TWI693260B - Curable composition, cured film, organic EL display device, liquid crystal display device, touch panel and touch panel display device - Google Patents

Abstract

The curable composition of the present invention contains an ethylenically unsaturated compound as component A, a polymerization initiator as component B, a mercapto compound as component C, and an organic solvent as component D, and component A contains 5 or more functional carbamates Ester (meth)acrylate, the content of the above 5-functional urethane (meth)acrylate is 20 to 100 parts by mass relative to 100 parts by mass of the component A, and the content of the above 5-functional urethane The (meth)acrylate includes a urethane (meth)acrylate having a weight average molecular weight of 10,000 or more and a urethane (meth)acrylate having a molecular weight of 5,000 or less.

Description

Curable composition, cured film, organic EL display device, liquid crystal display Device, touch panel and touch panel display device

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

Flat panel displays such as liquid crystal display devices and organic EL (Electroluminescence) display devices are widely used. Conventionally, in electronic components such as liquid crystal display elements, integrated circuit elements, solid-state imaging elements, organic EL, etc., generally, a flattening film for imparting flatness to the surface of the electronic component is formed to prevent deterioration or damage of the electronic component When using a protective film or an interlayer insulating film for maintaining insulation, a curable composition is used. For example, a TFT (Thin-Film Transistor, thin film transistor) type liquid crystal display element is provided with a polarizing plate on a glass substrate to form a transparent conductive circuit layer such as indium tin oxide (ITO) and a thin film transistor (TFT), with an interlayer insulating film It is coated to form a back panel. On the other hand, a polarizer is provided on a glass substrate, and a pattern of a black matrix layer and a color filter layer is formed as necessary, and a transparent conductive circuit layer and an interlayer insulating film are formed in this order to form an upper panel. The back panel and the upper panel are opposed to each other with a spacer, and liquid crystal is sealed between the two panels.

In addition, in recent years, with the popularity of smart phones and tablet terminals, electrostatic capacity touch panels have attracted attention. The structure of the sensor substrate of the capacitive touch panel generally has transparent electrodes (ITO (Indium Tin Oxide, IndiumTinOxide) or IZO (Indium Zinc) on glass or thin film Oxides, IndiumZincOxide, etc.) or metal electrodes (silver, copper, molybdenum, titanium, aluminum, etc., or their laminates or alloys, etc.) are patterned wiring, and also have an insulating film at the intersection of the wiring, protective ITO And metal protective film.

As a conventional curable composition used for such an insulating film or a protective film, the composition described in Patent Document 1 or 2 is known.

[Prior Art Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. 2011-126921

Patent Document 2: Japanese Patent Laid-Open No. 2010-39475

Recently, in the manufacturing steps of these display devices and the like, from the viewpoint of reducing damage to substrates, circuits, etc., and saving energy, it has been pointed out that the heating temperature of various cured films in the manufacturing step needs to be lowered.

The problem to be solved by the present invention is to provide a curable composition that can be cured at a low temperature, has excellent scratch resistance, and can obtain high hardness.

In addition, another problem to be solved by the present invention is to provide a cured film obtained by curing the curable composition, a liquid crystal display device, an organic EL display device, a touch panel, and a touch panel display device having the cured film.

The above-mentioned subject of the present invention is described in the following <1>, <10> or <13> to <16> Solution. It is described below together with <2> to <9>, <11> and <12> which are preferred embodiments.

<1> A curable composition characterized by containing an ethylenically unsaturated compound as component A, a polymerization initiator as component B, a mercapto compound as component C, and an organic solvent as component D, and component A contains 5 More than functional urethane (meth)acrylate, the content of the above five functional urethane (meth)acrylate is 20 to 100 parts by mass relative to 100 parts by mass of component A, and the above five functional The above urethane (meth)acrylate includes urethane (meth)acrylate having a weight average molecular weight of 10,000 or more and urethane (meth)acrylate having a molecular weight of 5,000 or less.

<2> The curable composition according to <1>, wherein Component B contains an oxime ester compound.

<3> The curable composition according to <1> or <2>, wherein Component A contains an ethylenically unsaturated compound other than the above-mentioned 5-functional urethane (meth)acrylate.

<4> The curable composition according to <3>, wherein the ethylenically unsaturated compound other than the above five-functional urethane (meth)acrylate is a polyfunctional ethylenically unsaturated compound.

<5> The curable composition according to any one of <1> to <4>, wherein the content of component A is 70% by mass or more with respect to the total organic solid content of the curable composition.

<6> The curable composition according to any one of <1> to <5>, wherein the above five-functional urethane (meth)acrylate contains two or more types of the molecular weight of 5,000 or less Of urethane (meth)acrylate.

<7> The curable composition according to any one of <1> to <6>, wherein Component C contains 2 Mercapto compounds above functional.

<8> The curable composition according to any one of <1> to <7>, further containing inorganic particles as component E.

<9> The curable composition according to any one of <1> to <8>, which further contains a blocked isocyanate compound and/or an alkoxysilane compound.

<10> A cured film obtained by curing the curable composition according to any one of <1> to <9>.

<11> The cured film according to <10>, which is a protective film.

<12> The cured film according to <10> or <11>, which has a pencil hardness of 2H or more under a load of 750 g measured in accordance with JISK5600:1999.

<13> An organic EL display device having the cured film according to any one of <10> to <12>.

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

<15> A touch panel having the cured film according to any one of <10> to <12>.

<16> A touch panel display device having the cured film according to any one of <10> to <12>.

According to the present invention, it is possible to provide a curable composition excellent in coatability and capable of obtaining high hardness even when cured at a low temperature.

In addition, according to the present invention, it is possible to provide a cured film obtained by curing the curable composition, a liquid crystal display device, an organic EL display device, a touch panel and a touch panel having the cured film Control panel display device.

1: TFT (thin film transistor)

2: wiring

3: insulating film

4: Flattening film

5: first electrode

6: Glass substrate

7: contact hole

8: insulating film

10: Liquid crystal display device

12: backlight unit

14, 15: glass substrate

16:TFT

17: hardened film

18: contact hole

19: ITO transparent electrode

20: LCD

22: Color filter

110: pixel substrate

111: polarizer

112: Transparent substrate

113: Common electrode

114: Insulation

115: pixel electrode

116: Alignment film

120: Opposite substrate

121: Alignment film

122: Color filter

123: Transparent substrate

124: retardation film

125: detection electrode for sensor

126: adhesive layer

127: Polarizer

130: Sensor Department

140: liquid crystal layer

200: lower display panel

210: the first insulating substrate

220: gate electrode

240: gate insulating film

250: semiconductor layer

260, 262: ohmic contact layer

270: source electrode

272: Drain electrode

280: insulating film

282: contact hole

290: Image electrode

300: upper display panel

310: Second insulating substrate

320: shading parts

330: Color filter

350: Alignment film

370: common electrode

400: liquid crystal layer

410: sensing electrode

420: insulating film

430: drive electrode

440: TFT

FIG. 1 is a conceptual diagram showing an example of an organic EL display device. A schematic cross-sectional view showing a substrate in a bottom-emission organic EL display device, including a planarizing film 4.

2 is a conceptual diagram showing an example of a liquid crystal display device. A schematic cross-sectional view showing an active matrix substrate in a liquid crystal display device, and has a cured film 17 as an interlayer insulating film.

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

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

Hereinafter, the content of the present invention will be described in detail. The description of the constituent elements described below is sometimes based on the representative embodiments of the present invention, but the present invention is not limited to such embodiments. In addition, in this specification, "~" is used as the meaning including the numerical value described before and after it as a lower limit and an upper limit. In addition, the organic EL element in the present invention refers to an organic electroluminescence element.

In the description of the group (atomic group) in the present specification, the description of substituted and unsubstituted does not include the group without a substituent and the group with a substituent. For example, "alkyl" includes not only an unsubstituted alkyl group (unsubstituted alkyl group) but also an substituted alkyl group (substituted alkyl group).

In addition, in this specification, "(meth)acrylate" means acrylate and methacrylate, "(meth)acrylic acid" means acrylic acid and methacrylic acid, "(meth)acrylic acid" "Base" means acryloyl and methacryloyl.

In the present invention, "ethylenically unsaturated compound" and the like are also simply referred to as "component A" and the like.

In addition, in the present invention, "mass%" and "weight%" have the same meaning, and "parts by mass" and "parts by weight" have the same meaning.

In addition, in the present invention, a combination of two or more preferred aspects is a more preferred aspect.

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

(Hardening composition)

The curable composition of the present invention (hereinafter, also simply referred to as "composition") is characterized by containing an ethylenically unsaturated compound as component A, a polymerization initiator as component B, a mercapto compound as component C, and as a component Organic solvent of D, component A contains more than 5 functional urethane (meth)acrylates, the content of the above 5 functional urethane (meth)acrylates relative to the content of component A is 100 parts by mass 20 to 100 parts by mass, the urethane (meth)acrylate having 5 or more functions includes a urethane (meth)acrylate having a weight average molecular weight of 10,000 or more and a urethane having a molecular weight of 5,000 or less ( Meth)acrylate.

The curable composition of the present invention preferably further contains inorganic particles as component E.

By including these components, sufficient film strength can be achieved. The mechanism is estimated as follows. By using two urethane (meth)acrylates with different molecular weights, the compatibility with the mercapto compound in the coated film is improved. It is considered that by hardening the coating film, it is uniform in the film The presence of soft segments derived from mercapto compounds and urethanes and hard segments derived from (meth)acrylates can prevent scratches when measuring the hardness of pencils and prevent flaking due to dispersed loads. In addition, it is considered that the effect of free radical chain transfer by the mercapto compound, in particular, the strength of the surface of the membrane increases, and the resistance to steel wool also improves. Therefore, by using the composition of the present invention, the above-mentioned problems can be solved.

In addition, the curable composition of the present invention may further contain other ethylenically unsaturated compounds, alkoxysilane compounds, and/or blocked isocyanate compounds other than urethane (meth)acrylates with more than 5 functions. Ingredients.

Ingredient A: ethylenically unsaturated compound

The curable composition of the present invention contains the ethylenically unsaturated compound as component A.

In addition, the curable composition of the present invention contains a urethane (meth)acrylate having 5 or more functions as an ethylenically unsaturated compound.

The ethylenically unsaturated compound in the present invention only needs to have an ethylenically unsaturated bond, and it may be a low-molecular compound, an oligomer, or a polymer.

In addition, the content of the ethylenically unsaturated compound is preferably 40% by mass or more, more preferably 50% by mass or more, further preferably 60% by mass or more, and particularly preferably 70% by mass or more in the entire organic solid content of the curable composition. . The upper limit is not particularly specified, but it is preferably 98% by mass or less, and more preferably 95% by mass or less.

In addition, when the inorganic particles described below are blended, the content of the ethylenically unsaturated compound is preferably 80% by mass or less, and more preferably 75% by mass or less in the total solid content of the curable composition. In addition, the "solid content" in the curable composition means components other than volatile components such as organic solvents, and the "organic solid component" in the curable composition means that there is no Components other than volatile components such as organic components and organic solvents.

In addition, in the present invention, a compound that is an ethylenically unsaturated compound and corresponds to an alkoxysilane compound described later, that is, a compound having an alkoxysilyl group and an ethylenically unsaturated group is an alkoxysilane compound.

In addition, in the present invention, the urethane (meth)acrylate is a compound having one or more urethane bonds and one or more (meth)acryloyloxy groups.

<5 or more functional urethane (meth)acrylate>

In the curable composition of the present invention, the content of the urethane (meth)acrylate having 5 or more functions is 20 to 100 parts by mass, preferably 20 to 69 parts by mass, relative to 100 parts by mass of the component A content. Within the above range, the effects of the present invention can be more effectively exhibited.

The number of (meth)acryloyloxy groups in the urethane (meth)acrylate having 5 or more functions is preferably 6 or more, more preferably 10 or more, and particularly preferably 12 or more. With such a structure, the effect of the present invention can be more effectively exerted.

In addition, the upper limit of the number of (meth)acryloyloxy groups is not particularly limited, but is preferably 500 or less. In the case of not having a polymer structure, it is more preferably 50 or less, further preferably 30 or less, and particularly preferably Below 20.

The curable composition of the present invention may contain only one kind of urethane (meth)acrylate having more than 5 functions, or may contain two or more kinds. When two or more types are included, the total amount is preferably within the above range. The upper limit of the kind of the urethane (meth)acrylate contained in more than 5 functions is not particularly limited, and may be 100 kinds or less.

Examples of urethane (meth)acrylates with more than 5 functions that can be used in the present invention include urethanes produced by the addition reaction of isocyanate groups and hydroxyl groups The addition polymerizable compound may be exemplified by urethane acrylates as described in Japanese Patent Laid-Open No. 51-37193, Japanese Patent No. 2-32293, and Japanese Patent No. 2-16765. Is incorporated into the specification of this application.

The (meth)acryloyloxy group in the urethane (meth)acrylate with more than 5 functions may be any one of acryloyloxy group and methacryloyloxy group, or both, but Preferably it is propylene acetyloxy.

The urethane (meth)acrylate having more than 5 functions is preferably an aliphatic urethane (meth)acrylate having more than 5 functions.

In addition, the urethane (meth)acrylate having 5 or more functions preferably has an isocyanuric acid ring structure.

In addition, the urethane (meth)acrylate having 5 or more functions is preferably composed of a core portion having at least one urethane bond and a (meth)acryl amide bonded to the core portion and having at least one The compound composed of the terminal part of the oxygen group is more preferably a compound in which two or more of the terminal parts are bonded to the core part.

The urethane (meth)acrylate having more than 5 functions is preferably a compound having at least the group represented by the following formula Ae-1 or formula Ae-2, and more preferably has at least the following formula Ae-1 Group of compounds. In addition, the urethane (meth)acrylate having 5 or more functions is more preferably selected from the group consisting of a group represented by the following formula Ae-1 and a group represented by the formula Ae-2, having two or more Group of compounds.

In addition, the terminal portion in the urethane (meth)acrylate having 5 or more functions is preferably a group represented by the following formula Ae-1 or formula Ae-2.

[Chemical Formula 1]

In Formula Ae-1 and Formula Ae-2, R independently represents an acrylic group or a methacrylic group, and the wavy line portion represents a bonding position with another structure.

The curable composition of the present invention contains a urethane (meth)acrylate having a weight average molecular weight of 10,000 or more and a urethane (meth)acrylate having a molecular weight of 5,000 or less as a urethane having 5 or more functions (Meth)acrylate.

In the curable composition of the present invention, the content of the urethane (meth)acrylate having a weight average molecular weight of 10,000 or more is preferably 100 parts by mass of the content of the urethane (meth)acrylate having 5 or more functions. It is 1 to 90 parts by weight, more preferably 5 to 70 parts by weight, and particularly preferably 10 to 60 parts by weight.

In the curable composition of the present invention, the content of the urethane (meth)acrylate having a molecular weight of 5,000 or less is preferably 10 with respect to 100 parts by mass of the urethane (meth)acrylate having 5 or more functions. ~99 parts by weight, more preferably 15 to 95 parts by weight, and particularly preferably 20 to 90 parts by weight.

<<urethane (meth)acrylate with a weight average molecular weight of 10,000 or more>>

The curable composition of the present invention contains a urethane (meth)acrylate having a weight average molecular weight of 10,000 or more as a urethane (meth)acrylate having 5 or more functions.

That is, the urethane (meth) acrylic acid having a weight average molecular weight of 10,000 or more The ester is a urethane (meth)acrylate having a weight average molecular weight of 10,000 or more and 5 or more functions.

The weight average molecular weight of the urethane (meth)acrylate having a weight average molecular weight of 10,000 or more is preferably 10,000 to 100,000, and more preferably 10,000 to 50,000.

The urethane (meth)acrylate having a weight average molecular weight of 10,000 or more is preferably a polymer having a repeating unit represented by the following formula Aa-1 or formula Aa-2.

In formula Aa-1 and formula Aa-2, L ⁵ to L ⁸ each independently represent a divalent linking group, A represents a group having a (meth)acryloyl group, and Ra represents a hydrogen atom or a number of carbon atoms. 1~5 alkyl.

L ⁵ to L ⁸ are each independently preferably an alkylene group having 2 to 20 carbon atoms, more preferably an alkylene group having 2 to 10 carbon atoms, and further preferably an alkylene group having 4 to 8 carbon atoms base. In addition, the alkylene group may have a branched or cyclic structure, but it is preferably a linear alkylene group.

A is preferably a group represented by the above formula Ae-1 or formula Ae-2.

Ra is preferably a hydrogen atom or a methyl group.

<<Carbamate (meth)acrylate with a molecular weight of 5,000 or less>>

The curable composition of the present invention contains a urethane (meth)acrylate having a molecular weight of 5,000 or less as a urethane (meth)acrylate having 5 or more functions.

That is, the urethane (meth)acrylate having a molecular weight of 5,000 or less is a urethane (meth)acrylate having a molecular weight of 5,000 or less and more than 5 functions.

In addition, when the urethane (meth)acrylate having a molecular weight of 5,000 or less is an oligomer or polymer having a molecular weight distribution, the molecular weight may be a weight average molecular weight.

The number of urethane bonds in the urethane (meth)acrylate having a molecular weight of 5,000 or less is not particularly limited, but it is preferably 1 to 30, more preferably 1 to 20, and still more preferably 2 to 10. It is particularly preferably 2 to 5.

From the viewpoint of the hardness of the cured film, the molecular weight of the urethane (meth)acrylate having a molecular weight of 5,000 or less is preferably 500 to 5,000, more preferably 800 to 5,000, and particularly preferably 800 to 3,000.

The above-mentioned 5-functional or more urethane (meth)acrylate preferably contains two or more kinds of the above-mentioned urethane (meth)acrylates having a molecular weight of 5,000 or less, and more preferably contains 2 to 4 kinds of the above-mentioned molecular weights of 5,000 or less It is particularly preferable to contain 2 or 3 kinds of urethane (meth)acrylates having a molecular weight of 5,000 or less. According to the above-mentioned aspect, the hardness of the obtained cured film is more excellent.

In addition, the number of (meth)acryloyloxy groups in the urethane (meth)acrylate having a molecular weight of 5,000 or less is preferably 5 to 30, more preferably 8 to 25, and particularly preferably 10 to 20. Within the above range, the hardness of the obtained cured film is more excellent.

Furthermore, the urethane (meth)acrylate having a molecular weight of 5,000 or less is preferably The compound having at least a group represented by the following formula Ac-1 or formula Ac-2 is more preferably a compound having at least a group represented by the following formula Ac-1.

In addition, the core part in the urethane (meth)acrylate having more than 5 functions is preferably a group represented by the following formula Ac-1 or formula Ac-2.

In Formula Ac-1 and Formula Ac-2, L ¹ to L ⁴ each independently represent a divalent hydrocarbon group having 2 to 20 carbon atoms, and the wavy line portion represents a bonding position with another structure.

L ¹ to L ⁴ are each independently preferably an alkylene group having 2 to 20 carbon atoms, more preferably an alkylene group having 2 to 10 carbon atoms, and further preferably an alkylene group having 4 to 8 carbon atoms base. In addition, the alkylene group may have a branched or cyclic structure, but it is preferably a linear alkylene group.

In addition, the urethane (meth)acrylate having a molecular weight of 5,000 or less is particularly preferably a group represented by the above formula Ac-1 or formula Ac-2 and a group selected from the group represented by the above formula Ae-1 and A compound in which two or three groups in the group consisting of groups represented by formula Ae-2 are bonded.

Hereinafter, the urethane (meth)acrylate having a molecular weight of 5,000 or less which is preferably used in the present invention will be exemplified, but the present invention is of course not limited to these.

[Chemical Formula 6]

Examples of commercially available products of urethane (meth)acrylates with more than 5 functions include U-6HA, UA-1100H, U-6LPA, U-15HA, and U available from Shin Nakamura Chemical Industry Co., Ltd. -6H, U-10HA, U-10PA, UA-53H, UA-33H (all registered trademarks), UA-306H, UA-306T, UA-306I, UA-510H available from Kyoeisha Chemical Co., Ltd. , Laromer UA-9048, UA-9050, PR9052 available from BASF, EBECRYL220, 5129, 8301, KRM8200, 8200AE, 8452, etc. available from DAICEL-ALLNEX LTD.

<Other ethylenically unsaturated compounds>

The curable composition of the present invention may contain an ethylenically unsaturated compound (also referred to as “other ethylenically unsaturated compound”) other than the urethane (meth)acrylate having more than 5 functions as the component A.

As the ethylenically unsaturated compound other than the urethane (meth)acrylate having more than 5 functions, it may be a polymer (for example, a molecular weight of 2,000 or more) or a monomer (for example, a molecular weight of less than 2,000, Preferably the molecular weight is 100 or more and less than 2,000), preferably a monomer.

As the ethylenically unsaturated compound other than the 5-functional urethane (meth)acrylate, a polyfunctional ethylenically unsaturated compound is preferred, and a 3 to 6-functional ethylenically unsaturated compound is more preferred.

As the ethylenically unsaturated compound other than the urethane (meth)acrylate having more than 5 functions, a (meth)acrylate compound is preferred. The number of (meth)acryloyloxy groups of the (meth)acrylate compound is preferably 2 to 15, and more preferably 3 to 6. With such a structure, the effect of the present invention can be more effectively exerted.

Specifically, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tri((methyl) ) Acryloyloxyethyl) isocyanurate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate modified ethylene oxide (EO), dipentaerythritol hexa( Meth)acrylate modified EO, etc.

In addition, as other ethylenically unsaturated compounds, urethane (meth)acrylates with less than 4 functions may be included.

As a urethane (meth)acrylate of less than 4 functions, the following compounds can be exemplified Thing.

[Chemical Formula 8]

When the curable composition of the present invention contains an ethylenically unsaturated compound other than a urethane (meth)acrylate of more than 5 functions, the olefin other than the urethane (meth)acrylate of more than 5 functions The content of the unsaturated compound is preferably in the range of 0.1 to 50% by mass, more preferably in the range of 0.5 to 40% by mass, and still more preferably in the range of 1 to 25% by mass relative to the total organic solid content of the curable composition.

The curable composition of the present invention may contain only one type of ethylenically unsaturated compound other than the urethane (meth)acrylate having more than 5 functions, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

Component B: polymerization initiator

The curable composition of the present invention contains the polymerization initiator as component B.

As the polymerization initiator, a radical polymerization initiator is preferably contained.

The free radical polymerization initiator that can be used in the present invention can be initiated and promoted by light and/or heat Compounds that are polymerized with ethylenically unsaturated compounds. Among them, a photopolymerization initiator is preferred, and a photoradical polymerization initiator is more preferred.

The “light” is not particularly limited as long as it is an active energy ray capable of imparting energy capable of generating an initiating species from the component B by irradiation, and broadly includes α-rays, γ-rays, X-rays, ultraviolet (UV), and visible rays , Electron beam, etc. Among them, it is preferable to contain at least ultraviolet light.

Examples of the photopolymerization initiator include oxime ester compounds, organic halogenated compounds, oxadiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxy compounds, azo compounds, and aromatic compounds. Bean compounds, azide compounds, metallocene compounds, hexaarylbiimidazole compounds, organic boric acid compounds, disulfonic acid compounds, onium salt compounds, acetylphosphine (oxide) compounds. Among them, from the viewpoint of sensitivity, oxime ester compounds and/or hexaarylbiimidazole compounds are preferred, and oxime ester compounds are more preferred.

As the oxime ester compound, Japanese Unexamined Patent Publication No. 2000-80068, Japanese Unexamined Patent Publication No. 2001-233842, Japanese Unexamined Patent Publication No. 2004-534797, Japanese Unexamined Patent Publication No. 2007-231000, or Japanese Unexamined Patent Publication No. 2009-134289 The compound described in No. Gazette. The oxime ester compound is preferably a compound represented by Formula 1 or Formula 2 below.

In Formula 1 or Formula 2, Ar represents an aromatic group or a heteroaromatic group, R ¹ represents an alkyl group, an aromatic group or an alkoxy group, R ² represents a hydrogen atom or an alkyl group, and further R ² may also be Ar groups are bonded to form a ring.

Ar represents an aromatic group or a heteroaromatic group, and is preferably a group obtained by removing one hydrogen atom from a benzene ring, a naphthalene ring, or a azole ring, and more preferably a naphthyl group or a naphthyl group which forms a ring together with R ² Oxazolyl.

R ¹ represents an alkyl group, an aromatic group or an alkoxy group, preferably methyl, ethyl, benzyl, phenyl, naphthyl, methoxy or ethoxy, more preferably methyl, ethyl, phenyl or Methoxy.

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 or a thioalkyl group that forms a ring with Ar.

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

In Formula 3 to Formula 5, R ¹ represents an alkyl group, an aromatic group or an alkoxy group, X represents -CH2-, -C2H4-, -O- or -S-, R ³ independently represents a halogen atom, R ⁴ independently represents an alkyl group, a phenyl group, an alkyl substituted amino group, an arylthio group, an alkylthio group, an alkoxy group, an aryloxy group or a halogen atom, R ⁵ represents a hydrogen atom, an alkyl group or an aryl group, and R ⁶ represents The alkyl group, n1 and n2 each independently represent an integer of 0 to 6, and n3 represents an integer of 0 to 5.

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

X is preferably a sulfur atom.

R ³ and R ⁴ may be bonded at any position on the aromatic ring.

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

In addition, the number of carbon atoms of R ⁴ is preferably 0-50, and more preferably 0-20.

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

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

n1 and n2 each represent the number of substitutions of R ³ on the aromatic ring in Formula 3 or Formula 4, and n3 represents the number of substitutions of R ⁴ on the aromatic ring in Formula 5

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

Hereinafter, examples of the oxime ester compound preferably used in the present invention are shown. However, the oxime ester compound used in the present invention is of course not limited to these. In addition, Me represents a methyl group and Ph represents a phenyl group.

[Chemical Formula 12]

As examples of organic halogenated compounds, specifically, "Bull Chem. Soc. Japan" 42, Wakabayashi et al., 42924 (1969), US Patent No. 3,905,815, Japanese Patent Publication No. 46-4605, Japanese Special JP-A 48-36281, JP-A 55-32070, JP-A 60-239736, JP-A 61-169835, JP-A 61-169837, JP Gazette 62-58241, Japan Compounds described in JP-A 62-212401, JP-A 63-70243, JP-A 63-298339, MPHutt, etc., "Journal of Heterocyclic Chemistry" 7,511 (1970), etc., In particular, trihalomethyl substituted oxazole compounds and s-triazine compounds can be cited.

Examples of the hexaarylbiimidazole compound include various compounds described in various specifications such as Japanese Patent Publication No. 6-29285, US Patent No. 3,479,185, US Patent No. 4,311,783, and US Patent No. 4,622,286.

Examples of the amide phosphine (oxide) compounds include monoamide phosphine oxide compounds and bis amide phosphine oxide compounds. Specifically, for example, IRGACURE 819, DAROCUR 4265, DAROCUR TPO, etc., manufactured by BASF Corporation can be cited. .

One type of polymerization initiator may be used alone or two or more types may be used in combination.

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

<sensitizer>

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

Typical sensitizers that can be used in the present invention include those disclosed in Crivello [JVCrivello, Adv. in Polymer Sci., 62, 1 (1984)], and specific examples include pyrene and perylene. , Acridine orange, thioxanthone, 2-chlorothioxanthone, benzoflavin, N-vinyl oxazole, 9,10-dibutoxyanthracene, anthraquinone, coumarin, ketone Beans, phenanthrene, camphorquinone, phenothiazine derivatives, etc. The sensitizer is preferably added at a ratio of 50 to 200 parts by mass relative to 100 parts by mass of the content of the polymerization initiator.

Component C: mercapto compound

The curable composition of the present invention contains a mercapto compound as component C. By containing a mercapto compound, the resulting cured film has excellent film strength.

As the mercapto compound, monofunctional mercapto compounds and polyfunctional mercapto compounds are suitably used.

As the monofunctional mercapto compound, either an aliphatic mercapto compound or an aromatic mercapto compound can be used, but from the viewpoint of film strength, an aromatic mercapto compound is preferred.

Specific examples of the monofunctional aliphatic mercapto compound include 1-octane mercaptan, 1-dodecane mercaptan, β-mercaptopropionic acid, methyl-3-mercaptopropionate, and 2-ethyl Hexyl-3-mercaptopropionate, n-octyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate, stearyl-3-mercaptopropionate, etc.

As the monofunctional aromatic mercapto compound, a compound represented by the following formula I is preferred.

In Formula I, X ^C represents an oxygen atom, a sulfur atom, or NR ^C , R ^C represents a hydrogen atom, an alkyl group, or an aryl group, and A represents an atomic group that forms a heterocycle together with N=CX ^C.

In Formula I, R ^C represents a hydrogen atom, an alkyl group or an aryl group.

Examples of the alkyl group include straight-chain, branched or cyclic alkyl groups having 1 to 20 carbon atoms, and more preferably straight-chain ones having 1 to 12 carbon atoms and 3 to 3 carbon atoms 12 is a branched or cyclic alkyl group having 5 to 10 carbon atoms. Specific examples thereof include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecane Group, hexadecyl, octadecyl, eicosyl, isopropyl, isobutyl, Second butyl, third butyl, isopentyl, neopentyl, 1-methylbutyl, isohexyl, 2-ethylhexyl, 2-methylhexyl, cyclohexyl, cyclopentyl, 2-nor Borneol and so on.

Examples of the aryl group include, in addition to aryl groups having a single ring structure, a group in which 1 to 3 benzene rings form a condensed ring, a group in which a benzene ring forms a condensed ring with a 5-membered unsaturated ring, and the like. Specific examples include phenyl, naphthyl, anthracenyl, phenanthrenyl, indenyl, acenaphthyl, fluorenyl and the like. Among them, phenyl and naphthyl are more preferred.

These alkyl groups and aryl groups may further have substituents. Examples of the substituents that can be introduced include linear, branched, or cyclic alkyl groups having 1 to 20 carbon atoms, and 2 carbon atoms. ~20 linear, branched or cyclic alkenyl groups, alkynyl groups with 2-20 carbon atoms, aryl groups with 6-20 carbon atoms, and acetyloxy groups with 1-20 carbon atoms , Alkoxycarbonyloxy having 2 to 20 carbon atoms, aryloxycarbonyloxy having 7 to 20 carbon atoms, carbamoyloxy having 1 to 20 carbon atoms, and 1 carbon atom Carboxamide group of ~20, sulfonamide group having 1-20 carbon atoms, carbamate group having 1-20 carbon atoms, sulfamoyl group, substituted sulfonamide having 1-20 carbon atoms Acyl, alkoxy having 1 to 20 carbon atoms, aryloxy having 6 to 20 carbon atoms, aryloxycarbonyl having 7 to 20 carbon atoms, alkoxy having 2 to 20 carbon atoms Carboxycarbonyl, N-acetylsulfamoylamino with 1 to 20 carbon atoms, N-aminosulfamoylaminocarbamoyl with 1 to 20 carbon atoms, alkylsulfonic acid with 1 to 20 carbon atoms Acyl, arylsulfonyl with 6-20 carbon atoms, alkoxycarbonylamino with 2-20 carbon atoms, aryloxycarbonylamino with 7-20 carbon atoms, amino, carbon atoms 1-20 substituted amino groups, 1-20 carbon imino groups, 3-20 carbon atoms (ammonio), carboxyl groups, sulfo groups, oxy groups, mercapto groups, 1-20 carbon atoms Alkylsulfinyl, arylsulfinyl with 6-20 carbon atoms, alkylthio with 1-20 carbon atoms, arylthio with 6-20 carbon atoms, 1 ~20 ureido group, heterocyclic group with 2 to 20 carbon atoms, acetyl group with 1 to 20 carbon atoms, sulfamoylamino group, substituted sulfamoylamino group with 1 to 2 carbon atoms, Silyl groups having 2 to 20 carbon atoms, isocyanate groups, isocyanide groups, halogen atoms (for example, fluorine atoms, chlorine atoms, bromine atoms, etc.), cyano groups, nitro groups, onium groups, hydroxyl groups, and the like.

In addition, in Formula I, A represents an atomic group that forms a heterocycle together with N=CX ^C.

Examples of the atoms constituting the atomic group include carbon atoms, nitrogen atoms, hydrogen atoms, sulfur atoms, and selenium atoms.

In addition, the heterocyclic ring formed by A and N=CX ^C may further have a substituent, and examples of the substituent that can be introduced include the same groups as the substituents that can be introduced into the above-mentioned alkyl group or aryl group.

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

In Formula II to Formula V, R ^C1 represents a hydrogen atom or an aryl group, X ^C1 independently represents a hydroxyl group, a halogen atom, an alkoxy group, an aryloxy group, an alkyl group or an aryl group, and R ^C2 represents an alkyl group or an aryl group, n represents an integer from 0 to 4, and m represents an integer from 0 to 5.

As the halogen atom in Formula II to Formula V, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are preferred.

Examples of the alkoxy group and aryloxy group in Formula II to Formula V include methoxy, ethoxy, and propylene Oxy, isopropoxy, butoxy, pentyloxy, hexyloxy, dodecyloxy, benzyloxy, allyloxy, phenethoxy, carboxyethoxy, methoxycarbonyl ethyl Oxy, ethoxycarbonylethoxy, methoxyethoxy, phenoxyethoxy, methoxyethoxyethoxy, ethoxyethoxyethoxy, morpholinoethoxy Group, morpholinopropoxy, allyloxyethoxyethoxy, phenoxy, tolyloxy, xylyloxy, mesityloxy, cumyloxy, methoxyphenoxy , Ethoxyphenoxy, chlorophenoxy, bromophenoxy, acetoxy, benzoyloxy, naphthoxy, etc.

The alkyl group in Formula II to Formula V has the same meaning as the alkyl group represented by R ^C in Formula I, and its preferred range is also the same.

In addition, the aryl group in Formula II to Formula V has the same meaning as the aryl group represented by R ^C in Formula I, and the preferred range thereof is also the same.

Each group in Formula II to Formula V may further have a substituent, and the substituent is the same as the group listed as the substituent that can be introduced into the alkyl group or aryl group represented by R ^C in Formula I.

In Formula II to Formula V, n and m being 0 are more preferable from the viewpoint of solubility in an organic solvent.

Among the compounds of Formula II to Formula V, the following compounds are more preferred. When these compounds are used, the film strength is improved and the storage stability is also good.

[Chemical Formula 16]

From the viewpoint of adhesion to the substrate, Component C is preferably a polyfunctional mercapto compound.

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

The number of functional groups of the polyfunctional mercapto compound is preferably 2 to 10 functions, more preferably 2 to 8 functions, and still more preferably 2 to 4 functions. If the number of functional groups becomes larger, the film strength is excellent. On the other hand, if the number of functional groups is small, the storage stability is excellent. In the case of the above range, these can be balanced.

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

In formula C-1, R ^1C represents a hydrogen atom or an alkyl group, A ^1C represents -CO- or -CH ₂ -, and the wavy line portion represents a bonding position with another structure.

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

The alkyl group in R ^1C in Formula C-1 is a linear, branched, or cyclic alkyl group, and the range of the number of carbon atoms is preferably 1 to 16, and more preferably 1 to 10. Specific examples of the alkyl group are methyl, ethyl, propyl, isopropyl, butyl, second butyl, third butyl, pentyl, hexyl, 2-ethylhexyl, etc., preferably methyl, Ethyl, propyl or isopropyl.

R ^{1C is} particularly preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, and an isopropyl group, and most preferably a methyl group or an ethyl group.

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

In formula C-2, R ^1C independently represents a hydrogen atom or an alkyl group, A ^1C independently represents -CO- or -CH ₂ -, L ^1C represents an nC-valent linking group, and nC represents an integer of 2 to 6 . From a synthetic viewpoint, R ^1C is preferably all the same groups, and A ^1C is preferably all the same groups.

R ^1C in formula C-2 has the same meaning as R ^1C in formula C-1 described above, and the preferred range is also the same. nC is preferably an integer of 2 to 4.

Examples of the nC-valent linking group in Formula C-2, that is, L ^1C include, for example, divalent linking groups such as -(CH ₂ ) _mC- (mC represents an integer of 2 to 6), trimethylolpropane Residues, trivalent linking groups such as isocyanuric acid rings with three -(CH ₂ ) _pC- (pC represents an integer of 2 to 6), tetravalent linking groups such as pentaerythritol residues or pentavalent Hexavalent linking groups such as the linking group of dipentaerythritol residues.

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

As the polyfunctional mercapto compound, specifically, ethylene glycol dithiopropionate, butanediol dithiopropionate, trimethylolpropane tris(3-mercaptopropionate), tri[ (3-Mercaptopropionyloxyethyl) isocyanurate, pentaerythritol tetrakis(3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate), dipentaerythritol hexa(3-mercapto Propionate), pentaerythritol tetrakis(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutyryloxyethyl) )-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1,2-benzenedithiol, 1,3-benzenedithiol, 1,2-ethane Alkane dithiol, 1,3-propane dithiol, 1,6-hexamethylene dithiol, 2,2'-(ethylene dithio) diethane thiol, meso-2 ,3-Dimercaptosuccinic acid, p-xylene dithiol, m-xylene dithiol, di(mercaptoethyl) ether, etc.

As the polyfunctional mercapto compound, preferably pentaerythritol tetrakis(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutane Acetyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, more preferably pentaerythritol tetrakis(3-mercaptobutyrate).

In the present invention, one type of mercapto compound may be used alone, or two or more types may be used in combination.

In the present invention, the content of the mercapto compound relative to the total solid content of the curable composition is preferably 1 to 20% by mass, more preferably 1 to 15% by mass, still more preferably 1.2 to 10% by mass, and particularly preferably 1.5 to 5 quality%. Within the above-mentioned range, it is preferable in terms of both the film strength and the storage stability.

Component D: Organic solvent

The curable composition of the present invention contains the organic solvent as component D. The curable composition of the present invention is preferably prepared as a liquid obtained by dissolving or dispersing component A, component B, component C, and optional components described below as essential components in an organic solvent.

As the organic solvent 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, and ethylene glycol monoalkyl ether acetic acid. Esters, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol Monoalkyl ethers, butanediol diacetates, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates, alcohols, esters, ketones, amides, lactones, etc. As specific examples of these organic solvents, reference can be made to paragraph 062 of Japanese Patent Laid-Open No. 2009-098616.

Specifically, propylene glycol monomethyl ether acetate, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, 1,3-butanediol diacetate are preferred , Cyclohexanol acetate, propylene glycol diacetate, tetrahydrofurfuryl alcohol.

From the viewpoint of coatability, the boiling point of the organic solvent is preferably 100°C to 300°C, and more preferably 120°C to 250°C.

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

From the viewpoint of adjusting the viscosity suitable for coating, the content of the organic solvent in the curable composition of the present invention is preferably 100 to 3,000 parts by mass, more preferably 200 with respect to 100 parts by mass of the total solid content of the curable composition. ~2,000 parts by mass, more preferably 250 to 1,000 parts by mass.

The solid content of the curable composition of the present invention is preferably 3 to 50% by mass, and more preferably 20 to 40% by mass.

The viscosity of the curable composition of the present invention is preferably 1 to 200 mPa. s, more preferably 2~100mPa. s, most preferably 3 ~ 80mPa. s. The viscosity is preferably measured at 25±0.2° C. using, for example, a RE-80L rotary viscometer manufactured by Toki Industries, Ltd. Regarding the rotation speed at the time of measurement, the viscosity is lower than 5 mPa. s is preferably carried out at 100rpm, viscosity is 5mPa. s above and below 10mPa. s is preferably carried out at 50rpm, viscosity is 10mPa. s above and below 30mPa. s is preferably carried out at 20rpm, viscosity is 30mPa. At s or more, it is preferably carried out at 10 rpm.

Component E: inorganic particles

The curable composition of the present invention preferably contains inorganic particles as component E. By containing inorganic particles, the hardness of the cured film becomes more excellent. In addition, 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 still more preferably 5 to 50 nm. The average particle diameter refers to the arithmetic average obtained by measuring the particle diameter of 200 arbitrary particles by an electron microscope. In addition, when the shape of the particles is not spherical, the longest side is used as the diameter.

In addition, 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 further preferably no voids. The void ratio of the particles is an arithmetic average of 200 area ratios of the void portions of the cross-sectional image obtained by an electron microscope and the entire particles.

As the inorganic particles, metal oxide particles are preferred.

In addition, the metal of the metal oxide in the present invention also includes semimetals such as B, Si, Ge, As, Sb, and Te.

The metal oxide particles preferably include Be, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Gd, Tb, Dy, Yb, Lu, Ti, Zr, Hf, Nb, Mo, W, Zn, Metal oxide particles of B, Al, Si, Ge, Sn, Pb, Sb, Bi, Te and other atoms are more preferably selected from silicon oxide, titanium oxide, titanium composite oxide, zinc oxide, zirconium oxide, indium/tin oxide Metal oxide particles in the group consisting of metal oxides and antimony/tin oxides, more preferably metal oxide particles selected from the group consisting of silicon oxide, titanium oxide, titanium composite oxide and zirconium oxide, silicon oxide particles or Titanium oxide particles are particularly preferred from the viewpoints of particle stability, availability, hardness of the cured film, transparency, and refractive index adjustment.

As the silicon oxide particles, preferably, silicon dioxide (silica) particles are used.

The silicon dioxide particles are not particularly problematic as long as they are inorganic oxide particles containing silicon dioxide, and particles containing silicon dioxide or its hydrate as a main component (preferably 80% by mass or more) are preferred. The particles may contain aluminate as a small amount of component (for example, less than 5% by mass). Examples of aluminates included as a small amount of components include sodium aluminate and potassium aluminate. In addition, the silicon dioxide particles may contain inorganic salts such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and ammonium hydroxide, or organic salts such as tetramethylammonium hydroxide. As an example of such a compound, colloidal silica can be exemplified.

The dispersion medium of colloidal silica is not particularly limited, and may be any of water, organic solvents, and mixtures thereof. These can be used alone or in combination of two or more.

In the present invention, the particles can also be used as a dispersion liquid prepared by mixing and/or dispersing using a mixing device such as a ball mill or a rod mill in an appropriate dispersant and solvent. In addition, in the curable composition of the present invention, the colloidal silica does not necessarily exist in a colloidal state.

From the viewpoint of hardness, the content of the inorganic particles in the curable composition of the present invention is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and even more preferably 100 parts by mass of the total solid content of the curable composition. 10 parts by mass or more. In addition, it is preferably 80 parts by mass or less, more preferably 50 parts by mass or less, still more 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. When two or more types are included, the preferable total amount is within the above range.

<A hardenable compound other than component A to component C, such as a compound having an epoxy group, a compound having an oxetane group, a blocked isocyanate compound, an alkoxysilane compound, etc.>

The curable composition of the present invention preferably contains a curable compound that is a component that is cured by heat or light other than Component A to Component C, and more preferably contains a compound selected from the group consisting of an epoxy group and an oxetane group. At least one of the group consisting of compounds, blocked isocyanate compounds, and alkoxysilane compounds. According to the above method, the hardness of the obtained cured product is more excellent.

<<Compounds with epoxy groups>>

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

As specific examples of compounds having two or more epoxy groups in the molecule, Examples include bisphenol A epoxy resin, bisphenol F epoxy resin, novolac epoxy resin, cresol novolac epoxy resin, and aliphatic epoxy resin.

They are available as commercial products. For example, the bisphenol A type epoxy resins are JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1055, JER1007, JER1009, JER1010 (above manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON860, EPICLON1050, EPICLON1051, EPICLON1055 ( The above are manufactured by DIC Corporation), etc., as bisphenol F type epoxy resins, JER806, JER807, JER4004, JER4005, JER4007, JER4010 (above manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON830, EPICLON835 (above DIC Corporation) ), LCE-21, RE-602S (above manufactured by Nippon Kayaku Co., Ltd.), etc., as novolac epoxy resins, are JER152, JER154, JER157S70, JER157S65 (above manufactured by Japan Epoxy Resin Co., Ltd.), EPICLONN-740, EPICLONN-740, EPICLONN-770, EPICLONN-775 (above manufactured by DIC Corporation), etc., as cresol novolac epoxy resin, are EPICLONN-660, EPICLONN-665, EPICLONN-670, EPICLONN- 673, EPICLONN-680, EPICLONN-690, EPICLONN-695 (above manufactured by DIC Corporation), EOCN-1020 (above manufactured by Nippon Kayaku Co., Ltd.), etc., as aliphatic epoxy resin, ADEKA RESIN EP-4080S , ADEKA RESIN EP-4085S, ADEKA RESIN EP-4088S (above manufactured by ADEKA Corporation), CELLOXIDE 2021P, CELLOXIDE 2081, CELLOXIDE 2083, CELLOXIDE 2085, EHPE3150, EPOLEAD PB 3600, EPOLEAD PB 4700 (above Daicel Chemical Industries., Ltd. System) etc. In addition, ADEKA RESIN EP-4000S, ADEKA RESIN EP-4003S, ADEKA RESIN EP-4010S, ADEKA RESIN EP-4011S (the above are (Made by ADEKA), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (the above is made by ADEKA Corporation), etc.

In addition, it is possible to suitably use the ethylene oxide described in Japanese Patent Publication No. 58-49860, Japanese Patent Publication No. 56-17654, Japanese Patent Publication No. 62-39417, or Japanese Patent Publication No. 62-39418 The content of skeleton carbamate compounds is incorporated into the specification of this application.

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

The curable composition of the present invention may contain only one kind of compound having an epoxy group, or may contain two or more kinds. When two or more types are included, the total amount is preferably within the above range.

<<Compounds with oxetane groups>>

The curable composition of the present invention may contain a compound having an oxetane group. The compound having an oxetane group may have one oxetane group in the molecule, but it is preferably two or more.

As specific examples of the compound having an oxetanyl group, ARONOXETANE OXT-121, OXT-221, OX-SQ, PNOX (above manufactured by Toa Synthesis Co., Ltd.) can be used.

In addition, the oxetanyl group-containing compound is preferably used alone or in combination with an epoxy group-containing compound.

When the curable composition of the present invention contains a compound having an oxetanyl group, it has The content of the oxetane compound relative to the total solid content of the curable composition is preferably in the range of 0.1 to 20% by mass, more preferably in the range of 0.5 to 10% by mass, and still more preferably 1 to 5% by mass Scope.

The curable composition of the present invention may contain only one kind of compound having an oxetane group, or may contain two or more kinds. When two or more types are included, the total amount is preferably within the above range.

<<Blocked isocyanate compound>>

The curable composition of the present invention may contain a blocked isocyanate compound.

The blocked isocyanate compound is not particularly limited as long as it has a blocked isocyanate group. From the viewpoint of curability, a compound having two or more blocked isocyanate groups in one molecule is preferred. The upper limit of the number of blocked isocyanate groups is not particularly limited, but is preferably 6 or less.

In addition, the skeleton of the blocked isocyanate compound is not particularly limited, as long as it is a compound having two isocyanate groups in one molecule, it may be any compound, and may be an aliphatic, alicyclic, or aromatic polyisocyanate. For example, 2,4-tolyl diisocyanate, 2,6-tolyl diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,3-trimethylene can be suitably used Diisocyanate, 1,4-tetramethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,9 -Nona methylene diisocyanate, 1,10-decamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 2,2'-diethyl ether diisocyanate, diphenylmethane-4,4' -Diisocyanate, o-xylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, methylene bis (cyclohexyl isocyanate), cyclohexane-1,3-dimethylene diisocyanate, cyclohexane -1,4-dimethylene diisocyanate, 1,5-naphthalene diisocyanate Cyanate, p-phenylene diisocyanate, 3,3'-methylene dimethylidene-4,4'-diisocyanate, 4,4'-diphenyl ether diisocyanate, tetrachlorophenyl diisocyanate , Isocyanate compounds such as norbornane diisocyanate, hydrogenated 1,3-xylylene diisocyanate, hydrogenated 1,4-xylylene diisocyanate, and prepolymer-type skeleton compounds derived from these compounds. Among them, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), and isophorone diisocyanate (IPDI) are particularly preferred.

Examples of the matrix structure of the blocked isocyanate compound in the curable composition of the present invention include biuret type, isocyanurate type, adduct type, and bifunctional prepolymer type.

Examples of the blocking agent that forms the blocking structure of the blocked isocyanate compound include oxime compounds, amide compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, and thiol compounds. Imidazole-based compounds, amide-based compounds, etc. Among them, a blocking agent selected from the group consisting of oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, and pyrazole compounds is particularly preferred.

The blocked isocyanate compound that can be used in the curable composition of the present invention can be obtained as a commercially available product. For example, CORONATE AP-STABLEM, CORONATE 2503, 2515, 2507, 2513, 2555, and MILLIONATE MS-50 (the above are Nippon Polyurethane Industry Co., Ltd.), TAKENATE B-830, B-815N, B-820NSU, B-842N, B-846N, B-870N, B-874N, B-882N (the above is Mitsui Chemicals Co., Ltd.) System), DURANATE 17B-60P, 17B-60PX, 17B-60P, TPA-B80X, TPA-B80E, MF-B60X, MF-B60B, MF-K60X, MF-K60B, E402-B80B, SBN-70D, SBB- 70P, K6000 (above manufactured by Asahi Kasei Chemicals Corporation), Desmodur BL1100, BL1265MPA/X, BL3575/1, BL3272MPA, BL3370MPA, BL3475BA/SN, BL5375MPA, VPLS2078/2, BL4265SN, PL340, PL350, Sumidur BL3175 (above manufactured by Sumika Bayer Urethane Co., Ltd.), etc.

When the curable composition of the present invention contains a blocked isocyanate compound, the content of the blocked isocyanate compound relative to the total solid content of the curable composition is preferably in the range of 0.1 to 20% by mass, and more preferably in the range of 0.5 to 10% by mass It is more preferably in the range of 1 to 5% by mass.

The curable composition of the present invention may contain only one kind of blocked isocyanate compound, or may contain two or more kinds. When two or more types are included, the total amount is preferably within the above range.

<<Alkoxysilane Compound>>

The curable composition of the present invention may contain an alkoxysilane compound.

If an alkoxysilane compound is used, the coatability and the hardness of the obtained cured film are more excellent, and the 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 as long as it has at least an alkoxy group directly bonded to a silicon atom, but preferably has a dialkoxysilyl group and/or trialkoxymethyl group The silane group compound is more preferably a compound having a trialkoxysilyl group.

In addition, as the alkoxysilane compound, an alkoxysilane compound having an ethylenically unsaturated group and/or an epoxy group such as a silane coupling agent described later is preferable.

The alkoxysilane compound that can be used in the curable composition of the present invention is preferably a substrate, a silicon compound such as silicon, silicon oxide, silicon nitride, etc., a metal such as gold, copper, molybdenum, titanium, aluminum, and an insulating film Compound with improved adhesion. Specifically, well-known silane coupling agents and the like are also effective. The use of a silane coupling agent having an ethylenically unsaturated group is particularly preferable because it has excellent adhesion to ITO. In addition, if a silane coupling agent having an epoxy group is used, the reliability is excellent.

Examples of the silane coupling agent include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrialkoxysilane, and γ-propylene oxide. Oxypropyldialkoxysilane, γ-methacryloxypropyltrialkoxysilane, γ-methacryloxypropyldialkoxysilane, γ-chloropropyltrialkoxy Silane, γ-mercaptopropyltrialkoxysilane, β-(3,4-epoxycyclohexyl)ethyltrialkoxysilane and vinyltrialkoxysilane. Among them, γ-methacryloxypropyltrialkoxysilane, γ-acryloxypropyltrialkoxysilane, vinyltrialkoxysilane and/or γ-propylene oxide are more preferred Oxypropyltrialkoxysilane. These can be used alone or in combination of two or more.

Examples of commercially available products include Shin-Etsu Chemical Co., Ltd., KBM-403, KBM-5103, KBM-303, KBM-503, KBE-503, KBM-3103, KBE-403, and the like.

The content of the alkoxysilane compound in the curable composition of the present invention is preferably 0.1 to 30% by mass, more preferably 0.5 to 15% by mass, and still more preferably 2 to 10% by mass relative to the total solid content of the curable composition. %. The alkoxysilane compound may be only one kind, or may contain two or more kinds. When two or more types are included, the total amount is preferably within the above range.

<<Polysulfide Compound>>

In addition, the curable composition of the present invention may contain a polysulfide compound. By containing a polysulfide compound, a cured film excellent in base material adhesion and moisture resistance can be obtained.

The polysulfide compound is not particularly limited as long as it has a polysulfide bond, but is preferably a compound having a disulfide bond, a trisulfide bond, a tetrasulfide bond, a pentasulfide bond, and a hexasulfide bond, and more preferably has a disulfide bond. The compound having a thioether bond, a trisulfide bond, and a tetrasulfide bond is more preferably a compound having a disulfide bond or a tetrasulfide bond. If a compound having a disulfide bond or a tetrasulfide bond is used, the moisture resistance is more excellent.

The polysulfide bond may be linear, branched, or cyclic, but it is preferably a linear polysulfide bond.

In addition, the polysulfide compound is preferably a monovalent group in which an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic group, or a combination of two or more thereof is bonded to both sides of the polysulfide bond, respectively. The compound is more preferably a compound in which an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a monovalent group obtained by combining two or more of them is bonded to both sides of a polysulfide bond. The aforementioned aliphatic hydrocarbon group, aromatic hydrocarbon group or heterocyclic group may have a substituent. The substituent is not particularly limited, and examples thereof include aliphatic hydrocarbon groups, aromatic hydrocarbon groups, heterocyclic groups, halogen atoms, carboxyl groups, amide groups, alkoxy groups, alkoxycarbonyl groups, and silyl groups. Among them, it is particularly preferable to have a trialkoxysilyl group as a substituent. That is, as the polysulfide compound, a compound in which an aliphatic hydrocarbon group having a trialkoxysilyl group is bonded to both sides of the polysulfide bond is particularly preferred.

Specific examples of polysulfide compounds are shown below, but the present invention is not limited to the following specific examples. In the following formula, Ph represents phenyl, Me represents methyl, and Et represents ethyl.

In the present invention, one kind of polysulfide compound may be used alone, or two kinds of Use together.

In the present invention, the content of the polysulfide 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 relative to the total solid content of the curable composition. Within the above range, a cured film excellent in base material adhesion and moisture resistance can be obtained.

The curable composition of the present invention may contain other compounds (for example, alkoxymethyl-containing compounds, etc.) other than the above within the scope not departing from the gist of the present invention.

Examples of the alkoxymethyl group-containing compound include the compounds described in paragraphs 0192 to 0194 of Japanese Patent Laid-Open No. 2011-221494.

In the present invention, the total content of the ethylenically unsaturated compound, the compound having an epoxy group, the compound having an oxetane group, the blocked isocyanate compound and the polyfunctional mercapto compound preferably accounts for the amount contained in the curable composition. The total content of the components hardened by heat or light is 90% by mass or more (more preferably 95% by mass or more), and the total content of the ethylenically unsaturated compound and the blocked isocyanate compound is more preferably accounted for by the amount contained in the curable composition. The total amount of components hardened by heat or light is 90% by mass or more (more preferably 95% by mass or more).

In addition, when it contains at least one kind of a compound having an epoxy group, a compound having an oxetane group, a blocked isocyanate compound, and a polyfunctional mercapto compound, it is preferable to account for the total The total content of the components hardened by heat or light is 0.1 to 20% by mass, and more preferably 1 to 10% by mass. With such a structure, the effect of the present invention can be more effectively exerted.

<surfactant>

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

As the surfactant, anionic, cationic, nonionic, or amphoteric can be used In either case, the preferred surfactant is a nonionic surfactant. The surfactant is preferably a nonionic surfactant, and more preferably a fluorine surfactant.

As surfactants usable in the present invention, for example, Megafac F142D, Megafac F172, Megafac F173, Megafac F176, Megafac F177, Megafac F183, Megafac F479, Megafac F482, Megafac F554, Megafac F780, Megafac F781, Megafac F781-F, Megafac R30, Megafac R08, Megafac F-472SF, Megafac BL20, Megafac R-61, Megafac R-90 (made by DIC Corporation), Fluorad FC-135, Fluorad FC-170C, Fluorad FC -430, Fluorad FC-431, NovecFC-4430 (made by Sumitomo 3M Limited), AsahiGuard AG7105, AsahiGuard AG7000, AsahiGuard AG950, AsahiGuard AG7600, Surflon S-112, Surflon S-113, Surflon S-131, Surflon S-141, Surflon S-145, Surflon S-382, Surflon SC-101, Surflon SC-102, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-106 (manufactured by Asahi Glass Co., Ltd.), EFTOP EF351, EFTOP EF352, EFTOP EF801, EFTOP EF802 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Ftergent 250 (manufactured by Neos Corporation). In addition to the above, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Megafac (manufactured by DIC Corporation) ), Fluorad (made by Sumitomo 3M Limited), AsahiGuard, Surflon (made by Asahi Glass Co., Ltd.), PolyFox (made by OMNOVA), etc.

In addition, as the surfactant, the compounds described in paragraphs 0119 to 0123 of JP-A-2014-238438 can also be cited as preferred examples.

When the content of the surfactant in the curable composition of the present invention is blended, it is The total solid content of the sexual composition is preferably 0.001 to 5.0% by mass, more preferably 0.01 to 2.0% by mass.

The surfactant may contain only one kind, or two or more kinds. When two or more types are included, the preferable total amount is within 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, it has the following advantages: it can prevent coloration of the cured film, or can reduce the reduction in film thickness due to decomposition, and it is excellent in heat resistance and transparency.

Examples of such antioxidants include phosphorus antioxidants, amides, hydrazines, hindered amine antioxidants, sulfur antioxidants, phenol antioxidants, ascorbic acids, zinc sulfate, sugars, and nitrite. , Sulfite, thiosulfate, hydroxylamine derivatives, etc. Among them, phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and/or sulfur-based antioxidants are particularly preferred from the viewpoint of coloration of the cured film and reduction in film thickness, and phenol-based antioxidants are most preferred. These can be used alone or in combination of two or more.

As specific examples, the compounds described in paragraphs 0026 to 0031 of Japanese Patent Laid-Open No. 2005-29515 and the compounds described in paragraphs 0106 to 0116 of Japanese Patent Laid-Open No. 2011-227106 can be cited, and their contents are incorporated in this application In the manual.

Preferred commercial products include ADEKA STAB AO-60, ADEKA STAB AO-80, ADEKA STAB AO-412S (above manufactured by ADEKA Corporation), IRGANOX 1035, and IRGANOX 1098 (above manufactured by BASF).

The content of the antioxidant is not particularly limited, but it is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, and still more preferably 0.5 to 4 relative to the total solid content of the curable composition. quality%.

<polymerization inhibitor>

The curable composition of the present invention may contain a polymerization inhibitor. The so-called polymerization inhibitor is to apply hydrogen supply (or hydrogen grant), energy supply (or energy grant), electron supply (or electron grant) to the polymerization initiation radical component generated by the polymerization initiator by exposure or heat , Substances that play a role in deactivating polymerization-initiating free radicals and inhibiting polymerization initiation. For example, the compounds described in paragraphs 0154 to 0173 of Japanese Patent Laid-Open No. 2007-334322 can be used.

Preferable compounds include phenothiazine, phenoxazine, hydroquinone, and 3,5-dibutyl-4-hydroxytoluene.

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

<Binder polymer>

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

The binder polymer is not particularly limited, and a known polymer can be used, but a linear organic polymer is preferably used. As such a linear organic polymer, a well-known polymer can be used arbitrarily. It is preferable to select a linear organic polymer that is soluble or swellable in water or weak alkaline water in order to enable water development or weak alkaline water development. The linear organic polymer is not only used as a film-forming agent, but also selected and used according to its use as a developer with respect to water, weak alkaline water, or an organic solvent-based developer. For example, if a water-soluble organic polymer is used, water development can be performed. Examples of such a linear organic polymer include a radical polymer having a carboxylic acid group in the side chain, for example, Japanese Patent Laid-Open No. 59-44615, Japanese Patent Laid-Open No. 54-34327, Japanese Patent Laid-Open 58-12577, Japanese Patent Publication No. 54-25957, Japanese Patent Publication No. 54-92723, Japanese Patent Publication No. 59-53836, Polymers described in Japanese Patent Publication No. 59-71048, A resin obtained by homopolymerizing or copolymerizing a monomer having a carboxyl group, a resin obtained by homopolymerizing or copolymerizing a monomer having an acid anhydride and hydrolyzing or semi-esterifying or semi-amidating an acid anhydride unit, and a Epoxy acrylate obtained by modifying saturated monocarboxylic acid and acid anhydride. Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and 4-carboxystyrene. Examples of the monomer having an acid anhydride include maleic anhydride Wait.

In addition, there are also acidic cellulose derivatives having a carboxylic acid group in the side chain. In addition, those obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group are useful.

The binder polymer is preferably an acrylic resin obtained by copolymerizing (meth)acrylic acid with other (meth)acrylate.

The content of the binder polymer in the curable composition of the present invention is not particularly limited, but it is preferably 1 to 40% by mass, more preferably 3 to 30% by mass, more preferably, relative to the total solid content of the curable composition. It is 4-20% by mass.

<other ingredients>

In the curable composition of the present invention, in addition to the above, other components such as a plasticizer, a thermal acid generator, and an acid multiplying agent may be added as necessary. Regarding these components, for example, those described in Japanese Patent Laid-Open No. 2009-98616 or Japanese Patent Laid-Open No. 2009-244801 and other known substances can be used. In addition, various ultraviolet absorbers, metal deactivators, and the like described in "New Development of Polymer Additives (Nikkei Kogyo Shimbun Co., Ltd.)" may be added to the curable composition of the present invention.

(Cured material, cured film, and their manufacturing method)

The cured product of the present invention is a cured product obtained by curing the curable composition of the present invention, and is preferably a cured product obtained by removing and curing at least a part of the organic solvent in the curable composition of the present invention. As the cured product, a cured film is preferred. In addition, the cured product of the present invention is preferably a cured product obtained by the method for producing a 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 of curing the curable composition of the present invention to produce a cured product, and preferably includes the following steps (1) to (3).

(1) Step of applying the curable composition of the present invention to a substrate

(2) Step of removing solvent from the applied curable composition

(3) Steps for thermal hardening

In addition, the method for producing a cured product of the present invention more preferably includes the following steps (1), (2), (2'), and (3).

(1) Step of applying the curable composition of the present invention to a substrate

(2) Step of removing organic solvent from the applied curable composition

(2') Step of curing the curable composition with the organic solvent removed by light

(3) The step of further hardening the hardened product hardened by light with heat

In addition, the above-mentioned method for producing a cured product of the present invention is preferably a method for producing a cured film.

In the step of applying (1), it is preferable to apply the curable composition of the present invention to a substrate to prepare a wet film containing a solvent. Before applying the curable composition to the substrate, the substrate may be washed such as alkaline cleaning or plasma cleaning. Furthermore, after the substrate is washed, the surface of the substrate can be treated with hexamethyldisilazane or the like. By performing this treatment, the adhesion of the curable composition to the substrate tends to be improved.

Examples of the above-mentioned substrates include inorganic substrates, resins, and resin composite materials.

Examples of inorganic substrates include glass, quartz, silicon, silicon nitride, and composite substrates on which molybdenum, titanium, aluminum, and copper are vapor-deposited.

Examples of the resin include polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, and poly Carbonate, polysulfonate, polyether sulfonate, polyarylate, allyl diethylene glycol carbonate, polyamide, polyimide, polyimide amideimine, polyetherimide, polybenzoxazole , Polyphenylene sulfide, polycycloolefin, norbornene resin, fluororesin such as polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, silicone resin, ionomer resin, cyanate resin, cross Substrates made of synthetic resins such as bifumarate diesters, cyclic polyolefins, aromatic ethers, maleimide-olefin copolymers, cellulose, and episulfide resins. These substrates are rarely used directly in the above-mentioned form. Generally, depending on the form of the final product, for example, a multilayer laminated structure such as a TFT (Thin-Film Transistor, thin-film transistor) element is formed.

Since the curable composition of the present invention has good adhesion to the metal film or metal oxide formed by sputtering, it is preferable that the substrate include a metal film formed by sputtering. As the metal, titanium, copper, aluminum, indium, tin, manganese, nickel, cobalt, molybdenum, tungsten, chromium, silver, neodymium, and their oxides or alloys are preferred, and molybdenum, titanium, aluminum, copper, and Their alloys. In addition, one kind of metal or metal oxide may be used alone, or a plurality of kinds may be used in combination.

The coating method on the substrate is not particularly limited, and for example, inkjet method, slit coating method, spray method, roll coating method, spin coating method, cast coating method, slit rotation method, printing method and the like can be used.

In the step of removing the solvent in (2), it is preferable to remove the solvent from the above-mentioned film by applying reduced pressure (vacuum) and/or heating to form a dry coating film on the substrate. Solvent removal The heating conditions in the step are preferably 70 to 130° C. and about 30 to 300 seconds. In addition, in the above solvent removal step, it is not necessary to completely remove the organic solvent in the curable composition, as long as at least a part is removed.

Furthermore, in the present invention, after (2) the step of removing the solvent and (3) before the step of thermally curing, from the viewpoint of improving the film hardness, a step of performing full-surface exposure may be included.

In addition, after (2) the step of removing the solvent and (3) before the step of thermally curing, from the viewpoint of improving the film hardness, it is preferable to include (2') the curable composition from which the organic solvent is removed by light The hardening step more preferably includes a step of hardening the curable composition from which the organic solvent has been removed by exposure to the entire surface. In addition, when curing by light as described above, 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 with a mercury lamp or an LED (Light emitting diode) lamp.

In addition, in order to form a pattern, the steps of pattern exposure and development may be performed after the solvent removal step of (2). The pattern exposure method is preferably a mask method, a direct drawing method using laser, or the like. It is preferable to perform these full-surface exposure or pattern exposure in a state where oxygen is blocked from the viewpoint of promoting curing. As a means for blocking oxygen, exposure may be exemplified in a nitrogen atmosphere, or an oxygen blocking film may be provided.

For pattern exposure and development, a well-known method and a well-known developer can be used. For example, the pattern exposure method and development method described in Japanese Patent Laid-Open No. 2011-186398 and Japanese Patent Laid-Open No. 2013-83937 can be suitably used.

In the step (3) of performing thermal curing, an ethylenically unsaturated compound or the like may be polymerized by heating to form a cured film, or the cured product after curing may be further cured. By adding When thermally polymerizing, the curable composition of the present invention preferably contains a thermal polymerization initiator.

The heating temperature is preferably 180°C or lower, more preferably 150°C or lower, and still more preferably 130°C or lower. The lower limit value is preferably 80°C or higher, and more preferably 90°C or higher. The heating method is not particularly limited, and a known method can be used. Examples include hot plates, ovens, infrared heaters, and the like.

In addition, the heating time is preferably about 1 minute to 30 minutes in the case of a hot plate, and preferably about 20 minutes to 120 minutes in other cases. Within this range, the substrate and the device can be cured without damage. From the viewpoint of shape adjustment after heating, heating may be performed at a lower temperature first, and then heating at a higher temperature (addition of an intermediate baking step. For example, first, heating is performed at 90°C for 30 minutes, and then 120°C, 30 minutes heating).

The cured film of the present invention is a cured film obtained by curing the curable composition of the present invention, and preferably a cured film obtained by removing at least a part of an organic solvent from 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. In addition, the cured film of the present invention is preferably a cured film obtained by the method for producing a cured film of the present invention.

According to the curable composition of the present invention, a cured film having sufficient hardness can be obtained even when cured at a low temperature. For example, a cured film having a pencil hardness of 2H or more under a load of 750 g measured in accordance with JISK5600:1999 can be obtained. The protective film formed by curing the curable composition of the present invention is excellent in physical properties of the cured film, and thus is useful for applications of organic EL display devices, liquid crystal display devices, touch panels, and touch panel display devices.

Since the curable composition of the present invention is excellent in curability and cured film characteristics, it is used as a structural part of a MEMS (Micro Electro Mechanical Systems) device It is used by assembling a cured product or a resist pattern obtained by curing the curable composition of the present invention as a partition wall or as a part of a mechanical drive member. Examples of such MEMS devices include SAW (Surface Acoustic Wave) filters, BAW (BulkAcoustic Wave) filters, gyro sensors, micro-shutters for displays, and image sensors. , Electronic paper, inkjet head, biochip, sealant and other components. More specific examples are exemplified in Japanese Patent Application Publication No. 2007-522531, Japanese Patent Application Publication No. 2008-250200, and Japanese Patent Application Publication No. 2009-263544.

Since the curable composition of the present invention is excellent in flatness and transparency, it can also be used in, for example, the bank layer (16) and the flattening film (57) described in FIG. 2 of Japanese Patent Application Laid-Open No. 2011-107476, Japanese Patent Partition wall (12) and flattening film (102) described in FIG. 4(a) of 2010-9793, and bank layer (221) and third in FIG. 10 of JP 2010-27591 Interlayer insulating film (216b), the second interlayer insulating film (125) and the third interlayer insulating film (126) described in FIG. 4(a) of JP 2009-128577, and JP 2010-182638 In the formation of the planarization film (12) and the pixel separation insulating film (14) described in FIG. In addition, it can also be suitably used as a spacer for keeping the thickness of a liquid crystal layer in a liquid crystal display device, a color filter or a color filter protective film of a liquid crystal display device, a facsimile, an electronic copier, a solid-state imaging element, etc. Color filter imaging optical system or fiber optic connector microlens.

(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 flattened film or an interlayer insulating film formed using the curable composition of the present invention, and examples include A well-known various organic EL display device or liquid crystal display device of this structure.

For example, specific examples of TFTs included in the organic EL display device of the present invention include amorphous silicon-TFTs, low-temperature polysilicon-TFTs, and oxide semiconductor TFTs. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.

FIG. 1 is a conceptual diagram of an example of an organic EL display device. A schematic cross-sectional view showing a substrate in a bottom-emission organic EL display device, including a planarizing film 4.

A bottom-gate TFT 1 is formed on the glass substrate 6, and an insulating film 3 made of Si ₃ N _{4 is} formed in a state of covering the TFT 1. After a contact hole (not shown here) is formed in the insulating film 3, a wiring 2 (height 1.0 μm) connected to the TFT 1 through the contact hole is formed in the insulating film 3. The wiring 2 is a wiring for connecting the organic EL element formed between the TFTs 1 or in the subsequent steps to the TFT 1.

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

On the planarizing film 4, a bottom emission type organic EL element is formed. That is, the first electrode 5 made of ITO is formed on the planarizing film 4 via the contact hole 7 and connected to the wiring 2. In addition, the first electrode 5 corresponds to the anode of the organic EL element.

The insulating film 8 is formed to cover the periphery of the first electrode 5. By providing the insulating film 8, a short circuit between the first electrode 5 and the second electrode formed in the subsequent step can be prevented.

Furthermore, although not shown in FIG. 1, a hole transport layer, an organic light-emitting layer, and an electron transport layer are sequentially deposited through a desired pattern mask, and then formed on the entire surface above the substrate. The second electrode composed of Al is sealed by bonding and sealing using a glass plate for sealing and an ultraviolet-curing epoxy resin to obtain a TFT 1 connected to each organic EL element for driving it The resulting active matrix organic EL display device.

(Liquid crystal display device)

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

The liquid crystal display device of the present invention is not particularly limited except that it has a protective film, a flattening film, or an interlayer insulating film formed using the curable composition of the present invention described above, and known liquid crystal display devices having various structures can be cited.

In addition, examples of the liquid crystal driving method that can be adopted for the liquid crystal display device of the present invention include a TN (Twisted Nematic) method, a VA (Vertical Alignment) method, and an IPS (In-Plane-Switching, in-plane Switching) method, FFS (Fringe Field Switching, fringe field switching) method, OCB (Optically Compensated Bend, optically compensated bending) method, etc.

In the panel configuration, even a COA (Color Filteron Array) type liquid crystal display device can use the cured film of the present invention, for example, it can be used as an organic insulating film of Japanese Patent Laid-Open No. 2005-284291 (115) , The organic insulating film (212) of Japanese Patent Laid-Open No. 2005-346054 is used. In addition, as a specific alignment method of the liquid crystal alignment film that can be adopted in the liquid crystal display device of the present invention, a rubbing alignment method, an optical alignment method, etc. may be mentioned. In addition, polymer alignment support may be performed by the PSA (Polymer Sustained Alignment) technology described in Japanese Patent Laid-Open Nos. 2003-149647 and 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 applications, and can be used in various applications. For example, in addition to the flattening film and the interlayer insulating film, it can also be suitably used as a protective film and a liquid crystal display device for keeping the thickness of the liquid crystal layer constant Spacers, microlenses provided on the color filter in the solid-state imaging element, and the like.

2 is a conceptual cross-sectional view showing an example of an active matrix liquid crystal display device 10. This color liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on the back, and the liquid crystal panel is provided with elements of TFTs 16 corresponding to all pixels disposed between two glass substrates 14 and 15 to which a polarizing film is attached. ITO transparent electrodes 19 forming pixel electrodes are wired to the contact holes 18 formed in the cured film 17 on each element formed on the glass substrate. On the ITO transparent electrode 19, a layer of liquid crystal 20 and an RGB color filter 22 in which a black matrix is arranged are provided.

The light source of the backlight is not particularly limited, and a known light source can be used. For example, white LEDs, multi-color LEDs such as blue, red, or green, fluorescent lamps (cold cathode tubes), organic EL, and the like can be mentioned.

In addition, the liquid crystal display device may be a 3D (stereoscopic view) type liquid crystal display device or a touch panel type liquid crystal display device. Furthermore, it can be made into a flexible type and can be used as the second interlayer insulating film (48) described in JP 2011-145686 and the interlayer insulating film (520) described in JP 2009-258758.

(Touch panel and touch panel display device)

The touch panel of the present invention is a touch panel having the cured film of the present invention.

The touch panel display device of the present invention is a touch panel display device having the cured film of the present invention, and is preferably a touch panel display device having the touch panel of the present invention.

The touch panel of the present invention may be any known method such as a resistive film method, an electrostatic capacitance method, an ultrasonic method, and an electromagnetic induction method. Among them, the electrostatic capacity method is preferred.

As the touch panel type, a so-called in-cell type (for example, Japanese The touch panels described in FIGS. 5, 6, 6, 7 and 8 of this Japanese Patent Publication No. 2012-517051, the so-called on-cell type (for example, Japanese Patent Laid-Open No. 2013-168125 19, the touch panel described in Japanese Patent Laid-Open No. 2012-89102, and the touch panel described in FIG. 5), OGS (One Glass Solution) type, TOL (Touch on lens) type (for example, Japan The touch panel described in FIG. 2 of JP-A-2013-54727 and the touch panel described in FIGS. 2, 3, 4 and 5 of JP-A 2015-15042), and other configurations (for example , The touch panel described in FIG. 6 of Japanese Patent Laid-Open No. 2013-164871) various out-cell types (so-called GG, G1.G2, GFF, GF2, GF1, G1F, etc.).

In addition, FIG. 3 shows a conceptual configuration diagram of an example of a liquid crystal display device having a touch panel function.

For example, the cured film of the present invention is suitably applied to the protective film between the layers in FIG. 3, and is also suitably applied to the interlayer insulating film that separates the detection electrodes of the touch panel. In addition, the detection electrode of the touch panel is preferably a transparent electrode (ITO (Indium Tin Oxide), IZO (Indium Tin Oxide), etc.), a metal electrode (silver, copper, molybdenum, titanium, aluminum, etc., a laminate thereof, or Alloy, etc.), or a laminate thereof.

In FIG. 3, 110 represents a pixel substrate, 140 represents a liquid crystal layer, 120 represents a counter substrate, and 130 represents a sensor portion. 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 order from the lower side of FIG. The counter substrate 120 has an alignment film 121, a color filter 122, and a transparent substrate 123 in this order from the lower side in FIG. 3. The sensor part 130 has a phase difference film 124, an adhesive layer 126, and a polarizing plate 127, respectively. In addition, in FIG. 3, 125 is a detection electrode for a sensor. The cured film of the present invention can be formed on the insulating layer (114) (also called an interlayer insulating film) of the pixel substrate portion, various protective films (not shown), and the pixel substrate portion It is used in various protective films (not shown), various protective films (not shown) on the opposite substrate portion, various protective films (not shown) in the sensor portion, and the like.

For the adhesive layer 126 and the polarizing plate 127, a well-known adhesive layer composition can be used.

Specific examples of the polarizing plate and the adhesive layer include the polarizing plate with an adhesive layer described in Example 1, Example 7, and Example 13 of Japanese Unexamined Patent Publication No. 2014-152319, and Japanese Unexamined Patent Publication No. 2014-152319. The polarizing plate with an adhesive layer described in Example 1, Example 3, and Example 6 of 191005, Example 1, Example 3, Example 6, and Example 11 of Japanese Patent Laid-Open No. 2013-100386 And the polarizing plate with an adhesive layer described in Example 14 and the adhesive layers described in Example 1, Example 2, Example 3, and Example 4 of JP-A-2013-163783.

In order to prevent static electricity, the adhesive layer preferably contains an antistatic agent.

As the antistatic agent, a known antistatic agent can be used. For example, ionic compounds such as metal particles, metal oxides, conductive polymers, fourth ammonium salts, and lithium salts can be used.

Specific examples of the antistatic agent include the antistatic agent described in paragraphs 0107 to 0115 of JP-A-2014-191005, and the antistatic agent described in paragraphs 0046-0054 of JP-A 2013-100386 And the antistatic agent described in paragraphs 0027 to 0047 of Japanese Patent Publication No. 2014-515046.

Furthermore, even a liquid crystal display device of a static drive method can display highly designed patterns by applying the present invention. As an example, the present invention can be applied as an insulating film of a polymer network liquid crystal as described in Japanese Patent Laid-Open No. 2001-125086.

In addition, FIG. 4 is a conceptual diagram of another configuration of a liquid crystal display device having a touch panel function.

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

The lower display panel 200 includes a first insulating substrate 210, a thin film transistor (TFT) disposed on the first insulating substrate 210, an insulating film 280 formed on an upper surface of the thin film transistor (TFT), and an insulating film 280上的Pixel electrode 290. A thin film transistor (TFT) may include a gate electrode 220, a gate insulating film 240 covering the gate electrode 220, a semiconductor layer 250, ohmic contact layers 260, 262, a source electrode 270, and a drain electrode 272.

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

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

In the liquid crystal display device shown in FIG. 4, the sensor electrode 410, the insulating film 420, the drive electrode 430, and the protective film 280 are arranged on the other surface of the second insulating substrate 310. As described above, in the manufacture of the liquid crystal display device shown in FIG. 4, when the upper display panel 300 is formed, the sensing electrode 410, the insulating film 420, the drive electrode 430, etc., which are constituent elements of the touch screen, 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.

On the protective film 280, a polarizing plate with an adhesive layer or an adhesive layer exemplified by the adhesive layer 126 and the polarizing plate 127 described above may also be bonded.

[Example]

The following examples illustrate the present invention more specifically. The materials, usage amounts, ratios, processing contents, processing steps, etc. 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 specific examples shown below. In addition, unless otherwise specified, "parts" and "%" are quality standards.

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

Mix 50.4 parts of hexamethylene diisocyanate terpolymer (manufactured by Asahi Kasei Corporation, TPA-100) in a toluene solvent, and add U-CATSA102 (Dazabicycloundecene (DBU)) as a curing catalyst Octanoate, manufactured by San-Apro Ltd.) 0.15 parts, and heated at 60°C for 1 hour in a nitrogen atmosphere. Thereto, 157.4 parts of a solution obtained by dissolving dipentaerythritol pentaacrylate (Aldrich product after column purification for use) dissolved in a toluene solvent was heated at 60°C for 5 hours in a nitrogen atmosphere.

After cooling, the reaction mixture was purified and separated by silica gel column chromatography to obtain (a-1)-1. The weight average molecular weight of the obtained (a-1)-1 measured by gel permeation chromatography (GPC) was 15,300.

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

[Chemical Formula 20]

A mixed solution of 2-isocyanatoethyl methacrylate (116.4 parts) and propylene glycol monomethyl ether acetate (PGMEA, 135.8 parts) was heated to 70° C. under a nitrogen stream. While stirring this mixed solution, radical polymerization initiator V-65 (trade name, 2,2'-azobis(2,4-dimethylvaleronitrile), Wako Pure Chemical Industries Ltd. was added dropwise over 2 hours Co., Ltd., 4 parts) and PGMEA (135.8 parts) mixed solution. After the dropwise addition, the reaction was carried out at 70°C for 4 hours.

To the obtained polymer, 87.1 parts of 2-hydroxyethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, 0.3 parts of p-methoxyphenol (manufactured by Wako Pure Chemical Industries, Ltd.), and U-CATSA102 (San-Apro Ltd.) were added. . System) 0.2 parts, heating at 60°C for 6 hours to obtain (a-1)-2.

The weight average molecular weight of the obtained (a-1)-2 measured by gel permeation chromatography (GPC) was 30,000.

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

[Chemical Formula 21]

In Synthesis Example 2, the addition amount of the polymerization initiator V-65 was changed to 8 parts, and the addition amount of PGMEA was all set to 232.7 parts, except that in the same manner as in Synthesis Example 2, a polymer (a- 1)'-3.

The weight average molecular weight of the obtained (a-1)'-3 measured by gel permeation chromatography (GPC) was 8,000.

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

[Chemical Formula 22]

50.4 parts of hexamethylene diisocyanate terpolymer (manufactured by Asahi Kasei Co., Ltd., TPA-100) and 157.4 parts of dipentaerythritol pentaacrylate (used after column purification by Aldrich) were mixed in toluene solvent and added as a hardener 0.2 parts of U-CATSA102 (manufactured by San-Apro Ltd.) of the catalyst was heated at 60°C for 6 hours in a nitrogen atmosphere.

After cooling, the reaction mixture was purified and separated by silica gel column chromatography to obtain (a-2)-1.

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

[Chemical Formula 23]

Except that the hexamethylene diisocyanate trimer in Synthesis Example 4 was changed to hexamethylene diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.), synthesis and purification were carried out in the same manner as in Synthesis Example 4 to obtain (a-2 )-2.

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

Except that the dipentaerythritol pentaacrylate in Synthesis Example 5 was changed to pentaerythritol triacrylate (using Aldrich's product after column purification), it was synthesized and purified in the same manner as in Synthesis Example 5 to obtain (a-2)-3 .

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

[Chemical Formula 25]

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

<urethane (meth)acrylate>

(a-1)-1: Urethane acrylate prepared in Synthesis Example 1, Mw: 15,300, number of functional groups: many, and having a structural repeating unit represented by the above formula Aa-1.

(a-1)-2: The urethane acrylate prepared in Synthesis Example 2, Mw: 30,000, the number of functional groups: many, and having the structural repeating unit represented by the above formula Aa-2.

(a-1)'-3: Urethane acrylate prepared in Synthesis Example 3, Mw: 8,000, official Number of energy groups: many, having the structural repeating unit represented by the above formula Aa-2.

(a-2)-1: Urethane acrylate prepared in Synthesis Example 4, molecular weight: 2,078, number of functional groups: 15

(a-2)-2: Urethane acrylate prepared in Synthesis Example 5, molecular weight: 1,218, number of functional groups: 10

(a-2)-3: Carbamate acrylate prepared in Synthesis Example 6, molecular weight: 764, number of functional groups: 6

(a-2)'-4: Urethane acrylate prepared in Synthesis Example 7, molecular weight: 853, number of functional groups: 3

<ethylenically unsaturated compounds other than urethane (meth)acrylate>

A-1: Dipentaerythritol hexaacrylate

A-2: Dipentaerythritol pentaacrylate

A-3: Pentaerythritol tetraacrylate

In addition, all of A-1 to A-3 were used after column purification from Aldrich.

<Component B: free radical polymerization initiator>

B-1: The following compound 1, oxime ester compound

B-2: IRGACUREOXE01 (manufactured by BASF), oxime ester compound, the following structure

B-3: IRGACUREOXE02 (manufactured by BASF), oxime ester compound, the following structure

B-4: IRGACURE907 (manufactured by BASF), aminoalkyl benzophenone compound, 2-methyl-4'-(methylthio)-2-morpholinophenylacetone

<Component C: mercapto compound>

C-1: KarenzMT-PE-1 (Pentaerythritol tetrakis(3-mercaptobutyrate), manufactured by Showa Denko Co., Ltd.)

C-2: KarenzMT-BD-1 (1,4-bis(3-mercaptobutyryloxy)butane, Showa Denko Co., Ltd. 10-type company)

C-3: Pentaerythritol tetrakis(3-mercaptopropionate)

C-4: Dipentaerythritol hexa(3-mercaptopropionate)

C-5: The following compounds

C-6: 1-dodecanethiol

C-7: The following compounds

<Component D: Organic solvent>

D-1: Propylene glycol monomethyl ether acetate (made by Daicel Corporation)

D-2: Methyl ethyl diethylene glycol (made by Japan Emulsifier Co., Ltd.)

D-3: 1,3-Butanediol diacetate

D-4: Tetrahydrofurfuryl alcohol

<Component E: Inorganic particles>

E-1: PMA-ST (manufactured by Nissan Chemical Industry Co., Ltd.), silica particles, average particle size 10-15 nm, solid content concentration 30%)

E-2: MIBK-ST-L (manufactured by Nissan Chemical Industry Co., Ltd.), silica particles, the average particle size is 40-50 nm, and the solid content concentration is 30%)

E-3: NanouseOZ-S30K-AC (zirconia particles, manufactured by Nissan Chemical Industry Co., Ltd., solid content concentration 30%)

<alkoxysilane compound>

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

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

<Blocked isocyanate compound>

S-3: TAKENATE B870N (oxime blocked isophorone diisocyanate, solid content concentration 60%, manufactured by Mitsui Chemicals Co., Ltd.)

S-4: DURANATE 17B-60P (blocked isocyanate compound whose parent structure has a biuret structure and the blocked structure is an oxime ester structure, the solid content concentration is 60%, manufactured by Asahi Kasei Chemicals Corporation)

<epoxy compound>

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

<Polysulfide compound>

S-6: KBE-846 (bis(triethoxysilylpropyl) tetrasulfide, manufactured by Shin-Etsu Chemical Co., Ltd.)

<sensitizer>

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

(In the formula, Bu represents butyl.)

<Antioxidant>

J-1: ADEKA STAB AO-60 (Hindered phenolic antioxidant, manufactured by ADEKA Corporation)

<polymerization inhibitor>

K-1: 4-methoxyphenol

<surfactant>

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

W-2: FTX-218 (manufactured by Neos Corporation), fluorine-based surfactant

(Examples 1 to 29 and Comparative Examples 1 to 5)

<Preparation of hardening composition>

As described in Tables 1 to 3 below, each component is mixed and stirred to prepare a solution and/or dispersion of an organic solvent, and filtered through a polytetrafluoroethylene filter with a pore size of 0.3 μm to obtain the cured product of the present invention Sexual composition. The unit of each component of the following Table 1-Table 3 is a mass part. In addition, except for the blocked isocyanate compound, the inorganic particles, and the organic solvent, it represents a mass part in terms of solid content. The blocked isocyanate compound and the inorganic particles represent the parts by mass of the solid content concentration solution. In addition, "-" in the table means that no corresponding compound is contained.

<Evaluation of film strength>

Each curable composition was spin-coated on a glass substrate, and prebaked at 90° C. for 120 seconds to obtain a coating film having a film thickness of 2.0 μm. Next, light irradiation of 500 mJ/cm ² (i-ray conversion) was performed by a high-pressure mercury lamp, and further baked at 120° C. for 60 minutes in an oven, thereby producing a cured film.

With respect to the obtained cured film, 10 round trips were rubbed with steel wool #0000 and a load of 500 g, and evaluation was performed visually.

In addition, similarly, with respect to the obtained cured film, a pencil hardness test was performed by a method according to JIS K5600: 1999 (a load of 750 g) to evaluate the film strength.

The results of the tests on the scratch resistance and pencil hardness of steel wool are summarized and evaluated as follows. 4 points or more is the practical range.

8: No damage to the steel wool was seen at all, and the pencil hardness was 5H or more.

7: No damage to the steel wool was seen at all, and the pencil hardness was above 3H and below 5H.

6: There are several steel wool injuries, the pencil hardness is above 3H and below 5H.

5: There are several steel wool injuries, the pencil hardness is above 2H and below 3H.

4: There is a wound of steel wool but through the back, the pencil hardness is above 2H and below 3H.

3: There is a wound of steel wool but the pencil hardness is lower than 2H through the back.

2: There are many wounds on the steel wool and the film is turbid and does not penetrate to the back. The pencil hardness is less than 2H.

1: The film was peeled off by steel wool. The pencil hardness is less than 2H.

As shown in Tables 1 to 3 above, the curable composition of the present invention has a high hardness even when cured at a low temperature, and has excellent scratch resistance.

(Example 30)

<Manufacture of display device>

In the display device shown in FIG. 4, the curable compositions obtained in Examples 1 to 29 were used for the formation of touch detection electrode protective films (insulating films, 420), respectively, to produce display devices. Specifically, the protective film (420) is an inkjet coating of the curable composition obtained in each of the examples, pre-baked at 90° C. for 120 seconds, and subjected to 500 mJ/cm ² (i-ray) by a high-pressure mercury lamp. (Converted) light irradiation, and then baked in an oven at 120°C for 60 minutes. The other parts of the display device are manufactured in accordance with the manufacturing method described in FIG. 19 in Japanese Patent Laid-Open No. 2013-168125. Any one of the manufactured display devices is excellent in display performance and touch detection performance.

Claims (15)

A curable composition, characterized by comprising: an acrylate-based ethylenically unsaturated compound as component A, the content of which is 40% by mass or more and 98% by mass or less in the total organic solid content of the curable composition, as The total amount of the polymerization initiator of component B is 0.5 to 30% by mass relative to the total solid content of the curable composition, and the content of the mercapto compound as component C is 1 to 20% by mass relative to the total solid content of the curable composition. %, and the organic solvent as component D, the content is 100 to 3,000 parts by mass relative to 100 parts by mass of the total solid content of the curable composition, and the component A contains 5 to 500 functional urethane (meth)acrylates, The content of the 5-500-functional urethane (meth)acrylate is 20-100 parts by mass relative to 100 parts by mass of the component A, and the 5-500-functional urethane (methyl) Acrylic esters include urethane (meth)acrylates with a weight average molecular weight of 10,000 to 100,000 and 2 to 100 kinds of urethane (meth)acrylates with a molecular weight of 500 to 5,000. The curable composition as described in item 1 of the patent application, wherein component B contains an oxime ester compound. The curable composition as described in claim 1 or claim 2, wherein component A contains an ethylenically unsaturated compound other than the 5-500 functional urethane (meth)acrylate. The curable composition as described in item 3 of the patent application scope, wherein the olefins other than the 5-500 functional urethane (meth)acrylate are not The saturated compound is a polyfunctional ethylenically unsaturated compound. The curable composition according to item 1 or 2 of the patent application, wherein the content of component A is 70 to 98% by mass relative to the total organic solid content of the curable composition. The curable composition as described in item 1 or 2 of the patent application, wherein component C contains a polyfunctional mercapto compound. The curable composition as described in claim 1 or claim 2 further contains inorganic particles as component E. The curable composition as described in the first or second patent application scope, further comprising a compound selected from the group consisting of an epoxy group compound, an oxetane group compound, a blocked isocyanate compound, and/or an alkyl group At least one of the group consisting of oxysilane compounds. A cured film obtained by curing the curable composition as described in any one of the first to eighth patent applications. The cured film as described in item 9 of the patent application scope is a protective film. The cured film as described in item 9 of the patent application range has a pencil hardness of 2H or more under a load of 750 g measured in accordance with JIS K5600:1999. An organic EL display device having a cured film as described in any one of claims 9 to 11. A liquid crystal display device having a cured film as described in any one of claims 9 to 11. A touch panel having the cured film according to any one of the patent application items 9 to 11. A touch panel display device having the cured film according to any one of the patent application items 9 to 11.

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