows a configuration conceptual diagram of an example of a liquid crystal display device having a touch panel function.
For example, the cured film of the present invention is preferably applied to the protective film between the layers in FIG. 3 and is also preferably applied to the interlayer insulating film which separates the detection electrodes of the touch panel. In addition, as a detection electrode of a touch panel, a transparent electrode (ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), etc.) and a metal electrode (silver, copper, molybdenum, titanium, aluminum etc., and their laminates and alloys) Etc.) or a laminate of these.
In FIG. 3, 110 indicates a pixel substrate, 140 indicates a liquid crystal layer, 120 indicates an opposing substrate, and 130 indicates a sensor portion. 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 this 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 the insulating layer (114) (also referred to as interlayer insulating film) of the pixel substrate portion, various protective films (not shown), various protective films (not shown) of the pixel substrate portion, and the opposing substrate portion Can be used as various protective films (not shown) of the above, various protective films (not shown) of a sensor part, etc.

For the adhesive layer 126 and the polarizing plate 127, known adhesive layer compositions can be used.
Specific examples of the polarizing plate and the adhesive layer include a polarizing plate with an adhesive layer described in Example 1, Example 7, and Example 13 of JP-A-2014-152319, Example 1 of JP-A-2014-191005, Example 3 and Example 6 with Polarizing Layer with Adhesive Layer, Example 1 of Example JP-A-2013-100386, Example 3, Example 6, Example 6 with Polarized Layer with Example 11 and Example 14 A board | substrate and the contact bonding layer as described in Example 1, Example 2, Example 3, and Example 4 of Unexamined-Japanese-Patent No. 2013-163783 can be mentioned.
The adhesive layer preferably contains an antistatic agent in order to prevent static charge.
A well-known thing can be used as an antistatic agent. For example, metal particles, metal oxides, conductive polymers, and ionic compounds such as quaternary ammonium salts and lithium salts can be used.
Specific examples of the antistatic agent include those described in paragraphs 0107 to 0115 of JP-A 2014-191005, those described in paragraphs 0046 to 0054 of JP-A 2013-100386, and JP-A-2014-515046. The thing as described in Paragraph 0027-0047 of the gazette can be mentioned.

  Furthermore, even in a static drive liquid crystal display device, it is possible to 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 Japanese Patent Application Laid-Open No. 2001-125086.

Moreover, FIG. 4 is a configuration conceptual diagram of another example of the liquid crystal display device having a touch panel function.
A lower display panel 200 corresponding to a thin film transistor array panel including a thin film transistor (TFT) 440, and a color filter array panel including a plurality of color filters 330 on the surface facing the lower display panel 200 facing the lower display panel 200. And a 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, a thin film transistor (TFT) disposed on the first insulating substrate 210, an insulating film 280 formed on the top 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 as to expose the drain electrode 272 of the thin film transistor (TFT).

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

In the liquid crystal display device illustrated in FIG. 4, the sensing electrode 410, the insulating film 420, the driving electrode 430, and the 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 forming the upper display panel 300, the sensing electrode 410, the insulating film 420, the driving electrode 430, etc. which are components of the touch screen are formed together. be able to. In particular, a cured film obtained by curing the curable composition of the present invention can be suitably used for the insulating film 420.
A polarizing plate with an adhesive layer or an adhesive layer exemplified for the adhesive layer 126 and the polarizing plate 127 can be attached to the protective film 280.

  Hereinafter, the present invention will be more specifically described by way of examples. The materials, amounts used, proportions, treatment contents, treatment procedures and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Accordingly, the scope of the present invention is not limited to the specific examples shown below. In addition, unless there is particular notice, "part" and "%" are mass references.

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

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

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

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

In Synthesis Example 2, a polymer (a-A) was prepared in the same manner as in Synthesis Example 2 except that the addition amount of the polymerization initiator V-65 was changed to 8 parts and the addition amounts of PGMEA were both 232.7 parts. 1) '-3 was obtained.
The weight average molecular weight of the obtained (a-1) '-3 measured by gel permeation chromatography (GPC) was 8,000.

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

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

Synthesis Example 5 Synthesis of (a-2) -2

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

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

  (A-2)-was synthesized and purified in the same manner as in Synthesis Example 5 except that dipentaerythritol pentaacrylate in Synthesis Example 5 was changed to pentaerythritol triacrylate (manufactured by Aldrich, Inc. by column purification). I got three.

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

  The synthesis and purification were carried out in the same manner as in Synthesis Example 4 except that dipentaerythritol pentaacrylate in Synthesis Example 4 was changed to 2-hydroxyethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), and (a-2) '-4 was obtained Obtained.

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

Ethylenically unsaturated compounds other than urethane (meth) acrylate
A-1: Dipentaerythritol hexaacrylate A-2: Dipentaerythritol pentaacrylate A-3: Pentaerythritol tetraacrylate In addition, as for all of A-1 to A-3, column purification made by Aldrich is used. did.

<Component B: Radical polymerization initiator>
B-1: Compound 1 below, oxime ester compound

B-2: IRGACURE OXE 01 (manufactured by BASF Corporation), oxime ester compound, structure below B-3: IRGACURE OXE 02 (manufactured by BASF Corporation), oxime ester compound, structure below B-4: IRGACURE 907 (manufactured by BASF Corporation), aminoalkyl Phenone compound, 2-methyl-4 '-(methylthio) -2-morpholinopropiophenone

<Component C: Alkoxysilane Compound>
C-1: KBM-403 (3-glycidoxypropyl trimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.)
C-2: KBM-5103 (3-acryloxypropyl trimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.)
C-3: KBM-503 (3-methacryloxypropyl trimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.)
C-4: KBM-303 (2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.)
C-5: KBM-3103 (decyl trimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.)

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

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

<Multifunctional mercapto compound>
S-1: Karenz MT-PE-1 (pentaerythritol tetrakis (3-mercaptobutyrate), Showa Denko KK-made), functional group number 4
S-2: Kalens MT-BD-1 (1,4-bis (3-mercaptobutyryloxy) butane, manufactured by Showa Denko KK), having 2 functional groups

<Blocked isocyanate compound>
S-3: Takenate B 870 N (oxime block of isophorone diisocyanate, solid concentration 60%, Mitsui Chemicals Co., Ltd.)
S-4: Duranate 17B-60P (blocked isocyanate compound whose matrix structure has a biuret structure and whose block structure is an oxime ester structure, solid concentration 60%, manufactured by Asahi Kasei Chemicals Corporation)
<Epoxy compound>
S-5: JER 157 S 65 (manufactured by Mitsubishi Chemical Holdings Corporation)

<Surfactant>
W-1: Megafac F 554 (manufactured by DIC Corporation), fluorinated surfactant W-2: FTX-218 (manufactured by Neos Corporation), fluorinated surfactant <sensitizer>
I-1: DBA (Dibutoxyanthracene of the following structure) (manufactured by Kawasaki Kasei Kogyo Co., Ltd.)

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

<Antioxidant>
J-1: Adekastab AO-60 (Hindered phenolic antioxidant, manufactured by ADEKA Co., Ltd.)
<Polymerization inhibitor>
K-1: 4-methoxyphenol

(Examples 1 to 26 and Comparative Examples 1 to 6)
<Preparation of a curable composition>
Each component is mixed and stirred as described in Tables 1 to 4 below to prepare a solution and / or dispersion of an organic solvent, and the solution is filtered through a polytetrafluoroethylene filter with a pore diameter of 0.3 μm to cure the present invention. The sex composition was obtained. The unit of each component of following Table 1-Table 4 is a mass part except the ratio of the component A in a total organic solid, and the ratio of the component A with respect to a total solid. Moreover, except for the block isocyanate compound, the inorganic particles, and the organic solvent, the parts by mass in terms of solid content are shown. About a block isocyanate compound and inorganic particle, the mass part of the solution of the said solid content concentration is shown. In the table, "-" indicates that the corresponding compound is not contained.

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

<Evaluation of coating property (wetting spreadability to a glass substrate with ITO)>
Each curable composition is slit-coated on a glass substrate with ITO (film thickness 0.2 μm) sputtered in half of 550 mm × 650 mm and half glass exposed so that the film thickness becomes 1.0 μm, The end of the solution was observed. It is better if the ends of both ITO and glass are aligned, and it is worse if one material side gets wet as compared to the other. Evaluation criteria are shown below. A is a practical range.
A: Difference in the spread of the end of the solution is less than 300 μm B: Difference in spread of the end of the solution is 300 μm or more

  As apparent from Tables 1 to 4 above, the curable composition of the present invention had high hardness even when cured at a low temperature, and was excellent in coatability.

(Example 27)
<Production of Display Device>
In the display device shown in FIG. 4, the curable compositions obtained in Examples 1 to 26 were respectively used for forming a touch detection electrode protective film (insulating film, 420) to produce display devices. Specifically, for the protective film (420), the curable composition obtained in each example is applied by inkjet, prebaked at 90 ° C. for 120 seconds, and 500 mJ / cm ² (i-line conversion) with a high pressure mercury lamp And then baked in an oven at 120 ° C. for 60 minutes. The other part of the display device was manufactured according to the manufacturing method described as FIG. 19 in JP-A-2013-168125. The manufactured display devices were all excellent in display performance and touch detection performance.

  1: TFT (thin film transistor) 2: wiring 3: insulating film 4: planarizing film 5: first electrode 6: glass substrate 7: contact hole 8: insulating film 10: liquid crystal display device 12 A 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: opposing substrate, 121: alignment film, 122: color filter, 123: transparent substrate, 124: retardation Film 126: adhesive layer 127: polarizing plate 130: sensor unit 140: liquid crystal layer 200: lower display panel 210: first insulating substrate 220: gate electrode 240 Gate insulating film, 250: semiconductor layer, 260, 262: ohmic contact layer, 270: source electrode, 272: drain electrode, 280: insulating film, 282: contact hole, 290: image electrode, 300: upper display panel, 310: Second insulating substrate, 320: light shielding member, 330: color filter, 350: alignment film, 370: common electrode, 400: liquid crystal layer, 410: sensing electrode, 420: insulating film, 430: drive electrode, 440: TFT

Claims (14)

As component A, an ethylenically unsaturated compound,
As component B, a polymerization initiator,
As component C, an alkoxysilane compound,
As component D, an organic solvent, and
Contains inorganic particles as component E,
Component A contains five or more functional urethane (meth) acrylates,
The content of the pentafunctional or higher urethane (meth) acrylate is 20 to 100 parts by mass with respect to 100 parts by mass of the component A,
The 5 or more functional urethane (meth) acrylate comprises a urethane (meth) acrylate is a weight average molecular weight of 10,000 to 100,000, and, the urethane (meth) acrylate having a molecular weight of 800 to 5,00 0,
The content of the urethane (meth) acrylate having a weight average molecular weight of 10,000 to 100,000 is 1 to 90 parts by weight with respect to 100 parts by weight of the content of urethane (meth) acrylate having five or more functional groups,
A curable composition characterized in that the urethane (meth) acrylate having a weight average molecular weight of 10,000 to 100,000 is a polymer having a structural repeating unit represented by the following formula Aa-1.

In Formula Aa-1, L ^{5 to} L ⁷ each independently represent a divalent linking group, and A represents a group having a (meth) acryloyl group.   The curable composition according to claim 1, wherein Component B comprises an oxime ester compound.   The curable composition according to claim 1 or 2, wherein Component A comprises an ethylenically unsaturated compound other than the pentafunctional or higher urethane (meth) acrylate.   The curable composition according to claim 3, wherein the ethylenically unsaturated compound other than the pentafunctional or higher urethane (meth) acrylate is a polyfunctional ethylenically unsaturated compound.   The curable composition according to any one of claims 1 to 4, wherein the content of component A is 70% by mass or more based on the total organic solid content of the curable composition. The 5 or more functional urethane (meth) acrylate, including the molecular weight 800 5,00 0, which is the urethane (meth) acrylates of two or more of the curable composition according to any one of claims 1 to 5 .   The curing according to any one of claims 1 to 6, further comprising at least one selected from the group consisting of a compound having an epoxy group, a compound having an oxetanyl group, a blocked isocyanate compound, and a polyfunctional mercapto compound. Sex composition.   A cured film obtained by curing a film formed from the curable composition according to any one of claims 1 to 7.   The cured film according to claim 8, which is a protective film.   The cured film according to claim 8 or 9, wherein the pencil hardness at a load of 750 g measured according to JIS K5600: 1999 is 3H or more.   The organic electroluminescence display which has a cured film of any one of Claims 8-10.   The liquid crystal display device which has a cured film of any one of Claims 8-10.   The touch panel which has a cured film according to any one of claims 8 to 10.   The touch panel display device which has a cured film of any one of Claims 8-10.