JP6165813B2 - Curable composition, cured film, organic EL display device, liquid crystal display device, and touch panel display device - Google Patents

Description

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

Flat panel displays such as liquid crystal display devices and organic EL display devices are widely used. Recently, in the manufacturing process of these displays, it is necessary to lower the heating temperature of various cured films in the manufacturing process from the viewpoint of reducing damage to substrates and circuits and saving energy.
As such a curable composition, for example, Patent Document 1 discloses (A) an alkali-soluble resin, (B) a compound having one or more ethylenically unsaturated groups selected from Formula a and Formula b, (C ) A radiation-sensitive resin composition for forming a protective film for a touch panel, which contains a radiation-sensitive polymerization initiator, and a method for forming the same.

(Here, X is selected from a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an acryloyl group or a methacryloyl group, at least one of which is an acryloyl group or a methacryloyl group. W is a carbon atom having 1 to 6 carbon atoms. An alkylene group, a C2-C6 alkylene group containing one unsaturated bond, a phenylene group, or a cyclohexyl group is shown.)

  Patent Document 2 discloses (a) 20 to 70 parts by weight of a compound represented by the following general formula [1] having two or more carboxyl groups and one or more (meth) acryloyl groups in one molecule. ,

(In the formula, m is an integer of 1 or 2, n is an integer of 1 to 3, R ¹ is a residue portion other than the hydroxyl group of H or n-valent alcohol, R ² is a residue other than the hydroxyl group of the hydroxyl group-containing (meth) acrylate) The base part, Z, represents an alicyclic or aromatic hydrocarbon residue having 4 to 10 carbon atoms.)

(B) 20 to 60 parts by weight of a compound represented by the following general formula [2],
_{[CH 2 = CHCOO- (CH 2 CH} 2 COO) p ] _q -R ³ [2]
(In the formula, p represents an integer of 1 to 10, q represents an integer of 2 or more, and R ³ represents a residue portion excluding the hydroxyl group of q-valent alcohol.)
(C) 0 to 40 parts by weight of a compound having one or more (meth) acryloyl groups in one molecule other than the components (a) and (b) above (however, the sum of the components (a) to (c)) (D) A resist composition characterized by comprising 0.1 to 10 parts by weight of a photopolymerization initiator is described.
Furthermore, in Patent Document 3, (A) (a) 10 to 50% by weight of a polymerizable unsaturated compound having an acidic functional group, (b) having an alicyclic hydrocarbon group, and having no acidic functional group. Polymerized 20 to 60% by weight of polymerizable unsaturated compound and (c) 5 to 40% by weight of other polymerizable unsaturated compound (however, (a) + (b) + (c) = 100% by weight) A radiation-sensitive resin composition for forming an interlayer insulating film, comprising: an alkali-soluble copolymer, (B) a polymerizable unsaturated compound, (C) a photopolymerization initiator, and (D) a coupling agent Is described.

Japanese Patent No. 5201066 Japanese Patent No. 3678922 JP 2006-91490 A

  The problems to be solved by the present invention include a curable composition excellent in patterning property, excellent adhesion of the resulting cured film and excellent discoloration resistance to the underlying metal, a cured film obtained by curing the curable composition, and It is to provide an organic EL display device, a liquid crystal display device and a touch panel display device using the cured film.

The above-described problems of the present invention have been solved by means described in the following <1>, <11>, or <13> to <15>. It describes below with <2>-<10> and <12> which are preferable embodiments.
<1> Component A as a polymerizable monomer, Component B as a photopolymerization initiator, Component C as a compound having at least a titanium atom or an aluminum atom and a (meth) acryloyl group, and Component D as a polymer A curable composition characterized in that component A contains a polymerizable monomer having one or more carboxyl groups,
<2> The curable composition according to <1>, wherein component C is a compound in which one or more alkoxy groups are directly bonded to a titanium atom or an aluminum atom,
<3> The curable composition according to <1> or <2>, wherein the component C is a compound represented by any one of the following formulas C-1 to C-3:

In Formula C-1 to Formula C-3, each R ¹ independently represents a hydrogen atom or a methyl group, each R ² independently represents an alkyl group, and each L independently represents a divalent linking group. M represents a titanium atom or an aluminum atom. When M is a titanium atom, m represents an integer of 1 to 4, n represents an integer of 0 to 3, m + n = 4 is satisfied, and M is an aluminum atom. In this case, m represents an integer of 1 to 3, n represents an integer of 0 to 2, and satisfies m + n = 3.

<4> The curable composition according to <3>, wherein the divalent linking group represented by L has 2 to 20 carbon atoms,
<5> Curable composition as described in any one of <1>-<4> whose content of component C is 0.1-20 mass% with respect to the total solid of a curable composition. ,
<6> The curable composition according to any one of <1> to <5>, wherein component A further comprises a compound having a (meth) acryloyl group and one or more urethane bonds,
<7> Curing according to any one of <1> to <6>, wherein Component A further comprises a compound having two or more (meth) acryloyl groups in the molecule and not having a carboxyl group Sex composition,
<8> The curable composition according to any one of <1> to <7>, further including inorganic particles as component E,
<9> The curable composition according to any one of <1> to <8>, wherein the content of component A is 50% by mass or more based on the total organic solid content in the curable composition,
<10> The curable composition according to any one of <1> to <9>, further including a copolymer having an acidic group as the component F.
<11><1> to a cured film obtained by curing the curable composition according to any one of <10>,
<12> The cured film according to <11>, which is a protective film for touch panel wiring,
<13> An organic EL display device having the cured film according to <11>,
<14> A liquid crystal display device having the cured film according to <11>,
<15> A touch panel display device having the cured film according to <11> or <12>.

  According to the present invention, a curable composition having excellent patterning properties, excellent adhesion of the obtained cured film and excellent resistance to discoloration to a base metal, a cured film obtained by curing the curable composition, and the cured film It was possible to provide an organic EL display device, a liquid crystal display device, and a touch panel display device using the above.

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

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

  In the present invention, the weight average molecular weight and number average molecular weight in the polymer component are weight average molecular weights in terms of polystyrene measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent.

(Curable composition)
The curable composition of the present invention (hereinafter also simply referred to as “composition”) includes a polymerizable monomer as component A, a photopolymerization initiator as component B, and a titanium atom or an aluminum atom as component C. A compound having at least a (meth) acryloyl group and a polymerization inhibitor as the component D are included, and the component A includes a polymerizable monomer having one or more carboxyl groups.
Moreover, it is preferable that the curable composition of this invention is a negative photosensitive composition.
The curable composition of the present invention is preferably capable of patterning by photolithography with an alkaline developer. When the curable composition of the present invention is patterned by photolithography with an alkaline developer, the resulting pattern is a negative pattern in which the photosensitive portion remains as a pattern.

In the conventional curable composition, when a polymerizable monomer having one or more carboxyl groups is used, the patterning property is improved due to the effect of improving the solubility of the developer by the carboxyl group, but the adhesion to the base metal is lowered. The present inventors have found that there is a problem to do.
On the other hand, as a result of intensive studies, the present inventors have used a compound having at least a titanium atom or an aluminum atom and a (meth) acryloyl group, thereby preventing adhesion deterioration and undercoating under high temperature and high humidity. We have found that it is possible to achieve both suppression of metal discoloration of the substrate. This is presumed to be due to the effect of forming a network with other polymerizable monomers at the time of firing with the (meth) acryloyl group and the protective effect due to the high affinity between the titanium atom or aluminum atom and the base metal.
Furthermore, as a result of investigations, the present inventors have made Component A to Component D, and Component A is a curable composition containing a polymerizable monomer having one or more carboxyl groups, It has been found that the cured film obtained is excellent in adhesion and discoloration resistance to the underlying metal, and further excellent in patterning properties, and the present invention has been completed.
Hereinafter, each component which the curable composition of this invention contains is demonstrated.

Component A: Polymerizable monomer The curable composition of the present invention contains a polymerizable monomer as Component A.
Component A may be a low molecular weight compound or an oligomer, but does not contain a polymer.
The molecular weight of component A used in the present invention (in the case of having a molecular weight distribution, the weight average molecular weight) is 100 to 10,000, preferably 200 to 5,000, from the viewpoint of the hardness of the cured film. 300 to 3,000 is more preferable.
Although there is no restriction | limiting in particular as a polymerizable monomer used for this invention, It is preferable that it is an ethylenically unsaturated compound, and it is more preferable that it is a (meth) acrylate compound.

<Component Aa: Polymerizable monomer having one or more carboxyl groups>
The curable composition of the present application contains, as Component A, a polymerizable monomer having one or more carboxyl groups (also referred to as Component Aa).
Component Aa preferably has three or more (meth) acryloyl groups in the molecule. The number of (meth) acryloyl groups contained in the molecule (in one molecule) is preferably 3 to 15, more preferably 3 to 10, and still more preferably 3 to 6. When the number of (meth) acryloyl groups is within the above range, hardness and reactivity are excellent.

Component Aa is a total of ₃ acryloyl (—C (═O) —CH═CH ₂ ) and methacryloyl groups (—C (═O) —C (CH ₃ ) ═CH ₂ ) in one molecule. Although it is preferable to have two or more, an acryloyloxy group (—O—C (═O) —CH═CH ₂ ) and a methacryloyloxy group (—O—C (═O) —C (CH ₃ ) ═CH ₂ ) In total is more preferably 3 or more. Moreover, it is preferable to have 3 or more acryloyl groups, and it is more preferable to have 3 or more acryloyloxy groups.
Compared with a methacryloyl group, an acryloyl group is preferable in that it is excellent in curability (reactivity). In addition, a (meth) acryloyloxy group is preferable in terms of excellent reactivity and easy synthesis.

  Component Aa has one or more carboxyl groups in the molecule (in one molecule). The number of carboxyl groups in one molecule is preferably 1 to 4, more preferably 1 to 3, and still more preferably 1 or 2. It is preferable for the component Aa to have the number of carboxyl groups in one molecule within the above range since the developability and substrate adhesion are excellent.

  In addition, it is preferable that component Aa does not have acid groups other than the said carboxyl group. Examples of the acid group other than the carboxyl group include a sulfonic acid group and a phosphoric acid group. If it has an acid group other than a carboxyl group, the substrate adhesion may be lowered.

  Component Aa is an ester of a polyhydroxy compound and an unsaturated carboxylic acid, and an unreacted hydroxy group of the polyhydroxy compound is reacted with a carboxylic acid anhydride to give an acid group (carboxyl group). The polymerizable monomer is preferably, and particularly preferably, the polyhydroxy compound is pentaerythritol and / or dipentaerythritol.

Component Aa is obtained, for example, by adding an acid anhydride to a compound having one or more (meth) acryloyl groups and a hydroxy group (hereinafter also referred to as “hydroxy polyfunctional (meth) acrylate”). Can do.
Examples of the hydroxy polyfunctional (meth) acrylate include an ester of a polyhydroxy compound having four or more hydroxy groups and (meth) acrylic acid.
The polyhydroxy compound having four or more hydroxy groups is preferably an aliphatic polyhydroxy compound, specifically, diglycerol, ditrimethylolethane, ditrimethylolpropane, ditrimethylolbutane, ditrimethylolhexane, pentaerythritol. , Dipentaerythritol, tripentaerythritol and the like. Among these, pentaerythritol and dipentaerythritol are preferable.
Moreover, you may use the alkylene oxide adduct of said polyhydroxy compound illustrated above as a polyhydroxy compound, and ethylene oxide, a propylene oxide, etc. are illustrated as an alkylene oxide.

A method for producing the hydroxy polyfunctional acrylate is not particularly limited as long as a known method is appropriately employed. Specifically, a method of heating and stirring a polyhydroxy compound and (meth) acrylic acid under an acidic catalyst is exemplified. Examples of the acidic catalyst include sulfuric acid, paratoluenesulfonic acid, methanesulfonic acid, and the like. The reaction temperature may be appropriately set according to the compound to be used and the purpose, but it is preferably 70 ° C to 140 ° C. Within the above temperature range, the reaction is fast and the reaction proceeds stably, and the generation of impurities and gelation are suppressed.
In the reaction, it is preferable to use an organic solvent having low solubility with water produced by the esterification reaction and promote dehydration while azeotropically distilling water. Preferred organic solvents include aromatic hydrocarbons such as toluene, benzene and xylene, aliphatic hydrocarbons such as hexane and heptane, and ketones such as methyl ethyl ketone and cyclohexanone. The organic solvent can be distilled off under reduced pressure after the reaction.
In addition, a polymerization inhibitor can be added to the reaction solution for the purpose of preventing polymerization of the resulting (meth) acrylic acid ester. Examples of such a polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, 2,6-ditertiary butyl-p-cresol, and phenothiazine.

Component Aa is suitably obtained by reaction of the hydroxy polyfunctional (meth) acrylate with an acid anhydride.
Examples of the acid anhydride include succinic anhydride, 1-dodecenyl succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, tetramethylene maleic anhydride, One in the same molecule such as tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride and trimellitic anhydride Compounds having an acid anhydride group, as well as pyromellitic anhydride, phthalic anhydride dimer, diphenyl ether tetracarboxylic dianhydride, diphenyl sulfone tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride and 1,2 , 3,4 Tantetracarboxylic dianhydride, diphenyl ether tetracarboxylic anhydride and trimellitic anhydride / ethylene glycol ester (commercially available products include, for example, trade name Ricacid TMEG-100 manufactured by Shin Nippon Rika Co., Ltd.) And compounds having two acid anhydride groups in the same molecule.
Among these, a compound having one acid anhydride group in the same molecule is preferable.

What is necessary is just to follow a conventional method as a manufacturing method of component Aa.
For example, a method in which a hydroxy polyfunctional (meth) acrylate and an acid anhydride are reacted at 60 to 110 ° C. for 1 to 20 hours in the presence of a catalyst can be used. Examples of the catalyst in this case include N, N-dimethylbenzylamine, triethylamine, tributylamine, triethylenediamine, benzyltrimethylammonium chloride, benzyltriethylammonium bromide, tetramethylammonium bromide, cetyltrimethylammonium bromide, and zinc oxide.

  Component Aa is preferably a compound represented by Formula a-1 or Formula a-2.

In formula a-1, each X ¹ independently represents an acryloyloxy group or a methacryloyloxy group, and W ¹ represents an alkylene group having 1 to 6 carbon atoms, an alkenylene group having 2 to 6 carbon atoms, or a phenylene group.
In formula a-2, each X ² independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an acryloyloxy group or a methacryloyloxy group, and at least three of the five X ² are An acryloyloxy group or a methacryloyloxy group. W ² represents an alkylene group having 1 to 6 carbon atoms, an alkenylene having 2 to 6 carbon atoms, or a phenylene group.

In the formula ^a-1, X 1 is preferably 3 Tsutomo are acryloyloxy groups.
In Formula a-1, W ¹ represents an alkylene group having 1 to 6 carbon atoms, an alkenylene group having 2 to 6 carbon atoms, or a phenylene group, and the alkylene group having 1 to 6 carbon atoms is linear, It may be either branched or annular. The alkylene group preferably has 2 to 6 carbon atoms, and examples thereof include an ethylene group, a propylene group, a butylene group, a pentyl group, a hexylene group, and a cyclohexylene group.
In Formula a-1, W ¹ is preferably an alkylene group having 1 to 6 carbon atoms, more preferably an alkylene group having 2 to 6 carbon atoms, and an alkylene group having 2 or 3 carbon atoms. More preferred is an ethylene group.

In Formula a-2, at least three of the five X ² represent an acryloyloxy group or a methacryloyloxy group, and are preferably an acryloyloxy group. Of the five X ² , 3 to 5 are acryloyloxy groups or methacryloyloxy groups, and 4 to 5 are preferably acryloyloxy groups or methacryloyloxy groups, and five are acryloyloxy groups or methacryloyl groups. It is preferably an oxy group.
X ² other than the acryloyloxy group or methacryloyloxy group represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. The alkyl group having 1 to 6 carbon atoms may be a linear, branched or cyclic alkyl group. Among these, X ² other than the (meth) acryloyloxy group is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and a hydrogen atom. More preferably.
In formula a-2, W ² has the same meaning as W ¹ in formula a-1, and the preferred range is also the same.

  As the component Aa, it is also possible to use a commercially available product. For example, as a polybasic acid-modified acrylic oligomer manufactured by Toagosei Co., Ltd., Aronix series M-510, M-520, TO-2349, TO-2359, and the like.

Component Aa may be used alone or in combination of two or more.
The content of component Aa is preferably 6 to 38% by mass, more preferably 5 to 35% by mass, and 5 to 25% by mass with respect to the total organic solid content of the curable composition. More preferably, it is most preferable that it is 8-20 mass%.
In the present invention, the “solid content” in the curable composition means a component excluding a volatile component such as an organic solvent. The “organic solid content” means a component obtained by removing volatile components such as organic solvents and inorganic components such as inorganic particles from the curable composition.

<Component Ab: Compound having (meth) acryloyl group and one or more urethane bonds>
In the present invention, the component A preferably contains a compound (also referred to as component Ab) having a (meth) acryloyl group and one or more urethane bonds.

  Examples of the component Ab that can be used in the present invention include urethane addition polymerizable compounds produced by an addition reaction of an isocyanate and a hydroxyl group. JP-A-51-37193, JP-B-2-32293 And urethane acrylates as described in Japanese Patent Publication No. 2-16765, and these descriptions are incorporated in the present specification.

The molecular weight of component Ab is preferably from 500 to 10,000, more preferably from 600 to 6,000, and even more preferably from 650 to 3,000, from the viewpoint of cured film hardness.
By adopting such a configuration, the effect of the present invention is more effectively exhibited.

The number of (meth) acryloyl groups in Component Ab is preferably 6 or more, more preferably 8 or more, still more preferably 10 or more, and particularly preferably 12 or more. The effect of this invention is more effectively exhibited as it is the said aspect.
The upper limit of the number of (meth) acryloyl groups is not particularly limited, but is preferably 50 or less, more preferably 30 or less, and still more preferably 20 or less.
The curable composition of this invention may contain only 1 type of component Ab, and may contain 2 or more types.

The (meth) acryloxy group in Component Ab may be either an acryloxy group or a methacryloxy group, or both, but is preferably an acryloxy group.
The number of urethane bonds in Component Ab is not particularly limited, but is preferably 1 to 30, more preferably 1 to 20, still more preferably 2 to 10, and 2 to 5. Particularly preferred is 2 or 3, most preferred.
Component Ab is preferably a urethane (meth) acrylate having 5 or more functional groups, more preferably a urethane (meth) acrylate having 6 or more functional groups, and an aliphatic urethane (meth) acrylate having 6 or more functional groups. More preferably.
Component Ab preferably has an isocyanuric ring structure.
Component Ab is preferably a compound comprising a core portion having one or more urethane bonds and a terminal portion bonded to the core portion and having one or more (meth) acryloxy groups. More preferably, it is a compound in which two or more of the terminal portions are bonded, more preferably a compound in which 2 to 5 of the terminal portions are bonded to the core portion, and 2 to the core portion. Or it is especially preferable that it is a compound which three said terminal parts couple | bonded.

Component Ab is preferably a compound having at least a group represented by the following formula Ae-1 or Ae-2, and more preferably a compound having at least a group represented by the following formula Ae-1. preferable. Component Ab is more preferably a compound having two or more groups selected from the group consisting of a group represented by the following formula Ae-1 and a group represented by formula Ae-2.
Moreover, it is preferable that the said terminal part in component Ab is group represented by the following formula Ae-1 or formula Ae-2.

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

Component Ab is preferably a compound having at least a group represented by the following formula Ac-1 or formula Ac-2, and preferably a compound having at least a group represented by the following formula Ac-1. Is more preferable.
Moreover, it is preferable that the said core part in component Ab is group represented by the following formula Ac-1 or formula Ac-2.

In Formula Ac-1 and Formula Ac-2, L ^{1 to} L ⁴ each independently represents a divalent hydrocarbon group having 2 to 20 carbon atoms, and the wavy line represents a bonding position with another structure.
L ^{1 to} L ⁴ are each independently preferably an alkylene group having 2 to 20 carbon atoms, more preferably an alkylene group having 2 to 10 carbon atoms, and an alkylene group having 4 to 8 carbon atoms. Is more preferable. The alkylene group may have a branched or ring structure, but is preferably a linear alkylene group.
Component Ab is 2 or 3 selected from the group consisting of a group represented by Formula Ac-1 or Formula Ac-2 and a group represented by Formula Ae-1 and Formula Ae-2. A compound in which a group is bonded is particularly preferable.

  In the following, although the component Ab preferably used in the present invention is exemplified, it goes without saying that the present invention is not limited to these.

  Examples of the component Ab that can be used in the present invention include urethane addition polymerizable compounds produced by an addition reaction between isocyanate and a hydroxyl group. JP-A-51-37193, JP-B-2 Examples of urethane acrylates described in Japanese Patent Publication No. 32293 and Japanese Patent Publication No. 2-16765 are illustrated, and these descriptions are incorporated in the present specification.

  Commercially available products of Component Ab include U-6HA, UA-1100H, U-6LPA, U-15HA, U-6H, U-10HA, U-10PA, UA available from Shin-Nakamura Chemical Co., Ltd. -53H, UA-33H (both registered trademarks), UA-306H, UA-306T, UA-306I, UA-510H available from Kyoeisha Chemical Co., Ltd., Lamarer UA-9048 available from BASF, Examples thereof include UA-9050, PR9052, EBECRYL 220, 5129, 8301, KRM8200, 8200AE, and 8452 available from Daicel Ornex Corporation.

<Component Ac: a compound having two or more (meth) acryloyl groups and no carboxyl group in the molecule>
The curable composition of the present invention may contain, as Component A, a compound having two or more (meth) acryloyl groups in the molecule and having no carboxyl group (also referred to as Component Ac). preferable.
Component A-c is a compound different from Component A-a having two or more (meth) acryloyl groups in the molecule (in one molecule).
Component Ac does not have a carboxyl group in the molecule, but preferably does not have any other acid group. Examples of other acid groups include sulfonic acid groups and phosphoric acid groups.
Component Ac may be a low molecular weight compound or an oligomer, but is not a polymer. That is, the component Ac has a molecular weight (weight average molecular weight in the case of having a molecular weight distribution) of 10,000 or less, preferably 5,000 or less, from the viewpoint of the hardness of the cured film. More preferably, it is 000 or less.

  Component Ac has two or more (meth) acryloyl groups in the molecule, preferably 3 to 15 (meth) acryloyl groups, more preferably 3 to 10, more preferably 3 to 6. Is more preferable. By setting it as said structure, the effect of this invention is exhibited more.

Examples of the component Ac used in the present invention include molecules described in paragraph 0011 of JP-A-2006-23696 and components described in paragraphs 0031 to 0047 of JP-A-2006-64921. Examples thereof include those having three or more (meth) acryloyl groups, and these descriptions are incorporated in the present specification.
As the component Ac, (meth) acrylic acid ester of polyhydroxy compound is preferably exemplified. Specifically, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) Acrylate, dipentaerythritol hexa (meth) acrylate, tri ((meth) acryloyloxyethyl) isocyanurate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate ethylene oxide (EO) modified product, dipentaerythritol Examples include hexa (meth) acrylate EO modified products.
As the component Ac, commercially available products may be used. Examples of the commercially available products include Aronix (registered trademark) M-309, M-400, M-405, M-450, Same M-7100, Same M-8030, Same M-8060, Same TO-1382, Same TO-1450 (manufactured by Toagosei Co., Ltd.), KAYARAD TMPTA, Same DPHA, Same DPCA-20, Same DPCA-30, Same DPCA-60, DPCA-120 (manufactured by Nippon Kayaku Co., Ltd.), Biscoat 295, 300, 360, GPT, 3PA, 400 (manufactured by Osaka Organic Chemical Industry Co., Ltd.) it can.
In addition, even if it is a compound applicable to component Ac, what corresponds to the alkoxysilane compound mentioned later shall be an alkoxysilane compound.

Component A-c may be used alone or in combination of two or more.
When component A contains component Ac, the content of component Ac is preferably 30 to 80% by weight, and 40 to 80% by weight, based on the total organic solid content of the curable composition. More preferably, it is more preferably 45 to 80% by mass.
Moreover, when component Aa and component Ac are contained as component A, content of component A is 10-40 mass% with respect to the total content of component Aa and component Ac. It is preferably 10 to 30% by mass, more preferably 10 to 25% by mass. When it is in the above range, a curable composition which is excellent in patterning property and excellent in adhesion of the obtained cured film is obtained.

Component A may contain other ethylenically unsaturated compounds other than Component Aa to Component Ac and Component C.
There is no restriction | limiting in particular as another ethylenically unsaturated compound, A well-known ethylenically unsaturated compound can be used.
The content of the ethylenically unsaturated compound other than the components Aa to Ac, component C and the alkoxysilane compound described later is 30% by mass or less based on the total organic solid content of the curable composition. It is preferably 10% by mass or less, more preferably 5% by mass or less, and the curable composition of the present invention comprises Component Aa to Component Ac, Component C and It is particularly preferred not to contain any other ethylenically unsaturated compound other than the alkoxysilane compound described below.
Moreover, it is preferable that the curable composition of this invention does not contain monofunctional ethylenically unsaturated compounds other than the component C and the alkoxysilane compound mentioned later.

Ingredient A may be contained individually by 1 type and may contain 2 or more types.
In the present invention, the content of component A is preferably 30% by mass or more, more preferably 40% by mass or more, and 50% by mass or more in the total organic solid content of the curable composition. More preferably, the upper limit is preferably 95% by mass or less, more preferably 90% by mass or less, and still more preferably 85% by mass or less. If content of component A is this range, the curable composition excellent in the film hardness of the cured film obtained can be obtained.

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

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

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

In Formula b-1 or Formula b-2, Ar represents an aromatic group or a heteroaromatic group, R ^B1 represents an alkyl group, an aromatic group, or an alkyloxy group, and R ^B2 represents a hydrogen atom or an alkyl group. Further, R ^B2 may be bonded to an Ar group to form a ring.

In Formula b-1 or Formula b-2, Ar represents an aromatic group or a heteroaromatic group, and is preferably a group obtained by removing one hydrogen atom from a benzene ring compound, a naphthalene ring compound, or a carbazole ring compound. , A naphthalenyl group and a carbazoyl group that form a ring with R ^B2 are more preferred. Preferable examples of the hetero atom in the heteroaromatic group include a nitrogen atom, an oxygen atom, and a sulfur atom.
R ^B1 represents an alkyl group, an aromatic group or an alkoxy group, preferably a methyl group, an ethyl group, a benzyl group, a phenyl group, a naphthyl group, a methoxy group or an ethoxy group, and a methyl group, an ethyl group, a phenyl group or a methoxy group Is more preferable.
R ^B2 represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or a substituted alkyl group, more preferably a substituted alkyl group or a toluenethioalkyl group that forms a ring with the hydrogen atom or Ar.
Ar is preferably a group having 4 to 20 carbon atoms, R ^B1 is preferably a group having 1 to 30 carbon atoms, and R ^B2 is a group having 1 to 50 carbon atoms. It is preferable.

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

In Formula b-3 to Formula b-5, R ^B7 represents an alkyl group, an aromatic group, or an alkoxy group, and X ^B represents —CH ₂ —, —C ₂ H ₄ —, —O—, or —S—. , R ^B3 each independently represents a halogen atom, and R ^B4 each 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, ^B5 represents a hydrogen atom, an alkyl group or an aryl group, R ^B6 represents an alkyl group, n1 and n2 each independently represents an integer of 0 to 6, and n3 represents an integer of 0 to 5.

R ^B7 represents an alkyl group, an aromatic group, or an alkoxy group, and a group represented by R ^B11 —X′-alkylene group— (R ^B11 represents an alkyl group or an aryl group, and X ′ represents a sulfur atom or an oxygen atom. Are preferred). R ^B11 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 ^B is preferably a sulfur atom.
R ^B3 and R ^B4 can be bonded at any position on the aromatic ring.
R ^B4 represents an alkyl group, a phenyl group, an alkyl-substituted amino group, an arylthio group, an alkylthio group, an alkoxy group, an aryloxy group or a halogen atom, preferably an alkyl group, a phenyl group, an arylthio group or a halogen atom, an alkyl group, an arylthio group A group or a halogen atom is more preferred, and an alkyl group or a halogen atom is still more preferred. As an alkyl group, a C1-C5 alkyl group is preferable and a methyl group or an ethyl group is more preferable. As a halogen atom, a chlorine atom, a bromine atom, or a fluorine atom is preferable.
The number of carbon atoms of R ^B4 is preferably 0 to 50, and more preferably from 0 to 20.
R ^B5 represents a hydrogen atom, an alkyl group or an aryl group, preferably an alkyl group. As an alkyl group, a C1-C5 alkyl group is preferable and a methyl group or an ethyl group is more preferable. As the aryl group, an aryl group having 6 to 10 carbon atoms is preferable.
R ^B6 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 substitution of R ^B3 on the aromatic ring in formula b-3 or b-4, and n3 represents the number of substitution of R ^B4 on the aromatic ring in formula b-5.
n1 to n3 are each independently preferably an integer of 0 to 2, and more preferably 0 or 1.

  Below, the example of the oxime ester compound preferably used by this invention is shown. However, it goes without saying that the oxime ester compounds used in the present invention are not limited to these. Me represents a methyl group and Ph represents a phenyl group. Further, the cis-trans isomerism of the double bond of oxime in these compounds may be either one of EZ or a mixture of EZ.

  Specific examples of the organic halogenated compounds include Wakabayashi et al., “Bull Chem. Soc. Japan” 42, 2924 (1969), US Pat. No. 3,905,815, and Japanese Examined Patent Publication No. 46-4605. JP, 48-34881, JP 55-3070, JP 60-239736, JP 61-169835, JP 61-169837, JP 62-58241, JP-A 62-212401, JP-A 63-70243, JP-A 63-298339, MP Hutt, et al., “Journal of Heterocyclic Chemistry” (1970), 7,511 etc. are mentioned, Especially the oxazole compound and s-triazine compound which the trihalomethyl group substituted are mentioned.

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

  Examples of the acylphosphine (oxide) compounds include monoacylphosphine oxide compounds and bisacylphosphine oxide compounds. Specific examples include Irgacure 819, Darocur 4265, Darocur TPO, etc. manufactured by Ciba Specialty Chemicals. Can be mentioned.

A photoinitiator can be used 1 type or in combination of 2 or more types.
The total amount of the photopolymerization initiator in the curable composition of the present invention is preferably 0.05 to 30 parts by mass with respect to 100 parts by mass of the total solid content in the curable composition. It is more preferable that it is a mass part, it is still more preferable that it is 0.1-10 mass parts, and it is especially preferable that it is 0.1-5 mass parts.

<Sensitizer>
In addition to the photopolymerization initiator, a sensitizer can be added to the curable composition of the present invention.
The sensitizer absorbs actinic rays or radiation and enters an excited state. The sensitizer in the excited state is capable of initiating / promoting polymerization by causing an action such as electron transfer, energy transfer, and heat generation due to the interaction with the component B.
Typical sensitizers that can be used in the present invention include those disclosed in Crivello [JV Crivello, Adv. In Polymer Sci., 62, 1 (1984)]. Examples include pyrene, perylene, acridine orange, thioxanthone, 2-chlorothioxanthone, benzoflavin, N-vinylcarbazole, 9,10-dibutoxyanthracene, anthraquinone, coumarin, ketocoumarin, phenanthrene, camphorquinone, and phenothiazine derivatives. The sensitizer is preferably added in a proportion of 50 to 200% by mass with respect to the photopolymerization initiator.

Component C: Compound having at least a titanium atom or aluminum atom and a (meth) acryloyl group The curable composition of the present invention contains a compound having at least a titanium atom or an aluminum atom and a (meth) acryloyl group as the component C. To do.
The number of (meth) acryloyl groups in Component C is not particularly limited, but is preferably 1 to 10, more preferably 1 to 4, still more preferably 1 or 2, and is 1. It is particularly preferred. The effect of this invention can be exhibited more as it is the said aspect.
Component C is preferably a compound having at least a titanium atom and a (meth) acryloyl group from the viewpoint of stability over time.
The number of titanium atoms or aluminum atoms in Component C is preferably 1 to 4, more preferably 1 or 2, and still more preferably 1.
Component C is preferably a compound in which one or more alkoxy groups are directly bonded to a titanium atom or an aluminum atom. In the case of a titanium atom, Component C is a compound in which 1 to 3 alkoxy groups are directly bonded. More preferably, the compound is more preferably a compound in which three alkoxy groups are directly bonded. In the case of an aluminum atom, a compound in which 1 to 2 alkoxy groups are directly bonded is more preferable, and a compound in which two alkoxy groups are directly bonded to an aluminum atom is more preferable.

  Component C is preferably a compound represented by any of the following formulas C-1 to C-3, and more preferably a compound represented by the following formula C-1 or formula C-2. More preferably, it is a compound represented by the following formula C-2.

In Formula C-1 to Formula C-3, each R ¹ independently represents a hydrogen atom or a methyl group, each R ² independently represents an alkyl group, and each L independently represents a divalent linking group. M represents a titanium atom or an aluminum atom. When M is a titanium atom, m represents an integer of 1 to 4, n represents an integer of 0 to 3, m + n = 4 is satisfied, and M is an aluminum atom. In this case, m represents an integer of 1 to 3, n represents an integer of 0 to 2, and satisfies m + n = 3.

R ¹ is preferably a methyl group.
Further, from the viewpoint of synthesis, it is preferable that R ¹ in one compound is all the same.
Each R ² is preferably independently an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and still more preferably an alkyl group having 3 or 4 carbon atoms. . The alkyl group may be linear, branched or have a ring structure.
Among these, R ² is particularly preferably an n-butyl group or an isopropyl group.
Further, from the viewpoint of synthesis, it is preferable that R ² in one compound is all the same.
L is each independently an alkylene group or a group obtained by combining one or more alkylene groups with one or more groups selected from the group consisting of a carbonyl group, an ester bond and an ether bond, Or it is more preferable that it is -alkylene group-OC (= O) -alkylene group-C (= O)-, and it is -alkylene group-OC (= O) -alkylene group-C (= O)-. Is more preferable.
Moreover, it is preferable that it is 2-20, and, as for carbon number of L, it is more preferable that it is 4-20.
Further, from the viewpoint of synthesis, it is preferable that all Ls in one compound are the same.
M is a titanium atom or an aluminum atom, and more preferably a titanium atom.
When M is a titanium atom, m is preferably an integer of 1 to 3. When M is an aluminum atom, m is preferably an integer of 1 to 2.
n is preferably an integer of 0 to 3 when M is a titanium atom. When M is an aluminum atom, n is preferably an integer of 0 to 2.

  Specific examples of component C include the following compounds, but are not limited thereto. Note that Bu represents an n-butyl group, and i-Pr represents an isopropyl group.

  As a method for synthesizing Component C, for example, a method in which a hydroxy compound having a (meth) acrylic acid or (meth) acryloyl group is allowed to act on titanium tetraalkoxide or aluminum tetraalkoxide and alcohol exchange is preferably exemplified.

Component C may be contained singly or in combination of two or more.
The content of Component C is preferably 0.1 to 20% by mass, more preferably 0.5 to 20% by mass, and 1 to 18% by mass with respect to the total solid content of the curable composition. % Is more preferable, and 2 to 15% by mass is particularly preferable.

Component D: Polymerization inhibitor The curable composition of the present invention contains a polymerization inhibitor as Component D.
By containing the component D, the polymerization reaction due to leakage light is suppressed, and the developability is excellent. A polymerization inhibitor means hydrogen donation (or hydrogen donation), energy donation (or energy donation), electron donation (or electron donation), etc. to the polymerization initiation radical component generated from the polymerization initiator by exposure or heat. Is a substance that plays a role in deactivating polymerization initiation radicals and inhibiting polymerization initiation. For example, compounds described in paragraphs 0154 to 0173 of JP2007-334322A can be used.
Although there is no restriction | limiting in particular in content of the component D in the curable composition of this invention, It is preferable that it is 0.005-0.5 mass% with respect to the total solid of a curable composition. It is more preferable that it is 01-0.5 mass%. By adjusting the blending amount of the polymerization inhibitor, the patterning property can be improved without impairing the sensitivity.

  As the kind of the polymerization inhibitor, those which are hard and do not lower the sensitivity are preferably employed. Such polymerization inhibitors include phenothiazine derivatives such as phenothiazine, chlorpromazine, levomepromazine, fluphenazine, thioridazine, phenoxazine, 3,7-bis (diethylamino) phenoxazine-5-ium perchlorate, 5-amino- 9- (Dimethylamino) -10-methylbenzo [a] phenoxazine-7-ium chloride, 7- (pentyloxy) -3H-phenoxazin-3-one, 5,9-diaminobenzo [a] phenoxazine-7- Ium acetate, phenoxazine derivatives such as 7-ethoxy-3H-phenoxazin-3-one, stable radicals such as tri-p-nitrophenylmethyl, diphenylpicrylhydrazyl, carbinoxyl, quinone, benzoquinone, chlorobenzoquinone, 2,5 -Di-chloro Nzoquinone, 2,6-di-chlorobenzoquinone, 2,3-di-methylbenzoquinone, 2,5-di-methylbenzoquinone, methoxybenzoquinone, methylbenzoquinone, tetrabromobenzoquinone, tetrachlorobenzoquinone, tetramethylbenzoquinone, trichlorobenzoquinone, Quinones such as trimethylbenzoquinone, amylquinone, amyloxyhydroquinone, 2,5-di-t-butylhydroquinone, 2,5-diphenyl-p-benzoquinone, α-naphthol, 2-nitro-1-naphthol, β-naphthol, Naphthols such as 1-nitro-2-naphthol, 4-methoxyphenol, 4-ethoxyphenol, hydroquinone, phenol, t-butylcatechol, methylhydroquinone, n-butylphenol, hydroquinone monopropyl Ether, t-butylcresol, p-cresol, 2,6-di-t-butyl-p-cresol, catechol resorcin, ot-butylphenol, 2,6-di-p-methoxyphenol, 2,6-di -T-butylphenol, 2,4-di-t-butylphenol, 3,5-di-t-butylphenol, 3,5-di-t-butyl-4-hydroxybenzoic acid, N, N'-bis-3- (3 ′, 5′-di-t-butyl-4-hydroxyphenyl) propionylhexamethylenediamine, 2,2′-methylenebis (6-t-butyl-p-cresol), n-octadecyl-3- (4- Hydroxy-3 ′, 5′-di-tert-butylphenyl) propionate, distearyl (4-hydroxy-3-methyl-5-tert-butyl) benzylmalonate, 2,4 6-tri-t-butylphenol, 1,6-hexanediol bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], triethylene glycol bis [3- (3-t-butyl -5-methyl-4-hydroxyphenyl) propionate], 2,2-thiodiethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 3,9-bis [1, 1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxyethyl-2,4,8,10-tetraoxaspiro [5,5] undecane, 2, 2'-ethylidenebis (2,4-di-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenylbutane, 1,3,5 Trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanate, tris [2- (3 ′, 5′-di-t-butyl-4′-hydroxyhydrocinnamoyloxyl) ethyl] isocyanate, tris (4-t-butyl-2,6-dimethyl-3-hydroxybenzyl) isocyanate, tetrakis [ Methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] phenols such as methane, 2,4-dinitrophenol, o-nitrophenol, m-nitrophenol, p- Nitrophenols such as nitrophenol, gallic acids such as gallic acid, methyl gallate, propyl gallate, and isoamyl gallate , Pigments such as methylene blue and malachite green, β-naphthylamine, N-nitrosocyclohexylamine salts, amines such as di-p-fluorophenylamine, pyrogallol, monobenzyl ether, benzoquinone, triphenylphosphine, cuprous chloride, Examples include phenothiazine, chloranil, pyridine, nitrobenzene, dinitrobenzene, p-toluidine, picric acid, and methyl salicylate.

Particularly preferable examples of the polymerization inhibitor include at least one selected from the group consisting of phenothiazine, phenoxazine, hindered amine, and derivatives thereof.
Examples of phenothiazine and derivatives thereof include phenothiazine, bis (α-methylbenzyl) phenothiazine, 3,7-dioctylphenothiazine, bis (α-dimethylbenzyl) phenothiazine, fluphenazine and thioridazine, and phenothiazine is preferred.
Phenoxazine and its derivatives include phenoxazine, 3,7-bis (diethylamino) phenoxazine-5-ium perchlorate, 5-amino-9- (dimethylamino) -10-methylbenzo [a] phenoxazine- Examples include 7-ium chloride, 7- (pentyloxy) -3H-phenoxazin-3-one, 5,9-diaminobenzo [a] phenoxazine-7-ium acetate, and 7-ethoxy-3H-phenoxazin-3-one. And phenoxazine is preferred.
Examples of the hindered amine and derivatives thereof include CHIMASSORB 2020 FDL, TINUVIN 144, 765, and 770 (above, manufactured by BASF), and TINUVIN 144 is preferable.

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

As a silicon oxide, a silica is mentioned preferably and a silica particle is mentioned more preferably.
The silica particles are not particularly limited as long as they are inorganic oxide particles containing silicon dioxide, and particles containing silicon dioxide or a hydrate thereof as a main component (preferably 80% by mass or more) are preferable. The said particle | grains may contain the aluminate as a minor component (for example, less than 5 mass%). Examples of the aluminate that may be contained as a minor component include sodium aluminate and potassium aluminate. The silica particles may contain inorganic salts such as sodium hydroxide, potassium hydroxide, lithium hydroxide and ammonium hydroxide, and organic salts such as tetramethylammonium hydroxide. Colloidal silica is exemplified as an example of such a compound.
There is no restriction | limiting in particular as a dispersion medium of colloidal silica, Any of water, an organic solvent, and these mixtures may be sufficient. These may be used individually by 1 type and can also use 2 or more types together.
In the present invention, the particles can be used as a dispersion prepared by mixing and dispersing in a suitable dispersant and solvent using a mixing device such as a ball mill or a rod mill. In the curable composition of the present invention, it is not essential that the colloidal silica exists in a colloidal state.
When blended, the content of the inorganic particles is preferably 1% by mass or more, more preferably 5% by mass or more, and still more preferably 10% by mass or more based on the total solid content of the curable composition from the viewpoint of hardness. Moreover, 80 mass% or less is preferable, 50 mass% or less is more preferable, 40 mass% or less is further more preferable, and 30 mass% or less is especially preferable.
One type of inorganic particles may be included, or two or more types may be included. When two or more types are included, the total amount is preferably within the above range.

Component F: Copolymer having an acidic group The curable composition of the present invention preferably contains a copolymer having an acidic group as the component F from the viewpoint of improving resolution and film properties.
As the acidic group, a carboxyl group is preferably exemplified.
There is no restriction | limiting in particular as a copolymer which has an acidic group, Although a well-known thing can be used, It is preferable to use the copolymer (linear organic polymer) which has a linear acidic group. As such a linear organic polymer, a well-known thing can be used arbitrarily. Preferably, a linear organic polymer that is soluble or swellable in water or weak alkaline water is selected to enable water development or weak alkaline water development. The linear organic polymer is selected and used not only as a film forming agent but also according to the use as water, weak alkaline water or an organic solvent developer. For example, when a water-soluble organic polymer is used, water development becomes possible. Examples of such linear organic polymers include radical polymers having a carboxylic acid group in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, and JP-B-sho. No. 54-25957, JP-A-54-92723, JP-A-59-53836, JP-A-59-71048, ie, a monomer having a carboxyl group alone or Copolymerized resin, acid anhydride monomer alone or copolymerized, acid anhydride unit hydrolyzed, half esterified or half amidated, epoxy resin unsaturated monocarboxylic acid and acid anhydride Examples include modified epoxy acrylate. 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. It is done.
Similarly, there is an acidic cellulose derivative 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 copolymer which has an acidic group may contain individually by 1 type, or may contain 2 or more types.
When the curable composition of the present invention contains a copolymer having an acidic group, the content of the copolymer having an acidic group is not particularly limited, but with respect to the total solid content of the curable composition, It is preferably 1 to 70% by mass, more preferably 2 to 50% by mass, and further preferably 5 to 30% by mass.

Component G: Alkoxysilane Compound The curable composition of the present invention preferably contains an alkoxysilane compound as Component G. When an alkoxysilane compound is used, the adhesion between the film formed from 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 one group in which an alkoxy group is directly bonded to a silicon atom, but may be a compound having a dialkoxysilyl group and / or a trialkoxysilyl group. Preferably, it is a compound having a trialkoxysilyl group.
The alkoxysilane compound that can be used in the curable composition of the present invention includes a base material, for example, a silicon compound such as silicon, silicon oxide, and silicon nitride, a metal such as gold, copper, molybdenum, titanium, and aluminum, and a cured film. It is preferable that it is a compound which improves the adhesiveness of. Specifically, a known silane coupling agent or the like is also effective. A silane coupling agent having an ethylenically unsaturated bond is preferred.
Examples of the silane coupling agent include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrialkoxysilane, γ-glycidoxypropyl dialkoxysilane, and γ-methacryloxypropyl. Trialkoxysilane, γ-methacryloxypropyl dialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, vinyltrialkoxysilane It is done. Of these, γ-methacryloxypropyltrialkoxysilane, γ-acryloxypropyltrialkoxysilane, vinyltrialkoxysilane, and γ-glycidoxypropyltriacoxysilane are more preferable. These can be used alone or in combination of two or more.
Examples of commercially available products include KBM-403 and KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd.

0.1-30 mass% is preferable with respect to the total solid of a curable composition, as for content of the alkoxysilane compound in the curable composition of this invention, 2-20 mass% is more preferable, 2-15 mass % Is more preferable. Only one type of alkoxysilane compound may be included, or two or more types may be included. When two or more types are included, the total amount is preferably within the above range.
The alkoxysilane compound is regarded as an organic solid content.

Component H: Solvent The curable composition of the present invention preferably contains a solvent as Component H.
It is preferable that the curable composition of this invention is prepared as a solution which melt | dissolved the component A-component D which is an essential component, and an arbitrary component in the solvent.
Component H is preferably an organic solvent, and known solvents can be used as the organic solvent used in the curable composition of the present invention, such as ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol. Monoalkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, butylene glycol di Acetates, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates, Alcohols, esters, ketones, amides, lactones and the like. As specific examples of these organic solvents, reference can be made to paragraph 0062 of JP-A-2009-098616.

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

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

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

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

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

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

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

When blended, the content of the surfactant in the curable composition of the present invention is preferably 0.001 to 5.0 parts by mass with respect to 100 parts by mass in the total solid content of the curable composition. 01-2.0 mass parts is more preferable.
Only one type of surfactant may be included, or two or more types of surfactants may be included. When two or more types are included, the total amount is preferably within the above range.

<Other ingredients>
<< Compound having epoxy group, compound having oxetanyl group, blocked isocyanate compound >>
The curable composition of the present invention preferably contains at least one selected from the group consisting of a compound having an epoxy group, a compound having an oxetanyl group, and a blocked isocyanate compound. It is excellent in the hardness of the obtained cured film as it is the said aspect.

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

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

These are available as commercial products. For example, as bisphenol A type epoxy resin, JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1055, JER1007, JER1009, JER1010 (above, manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON860, EPICLON1050, EPICLON1051, EPICLON1051, EPICLON1051 And bisphenol F-type epoxy resins such as JER806, JER807, JER4004, JER4005, JER4007, JER4010 (above, Japan Epoxy Resin Co., Ltd.), EPICLON830, EPICLON835 (above, DIC Co., Ltd.), LCE-21, RE-602S (above, Nippon Kayaku Co., Ltd.) As the phenol novolac type epoxy resin, JER152, JER154, JER157S70, JER157S65 (above, manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON N-740, EPICLON N-740, EPICLON N-770, EPICLON N-775 (or higher) The cresol novolac type epoxy resin is EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695 (above, manufactured by DIC Corporation), EOCN-1020 (above, manufactured by Nippon Kayaku Co., Ltd.) and the like, and as an aliphatic epoxy resin, ADEKA RESIN EP-408 S, EP-4085S, EP-4088S (above, manufactured by ADEKA Corporation), Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, EHPE3150, EPOLEAD PB 3600, PB 4700 (above, Daicel Chemical Industries, Ltd.) ))). In addition, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4010S, EP-4011S (above, manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above, manufactured by ADEKA Corporation) and the like can be mentioned.
Also, urethane compounds having an ethylene oxide skeleton described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 are preferably used. The contents of which are incorporated herein by reference.

When the curable composition of this invention contains the compound which has an epoxy group, it is preferable to contain in the range of 0.1-20 mass% of the total solid of a composition, In the range of 0.5-10 mass% It is more preferable to include, and it is still more preferable to include in 1-5 mass%.
The curable composition of the present invention may contain only one type of compound having an epoxy group, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

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

As specific examples of the compound having an oxetanyl group, Aron oxetane OXT-121, OXT-221, OX-SQ, and PNOX (manufactured by Toagosei Co., Ltd.) can be used.
Moreover, it is preferable to use the compound containing an oxetanyl group individually or in mixture with the compound containing an epoxy group.

When the curable composition of the present invention includes a compound having an oxetanyl group, the curable composition preferably includes 0.1 to 20% by mass of the total solid content of the composition, and ranges from 0.5 to 10% by mass. It is more preferable to include, and it is still more preferable to include in 1-5 mass%.
The curable composition of the present invention may contain only one type of compound having an oxetanyl group, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

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

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

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

When the curable composition of this invention contains a block isocyanate compound, it is preferable to contain in the range of 0.1-20 mass% of the total solid of a composition, and to contain in the range of 0.5-10 mass% Is more preferable, and it is still more preferable to contain in 1-5 mass%.
The curable composition of the present invention may contain only one type of blocked isocyanate compound, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

  The curable composition of the present invention may contain other compounds (for example, an alkoxymethyl group-containing compound) other than those described above without departing from the spirit of the present invention. Examples of the alkoxymethyl group-containing compound include those described in paragraphs 0192 to 0194 of JP2011-221494A.

<Antioxidant>
The curable composition of this invention may contain antioxidant other than said component.
As an antioxidant, a well-known antioxidant can be contained. By adding an antioxidant, there is an advantage that coloring of the cured film can be prevented, or a decrease in film thickness due to decomposition can be reduced, and heat-resistant transparency is excellent.
Examples of such antioxidants include phosphorus antioxidants, amides, hydrazides, hindered phenol antioxidants, ascorbic acids, zinc sulfate, saccharides, nitrites, sulfites, thiosulfates, hydroxyls. An amine derivative etc. can be mentioned. Among these, hindered phenolic antioxidants and phosphorus antioxidants are particularly preferable from the viewpoints of coloring of the cured film and reduction in film thickness, and hindered phenolic antioxidants are most preferable. These may be used individually by 1 type and may mix 2 or more types.
As a preferable commercial item, ADK STAB AO-60, ADK STAB AO-80 (above, the product made from ADEKA), and Irganox 1098 (above, the product made from BASF) can be mentioned.
Although there is no restriction | limiting in particular in content of antioxidant, It is preferable that it is 0.1-10 mass% with respect to the total solid of a curable composition, and it is 0.2-5 mass%. More preferably, it is more preferable that it is 0.5-4 mass%.

  In addition to those described above, other components such as a plasticizer, a thermal acid generator, and an acid proliferating agent can be added to the curable composition of the present invention as necessary. As these components, for example, those described in JP2009-98616A, JP2009-244801A, and other known ones can be used. In addition, various ultraviolet absorbers described in “New Development of Polymer Additives (Nikkan Kogyo Shimbun Co., Ltd.)”, metal deactivators and the like may be added to the curable composition of the present invention.

<Method for preparing curable composition>
There is no restriction | limiting in particular as a preparation method of the curable composition of this invention, It can prepare by a well-known method, For example, each component is mixed by a predetermined ratio and arbitrary methods, and stir-dissolves and / or It can be dispersed to prepare a curable composition. For example, after making each component into the solution which respectively melt | dissolved in the solvent previously, these can be mixed in a predetermined ratio and a curable composition can also be prepared. The curable composition prepared as described above can be used after being filtered using, for example, a filter having a pore diameter of 0.2 μm.

(Curing film, cured product and method for producing the same)
The cured product of the present invention is a cured product obtained by curing the curable composition of the present invention. The cured product is preferably a cured film. Moreover, it is preferable that the cured film of this invention is a cured film obtained by the manufacturing method of the cured film of this invention.
The method for producing a cured film of the present invention is not particularly limited as long as it is a method for producing a cured film by curing the curable composition of the present invention, but may include the following steps 1 to 5 in this order. preferable.
Process 1: Application | coating process which apply | coats the curable composition of this invention on a board | substrate Process 2: The solvent removal process of removing a solvent from the apply | coated curable composition Process 3: At least curable composition from which the solvent was removed An exposure process in which a part is exposed with actinic rays. Step 4: A development process in which the exposed curable composition is developed with an aqueous developer. Step 5: A heat treatment process in which the developed curable composition is heat treated. More preferably, the manufacturing method of the product further includes the following step 4 ′ between step 4 and step 5.
Step 4 ′: a post-exposure step of further irradiating the developed curable composition with light

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

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

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

In the solvent removal step, it is preferable to remove the solvent from the applied film by vacuum (vacuum) and / or heating to form a dry coating film on the substrate. The heating conditions for the solvent removal step are preferably 70 to 130 ° C. and about 30 to 300 seconds. Moreover, in the said solvent removal process, it is not necessary to remove the solvent in a curable composition completely, and at least one part should just be removed.
In addition, the said application | coating process and the said solvent removal process may be performed in this order, may be performed simultaneously, or may be repeated alternately. For example, the solvent removal step may be performed after the inkjet coating in the coating step is completed, or the substrate is heated and the solvent is discharged while the curable composition is discharged by the inkjet coating method in the coating step. Removal may be performed.

The exposure step generates a polymerization initiation species from a photopolymerization initiator using an actinic ray, polymerizes a compound having an ethylenically unsaturated group, and cures at least a part of the curable composition from which the solvent is removed. It is a process to do.
In the exposure step, it is preferable to irradiate the obtained coating film with an actinic ray having a wavelength of 300 nm to 450 nm in a predetermined pattern.
As an exposure light source that can be used in the above exposure process, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, an LED light source, an excimer laser generator, and the like can be used, i-line (365 nm), h-line (405 nm). ) And actinic rays having a wavelength of 300 nm to 450 nm, such as g-line (436 nm), can be preferably used. Moreover, irradiation light can also be adjusted through spectral filters, such as a long wavelength cut filter, a short wavelength cut filter, and a band pass filter, as needed. The exposure amount is preferably 1 to 500 mJ / cm ² .
As the exposure apparatus, various types of exposure machines such as a mirror projection aligner, a stepper, a scanner, a proximity, a contact, a microlens array, a lens scanner, and a laser exposure can be used.
The exposure in the exposure step is preferably performed in a state where oxygen is blocked from the viewpoint of curing acceleration. Examples of means for blocking oxygen include exposure in a nitrogen atmosphere and exposure with an oxygen blocking film.
Moreover, the exposure in the said exposure process should just be performed to at least one part of the curable composition from which the solvent was removed, for example, may be whole surface exposure or pattern exposure.
Further, after the exposure step, post-exposure heat treatment (Post Exposure Bake (hereinafter also referred to as “PEB”)) can be performed. The temperature for performing PEB is preferably 30 ° C. or higher and 130 ° C. or lower, more preferably 40 ° C. or higher and 110 ° C. or lower, and particularly preferably 50 ° C. or higher and 100 ° C. or lower.
The heating method is not particularly limited, and a known method can be used. For example, a hot plate, an oven, an infrared heater, etc. are mentioned.
The heating time is preferably about 1 to 30 minutes in the case of a hot plate, and is preferably about 20 to 120 minutes in other cases. If it is the said temperature range, it can suppress and damage to a board | substrate and an apparatus, and can heat.

In the development step, the uncured curable composition is developed and removed using an aqueous developer to form a negative image. The developer used in the development step is preferably an alkaline aqueous developer.
The developer used in the development step preferably contains a basic compound. Examples of basic compounds include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkali metal carbonates such as sodium carbonate, potassium carbonate, and cesium carbonate; sodium bicarbonate, potassium bicarbonate Alkali metal bicarbonates such as: tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, diethyldimethylammonium hydroxide, and other tetraalkylammonium hydroxides: Alkyl) trialkylammonium hydroxides; silicates such as sodium silicate and sodium metasilicate; ethylamine, propylamine, diethylamine, triethylammonium Alkylamines such as diamine; alcohol amines such as dimethylethanolamine and triethanolamine; 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0]- Alicyclic amines such as 5-nonene can be used.
Of these, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide) are preferable.
An aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the alkaline aqueous solution can also be used as a developer.
As a preferred developing solution, a 0.4 to 2.5% by mass aqueous solution of tetramethylammonium hydroxide can be mentioned.
The pH of the developer is preferably 10.0 to 14.0.
The development time is preferably 30 to 500 seconds, and the development method may be any of a liquid piling method (paddle method), a shower method, a dip method, and the like.
A rinsing step can also be performed after development. In the rinsing step, the developed substrate and the development residue are removed by washing the developed substrate with pure water or the like. A known method can be used as the rinsing method. For example, a shower rinse, a dip rinse, etc. can be mentioned.
For pattern exposure and development, a known method or a known developer can be used. For example, the pattern exposure method and the development method described in JP 2011-186398 A and JP 2013-83937 A can be suitably used.

It is preferable that the manufacturing method of the cured film of this invention includes the process (post-baking) of heat-processing the developed curable composition after the said image development process. By performing heat treatment after developing the curable composition of the present invention, a cured film having higher strength can be obtained.
As heat processing temperature in the said heat processing process, 180 degrees C or less is preferable, 150 degrees C or less is more preferable, and 130 degrees C or less is still more preferable. As a lower limit, 80 degreeC or more is preferable and 90 degreeC or more is more preferable. The heating method is not particularly limited, and a known method can be used. For example, a hot plate, an oven, an infrared heater, etc. are mentioned.
The heating time is preferably about 1 to 30 minutes in the case of a hot plate, and is preferably about 20 to 120 minutes in other cases. If it is the said temperature range, it can harden | cure, suppressing the damage to a board | substrate and an apparatus.
In addition, the heat treatment step can be performed after baking at a relatively low temperature before the heat treatment step (post-bake) (addition of a middle bake step). When performing middle baking, it is preferable to heat-treat at a temperature of 100 ° C. or higher after heating at 90 to 150 ° C. for 1 to 60 minutes. Further, middle baking and post baking can be heated in three or more stages. The shape of the pattern can be adjusted by devising such middle baking and post baking. These heating methods can use well-known heating methods, such as a hotplate, oven, and an infrared heater.

Moreover, it is preferable to include the post-exposure process which irradiates light further to the developed curable composition from a viewpoint of film | membrane hardness improvement after a image development process and before a heat processing process.
In the post-exposure step, it is preferable to expose the entire surface of the developed curable composition. By post-baking after the post-exposure, it is possible to generate an initiation species from the photopolymerization initiator remaining in the exposed portion and to function as a catalyst for accelerating the crosslinking step, and to accelerate the film curing reaction. In the post-exposure step, it is preferable to perform energy exposure of about 50 to 3,000 mJ / cm ² with a mercury lamp or an LED lamp.

The cured film of the present invention is a cured film obtained by curing the curable composition of the present invention.
The cured film of the present invention can be suitably used as an interlayer insulating film (insulating film) or an overcoat film (protective film), more preferably used as an overcoat film for a touch panel, and as an overcoat film for an on-cell structure touch panel. Further preferably used. The on-cell touch panel is synonymous with an on-cell touch panel display device described later. Moreover, it is preferable that the cured film of this invention is a cured film obtained by the manufacturing method of the cured film of this invention.
With 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 hardness of 4H or more can be obtained. Since the protective film formed by curing the curable composition of the present invention is excellent in cured film properties, it is useful for applications of organic EL display devices and liquid crystal display devices.
Especially, the cured film of this invention can be used suitably as a protective film for touchscreen wiring, and can be used more suitably as a protective film for wiring in an on-cell structure touchscreen.

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

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

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

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

FIG. 2 is a conceptual cross-sectional view showing an example of the active matrix type liquid crystal display device 10. The color liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on the back surface, and the liquid crystal panel includes all pixels disposed between two glass substrates 14 and 15 having a polarizing film attached thereto. The elements of the TFT 16 corresponding to are arranged. Each element formed on the glass substrate is wired with an ITO transparent electrode 19 that forms a pixel electrode through a contact hole 18 formed in the cured film 17. On the ITO transparent electrode 19, an RGB color filter 22 in which a liquid crystal 20 layer and a black matrix are arranged is provided.
The light source of the backlight is not particularly limited, and a known light source can be used. For example, white LED, multicolor LED such as blue, red, and green, fluorescent lamp (cold cathode tube), organic EL, and the like can be mentioned.
Further, the liquid crystal display device can be a 3D (stereoscopic) type or a touch panel type (touch panel display device). Further, a flexible type can also be used, and it is used as the second interlayer insulating film (48) described in JP2011-145686A or the interlayer insulating film (520) described in JP2009-258758A. Can do.

(Touch panel and touch panel display device)
The touch panel of the present invention is a touch panel in which all or part of the insulating layer and / or protective layer is made of a cured product of the curable composition of the present invention. Moreover, it is preferable that the touch panel of this invention has a transparent substrate, an electrode, an insulating layer, and / or a protective layer at least.
The touch panel display device of the present invention is preferably a touch panel display device having the touch panel of the present invention. As the touch panel of the present invention, any of known methods such as a resistive film method, a capacitance method, an ultrasonic method, and an electromagnetic induction method may be used. Among these, the electrostatic capacity method is preferable.
Examples of the capacitive touch panel include those disclosed in JP 2010-28115 A and those disclosed in International Publication No. 2012/057165.
As a touch panel display device, a so-called in-cell type (for example, FIG. 5, FIG. 6, FIG. 7 and FIG. 8 of Japanese Patent Publication No. 2012-517051), a so-called on-cell type (for example, Japanese Patent Application Laid-Open No. 2012-43394). 14, International Publication No. 2012/141148, FIG. 2 (b)), OGS type, TOL type, and other configurations (for example, FIG. 6 of JP2013-164871A).
FIG. 3 is a conceptual diagram illustrating an example of a touch panel display device.
For example, the cured film of the present invention is preferably applied to the protective film between the layers in FIG. 3, and is also preferably applied to an interlayer insulating film that separates the detection electrodes of the touch panel. In addition, as a detection electrode of a touch panel, it is preferable that they are silver, copper, aluminum, titanium, molybdenum, and these alloys.
In FIG. 3, reference numeral 110 denotes a pixel substrate, 140 denotes a liquid crystal layer, 120 denotes a counter substrate, and 130 denotes a sensor unit. The pixel substrate 110 includes a polarizing plate 111, a transparent substrate 112, a common electrode 113, an insulating layer 114, a pixel electrode 115, and an alignment film 116 in order from the lower side of FIG. The counter substrate 120 includes an alignment film 121, a color filter 122, and a transparent substrate 123 in order from the lower side of FIG. The sensor unit 130 includes a retardation film 124, an adhesive layer 126, and a polarizing plate 127. In FIG. 3, reference numeral 125 denotes a sensor detection electrode. The cured film of the present invention includes an insulating layer (114) (also referred to as an interlayer insulating film) in the pixel substrate portion, various protective films (not shown), various protective films (not shown) in the pixel substrate portion, and a counter substrate portion. Can be used for various protective films (not shown), various protective films (not shown) for the sensor portion, and the like.

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

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

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

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

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

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

(Examples 1-34 and Comparative Examples 1-6)
-Preparation of curable composition-
Each component was blended and stirred as shown in Table 1 or Table 2 to prepare a solvent preparation, filtered through a polytetrafluoroethylene filter having a diameter of 0.3 μm, and Examples 1 to 34 and Comparative Examples 1 to 6 Each curable composition was obtained. In addition, the unit of each component in Table 1 and Table 2 is a mass part.

<Polymerizable monomer>
<< Component Aa: Polymerizable monomer having one or more carboxyl groups >>
A-1: Aronix M-510 (polyfunctional acrylate compound having a carboxyl group, manufactured by Toagosei Co., Ltd.)
A-2: Aronix M-520 (polyfunctional acrylate compound having a carboxyl group, manufactured by Toagosei Co., Ltd.)
A-3: The following compound

<< Component Ab: Compound having (meth) acryloyl group and one or more urethane bonds >>
A-4: NK Oligo U-15HA (manufactured by Shin-Nakamura Chemical Co., Ltd., urethane (meth) acrylate compound having no carboxyl group)

<< Component Ac: Compound having two or more (meth) acryloyl groups and no carboxyl group in the molecule >>
A-5: A-DPH (dipentaerythritol hexaacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.)
A-6: 9PG (polypropylene glycol # 400 dimethacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.)

<Radical polymerization initiator>
B-1: Compound 1 (synthetic product, see below, oxime ester compound)
B-2: IRGACURE 379 (manufactured by BASF, acetophenone compound)

<Compound having at least titanium atom or aluminum atom and (meth) acryloyl group>
C-1: see below C-2: see below C-3: see below C-4: see below C-5: see below C-6: see below C-7: see below C-8: see below

  Note that Bu represents an n-butyl group, and i-Pr represents an isopropyl group.

<Polymerization inhibitor>
D-1: Hydroquinone monomethyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.)
D-2: Phenoxazine (manufactured by Tokyo Chemical Industry Co., Ltd.)
D-3: Phenothiazine (Seiko Chemical Co., Ltd.)
<Inorganic particles>
E-1 :: PMA-ST (manufactured by Nissan Chemical Industries, Ltd.), silica particles, average particle size of 10-15 nm
<Copolymer having acidic group>
F-1: A copolymer obtained by copolymerizing 53 parts by mass of methyl methacrylate (MMA), 18 parts by mass of 2-hydroxyethyl methacrylate (HEMA), and 1 part by mass of methacrylic acid (MAA)

<Alkoxysilane compound>
G-1: KBM-403 (3-glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.)
G-2: KBM-5103 (3-acryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.)
<Organic solvent>
H-1: Propylene glycol monomethyl ether acetate (manufactured by Daicel Corporation)
<Surfactant>
W-1: Megafax F554 (manufactured by DIC Corporation, fluorosurfactant)

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

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

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

Moreover, the structure of obtained compound B-1 was identified by NMR.
¹ H-NMR (400 MHz, CDCl ₃ ): δ = 8.86 (s, 1H), 8.60 (s, 1H), 8.31 (d, 1H, J = 8.0 Hz), 8.81 ( d, 1H, J = 8.0 Hz), 7.51-7.24 (m, 10H), 7.36 (q, 2H, 7.4 Hz), 3.24-3.13 (m, 4H), 2.36 (s, 3H), 2.21 (s, 3H), 1.50 (t, 3H, 7.4 Hz).

<Evaluation method>
~ Evaluation of patterning ability ~
A glass substrate (100 mm × 100 mm, EAGLE XG, 0.7 mm thickness, manufactured by Corning) was exposed to hexamethyldisilazane (HMDS) vapor for 30 seconds, and each curable composition prepared above was spin-coated. Then, the solvent was volatilized by prebaking on a hot plate at 90 ° C./120 seconds to form a film having a thickness of 3.0 μm.
Next, the film was exposed through a predetermined mask using MPA 5500CF (high pressure mercury lamp) manufactured by Canon Inc. The exposed film was developed with an alkali developer (2.38% tetramethylammonium hydroxide aqueous solution) at 23 ° C./60 seconds, and then rinsed with ultrapure water for 20 seconds. The optimum i-line exposure amount (Eopt) when resolving a 1 mm hole by these operations was taken as the sensitivity.
The hole diameter at the time of producing a permanent film having a hole pattern with the most appropriate exposure amount to be resolved for each mask diameter was evaluated. In the subsequent evaluation, the actual hole pattern diameter was defined by the size of the bottom (bottom) of the resist. The smaller the difference between the hole diameter and the mask diameter (that is, the higher the mask linearity), the easier the panel design becomes, and this is preferable.
The evaluation criteria are as follows, and 1, 2, and 3 are practical ranges.
1: Ratio of mask diameter to actual hole pattern diameter is within ± 10% 2: Ratio of mask diameter to actual hole pattern diameter exceeds ± 10% and within ± 20% 3: Mask diameter to actual hole Pattern diameter ratio exceeds ± 20% and within ± 30% 4: Mask diameter and actual hole pattern ratio exceeds ± 30% and within ± 40% 5: Mask diameter and actual hole Pattern diameter ratio exceeds ± 40%

~ Evaluation of adhesion ~
Each curable composition prepared above is spin-coated on a glass substrate (100 mm × 100 mm) on which copper is deposited, and prebaked at 100 ° C. for 120 seconds to obtain a coating film having a thickness of 2.0 μm. It was. Next, light irradiation of 500 mJ / cm ² (i-line conversion) was performed with a high-pressure mercury lamp, and a cured film was prepared by baking in an oven at 125 ° C. for 60 minutes. About the obtained cured film, the crosscut test of 100 squares was done by the method based on JISK5600, and adhesiveness was evaluated.
Each cured composition prepared above is spin-coated on a glass substrate (100 mm × 100 mm) on which ITO is vapor-deposited, and a cured film produced under the same conditions as described above also conforms to JIS K5600. The cross cut test of 100 squares was done by the method which was done, and adhesiveness was evaluated. In the following evaluation, 1 to 3 is a practical range.
1: No peeling at all.
2: Slightly peels but peels off less than 2%.
3: The peeling rate is 2% or more and less than 5%.
4: The peeling ratio is 5% or more and less than 15%.
5: The peeling rate is 15% or more.

~ Evaluation of hardness (Abrasion resistance evaluation) ~
Each composition prepared above was spin-coated on a glass substrate (100 mm × 100 mm) and prebaked at 100 ° C. for 120 seconds to obtain a coating film having a thickness of 2.0 μm. Next, light irradiation of 500 mJ / cm ² (i-line conversion) was performed with a high-pressure mercury lamp, and a cured film was prepared by baking in an oven at 125 ° C. for 60 minutes. After the obtained cured film was rubbed with steel wool, the surface of the cured film was observed with an optical microscope (Olympus Co., Ltd.) 500 times to evaluate the surface shape. 1, 2, and 3 are practical ranges.
1: No scratches are seen.
2: Scratches are seen in a very small part.
3: Scratches are seen.
4: Scratches are seen throughout.
5: Scratches and wrinkles are seen throughout.

〜Evaluation of discoloration resistance to base metal (metal discoloration resistance evaluation) 〜
Each of the curable compositions prepared above is spin-coated on a glass substrate (100 mm × 100 mm) on which aluminum is deposited, and prebaked at 100 ° C. for 120 seconds to obtain a coating film having a thickness of 2.0 μm. It was. Next, light irradiation of 500 mJ / cm ² (i-line conversion) was performed with a high-pressure mercury lamp, and a cured film was prepared by baking in an oven at 125 ° C. for 60 minutes. The prepared sample was exposed for 20 hours under conditions of a temperature of 60 ° C. and a humidity of 85%, and then the aluminum surface was observed with an optical microscope (Olympus Co., Ltd.) 200 times to evaluate the surface state. 1-3 is a practical range.
1: No discoloration is observed on the entire surface.
2: Discoloration is observed in an area of 1/4 or less of the entire substrate.
3: Discoloration is seen in the area of more than 1/4 of the whole substrate and 1/2 or less.
4: Discoloration is seen in the area of more than 1/2 of the whole substrate and 3/4 or less.
5: Discoloration is seen over the entire substrate.

  The evaluation results are summarized in Table 3.

  1: TFT (thin film transistor), 2: wiring, 3: insulating film, 4: flattening film, 5: first electrode, 6: glass substrate, 7: contact hole, 8: insulating film, 10: liquid crystal display device, 12 : Backlight unit, 14, 15: Glass substrate, 16: TFT, 17: Cured film, 18: Contact hole, 19: ITO transparent electrode, 20: Liquid crystal, 22: Color filter, 110: Pixel substrate, 111: Polarizing plate 112: transparent substrate, 113: common electrode, 114: insulating layer, 115: pixel electrode, 116: alignment film, 120: counter substrate, 121: alignment film, 122: color filter, 123: transparent substrate, 124: phase difference Film: 125: Detection electrode for sensor, 126: Adhesive layer, 127: Polarizing plate, 130: Sensor part, 140: Liquid crystal layer, 200: Lower display panel, 210: First insulating substrate, 20: 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: pixel electrode, 300 : Upper display board, 310: second insulating substrate, 320: light shielding member, 330: color filter, 350: alignment film, 370: common electrode, 400: liquid crystal layer, 410: sensing electrode, 420: insulating film, 430: driving Electrode, 440: TFT

Claims (15)

As component A, a polymerizable monomer,
As component B, a photopolymerization initiator,
As component C, a compound having at least a titanium atom or an aluminum atom and a (meth) acryloyl group, and
Component D includes a polymerization inhibitor,
Component A includes a polymerizable monomer having one or more carboxyl groups,
The curable composition whose component C is a compound represented by either of the following formula C-1 to formula C-3.

In Formula C-1 to Formula C-3, each R ¹ independently represents a hydrogen atom or a methyl group, each R ² independently represents an alkyl group, and each L independently represents a divalent linking group. M represents a titanium atom or an aluminum atom. When M is a titanium atom, m represents an integer of 1 to 4, n represents an integer of 0 to 3, m + n = 4 is satisfied, and M is an aluminum atom. In this case, m represents an integer of 1 to 3, n represents an integer of 0 to 2, and satisfies m + n = 3.   When M is a titanium atom, m represents an integer of 1 to 3, n represents an integer of 1 to 3, m + n = 4 is satisfied, and when M is an aluminum atom, m represents 1 or 2, and n represents The curable composition of Claim 1 which represents 1 or 2 and satisfy | fills m + n = 3.   The curable composition of Claim 1 or 2 whose component C is a compound represented by the said Formula C-1 or Formula C-2.   The curable composition according to any one of claims 1 to 3, wherein the divalent linking group represented by L has 2 to 20 carbon atoms.   The curable composition of any one of Claims 1-4 whose content of the component C is 0.1-20 mass% with respect to the total solid of a curable composition. The curable composition according to any one of claims 1 to 5 , wherein Component A further comprises a compound having a (meth) acryloyl group and one or more urethane bonds. The curable composition according to any one of claims 1 to 6 , wherein Component A further comprises a compound having two or more (meth) acryloyl groups in the molecule and having no carboxyl group. The curable composition according to any one of claims 1 to 7 , further comprising inorganic particles as component E. The curable composition according to any one of claims 1 to 8 , wherein the content of component A is 50% by mass or more based on the total organic solid content in the curable composition. The curable composition according to any one of claims 1 to 9 , further comprising a copolymer having an acidic group as the component F. Cured film obtained by curing the curable composition according to any one of claims 1-10. The cured film of Claim 11 which is a protective film for touchscreen wiring. An organic EL display device having the cured film according to claim 11 . A liquid crystal display device comprising the cured film according to claim 11 . The touch panel display device having the cured film according to claim 11 or 12.