KR101791452B1 - Curable composition, method for producing cured film, cured film, and display device - Google Patents

Abstract

It is another object of the present invention to provide a curable composition which can obtain high hardness even when heated at a low temperature and to provide a cured film production method and a cured film using the curable composition and an organic EL display device and a liquid crystal display device using the cured film do.
The curable composition of the present invention contains a polymerizable compound having an ethylenically unsaturated bond, a polymerization initiator, an alkoxysilane compound, and an organic solvent, and is characterized in that the solid content of the solid component excluding the inorganic substance, the polymerization initiator and the alkoxysilane compound, And a ratio of urethane (meth) acrylate having a functionality of 70% by mass to 100% by mass.

Description

TECHNICAL FIELD [0001] The present invention relates to a curable composition, a method of producing a cured film, a cured film,

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

Flat panel displays such as liquid crystal display devices and organic EL display devices are widely used. In recent years, in order to reduce damage to a substrate or a circuit, and reduce energy consumption, it is required to lower the heating temperature of various cured films in the manufacturing process in these display manufacturing processes.

As such a curable composition, for example, Patent Document 1 is characterized in that a copolymer of an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride, an epoxy group-containing radically polymerizable compound and a monoolefinically unsaturated compound is dissolved in an organic solvent Based on the total weight of the thermosetting resin composition.

Patent Document 1: JP-A-6-157716

However, the curable composition described in Patent Document 1 requires a heating temperature of 200 占 폚 or higher, and when heated at a low temperature (for example, 180 占 폚 or lower, or even 150 占 폚 or lower), sufficient hardness can not be obtained.

An object of the present invention is to provide a curable composition which can obtain high hardness even when heated at a low temperature. It is also an object of the present invention to provide a cured film production method and cured film using the curable composition, and an organic EL display device and a liquid crystal display device using the cured film.

The above object of the present invention has been solved by the means according to the following <1>, <7>, <10>, <13> or <14>. Are described below together with <2> to <6>, <8>, <9>, <11> and <12> which are the preferred embodiments.

(1) A positive resist composition comprising (A) a polymerizable compound having an ethylenically unsaturated bond, (B) a polymerization initiator, (C) an alkoxysilane compound, and (D) an organic solvent, (Meth) acrylate having 12 or more and 50 or less functionalities in a solid content excluding a silane compound is 80% by mass to 100% by mass,

<2> A curable composition according to <1>, further comprising (E) inorganic particles,

<3> The curable composition according to <1> or <2>, wherein the polymerization initiator (B) comprises an oxime ester compound,

<4> A thermosetting resin composition according to <1>, wherein the polymerizable compound having an ethylenically unsaturated bond (A) comprises a polymerizable compound having an ethylenic unsaturated bond other than urethane (meth) To < 3 >, the curable composition according to any one of &

<5> The curable composition according to any one of <1> to <4>, which further comprises a polyfunctional mercapto compound.

<6> The curable composition according to any one of <1> to <5>, which further comprises a block isocyanate compound.

(1) a step of applying the curable composition according to any one of <1> to <6> on a substrate, (2) a step of removing the solvent from the applied curable composition, and (3) A method for producing a cured film,

(3) A process for producing a cured film according to <7>, wherein the thermosetting temperature in the step of thermosetting is 80 ° C. to 150 ° C.,

<7> A method for producing a cured film according to <7> or <8>, which comprises a step of (2) a step of removing solvent, and (3)

&Lt; 10 > A cured film obtained by curing a curable composition according to any one of < 1 > to < 6 &

&Lt; 11 > a protective film, < 10 > a cured film,

<12> A cured film according to <10> or <11>, wherein the pencil hardness at a load of 750 g measured according to JIS K5600 is at least 2H,

&Lt; 13 > An organic EL display device having a cured film according to any one of < 10 > to < 12 &

<14> A liquid crystal display device having a cured film according to any one of <10> to <12>.

According to the present invention, it becomes possible to provide a curable composition which can obtain high hardness even when heated at a low temperature. It is also possible to provide a method for producing a cured film, a cured film using the curable composition, and an organic EL display device and a liquid crystal display device using the cured film.

Fig. 1 shows a configuration diagram of an example of an organic EL display device. 1 is a schematic cross-sectional view of a substrate in a bottom emission type organic EL display device, and has a planarization film 4.
2 is a conceptual diagram showing an example of the configuration of a liquid crystal display device. Sectional view of an active matrix substrate in a liquid crystal display device and has a cured film 17 as an interlayer insulating film.
Fig. 3 shows a configuration diagram of an example of a liquid crystal display device having a function of a touch panel.
4 is a conceptual diagram showing another example of a liquid crystal display device having a touch panel function.

Hereinafter, the contents of the present invention will be described in detail. Descriptions of the constituent elements described below may be made on the basis of exemplary embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, "" is used to mean that the numerical values described before and after the lower limit and the upper limit are included. The organic EL element in the present invention refers to an organic electroluminescence element.

In the notation of the group (atomic group) in the present specification, the notation in which substitution and non-substitution are not described includes those having a substituent and having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (an unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

In the present specification, "(meth) acrylate" refers to acrylate and methacrylate, "(meth) acryl" refers to acryl and methacryl, "(meth) acryloyl" And methacryloyl.

In the present invention, "mass%" and "% by weight" are synonyms, and "part by mass" and "part by weight"

Further, in the present invention, a combination of preferred embodiments is more preferable.

In the present invention, the molecular weight of the polymerizable compound (A) having an ethylenically unsaturated bond is measured by ESI-MS (Electrospray Ionization Mass Spectrometry). The polymer component is a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) when tetrahydrofuran (THF) is used as a solvent.

Even in the case of (A) a polymerizable compound having an ethylenically unsaturated bond, the weight of the compound having a molecular weight of 5,001 or more, in terms of polystyrene reduced by gel permeation chromatography (GPC) when tetrahydrofuran (THF) Average molecular weight.

(A) a polymerizable compound having an ethylenic unsaturated bond, (B) a polymerization initiator, (C) an alkoxysilane compound, and (D) an organic solvent (Meth) acrylate in a solid content excluding an inorganic substance, a polymerization initiator and an alkoxysilane compound from a total solid content of the composition is 70% by mass to 100% by mass. With such a constitution, a cured film which can be cured at a low temperature and has a high hardness can be obtained.

The curable composition of the present invention may further contain (E) an inorganic particle, a polymerizable compound having an ethylenically unsaturated bond other than a urethane (meth) acrylate having 6 or more functional groups, a polyfunctional mercapto compound, a block isocyanate compound And may contain other components.

Specifically, a composition comprising the following components is illustrated as a specific embodiment.

&Lt; First Embodiment >

Six or more functionalized urethane (meth) acrylates

(B) Polymerization initiator

(C) an alkoxysilane compound

(D) Organic solvents

(Preferably a polymerizable monomer having an ethylenically unsaturated bond) having an ethylenic unsaturated bond other than a urethane (meth) acrylate compound having 6 or more functionalities,

&Lt; Second Embodiment >

Six or more functionalized urethane (meth) acrylates

(B) Polymerization initiator

(C) an alkoxysilane compound

(D) Organic solvents

Polyfunctional mercapto compound

&Lt; Third Embodiment >

Six or more functionalized urethane (meth) acrylates

(B) Polymerization initiator

(C) an alkoxysilane compound

(D) Organic solvent block isocyanate compound

&Lt; Fourth Embodiment &

Six or more functionalized urethane (meth) acrylates

(B) Polymerization initiator

(C) an alkoxysilane compound

(D) Organic solvents

(E) an inorganic particle having an average particle diameter of 1 to 200 nm

&Lt; Embodiment 5 >

Six or more functionalized urethane (meth) acrylates

(B) Polymerization initiator

(C) an alkoxysilane compound

(D) Organic solvents

(Preferably a polymerizable monomer having an ethylenically unsaturated bond) having an ethylenic unsaturated bond other than a urethane (meth) acrylate compound having 6 or more functionalities,

Polyfunctional mercapto compound

&Lt; Sixth Embodiment &

Six or more functionalized urethane (meth) acrylates

(B) Polymerization initiator

(C) an alkoxysilane compound

(D) Organic solvent Multifunctional mercapto compound block Isocyanate compound

&Lt; Seventh Embodiment &

Six or more functionalized urethane (meth) acrylates

(B) Polymerization initiator

(C) an alkoxysilane compound

(D) Organic solvents

(E) an inorganic particle having an average particle diameter of 1 to 200 nm

(Preferably a polymerizable monomer having an ethylenically unsaturated bond) having an ethylenic unsaturated bond other than a urethane (meth) acrylate compound having 6 or more functionalities,

Polyfunctional mercapto compound

&Lt; Embodiment 8 >

Six or more functionalized urethane (meth) acrylates

(B) Polymerization initiator

(C) an alkoxysilane compound

(D) Organic solvents

(E) Inorganic particles having an average particle diameter of 1 to 200 nm Multifunctional mercapto compound Block isocyanate compound

&Lt; Ninth Embodiment &

Six or more functionalized urethane (meth) acrylates

(B) Polymerization initiator

(C) an alkoxysilane compound

(D) Organic solvents

(E) an inorganic particle having an average particle diameter of 1 to 200 nm

(Preferably a polymerizable monomer having an ethylenically unsaturated bond) having an ethylenic unsaturated bond other than a urethane (meth) acrylate compound having 6 or more functionalities,

Polyfunctional mercapto compound block isocyanate compound

<Tenth Embodiment>

In any one of the first to ninth embodiments, the embodiment in which the surfactant is further blended

&Lt; (A) Polymerizable compound having ethylenically unsaturated bond >

The curable composition of the present invention contains (A) a polymerizable compound having an ethylenic unsaturated bond.

The polymerizable compound having an ethylenically unsaturated bond in the present invention may contain an ethylenic unsaturated bond, may be a low molecular weight compound, may be an oligomer or a polymer.

The content of the (A) polymerizable compound having an ethylenically unsaturated bond is preferably 40% by mass or more, more preferably 50% by mass or more, and more preferably 60% by mass or less, based on the total amount of (A) in the solid content of the curable resin composition More preferably at least 70% by mass, and particularly preferably at least 70% by mass. The upper limit is not particularly limited, but is preferably 99 mass% or less, more preferably 95 mass% or less, for example. When blending inorganic particles to be described later, it is preferably 80 mass% or less, and more preferably 75 mass% or less. The "solid content" in the curable composition means a component excluding volatile components such as an organic solvent.

The polymerizable compound having an ethylenically unsaturated bond used in the present invention includes urethane (meth) acrylate having 6 or more functionalities.

As the polymerizable compound having an ethylenic unsaturated bond, an alkoxysilane compound corresponding to the alkoxysilane compound described later is used.

<< 6-Functional Euretene (Meth) Acrylate >>

The curable composition of the present invention is such that the ratio of the urethane (meth) acrylate having 6 or more functional groups in the solid content excluding the inorganic substance, the polymerization initiator and the alkoxysilane compound from 70% by mass to 100% By mass, more preferably from 80 to 100% by mass, still more preferably from 85 to 100% by mass.

The polymerizable compound having an ethylenically unsaturated bond used in the present invention preferably contains a urethane (meth) acrylate having 6 or more functionalities in a proportion of 70 to 100 mass%, preferably 75 to 100 mass% More preferably 100% by mass, and still more preferably 95% by mass to 100% by mass. In the above-described aspect, the effect of the present invention is more effectively exhibited.

The content of the urethane (meth) acrylate having 6 or more functional groups is preferably 40% by mass or more, more preferably 50% by mass or more, further preferably 65% by mass or more based on the total solid content of the curable composition , And the upper limit is not particularly limited, but is preferably 95% by mass or less.

The content of the urethane (meth) acrylate having six or more functional groups is preferably at least 60% by mass based on the solid content excluding the inorganic substances (inorganic particles, etc.), the polymerization initiator and the alkoxysilane compound from the total solid content of the curable composition By mass, more preferably not less than 70% by mass, and most preferably not less than 80% by mass.

The content of the urethane (meth) acrylate having 6 or more functional groups is preferably 60% by mass or more, more preferably 70% by mass or more, and most preferably 80% by mass or more, of the organic solid content of the curable composition. The term "organic solid content" as used herein means a solid content of an organic substance, excluding organic particles such as polymer particles, inorganic particles such as metal oxide particles, and pigment components such as organic inorganic pigments, from the solid content of the composition.

The number of (meth) acryloxy groups in the urethane (meth) acrylate having 6 or more functionalities is preferably 8 or more, more preferably 10 or more, and most preferably 12 or more. With this configuration, the effects of the present invention are more effectively exhibited.

The upper limit of the number of the (meth) acryloxy groups is not particularly limited, but when it is not a polymer structure, it is preferably 50 or less, more preferably 30 or less, still more preferably 20 or less.

The curable composition of the present invention may contain only one type of urethane (meth) acrylate having six or more functional groups, or two or more kinds thereof. When two or more kinds are included, it is preferable that the total amount falls within the above range.

Examples of the urethane (meth) acrylate having six or more functional groups usable in the present invention include urethane addition polymerizable compounds prepared by the addition reaction of isocyanate and hydroxyl group, and JP-A- 51-37193, JP-A-2-32293 and JP-A-2-16765 are exemplified, and these bases are used in the specification of the present invention.

The molecular weight of the urethane (meth) acrylate having six or more functionalities is preferably 500 to 20,000, more preferably 650 to 6,000, and even more preferably 800 to 3,000 from the viewpoint of the hardness of the cured film.

With this configuration, the effects of the present invention are more effectively exhibited.

The (meth) acryloxy group in the urethane (meth) acrylate having 6 or more functionalities may be either an acryloxy group or a methacryloxy group, or both may be an acryloxy group.

The number of urethane bonds in the urethane (meth) acrylate having 6 or more functionalities is not particularly limited, but is preferably 1 to 30, more preferably 1 to 20, and more preferably 2 to 10 Particularly preferably 2 to 5, and most preferably 2 or 3.

The urethane (meth) acrylate having 6 or more functionalities is preferably an aliphatic urethane (meth) acrylate having 6 or more functionalities.

It is preferable that the urethane (meth) acrylate having 6 or more functional groups has an isocyanur ring structure.

The urethane (meth) acrylate having 6 or more functional groups is a compound composed of a core moiety having at least one urethane bond and a terminal moiety bonded to the core moiety and having at least one (meth) acryloxy group More preferably, the core portion is a compound having two or more of the terminal portions bonded thereto, more preferably a compound having two to five of the terminal portions bonded to the core portion, Or a compound in which the three terminal portions are bonded.

The urethane (meth) acrylate having 6 or more functionalities is preferably a compound having at least a group represented by the following formula (Ae-1) or (Ae-2), and preferably has a group represented by the following formula Compound is more preferable. The urethane (meth) acrylate having 6 or more functionalities is more preferably a compound having two or more groups selected from the group consisting of a group represented by the following formula (Ae-1) and a group represented by the formula (Ae-2).

The end portion of the urethane (meth) acrylate having 6 or more functional groups is preferably a group represented by the following formula (Ae-1) or (Ae-2).

[Chemical Formula 1]

In the formulas (Ae-1) and (Ae-2), each R independently represents an acrylic group or a methacryl group, and a broken line portion represents a bonding position with another structure.

The urethane (meth) acrylate having 6 or more functionalities is preferably a compound having at least a group represented by the following formula (Ac-1) or (Ac-2) Is more preferable.

The core portion of the urethane (meth) acrylate having six or more functional groups is preferably represented by the following formula (Ac-1) or (Ac-2) from the viewpoints of hardness, low temperature curability, adhesion, solvent resistance, Lt; / RTI &gt;

(2)

In the formulas (Ac-1) and (Ac-2), L ¹ to L ⁴ each independently represent a divalent hydrocarbon group having 2 to 20 carbon atoms, and the broken line indicates the bonding position with other structures.

L ¹ to L ⁴ each independently represent an alkylene group having 2 to 20 carbon atoms, more preferably an alkylene group having 2 to 10 carbon atoms, and more preferably an alkylene group having 4 to 8 carbon atoms. The alkylene group may have a branched or cyclic structure, but is preferably a straight chain alkylene group.

The urethane (meth) acrylate having 6 or more functional groups is a group comprising a group represented by the formula (Ac-1) or (Ac-2) and a group represented by the formula (Ae-1) Is a compound in which two or three groups selected from the above-mentioned groups are bonded.

Hereinafter, the urethane (meth) acrylate having six or more functions, which is preferably used in the present invention, is exemplified, but it is needless to say that the present invention is not limited thereto.

(3)

[Chemical Formula 4]

[Chemical Formula 5]

U-6HA, U-6HA, U-6HA, U-6HA, U-6HA, U-6HA available from Shin Nakamura Kagaku Kogyo Co., Ltd. as commercially available products of urethane (meth) UA-306H, UA-306H, UA-510H, and BASF available from Kyoeisha Chemical Co., Ltd., U-10PA, UA-53H, Larger UA-9048, UA-9050, PR9052, EBECRYL 220, 5129, 8301, KRM8200, 8200AE, 8452 available from Daicelonex Co.,

<< Other polymerizable compounds having ethylenically unsaturated bonds >>

The curable composition of the present invention contains a polymerizable compound having an ethylenic unsaturated bond other than a urethane (meth) acrylate having 6 or more functional groups (also referred to as "polymerizable compound having other ethylenic unsaturated bond") But it is preferable not to include it.

The polymerizable compound having an ethylenic unsaturated bond other than the urethane (meth) acrylate having 6 or more functionalities may be a polymer (for example, a molecular weight of 2,000 or more), a monomer (for example, , Molecular weight of 100 or more and less than 2,000), and monomers are preferable.

As the polymerizable compound having an ethylenically unsaturated bond other than the urethane (meth) acrylate having 6 or more functionalities, a (meth) acrylate compound is preferable. The number of functional groups of the (meth) acrylate compound is preferably 2 to 6, more preferably 3 to 6. With this configuration, the effects of the present invention are more effectively exhibited.

Specific examples include pentaerythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate ethylene oxide (EO) modified product, dipentaerythritol hexa Rate EO modified product, and the like.

The other polymerizable compound having an ethylenically unsaturated bond may contain urethane (meth) acrylate having five or less functionalities. As the urethane (meth) acrylate having five or less functionalities, the following compounds are exemplified.

[Chemical Formula 6]

(7)

When the curable composition of the present invention contains a polymerizable compound having an ethylenically unsaturated bond other than a urethane (meth) acrylate having 6 or more functionalities, it is contained in an amount of 0.1 to 20 mass% of the total solid content of the composition , More preferably in the range of 0.5 to 10 mass%, and more preferably in the range of 1 to 5 mass%.

The curable composition of the present invention may contain only one type of polymerizable compound having an ethylenic unsaturated bond other than a urethane (meth) acrylate having 6 or more functionalities, or may contain two or more kinds. When two or more kinds are included, it is preferable that the total amount falls within the above range.

&Lt; (B) Polymerization initiator >

The curable composition of the present invention contains (Component B) a polymerization initiator.

As the polymerization initiator, it is preferable to include a radical polymerization initiator.

The radical polymerization initiator usable in the present invention is a compound capable of initiating and promoting polymerization of a urethane (meth) acrylate compound having 6 or more functions by light and / or heat. Among them, a photopolymerization initiator is preferable, and a photoradical polymerization initiator is more preferable.

The "light" is not particularly limited as long as it is an active energy ray capable of imparting energy capable of generating an open species from the component B by the irradiation. The light is broadly classified into? Rays,? Rays, X rays, ultraviolet rays (UV) Visible light, electron beam, and the like. Of these, light containing at least ultraviolet light is preferable.

Examples of the photopolymerization initiator include oxime ester compounds, organic halogenated compounds, oxadiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxide compounds, azo compounds, coumarin compounds, Compounds, metallocene compounds, hexaarylbimidazole compounds, organic boric acid compounds, disulfonic acid compounds, onium salt compounds, and acylphosphine (oxide) compounds. Of these, oxime ester compounds and hexaarylbimidazole compounds are preferable from the viewpoint of sensitivity, and oxime ester compounds are more preferable.

As the oxime ester compound, there can be mentioned, for example, JP-A 2000-80068, JP-A 2001-233842, JP-A 2004-534797, JP-A 2007-231000, and JP-A 2009-134289 The compounds described can be used.

Oxime ester compound is preferably a compound represented by the following formula (1) or (2).

[Chemical Formula 8]

Formula (1) or (2) of, Ar represents an aromatic group or heteroaromatic group, R ¹ represents an alkyl group, an aromatic group or alkyloxy, R ² represents a hydrogen atom or an alkyl group, and R ² is Ar group They may be combined to form a ring.

Ar represents an aromatic group or a heteroaromatic group, preferably a group obtained by removing one hydrogen atom from a benzene ring, a naphthalene ring or a carbazole ring, more preferably a naphthalenylene group or carbazolyl group forming a ring together with R ² .

R ¹ represents an alkyl group, an aromatic group or an alkyloxy group, preferably a methyl group, an ethyl group, a benzyl group, a phenyl group, a naphthyl group, a methoxy group or an ethoxy group, and more preferably a methyl group, an ethyl group, a phenyl group or a methoxy group.

R ² represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or a substituted alkyl group, more preferably a hydrogen atom, a substituted alkyl group forming a ring together with Ar or a toluenethioalkyl group.

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

[Chemical Formula 9]

Formula (3) to (5) of, R ¹ represents an alkyl group, an aromatic group or an alkoxy group, X is _{-CH 2 -, -C 2 H 4} -, denotes -O- or -S-, R ³ is each independently represents a halogen atom, R ⁴ are, each independently, an alkyl group, a phenyl group, an alkyl a substituted amino group, an aryl Sy, import an alkylthio, an alkoxy group, a represents an aryloxy group or a halogen atom, R ⁵ is hydrogen An alkyl group or an aryl group; R ⁶ represents an alkyl group; n 1 and n 2 each independently represent an integer of 0 to 6; and n 3 represents an integer of 0 to 5.

R ¹ represents an alkyl group, an aromatic group or an alkoxy group, preferably a group represented by R ¹¹ -X'-alkylene group (R ¹¹ represents an alkyl group or an aryl group, and X 'represents a sulfur atom or an oxygen atom). R ¹¹ is preferably an aryl group, and more preferably a phenyl group. The alkyl group and aryl group as R ¹¹ may be substituted with a halogen atom (preferably a fluorine atom, a chlorine atom or a bromine atom) or an alkyl group.

X is preferably a sulfur atom.

R ³ and R ⁴ may be bonded at arbitrary positions on the aromatic ring.

R ⁴ represents an alkyl group, a phenyl group, an alkyl substituted amino group, an arylthio group, an alkylthio group, an alkoxy group, an aryloxy group or a halogen atom, An oxygen atom or a halogen atom is more preferable, and an alkyl group or a halogen atom is more preferable. As the alkyl group, an alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group or an ethyl group is more preferable. The halogen atom is preferably a chlorine atom, a bromine atom or a fluorine atom.

The carbon number of R ⁴ is preferably 0 to 50, more preferably 0 to 20.

R ⁵ represents a hydrogen atom, an alkyl group or an aryl group, and an alkyl group is preferable. As the alkyl group, an alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group or an ethyl group is more preferable. The aryl group is preferably an aryl group having 6 to 10 carbon atoms.

R ⁶ represents an alkyl group, preferably an alkyl group having 1 to 5 carbon atoms, more preferably a methyl group or an ethyl group.

n1 and n2 each represent a substituted number of R ³ on the aromatic ring in the formula (3) or (4), and n3 represents the substituted number of the R ⁴ on the aromatic ring in the formula (5).

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

Examples of oxime ester compounds preferably used in the present invention are shown below. However, it is needless to say that the oxime ester compound used in the present invention is not limited to these. Also, Me represents a methyl group, and Ph represents a phenyl group.

[Chemical formula 10]

(11)

Specific examples of the organohalogenated compound include "Bull Chem. Soc. Japan" 42, 2924 (1969), U.S. Patent No. 3,905,815, Japanese Examined Patent Publication 46-4605, Japanese Patent Application Laid-Open Nos. 48-36281, 55-32070, 60-239736, 61-169835, 61-169837, JP Hutt "Journal of Heterocyclic Chemistry" 1 (No 3), JP-A-62-58241, JP-A 62-212401, JP-A 63-70243, JP-A 63-298339, , (1970), and the like. Among them, an oxazole compound and an s-triazine compound substituted with a trihalomethyl group are particularly exemplified.

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

Examples of the acylphosphine (oxide) compound include a monoacylphosphine oxide compound and a bisacylphosphine oxide compound. Specific examples thereof include Irgacure 819 manufactured by Chiba Specialty Chemicals Co., Cure 4265, and Multi-cure TPO.

The polymerization initiator may be used alone or in combination of two or more.

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

<Increase / decrease>

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

As a typical sensitizer that can be used in the present invention, V. Crivello, Adv. in Polymer Sci., 62, 1 (1984), and specific examples thereof include pyrene, perylene, acridine orange, thiazonthone, 2-chlorothiozantone, N-vinylcarbazole, 9,10-dibutoxyanthracene, anthraquinone, coumarin, ketocoumarin, phenanthrene, camphorquinone, and phenothiazine derivatives. The sensitizer is preferably added in a proportion of 50 to 200 mass% with respect to the polymerization initiator.

&Lt; (C) Alkoxysilane compound >

The curable composition of the present invention contains (C) an alkoxysilane compound. When the alkoxysilane compound is used, adhesion between the film formed by the curable composition of the present invention and the substrate can be improved.

The alkoxysilane compound is not particularly limited so long as it is a compound having at least a group in which the alkoxy group is directly bonded to the silicon atom, but a compound having a dialkoxysilyl group and / or a trialkoxysilyl group is preferable, and a compound having a trialkoxysilyl group More preferable.

The alkoxysilane compound that can be used in the curable composition of the present invention can be suitably selected from the group consisting of a substrate, a silicon compound such as silicon oxide, silicon oxide, and silicon nitride; a metal such as gold, copper, molybdenum, titanium, Is preferable. Specifically, known silane coupling agents and the like are also effective. A silane coupling agent having an ethylenically unsaturated bond is preferable.

As the silane coupling agent, there may be mentioned, for example,? -Aminopropyltrimethoxysilane,? -Aminopropyltriethoxysilane,? -Glycidoxypropyltrialkoxysilane,? -Glycidoxypropyldialkoxysilane ,? -methacryloxypropyltrialkoxysilane,? -methacryloxypropyldialkoxysilane,? -chloropropyltrialkoxysilane,? -mercaptopropyltrialkoxysilane,? - (3,4-epoxy Cyclohexyl) ethyltrialkoxysilane, vinyltrialkoxysilane, and the like. Among these,? -Methacryloxypropyltrialkoxysilane,? -Acryloxypropyltrialkoxysilane, vinyltrialkoxysilane and? -Glycidoxypropyltrialkoxysilane are more preferable. These may be used alone or in combination of two or more.

Commercially available products include KBM-403 and KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd.

The content of the alkoxysilane compound in the curable composition of the present invention is preferably from 0.1 to 30 parts by mass, more preferably from 2 to 20 parts by mass, still more preferably from 2 to 15 parts by mass per 100 parts by mass of the total solid content of the curable composition More preferred is an addition. The alkoxysilane compound may be a single kind or two or more kinds. When two or more kinds are included, the total amount is preferably in the above range.

&Lt; (D) Organic solvent >

The curable composition of the present invention contains (D) an organic solvent. The curable composition of the present invention is preferably prepared as a solution in which a component A, a component B, and a component C which are essential components and an optional component described later are dissolved in a solvent.

As the organic solvent to be used in the curable composition of the present invention, known solvents can be used, and examples thereof include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene But are not limited to, glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, Diethylene glycol monoalkyl ether, dipropylene glycol monoalkyl ether, butyleneglycol diacetates, dipropylene glycol dialkyl ether, dipropylene glycol monoalkyl ether acetates, alcohols, esters, ketones, amides , Lactones, and the like. As specific examples of these organic solvents, reference can be made to paragraph 0062 of Japanese Laid-Open Patent Publication No. 2009-098616.

Specific examples thereof include propylene glycol monomethyl ether acetate, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, 1,3-butylene glycol Cole diacetate, cyclohexanol acetates, propylene glycol diacetate, and tetrahydrofurfuryl alcohol are preferred.

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

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

The content of the organic solvent in the curable composition of the present invention is preferably from 100 to 3,000 parts by mass, more preferably from 200 to 2,000 parts by mass, per 100 parts by mass of the total solid content of the curable composition, from the viewpoint of adjusting the viscosity to a suitable viscosity for application And more preferably 250 to 1,000 parts by mass.

The solid content concentration of the curable composition is preferably from 3 to 50 mass%, more preferably from 20 to 40 mass%.

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

<(E) Inorganic Particles>

The curable composition of the present invention may contain inorganic particles. By containing the inorganic particles, the hardness of the cured film becomes more excellent. Further, by containing the inorganic particles, the adhesion to the substrate can be improved.

The average particle diameter of the inorganic particles used in the present invention is preferably 1 to 200 nm, more preferably 5 to 100 nm, and most preferably 5 to 50 nm. The average particle diameter refers to an arithmetic mean of 200 particle diameters of arbitrary particles measured by an electron microscope. When the particle shape is not spherical, the longest side is a 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 void. The porosity of the particles is 200 arithmetic mean of the area ratio of the void portion and the whole particle of the cross-sectional image by the electron microscope.

Examples of the inorganic particles include inorganic particles such as Be, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Gd, Tb, Dy, Yb, Lu, Ti, Zr, Hf, Nb, Mo, W, Metal oxide particles containing atoms such as Si, Ge, Sn, Pb, Sb, Bi and Te are preferable and silicon oxide, titanium oxide, titanium composite oxide, zinc oxide, zirconium oxide, indium / Tin oxide is more preferable, and silicon oxide, titanium oxide, titanium composite oxide, and zirconium oxide are more preferable, and silicon oxide or titanium oxide is preferable in view of stability of particle, ease of acquisition, hardness of hardened film, transparency, .

As the silicon oxide, silica is preferably used, and silica particles are more preferable.

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 a hydrate thereof as a main component (preferably 80 mass% or more) are preferable. The particles may contain an aluminate as a minor component (for example, less than 5 mass%). Examples of the aluminate salt which may be contained as a minor component include sodium aluminate and potassium aluminate. In addition, the silica particles may contain inorganic salts such as sodium hydroxide, potassium hydroxide, lithium hydroxide and ammonium hydroxide, and organic salts such as tetramethylammonium hydroxide. As an example of such a compound, colloidal silica is exemplified.

The dispersion medium of the colloidal silica is not particularly limited and may be any one of water, an organic solvent, and a mixture thereof. These may be used alone, or two or more kinds may be used in combination.

In the present invention, the particles may be provided for use as a dispersion prepared by mixing and dispersing in an appropriate dispersant and a solvent using a mixing device such as a ball mill or a rod mill. In the curable composition of the present invention, it is not essential that the colloidal silica exists in a colloidal state.

The content of the inorganic particles is preferably not less than 1 part by mass, more preferably not less than 5 parts by mass, and more preferably not less than 10 parts by mass, per 100 parts by mass of the total solid content of the curable composition, from the viewpoint of hardness. It is preferably 80 parts by mass or less, more preferably 50 parts by mass or less, further preferably 40 parts by mass or less, and particularly preferably 30 parts by mass or less.

The inorganic particles may contain only one kind or two or more kinds of inorganic particles. When two or more kinds are included, the total amount is preferably in the above range.

&Lt; Compound having an epoxy group, compound having an oxetanyl group, block isocyanate compound, polyfunctional mercapto compound >

The curable composition of the present invention preferably contains at least one member selected from the group consisting of a compound having an epoxy group, a compound having an oxetane group, a block isocyanate compound, and a polyfunctional mercapto compound. In the above embodiment, the hardness of the resulting cured product is more excellent.

&Lt; Compound having an epoxy group &gt;

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 per molecule, but preferably two or more.

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

These are available as commercial products. Examples of the bisphenol A epoxy resin include epoxy resins such as JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1055, JER1007, JER1009, JER1010 (manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON860, EPICLON1050, EPICLON1051, EPICLON1055 JER4005, JER4007, JER4010 (manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON830, EPICLON835 (manufactured by DIC Corporation), and the like can be used as the bisphenol F type epoxy resin. JER152, JER154, JER157S70, and JER157S65 (manufactured by Japan Epoxy Resins Co., Ltd.) as the phenol novolak type epoxy resin, EPICLON N-670, EPICLON N-770 and EPICLON N-775 (manufactured by DIC Corporation), and EPICLON N-660, EPICLON N-665, EPICLON N-690, EPICLON N-695 (manufactured by DIC Corporation) and EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd.) ADEKA RESIN EP-4 (Manufactured by ADEKA), Celloxide 2021P, Celloxide 2081, Celloxide 2083, Celloxide 2085, EHPE 3150, EPOLEAD PB 3600, PB 4700 (manufactured by ADEKA) Manufactured by Sekigaku Kogyo Co., Ltd.). In addition, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S and EP-4011S (manufactured by ADEKA), NC-2000, NC-3000, NC-7300, XD- -501, and EPPN-502 (manufactured by ADEKA Co., Ltd.).

In addition, the ethylene oxide skeleton having a skeleton of ethylene oxide described in Japanese Patent Publication No. 58-49860, Japanese Examined Patent Publication No. 56-17654, Japanese Examined Patent Publication No. 62-39417, Japanese Examined Patent Publication No. 62-39418 Phosphorus compounds are also suitably utilized, the contents of which are incorporated herein by reference.

When the curable composition of the present invention contains a compound having an epoxy group, it is preferably contained in an amount of 0.1 to 20 mass%, more preferably 0.5 to 10 mass%, of the total solid content of the composition, More preferably in the range of 1 to 5% by mass.

The curable composition of the present invention may contain only one type of epoxy group-containing compound, or may contain two or more kinds of compounds having an epoxy group. When two or more kinds are included, it is preferable that the total amount falls within 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 two or more is preferable.

Specific examples of the compound having an oxetanyl group may include Aromoxethene OXT-121, OXT-221, OX-SQ and PNOX (manufactured by DOA GOSEI CO., LTD.).

The oxetanyl group-containing compound is preferably used alone or in combination with a compound containing an epoxy group.

When the curable composition of the present invention contains a compound having an oxetanyl group, it is preferably contained in an amount of 0.1 to 20 mass%, more preferably 0.5 to 10 mass%, of the total solid content of the composition , More preferably in the range of 1 to 5% by mass.

The curable composition of the present invention may contain only one kind of oxetanyl group-containing compound or two or more kinds thereof. When two or more kinds are included, it is preferable that the total amount falls within the above range.

<< Block isocyanate compound >>

The curable composition of the present invention may contain a block isocyanate compound. The block isocyanate compound is not particularly limited as long as it is a compound having a block isocyanate group, but from the viewpoint of curability, a compound having two or more block isocyanate groups in one molecule is preferable. The upper limit of the number of the block isocyanate groups is not particularly limited, but is preferably 6 or less.

The skeleton of the block isocyanate compound is not particularly limited and may be any of those having two isocyanate groups in one molecule, and may be an aliphatic, alicyclic or aromatic polyisocyanate . For example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, isophoronediisocyanate, 1,6-hexamethylene diisocyanate, 1,3 -Trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate Hexamethylene diisocyanate, 1,9-nonamethylene diisocyanate, 1,10-decamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 2,2'-diethyl ether diisocyanate Cyanate, diphenylmethane-4,4'-diisocyanate, o-xylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, Methylene bis (cyclohexyl isocyanate), cyclohexane-1,3-dimethyl Diisocyanate, cyclohexane-1,4-dimethylene diisocyanate, 1,5-naphthalene diisocyanate, p-phenylene diisocyanate, 3,3'-methylene di Tolylene-4,4'-diisocyanate, 4,4'-diphenyl ether isocyanate, tetrachlorophenylene diisocyanate, norbornane diisocyanate, hydrogenated 1,3 - isocyanate compounds such as xylylene diisocyanate and hydrogenated 1,4-xylylene diisocyanate, and prepolymer type skeleton compounds derived from these compounds can be suitably used. Among them, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI) and isophoronediisocyanate (IPDI) are particularly preferable. desirable.

Examples of the parent structure of the block isocyanate compound in the composition of the present invention include buret type, isocyanurate type, adduct type, bifunctional prepolymer type and the like.

Examples of the block agent for forming the block structure of the block isocyanate compound include oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptane compounds, imidazole compounds, And the like. Among them, a block agent selected from an oxime compound, a lactam compound, a phenol compound, an alcohol compound, an amine compound, an active methylene compound, and a pyrazole compound is particularly preferable.

The block isocyanate compounds which can be used in the composition of the present invention are commercially available, for example, Colonate AP Stable M, Colonate 2503, 2515, 2507, 2513, 2555, Millionate MS-50 B-812N, B-820NSU, B-842N, B-846N, B-870N, B-874N and B-882N (manufactured by Nippon Polyurethane Industry Co., B60E, MF-B60X, MF-B60B, MF-K60X, MF-K60B, and E402-TPA-B80X, TPA-B80E, (Manufactured by Asahi Kasei Chemicals Co., Ltd.), Desmodur BL1100, BL1265 MPA / X, BL3575 / 1, BL3272MPA, BL3370MPA, BL3475BA / SN, BL5375MPA, VPLS2078 / 2, BL4265SN, PL340, PL350, and Sumidury BL3175 (manufactured by Sumika Bayer Co., Ltd.).

When the block isocyanate compound is included in the curable composition of the present invention, it is preferably contained in the range of 0.1 to 20 mass%, more preferably in the range of 0.5 to 10 mass%, of the total solid content of the composition , More preferably in the range of 1 to 5% by mass.

The curable composition of the present invention may contain only one type of block isocyanate compound, or may contain two or more kinds of block isocyanate compounds. When two or more kinds are included, it is preferable that the total amount falls within the above range.

<< Multifunctional mercapto compounds >>

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 the polyfunctional mercapto compound, an aliphatic polyfunctional mercapto compound is preferable. Preferable examples of the aliphatic polyfunctional mercapto compound include a compound composed of a combination of an aliphatic hydrocarbon group and -O-, -C (= O) -, a compound in which at least two hydrogen atoms of an aliphatic hydrocarbon group are substituted with a mercapto group .

Examples of the aliphatic polyfunctional mercapto compound include pentaerythritol tetrakis (3-mercaptobutylate), 1,4-bis (3-mercaptobutyryloxy) butane and the like. Examples of commercially available products include a car lens MT-PE-1, a car lens MT-BD-1, and a car lens MT-NR-1 (manufactured by Showa Denko K.K.).

When the curable composition of the present invention contains a polyfunctional mercapto compound, it is preferably contained in the range of 0.1 to 20 mass%, more preferably in the range of 0.5 to 10 mass%, of the total solid content of the composition , And more preferably 1 to 5 mass%.

The curable composition of the present invention may contain only one kind of polyfunctional mercapto compound, or may contain two or more kinds. When two or more kinds are included, it is preferable that the total amount falls within the above range.

<< Sulfide compound >>

The curable composition of the present invention may contain a sulfide compound. By containing the sulfide compound, a cured film excellent in substrate adhesion and moisture resistance can be obtained.

The sulfide compound is not particularly limited as long as it has a polysulfide bond, but it is preferably a compound having a disulfide bond, a triisulfide bond, a tetrasulfide bond, a pentasulfide bond, a hexasulfide bond, a disulfide bond, More preferably a compound having a tetrasulfide bond, and more preferably a compound having a disulfide bond or a tetrasulfide bond. When a compound having a disulfide bond or a tetrasulfide bond is used, moisture resistance is better.

The polysulfide bond may be linear, branched or cyclic, but is preferably a straight-chain polysulfide bond.

The sulfide compound is preferably a compound in which an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic group, or a monovalent group formed by combining two or more thereof is bonded to both sides of the polysulfide bond. A compound in which a hydrogen group, an aromatic hydrocarbon group, or a monovalent group combining two or more thereof is bonded is 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 amide 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 sulfide compound, a compound in which an aliphatic hydrocarbon group having a trialkoxysilyl group is bonded to both sides of the polysulfide bond is particularly preferable.

Specific examples of the sulfide compound are shown below, but the present invention is not limited to the following specific examples. In the following formulas, Ph represents a phenyl group, Me represents a methyl group, and Et represents an ethyl group.

[Chemical Formula 12]

In the present invention, the sulfide compounds may be used singly or in combination of two or more.

In the present invention, the content of the sulfide compound is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass, and still more preferably 0.5 to 5% by mass, based on the total solid content of the curable composition . Within the above range, a cured film having excellent substrate adhesion and moisture resistance can be obtained.

The curable composition of the present invention may contain a compound other than the above (for example, an alkoxymethyl group-containing compound and the like) within a range not deviating from the gist of the present invention. Examples of the alkoxymethyl group-containing compound include those described in paragraphs 0192 to 0194 of Japanese Laid-Open Patent Publication No. 2011-221494.

In the present invention, in the total of compounds selected from a polymerizable compound having an ethylenic unsaturated bond, a compound having an epoxy group, a compound having an oxetanyl group, a block isocyanate compound, and a polyfunctional mercapto compound, (Preferably 95% by mass or more) of the total amount of the components to be cured by heat or light, and more preferably 90% by mass or more (preferably 95% by mass or more) of the polymerizable compound having an ethylenic unsaturated bond and the block isocyanate compound It is more preferable that the total amount of the compounds selected accounts for 90% by mass or more (preferably 95% by mass or more) of the curable compound.

In the case of containing at least one of a polymerizable compound having an ethylenic unsaturated bond, a compound having an epoxy group, a compound having an oxetanyl group, a block isocyanate compound, and a polyfunctional mercapto compound, , Preferably 0.1 to 20 mass%, more preferably 1 to 10 mass%, of the curable compound. With this 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 may be used, but preferred surfactants are nonionic surfactants. The surfactant is preferably a nonionic surfactant, more preferably a fluorinated surfactant.

Examples of the surfactant that can be used in the present invention include commercially available products such as MegaPark F142D, copper F172, copper F173, copper F176, copper F177, copper F183, copper F479, copper F482, copper F554, copper F780, copper F781, FC-135, FC-170C, FC-170C, FC-170C, FC-170C, FC-170C, and FC- S-113, S-131, S-141 (manufactured by Sumitomo 3M Ltd.), Asahi Guard AG7105, 7000, 950, 7600, Surfron S- S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105 and SC-106 (manufactured by Asahi Glass Co., (Available from Mitsubishi Material Denshi Kasei Co., Ltd.) and Fotogen 250 (manufactured by Neos Co., Ltd.). In addition to the above, other materials such as KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyfluor (manufactured by Kyoeisha Chemical Co., Ltd.), Epson (manufactured by Mitsubishi Material Denshi Kasei Co., (Manufactured by Sumitomo 3M Ltd.), Asahi Guard, Surfron (manufactured by Asahi Glass Co., Ltd.), PolyFox (manufactured by OMNOVA), and the like.

As the surfactant, the weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography with the constituent unit A and the constituent unit B represented by the following formula (W) and using tetrahydrofuran as a solvent is 1,000 Or more and 10,000 or less is a preferred example.

[Chemical Formula 13]

In the formula (W), R ^W1 and R ^W3 each independently represent a hydrogen atom or a methyl group, R ^W2 represents a straight chain alkylene group having 1 to 4 carbon atoms and R ^W4 represents a hydrogen atom or a C1- represents an alkyl group, L ^W represents an alkylene or less carbon atoms more than 3 6, p and q is a weight representing the polymerization ratio percentage, p represents a numerical value of less than 10% by mass to 80% by weight, q is 20 mass% Or more and 90 mass% or less, r is an integer of 1 or more and 18 or less, and s is an integer of 1 or more and 10 or less.

It is preferable that L ^W is a branched alkylene group represented by the following formula (W-2). R ^W5 in the formula (W-2) represents an alkyl group having 1 to 4 carbon atoms and is preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability to a surface to be coated, An alkyl group is more preferred.

It is preferable that the sum (p + q) of p and q in the formula (W) is p + q = 100, that is, 100 mass%.

The weight average molecular weight (Mw) of the copolymer is more preferably from 1,500 to 5,000.

[Chemical Formula 14]

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

The surfactant may be contained only in one kind or in two or more kinds. When two or more kinds are included, the total amount is preferably in the above range.

<Antioxidant>

The curable composition of the present invention may contain an antioxidant. As the antioxidant, a known antioxidant may be contained. By adding an antioxidant, coloring of the cured film can be prevented, or film thickness reduction due to decomposition can be reduced, and furthermore, there is an advantage that the heat resistance and transparency are excellent.

Examples of such antioxidants include antioxidants such as phosphorus antioxidants, amides, hydrazides, hindered amine antioxidants, sulfur antioxidants, phenol antioxidants, ascorbic acids, zinc sulfate, sugars, nitrites, Thiosulfate, hydroxylamine derivatives, and the like. Among them, a phenol-based antioxidant, a hindered amine-based antioxidant, a phosphorus-based antioxidant and a sulfur-based antioxidant are particularly preferable from the viewpoint of coloring of the cured film and reduction of the film thickness. These may be used alone or in combination of two or more.

Specific examples include the compounds described in paragraphs 0026 to 0031 of Japanese Laid-Open Patent Publication No. 2005-29515, and those described in paragraphs 0106 to 0116 of Japanese Laid-Open Patent Publication No. 2011-227106, the contents of which are incorporated herein by reference.

Adekastab AO-80, adecastab AO-412S (manufactured by ADEKA), Irganox 1035, and Irganox 1098 (manufactured by BASF) were used as preferred commercial products, .

The content of the antioxidant is not particularly limited, but is preferably 0.1 to 10 mass%, more preferably 0.2 to 5 mass%, and even more preferably 0.5 to 4 mass%, based on the total solid content of the curable composition .

<Polymerization inhibitor>

The curable composition of the present invention may contain a polymerization inhibitor. The polymerization inhibitor refers to a polymerization inhibitor which is obtained by conducting hydrogen donation (or hydrogen donation), energy donation (or energy donation), electron donation (or electron donation), etc. to the polymerization initiating radical component generated from the polymerization initiator by exposure or heat, Is a substance that plays a role of inactivating the polymerization initiation radical and inhibiting the polymerization initiation. For example, the compounds described in paragraphs 0154 to 0173 of JP-A No. 2007-334322 and the like can be used.

Preferred examples of the compound include phenothiazine, phenoxazine, hydroquinone, and 3,5-dibutyl-4-hydroxytoluene.

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

&Lt; Binder polymer &

The curable composition of the present invention may contain a binder polymer from the viewpoints of improving the resolution and film properties.

The binder polymer is not particularly limited and a known one can be used, but a linear organic polymer is preferably used. As such a linear organic polymer, any known one can be used. Preferably, a linear organic polymer that is soluble or swellable in water or weak alkaline water is selected to enable water development or weak alkaline water development. The linear organic polymer is selectively used not only as a film-forming agent, but also as a water, weakly alkaline water or organic solvent developer. For example, water-soluble organic polymers enable water development. Examples of such linear organic polymers include radical polymers having a carboxylic acid group in the side chain, for example, JP-A 59-44615, JP-A 54-34327, JP-A 58-12577, Japanese Patent Application Laid-Open No. 54-25957, Japanese Patent Application Laid-Open No. 54-92723, Japanese Patent Application Laid-Open No. 59-53836, Japanese Patent Application Laid-Open No. 59-71048, that is, A resin in which an acid anhydride unit is hydrolyzed, half-esterified or half-aminated, or an epoxy acrylate in which an epoxy resin is modified with an unsaturated monocarboxylic acid and an acid anhydride, or the like, . Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid and 4-carboxystyrene. Monomers having an acid anhydride include maleic anhydride.

Similarly, there is an acidic cellulose derivative having a carboxylic acid group in the side chain. In addition, it is useful to add a cyclic acid anhydride to the polymer having a hydroxyl group.

As the binder polymer, a resin obtained by copolymerizing (meth) acrylic acid with 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 from 1 to 40% by mass, more preferably from 3 to 30% by mass, More preferably 20% by mass.

<Other components>

To the curable composition of the present invention, other components such as plasticizers, thermal acid generators, acid proliferators and the like may be added, if necessary, in addition to the above-mentioned components. As for these components, for example, those disclosed in Japanese Patent Laid-Open Publication No. 2009-98616, Japanese Patent Laid-Open Publication No. 2009-244801, and other known ones can be used. In addition, various ultraviolet absorbers, metal deactivators, and the like described in "New developments of polymer additives (Nikken Kogyo Shinbashi Co., Ltd.") may be added to the curable composition of the present invention.

&Lt; Cured article and manufacturing method thereof &

The cured product of the present invention is a cured product obtained by curing the curable composition of the present invention. The cured product is preferably a cured film. The cured product of the present invention is preferably a cured product obtained by the production method of the cured product of the present invention.

The method for producing a cured product of the present invention is not particularly limited as long as it is a method for producing a cured product by curing the curable composition of the present invention, but preferably includes the following steps (1) to (3).

(1) a step of applying the curable composition of the present invention on a substrate

(2) a step of removing the solvent from the applied curable composition

(3) Process for thermosetting

It is more preferable that the method for producing a cured product of the present invention includes 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 the organic solvent from the coated curable composition

(2 ') a step of light curing the curable composition from which the organic solvent has been removed

(3) a step of further curing the light cured cured material by heat

The method for producing a cured product of the present invention is preferably a method for producing a cured film.

In the step of coating the substrate (1), it is preferable that the curable composition of the present invention is applied to a substrate to form a wet film containing a solvent. The substrate can be cleaned, such as alkali cleaning or plasma cleaning, before the curable composition is applied to the substrate. After the substrate is cleaned, the surface of the substrate can be treated with hexamethyldisilazane or the like. By carrying out this treatment, the adhesion of the curable composition to the substrate tends to be improved.

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

Examples of the inorganic substrate include glass, quartz, silicon, silicon nitride, and composite substrates obtained by depositing molybdenum, titanium, aluminum, copper or the like on a substrate such as glass, quartz, silicon or silicon nitride.

Examples of the resin include polyolefin resins such as polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polystyrene naphthalate, polystyrene, polycarbonate, polysulfone, polyethersulfone, polyarylate, allyl diglycolcarbonate, Fluorine resins such as polyimide, polyamideimide, polyetherimide, polybenzazole, polyphenylene sulfide, polycycloolefin, norbornene resin and polychlorotrifluoroethylene, liquid crystal polymers, acrylic resins, epoxy resins, silicone A substrate made of a synthetic resin such as a resin, an ionomer resin, a cyanate resin, a crosslinked fumaric acid diester, a cyclic polyolefin, an aromatic ether, a maleimide-olefin copolymer, a cellulose or an episulfide resin. These substrates are rarely used in the above-described form, and a multi-layered laminate structure such as a TFT element is usually formed depending on the shape of the final product.

Since the curable composition of the present invention has good adhesion to the metal film or the metal oxide formed by sputtering, it is preferable that the substrate includes a metal film formed by sputtering. The metal is preferably titanium, copper, aluminum, indium, tin, manganese, nickel, cobalt, molybdenum, tungsten, chromium, silver, neodymium and their oxides or alloys. Molybdenum, , Copper, and an alloy thereof. The metal or metal oxide may be used singly or in combination.

The coating method for the substrate is not particularly limited and methods such as ink jet method, slit coat method, spray method, roll coating method, spin coating method, flexible coating method, slit-and-spin method, .

In the step of removing the solvent in the step (2), it is preferable that the solvent is removed from the applied film by vacuum (vacuum pressure) and / or heating to form a dry film on the substrate. The heating condition of the solvent removing step is preferably about 70 to 130 DEG C for about 30 to 300 seconds. In the solvent removing step, it is not necessary to completely remove the organic solvent in the curing composition, and at least part of the organic solvent may be removed.

The present invention may also include a step of exposing the entire surface from the viewpoint of (2) the step of removing the solvent, and (3) the step of hardening the film before the step of hardening the film.

In addition, from the viewpoint of improving the film hardness, (2 ') the step of curing the curable composition from which the organic solvent has been removed is cured by light before (2) the step of removing the solvent, and (3) It is more preferable to include a step of curing the curable composition from which the organic solvent has been removed by full-surface exposure. In the case of curing by light as in the above embodiment, the curable composition of the present invention preferably contains a photopolymerization initiator.

In this case, it is preferable to perform energy exposure of about 50 to 3,000 mJ / cm ^{2 using a} mercury lamp or an LED lamp.

For the pattern formation, pattern exposure and development steps can be performed after the solvent removal step (2). The pattern exposure method is preferably a method using a mask, or a method such as direct imaging with a laser or the like. It is preferable from the viewpoint of accelerated curing to perform these whole surface exposure or pattern exposure in an oxygen-cut state. As a means for blocking oxygen, it is exemplified that exposure is performed in a nitrogen atmosphere or an oxygen blocking film is provided.

For pattern exposure and development, a known method or a known developer may be used. For example, the pattern exposure method and the developing method described in JP-A-2011-186398 and JP-A-2013-83937 can be suitably used.

(3) In the step of thermosetting, a polymerizable compound having an ethylenic unsaturated bond may be polymerized by heating to form a cured film, or the cured cured product may be further cured. When the polymerization is carried out by heating, the curable composition of the present invention preferably contains a thermal polymerization initiator.

The heating temperature is preferably 180 占 폚 or lower, more preferably 150 占 폚 or lower, and even more preferably 130 占 폚 or lower. The lower limit value is preferably 80 DEG C or higher, more preferably 90 DEG C or higher. The method of heating is not particularly limited, and a known method can be used. Examples thereof include a hot plate, an oven, and an infrared heater.

The heating time is preferably about 1 minute to 30 minutes in the case of the hot plate, and preferably about 20 minutes to 120 minutes in the other cases. Within this range, it is possible to cure without damage to the substrate or the apparatus. From the viewpoint of shape adjustment after heating, heating can be carried out at a lower temperature than at the first time and later at a higher temperature (for example, addition of a middle baking step, for example, heating at 90 캜 for 30 minutes and then at 120 캜 for 30 minutes).

The cured film of the present invention is a cured film obtained by curing the curable composition of the present invention.

The cured film of the present invention can be suitably used as a protective film or an interlayer insulating film. It is preferable that the cured film of the present invention is a cured film obtained by the method for producing a cured film of the present invention.

By the curable composition of the present invention, a cured film having sufficient hardness even at a low temperature can be obtained. For example, a cured film having a pencil hardness of 2H or more is obtained. The protective film formed by curing the curable composition of the present invention is useful for an organic EL display device or a liquid crystal display device because of excellent physical properties of the cured film.

Since the curable composition of the present invention has excellent curability and cured film properties, the cured product or the resist pattern cured by the curable composition of the present invention may be used as a structural member of a MEMS device or may be introduced as part of a mechanical drive component Is used. Examples of such MEMS devices include SAW filters, BAW filters, gyro sensors, micro-shutters for displays, image sensors, electronic paper, inkjet heads, biochips, and sealants. More specific examples are exemplified 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 planarization film 57 shown in Fig. 2 of Japanese Laid-Open Patent Publication No. 2011-107476, The bank layer 221 and the third interlayer insulating film 216b shown in FIG. 10 of Japanese Laid-Open Patent Publication No. 2010-27591, the barrier layer 12 and the planarization film 102 described in FIG. 4 (a) The second interlayer insulating film 125 and the third interlayer insulating film 126 shown in Fig. 4A of JP-A No. 128577, the planarization film 12 and the pixel isolation insulating film 14 described in Fig. 3 of JP-A No. 2010-182638 May also be used for the formation of &lt; RTI ID = In addition, a spacer for keeping the thickness of the liquid crystal layer in the liquid crystal display device constant, a focusing optical system of an on-chip color filter such as a color filter, a color filter protective film, a facsimile, an electronic copying machine, It can be suitably used for a micro lens of 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 or an interlayer insulating film formed using the curable composition of the present invention, and various known organic EL display devices and liquid crystal display devices having various structures .

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

1 is a conceptual diagram showing an example of an organic EL display device. 1 is a schematic cross-sectional view of a substrate in a bottom emission type organic EL display device, and has a planarization film 4.

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. A contact hole (not shown) is formed in the insulating film 3 and a wiring 2 (height 1.0 mu m) connected to the TFT 1 through the contact hole is formed on the insulating film 3 . The wiring 2 is for connecting the organic EL element formed between the TFTs 1 or the subsequent steps and the TFT 1. [

The flattening film 4 is formed on the insulating film 3 in a state of filling the irregularities formed by the wirings 2 in order to planarize the irregularities due to the formation of the wirings 2.

On the planarizing film 4, a bottom-emission organic EL element is formed. That is, the first electrode 5 made of ITO is formed on the planarization film 4 by being connected to the wiring 2 through the contact hole 7. The first electrode 5 corresponds to the anode of the organic EL element.

The insulating film 8 is formed so as to cover the periphery of the first electrode 5. By providing the insulating film 8, the short circuit between the first electrode 5 and the second electrode formed in the subsequent steps Can be prevented.

Although not shown in FIG. 1, a hole transporting layer, an organic light emitting layer, and an electron transporting layer are sequentially deposited and formed through a desired pattern mask. Then, a second electrode made of Al is formed on the entire upper surface of the substrate, It is possible to obtain an active matrix type organic EL display device in which the sealing glass plate and the ultraviolet curable epoxy resin are used to seal each other by sealing and the TFT 1 for driving each organic EL element is connected.

<Liquid Crystal Display Device>

The liquid crystal display device of the present invention is characterized by having the cured film of the present invention.

As the liquid crystal display of the present invention, there is no particular limitation but a known liquid crystal display device having various structures other than those having a protective film, a planarizing film and an interlayer insulating film formed using the curable composition of the present invention.

As a liquid crystal driving method that can be adopted by the liquid crystal display of the present invention, twisted nematic (TN), VA (virtual alignment), IPS (in-place switching) Optically Compensated Bend) method.

In the panel configuration, the cured film of the present invention can also be used in a liquid crystal display device of a color filter on array (COA) system. For example, the organic insulating film 115 of Japanese Patent Laid-Open Publication No. 2005-284291, -346054, which is an organic insulating film. Specific examples of the alignment method of the liquid crystal alignment film that the liquid crystal display device of the present invention can take include a rubbing alignment method and a photo alignment method. It may also be polymer-oriented supported by the PSA (Polymer Sustained Alignment) technique described in Japanese Unexamined Patent Application Publication No. 2003-149647 or Japanese Unexamined Patent Publication No. 2011-257734.

In addition, the curable composition of the present invention and the cured film of the present invention are not limited to the above-mentioned applications and can be used for various purposes. For example, in addition to a planarizing film and an interlayer insulating film, a protective film, a spacer for keeping the thickness of the liquid crystal layer in the liquid crystal display device constant, and a microlens provided on a color filter in a solid- have.

2 is a conceptual cross-sectional view showing an example of the liquid crystal display device 10 of the active matrix type. The color liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on its back surface and the liquid crystal panel is a liquid crystal display panel in which all the pixels And the elements of the TFT 16 corresponding to the TFTs 16 are disposed. 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 the liquid crystal 20 and a black matrix are arranged is provided.

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

The liquid crystal display device may be a 3D (stereoscopic) type or a touch panel type. It can also be used as a flexible type, and can be used as the second interlayer insulating film 48 described in JP-A-2011-145686 or the interlayer insulating film 520 described in JP-A-2009-258758.

Examples of the touch panel type include so-called in-cell type (for example, Japanese Laid-Open Patent Publication No. 2012-517051, FIGS. 5, 6, 7 and 8) (Fig. 14 of Japanese Patent Application Laid-Open No. 43394, Fig. 2 (b) of International Publication No. 2012/141148), OGS type, TOL type, and other configurations (for example, Fig. 6 of Japanese Laid-Open Patent Publication No. 2013-164871).

3 is a conceptual diagram showing an example of a liquid crystal display device having a touch panel function.

For example, it is preferable that the cured film of the present invention is applied to a protective film between layers in Fig. 3, and it is also suitable to be applied to an interlayer insulating film which intercepts detection electrodes of a touch panel. The detection electrode of the touch panel is preferably silver, copper, aluminum, titanium, molybdenum, or an alloy thereof.

In Fig. 3, reference numeral 110 denotes a pixel substrate, 140 denotes a liquid crystal layer, 120 denotes an opposing substrate, and 130 denotes a sensor section. The pixel substrate 110 has 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. 3 have. The counter substrate 120 has an alignment film 121, a color filter 122, and a transparent substrate 123 in this order from the bottom of Fig. The sensor unit 130 has a retardation film 124, an adhesive layer 126, and a polarizing plate 127, respectively. 3, reference numeral 125 denotes a sensing electrode for a sensor. The cured film of the present invention can be applied to various protective films (not shown) of an insulating layer 114 (also referred to as an interlayer insulating film) or various protective films (not shown) of a pixel substrate portion, various protective films (Not shown) of the sensor portion, and the like.

Also, in the liquid crystal display device of the static driving system, it is also possible to display a pattern having high designability by applying the present invention. For example, the present invention can be applied to an insulating film of a polymer network type liquid crystal as described in Japanese Patent Application Laid-Open No. 2001-125086.

4 is a conceptual diagram showing another example of a liquid crystal display device having a touch panel function.

A lower panel 200 corresponding to a thin film transistor panel having a thin film transistor (TFT) 440, a plurality of color filters 330 provided on a surface facing the lower panel 200 opposite to the lower panel 200 And a liquid crystal layer 400 formed between the lower panel 200 and the upper panel 300. The liquid crystal layer 400 includes liquid crystal molecules (not shown).

The lower display panel 200 includes a first insulating substrate 210, a thin film transistor (TFT) arranged on the first insulating substrate 210, an insulating film 280 formed on the upper surface of the thin film transistor TFT, And a pixel electrode 290 disposed on the pixel electrode 290. The thin film transistor TFT includes 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, (272).

A contact hole 282 is formed in the insulating film 280 so that the drain electrode 272 of the thin film transistor TFT is exposed.

The upper display panel 300 includes a light shielding member 320 arranged on one surface of a second insulating substrate 310 and arranged in a matrix form, a color filter 330 arranged on the second insulating substrate 310, And a common electrode 370 for applying a voltage to the liquid crystal layer 400 in correspondence with the pixel electrode 290 of the lower panel 200.

4, a sensing electrode 410, an insulating film 420, a driving electrode 430, and a protective film 280 are disposed on the other surface of the second insulating substrate 310. 4, the sensing electrode 410, the insulating film 420, the driving electrode 430, and the like, which are components of the touch screen, are formed at the time of forming the upper panel 300. In this case, Can be formed together. In particular, the cured film obtained by curing the curable composition of the present invention can be suitably used for the insulating film 420.

Example

Hereinafter, the present invention will be described in more detail by way of examples. The materials, the amounts to be used, the ratios, the contents of the treatments, the processing procedures, and the like shown in the following examples can be appropriately changed as long as they do not depart from the gist of the present invention. Therefore, the scope of the present invention is not limited to the following specific examples. Unless otherwise specified, "part" and "%" are based on mass.

&Lt; Synthesis Example 1: Synthesis of A-5 >

50.4 g of hexamethylene diisocyanate trimer (TPA-100, manufactured by Asahi Kasei Corporation) and 157.4 g of dipentaerythritol pentaacrylate (obtained by column refining the Aldrich agent) were mixed in a toluene solvent, followed by curing 0.2 g of U-CAT SA 102 (manufactured by SAN-A PRO) was added as a catalyst, and the mixture was heated at 60 캜 for 6 hours under a nitrogen atmosphere.

After cooling, the reaction mixture was purified and separated by silica gel column chromatography to obtain 15-functional urethane acrylate A-5.

[Chemical Formula 15]

&Lt; Synthesis Example 2: Synthesis of A-6 >

Synthesis and purification were carried out in the same manner as in Synthesis Example 1 except that hexamethylene diisocyanate trimer in Synthesis Example 1 was changed to hexamethylene diisocyanate (manufactured by Tokyo Kasei Kogyo Co., Ltd.) Of urethane acrylate A-6 was obtained.

[Chemical Formula 16]

<Euretne Acrylate>

A-1: NK oligo U-15HA (manufactured by Shin Nakamura Kagaku Kogyo Co., Ltd.), the number of functional groups 15

A-2: UA-306H (manufactured by Kyoeisha Chemical Co., Ltd.), the number of functional groups 6

A-3: Laromer UA-9050 (manufactured by BASF), number of functional groups 8

A-4: NK Oligo U-10HA (manufactured by Shin Nakamura Kagaku Kogyo Co., Ltd.), the number of functional groups 10

A-5: Synthesis Example 1, the number of functional groups 15

A-6: Synthesis Example 2, the number of functional groups 10

A'-1: NK oligo U-2PPA (manufactured by Shin Nakamura Kagaku Kogyo Co., Ltd.), the number of functional groups 2

<Acrylate>

A'-2: dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.)

&Lt; Radical polymerization initiator &

B-1: Compound 1 (synthesized product, see below), oxime ester compound

B-2: IRGACURE OXE-01 (manufactured by BASF), oxime ester compound,

B-3: IRGACURE OXE-02 (manufactured by BASF), oxime ester compound,

B-4: IRGACURE 907 (manufactured by BASF), aminoalkylphenone compound

[Chemical Formula 17]

<Alkoxysilane compound>

C-1: KBM-403 (3-glycidoxypropyltriethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.)

C-2: KBM-5103 (3-acryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.)

<Organic solvents>

D-1: Propylene glycol monomethyl ether acetate (Daicel Co.)

D-2: Methyl ethyda diglycol (Daicel Co., Ltd.)

D-3: 1,3-Butylene glycol diacetate

D-4: Tetrahydrofurfuryl alcohol

<Inorganic Particles>

E-1: PMA-ST (manufactured by Nissan Chemical Industries, Ltd.), silica particles, average particle diameter of 10 to 15 nm

E-2: MIBK-ST-L (manufactured by Nissan Chemical Industries, Ltd.), silica particles, average particle diameter of 40 to 50 nm

<Multifunctional mercapto compound>

S-1: Car lens MT-PE-1 (pentaerythritol tetrakis (3-mercaptobutylate), manufactured by Showa Denko K.K.), number of functional groups 4

S-2: Car lens MT-BD-1 (1,4-bis (3-mercaptobutyryloxy) butane, manufactured by Showa Denko K.K.)

&Lt; Block isocyanate compound >

S-3: Takenate B870N (oxime block of isophoronediisocyanate, manufactured by Mitsui Chemicals, Inc.)

S-4: Dyuranate 17B-60P (a block isocyanate compound having a biuret structure and a block structure of oxime ester structure, manufactured by Asahi Kasei Chemicals Co., Ltd.)

<Surfactant>

W-1: Megafac F554 (manufactured by DIC Corporation), fluorochemical surfactant

W-2: FTX-218 (manufactured by Neos Co., Ltd.), a surfactant

<Increase / decrease>

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

<Antioxidant>

J-1: adecastab AO-60 (hindered phenol antioxidant, manufactured by ADEKA Corporation)

<Polymerization inhibitor>

K-1: phenothiazine

<Sulfide compound>

L-1: Compound of the following structure

[Chemical Formula 18]

(Wherein Bu represents a butyl group).

[Chemical Formula 19]

(Wherein Et represents an ethyl group).

&Lt; Synthesis of Compound (B-1) >

<< Synthesis of Compound A >>

Ethyl carbazole (100.0 g, 0.512 mol) was dissolved in 260 ml of chlorobenzene, cooled to 0 占 폚, and then aluminum chloride (70.3 g, 0.527 mol) was added. Then, o-toluoyl chloride (81.5 g, 0.527 mol) was added dropwise over 40 minutes, the temperature was raised to room temperature (25 캜, the same applies hereinafter) and the mixture was stirred for 3 hours. Next, after cooling to 0 占 폚, aluminum chloride (75.1 g, 0.563 mol) was added. 4-Chlorobutyryl chloride (79.4 g, 0.563 mol) was added dropwise over 40 minutes, the temperature was raised to room temperature, and the mixture was stirred for 3 hours. A mixed solution of 156 ml of a 35 mass% aqueous hydrochloric acid solution and 392 ml of distilled water was cooled to 0 deg. C, and the reaction solution was added dropwise. The precipitated solid was subjected to suction filtration, washed with distilled water and methanol, and recrystallized from acetonitrile to obtain Compound A (yield: 164.4 g, yield: 77%) of the following structure.

[Chemical Formula 20]

<< Synthesis of Compound B >>

Compound A (20.0 g, 47.9 mmol) obtained above was dissolved in 64 ml of tetrahydrofuran (THF), 4-chlorobenzene thiol (7.27 g, 50.2 mmol) and sodium iodonate (0.7 g, 4.79 mmol) Was added. Sodium hydroxide (2.0 g, 50.2 mmol) was then added to the reaction solution and the mixture was refluxed for 2 hours. Next, SM-28 (11.1 g, 57.4 mmol, 28% methanol solution of sodium methoxide, manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise over 20 minutes, cooled to 0 캜, stirred at room temperature for 2 hours did. Next, after cooling to 0 占 폚, isopentyl nitrite (6.73g, 57.4mmol) was added dropwise over 20 minutes, the temperature was raised to room temperature and stirred for 3 hours. The reaction solution was diluted with 120 ml of acetone and added dropwise to a 0.1N hydrochloric acid aqueous solution cooled to 0 占 폚. The precipitated solid was subjected to suction filtration and then washed with distilled water. Subsequently, recrystallization from acetonitrile was conducted to obtain compound B (yield: 17.0 g, yield 64%) of the following structure.

[Chemical Formula 21]

<< Synthesis of Compound 1 >>

Compound B (18.0 g, 32.4 mmol) was dissolved in 90 ml of N-methylpyrrolidone (NMP) and triethylamine (Et ₃ N, 3.94 g, 38.9 mmol) was added. Then, after cooling to 0 캜, acetyl chloride (AcCl, 3.05 g, 38.9 mmol) was added dropwise over 20 minutes, the temperature was raised to room temperature, and the mixture was stirred for 2 hours. The reaction solution was added dropwise to 150 ml of distilled water cooled to 0 占 폚. The precipitated solid was filtered by suction and washed with 200 ml of isopropyl alcohol cooled to 0 占 폚. After drying, Compound 1 (yield 19.5 g, yield 99%) .

[Chemical Formula 22]

The structure of Compound 1 thus obtained was identified by NMR.

^{1 H-NMR (400MHz, CDCl} 3): δ = 8.86 (s, 1H), 8.60 (s, 1H), 8.31 (d, 1H, J = 8.0Hz), 8.81 (d, 1H, J = 8.0Hz) , 7.51-7.24 (m, 10H), 7.36 (q, 2H, 7.4 Hz), 3.24-3.13 (m, 4H), 2.36 Hz).

(Examples 1 to 19 and Comparative Examples 1 to 3)

<Preparation of Curable Composition>

As shown in Tables 1 and 2, each component was mixed and stirred to prepare a solution and / or dispersion of an organic solvent, which was then filtered through a polytetrafluoroethylene filter having a pore diameter of 0.3 m to obtain a curable composition of the present invention . The unit of each component in the following table is the mass part excluding the solid content concentration. In addition to the organic solvent, it represents the part by mass in terms of solid content.

&Lt; Evaluation of pencil hardness &

Each of the curable compositions prepared above was spin-coated on a glass substrate and prebaked at 90 캜 for 120 seconds to obtain a coated film having a thickness of 2.0 탆. Next, light irradiation at 500 mJ / cm ² (i line conversion) was performed by a high-pressure mercury lamp, and the cured film was baked at 120 ° C for 60 minutes in an oven.

The obtained cured film was subjected to a pencil hardness test by a method (load: 750 g) in accordance with JIS K5600 to evaluate the film strength. 2H is the practical range.

[Table 1]

[Table 2]

As is apparent from Tables 1 and 2, the curable composition of the present invention had a high hardness even when cured at a low temperature.

<Fabrication of Display Device>

In the display device shown in Fig. 4, the display device was manufactured by using the curable composition obtained in each of the examples of the present invention for the touch detection electrode protective film (insulating film) 420. Specifically, the protective film 420, makes the inkjet coating and, 90 ℃, 120 seconds pre-bake the curable compositions obtained in the respective examples of the present invention, the light of 500mJ / cm ² (i-ray conversion) by the high pressure mercury lamp Followed by baking at 120 DEG C for 60 minutes in an oven. The other parts of the display device were produced in accordance with the manufacturing method described in Japanese Laid-Open Patent Publication No. 2013-168125 as shown in Fig. The produced display device was 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
12: Backlight unit
14, 15: glass substrate
16: TFT
17:
18: Contact hole
19: ITO transparent electrode
20: liquid crystal
22: Color filter
110: pixel substrate
111: polarizer
112: transparent substrate
113: common electrode
114: insulating layer
115:
116: Orientation film
120: opposing substrate
121: alignment film
122: Color filter
123: transparent substrate
124: retardation film
126: Adhesive layer
127: polarizer
130:
140: liquid crystal layer
200: Lower 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 panel
310: second insulating substrate
320:
330: Color filter
370: common electrode
400: liquid crystal layer
410: sensing electrode
420: insulating film
430: driving electrode
440: TFT

Claims (14)

A polymerizable compound having an ethylenically unsaturated bond,
Polymerization initiator,
An alkoxysilane compound, and
Containing organic solvent,
(Meth) acrylate having 12 or more and 50 or less functional groups in a solid content excluding an inorganic substance, a polymerization initiator and an alkoxysilane compound from 80% by mass to 100% by mass
Curable composition. The method according to claim 1,
Wherein the curable composition further contains inorganic particles. The method according to claim 1 or 2,
Wherein the polymerization initiator comprises an oxime ester compound. The method according to claim 1 or 2,
Wherein the polymerizable compound having an ethylenically unsaturated bond comprises a polymerizable compound having an ethylenically unsaturated bond other than the above-mentioned 12-functional and 50-functional urethane (meth) acrylates. The method according to claim 1 or 2,
A curable composition, further comprising a polyfunctional mercapto compound. The method according to claim 1 or 2,
&Lt; / RTI &gt; further comprising a block isocyanate compound. A step of applying the curable composition according to claim 1 or 2 on a substrate,
Removing the solvent from the applied curable composition, and
Comprising a step of thermal curing
A method for producing a cured film. The method of claim 7,
Wherein the thermosetting temperature in the thermosetting step is 80 deg. C or more and 150 deg. C or less. The method of claim 7,
And a step of exposing the entire surface after the step of removing the solvent and before the step of thermosetting. A cured film obtained by curing the curable composition according to claim 1 or 2. The method of claim 10,
A protective film, a cured film. The method of claim 10,
A cured film having a pencil hardness of 2H or more at a load of 750 g measured according to JIS K5600. An organic EL display device having a cured film according to claim 10. A liquid crystal display device having a cured film according to claim 10.

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