JP2005165294A - Curable composition, cured object, color filter and liquid-crystal display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable composition which not only has high sensitivity but is excellent in adhesion to substrates and thermal stability of the adhesion, especially a curable composition suitable for use as a solder resist or in direct drawing with a laser light, and to also provide a curable composition which has high curability and excellent mechanical properties and is for use in producing a color filter, black matrix, overcoat, rib and spacer for use in a liquid-crystal panel for, e.g., a liquid-crystal display; and a curable object thereof. <P>SOLUTION: The curable composition contains a compound represented by formula (I) [wherein R<SP>1</SP>represents optionally substituted alkylene or optionally substituted arylene; n is an integer of 0-10; the four benzene rings may be further substituted; R<SP>2</SP>represents carbonyloxy containing optionally substituted ≥5C ethylenically unsaturated group; and R<SP>3</SP>and R<SP>4</SP>each independently represents any desired substituent]. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a curable composition by light or heat, and more particularly, a solder resist in a printed wiring board, a liquid crystal display element, a plasma display, a large scale integrated circuit, a thin transistor, a semiconductor package, a color filter, an organic electroluminescence, and the like. The present invention relates to a curable composition that is useful for forming a film, a coverlay film, and an insulating coating layer for various electronic components, and particularly suitable for direct drawing with a laser beam.

  The present invention also relates to a curable composition for a color filter, a black matrix, an overcoat, a rib and a spacer used for a liquid crystal panel such as a liquid crystal display, and a cured product formed using the same. The present invention relates to a color filter and a liquid crystal display device.

  Conventionally, for example, in a printed wiring board, when soldering and wiring an electronic component, as a protective film for preventing solder from adhering to unnecessary portions and preventing the circuit from being directly exposed to air. A solder resist is provided on the surface of the circuit conductor excluding the part to be soldered. Lithography using a photosensitive image forming material (hereinafter sometimes referred to as image forming material (A)) or the like is widely used for forming the solder resist.

The image forming material (A) refers to a dry film resist material or the like in which a photosensitive composition layer is formed on a temporary support film and the surface of the photosensitive composition layer is covered with a coating film.
The lithography method is performed according to the following procedure. First, a photosensitive image forming material (hereinafter sometimes referred to as an image forming material (B)) is produced by peeling off the coating film of the image forming material (A) and laminating it on a substrate to be processed. For the image forming material (B), a photosensitive composition coating liquid is directly applied onto a substrate to be processed and dried to form a photosensitive composition layer. If necessary, the surface of the photosensitive composition layer is protected. It is also produced by covering with a layer.

  Next, the photosensitive composition layer of the image forming material (B) on the substrate to be processed is image-exposed through a mask film on which a circuit pattern is drawn. Then, the temporary support film or the protective layer is peeled off, and a resist image corresponding to the circuit pattern is formed by developing using the difference in solubility between the exposed portion and the unexposed portion in the developer. Furthermore, the circuit pattern drawn on the mask film is formed on the substrate by subjecting the resist image as a resist to solder processing on the substrate to be processed.

On the other hand, in recent years, a laser direct drawing method that directly forms an image from digital information such as a computer without using a mask film by using laser light as an exposure light source is not only productive, but also resolution and positional accuracy. As a result, the use of laser light has been actively studied in the lithography method.
By the way, various laser light sources from the ultraviolet region to the infrared region are known as laser light sources, but as laser light sources that can be used for image exposure, argon, from the viewpoint of output, stability, photosensitive ability, cost, etc. The main products are lasers that emit light in the visible to infrared region, such as ion lasers, helium neon lasers, YAG lasers, and semiconductor lasers. For example, argon ion lasers with a wavelength of 488 nm and FD-YAG lasers with a wavelength of 532 nm The lithography method that has been used has already been put to practical use. In addition, due to significant progress in laser technology in recent years, semiconductor lasers that can stably oscillate in the blue-violet region have become available. However, the conventional photosensitive composition still does not necessarily have sufficient sensitivity in the direct drawing method using laser light, and in particular, in the case of a blue-violet semiconductor laser, its output is in comparison with other visible regions. The sensitivity, developability, and the like of the photosensitive composition corresponding thereto are not at a level that can be put to practical use not only in the direct drawing method but also in the lithography method. For this reason, a solder resist material capable of laser exposure is strongly demanded.

  On the other hand, as a solder resist for a printed wiring board, a liquid resist ink is used from the viewpoint of high accuracy, high density, consideration of environmental problems, etc., and as the liquid resist ink, for example, epoxy resin has been used for a long time. A photocurable resist ink composition containing a reaction product of an α, β-unsaturated monocarboxylic acid addition product and a dibasic carboxylic acid anhydride, a photopolymerizable monomer, and a photopolymerization initiator, etc. Are known.

  In addition, for the purpose of improving the sensitivity and developability of the photocurable photosensitive composition for plating resist, etching resist, solder resist, etc., and durability of the image formed thereby, α, β of the epoxy resin is used. -A photosensitive composition containing an alkali-soluble modified epoxy acrylate resin in which a polyvalent carboxylic acid or an anhydride thereof is added to an unsaturated monocarboxylic acid adduct, and a dry film resist material on the substrate. The image forming material for photoresist formed with a composition coating solution on a substrate and dried to form a photosensitive composition layer is exposed and developed with a high-pressure mercury lamp, a visible laser, or an infrared laser. Image forming methods to be processed (for example, see Patent Document 1, Patent Document 2, and Patent Document 3) are known.

Furthermore, a modified epoxy obtained by reacting a reaction product of bis (hydroxyphenyl) fluorene type epoxy resin and (meth) acrylic acid with a polybasic carboxylic acid or its anhydride for the purpose of improving solder heat resistance and the like. A solder resist resin composition using an acrylate resin is also known (see, for example, Patent Document 4).
However, the photocurable compositions described therein still leave room for improvement in terms of sensitivity, and adhesion to the substrate to be processed, particularly when placed under high temperature as a solder resist or the like. The adhesion was inferior.

  On the other hand, in the field of liquid crystal displays and the like, when forming color filters, black matrices, overcoats, ribs and spacers used in liquid crystal panels, a resin composition comprising a resin, a photopolymerizable monomer, a photopolymerization initiator, and the like. Has been used. Various compositions of resin compositions have been proposed from the viewpoints of developability, pattern accuracy, adhesion, etc. As one of them, the above resin is used for the purpose of improving formation and yield in a short time in the formation process. Technology using an unsaturated group-containing resin obtained by further reacting a reaction product of an epoxy resin and an unsaturated group-containing carboxylic acid or its anhydride with a polybasic carboxylic acid or its anhydride as a resin contained in the composition Is disclosed (Patent Document 5). On the other hand, the resin composition for liquid crystal panels may be required to have high curability and excellent mechanical properties.

  For example, a spacer (in the present specification, “spacer” is formed of a resin composition and indicates a so-called columnar spacer, photospacer, etc.) is a distance between two substrates in a liquid crystal panel. Although it is used for the purpose of maintaining a constant level, it undergoes a process of pressure bonding the color filter and the substrate under high temperature and high pressure when manufacturing a liquid crystal panel, so that there is little deformation before and after pressure bonding and the spacer function is maintained. Physical properties were required. That is, even if the external pressure is deformed in an actual use environment, it is necessary as a mechanical characteristic of the spacer resin composition to return to the original shape when the external pressure is removed. As a material satisfying this mechanical property, a resin composition that defines the content of a polyfunctional acrylate monomer has been proposed (Patent Document 6).

However, such a spacer is required to have pattern accuracy and adhesion while having the above mechanical characteristics. On the other hand, for the purpose of improving pattern accuracy and adhesion, a resin composition having mechanical properties suitable for spacers cannot be formed simply by using the above-mentioned general unsaturated group-containing resin. In addition, among the required mechanical properties, the total deformation amount in the crimping process is large, that is, there is a demand for a soft spacer, but only using the above-mentioned general unsaturated group-containing resin, a soft spacer is simply formed. Although it was possible, recovery after the external pressure was removed was insufficient, and it was not able to withstand practical use.
JP-A-5-204150 JP 2000-147767 A JP 2001-228611 A JP-A-4-355450 JP 2001-174621 A JP 2002-174812 A

The present invention has been made in view of the above-described prior art. Accordingly, an object of the present invention is a curable composition that is highly sensitive and has excellent adhesion to a substrate to be processed and its heat resistance. In particular, an object of the present invention is to provide a curable composition suitable for use as a solder resist and for direct writing with a laser beam.
Another object of the present invention is to provide a curable composition for image formation of a color filter, for a black matrix, for an overcoat, for a rib and for a spacer, which is used for a liquid crystal panel such as a liquid crystal display, which solves the above-mentioned problems. It is to provide.

As a result of intensive studies on the above problems, the present inventors have found that the curable composition has a specific unsaturated group (particularly characterized by having an ethylenically unsaturated group-containing carbonyloxy group having 5 or more carbon atoms). It has been found that the above-mentioned object can be achieved by containing a compound, and the present invention has been completed. That is, the gist of the present invention is as follows.
1. Curable composition containing a compound represented by the following general formula (I)

[In the formula (I), R ¹ represents an alkylene group which may have a substituent or an arylene group which may have a substituent, n is an integer of 0 to 10, The benzene ring may further have a substituent. R ² represents an optionally substituted ethylenically unsaturated group-containing carbonyloxy group having 5 or more carbon atoms, and R ³ and R ⁴ each independently represents an arbitrary substituent. ]
2. In a load-unloading test using a microhardness meter, the load N when the total deformation is 1.35 μm or more and / or the displacement at the time of loading is 0.25 μm is 0.50 gf or less, and the elastic recovery rate is 50 % And / or a cured product having a recovery rate of 80% or more can be formed.

3. A curable composition capable of forming a cured product having a bottom cross-sectional area of 25 μm ² or less and an elastic recovery rate of 50% or more and / or a recovery rate of 85% or more.
4). A cured product formed using the curable composition according to 1 or 2 above.
5). 5. A color filter having the cured product according to 4 above.
6). 5. A liquid crystal display device having the cured product as described in 4 above.

The present invention is a curable composition having high sensitivity and excellent adhesion to a substrate and its heat resistance, and particularly suitable for use as a solder resist or for direct drawing with a laser beam. You can provide things.
In addition, the present invention provides a curable composition for a color filter, a black matrix, an overcoat, a rib and a spacer, which is used for a liquid crystal panel such as a liquid crystal display, having high curability and excellent mechanical properties. I can do it.

Hereinafter, the present invention will be described in detail. In addition, the following description is an example of the embodiment of this invention, and this invention is not specified to these, unless the summary is exceeded.
[1] Curable composition The curable composition of the present invention comprises (A-1) a compound represented by general formula (I) and / or (A-2).
Compound having trisphenol methane structure {Hereinafter, it may be collectively referred to as component (A). } Is a feature. Furthermore, it is preferable to further contain (B) a photopolymerization initiator and / or a thermal polymerization initiator, and (C) an ethylenically unsaturated compound.

  Further, when the curable composition of the present invention is used for solder resist, overcoat, rib or spacer, (D) an epoxy compound, (E) an epoxy curing agent, (F) an amino compound, ( H) An inorganic filler may be included. Further, when the curable composition of the present invention is used for a color filter or a black matrix, it is preferable to further contain (L) a color material and (M) a dispersant and / or a dispersion aid.

Moreover, when using the curable composition of this invention for a laser direct drawing method, it is preferable to contain (J) sensitizing dye further.
Further, as other constituents, (G) a polymerization accelerator, (I) a surfactant, (K) other alkali-soluble resin, (N) other additives, and the like can be further mentioned.
Alternatively, the curable composition of the present invention has a load N when the total deformation is 1.35 μm or more and / or the displacement at the time of loading is 0.25 μm in a load-unloading test using a microhardness meter described later.
. It is characterized in that it can form a cured product having an elastic recovery rate of 50% or more and / or a recovery rate of 80% or more, and 50 gf or less.

Alternatively, the curable composition of the present invention can form a cured product having a bottom cross-sectional area to be described later of 25 μm ² or less and an elastic recovery rate of 50% or more and / or a recovery rate of 85% or more. It is a feature.
Hereinafter, each component of the curable composition of the present invention will be described.
[1-1] (A-1) Compound Represented by General Formula (I) The curable composition of the present invention contains a compound (A-1) represented by the following general formula (I). It is.

[In Formula (I), R < ¹ > shows the alkylene group which may have a substituent, or the arylene group which may have a substituent. R ² represents an ethylenically unsaturated group-containing carbonyloxy group having 5 or more carbon atoms, which may have a substituent. R ³ and R ⁴ each independently represents an arbitrary substituent. n is an integer of 0-10. The four benzene rings may each independently have a substituent. ]
Here, the alkylene group for R ¹ preferably has 1 to 5 carbon atoms, more preferably a methylene group, an ethylene group, a propylene group, or a butylene group, and the arylene group has 6 to 6 carbon atoms. It is preferably 10, and more preferably a phenylene group. Among them, an alkylene group is preferable in the present invention. Moreover, as a substituent of these alkylene groups and arylene groups, a C1-C15 alkyl group etc. are mentioned, for example. N is an integer of 0 to 10, preferably 0 to 5, and more preferably 0 to 3. When n exceeds the above range, when a curable composition is used as a cured product, film loss or the like occurs as an image portion during development, or heat resistance decreases.

Examples of the substituent that R ¹ may have include a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a phenyl group, a carboxyl group, A sulfanyl group, a phosphino group, an amino group, a nitro group, etc. are mentioned.
The upper limit is not particularly limited as long as the carbon number of the ethylenically unsaturated group-containing carbonyloxy group which may have a substituent of R ² is 5 or more, but is preferably 50, more preferably 30. When the curable composition of the present invention is used for a solder resist, the upper limit of the carbon number is more preferably 20, and 15 is particularly preferable.

The ethylenically unsaturated group-containing carbonyloxy group represented by R ² is more preferably a group represented by the following general formula (II).

[In the formula (II), R ⁷ , R ⁸ and R ⁹ each independently represent a hydrogen atom or a methyl group, and Y ¹ represents an arbitrary divalent group. In the formula, * represents a bond between —CH ₂ — and R ² of the compound represented by the general formula (I). ]

Y ¹ is preferably a divalent group including an alkylene group which may have a substituent or / and an arylene group which may have a substituent and a carbonyloxy group.

More preferably, it contains a C1-C10 alkylene group which may have a substituent and / or a C1-C10 arylene group which may have a substituent, and a carbonyloxy group. Indicates a group.
R ³ preferably represents a hydrogen atom, a substituent represented by the following formula (IIIa), and a substituent represented by (IIIb).

[In the formula (IIIa), R ⁵¹ represents an alkyl group which may have a substituent, an alkenyl group which may have a substituent, a cycloalkyl group which may have a substituent, or a substituent. The cycloalkenyl group which may have and the aryl group which may have a substituent are shown. ]
Here, the alkyl of R ⁵¹ preferably has 1 to 20 carbon atoms, the alkenyl group preferably has 2 to 20 carbon atoms, and the cycloalkyl group has 3 carbon atoms. The cycloalkenyl group preferably has 3 to 20 carbon atoms, and the aryl group preferably has 6 to 20 carbon atoms.

Examples of the substituent that may be included in the substituent of R ⁵¹ include a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a phenyl group, Examples thereof include a carboxyl group, a carbonyl group, a sulfanyl group, a phosphino group, an amino group, and a nitro group. Among these, it is preferable to have a carboxyl group.

[In the formula (IIIb), R ⁵² represents an alkyl group which may have a substituent, an alkenyl group which may have a substituent, a cycloalkyl group which may have a substituent, or a substituent. The cycloalkenyl group which may have and the aryl group which may have a substituent are shown. ]
Here, the alkyl group of R ⁵² preferably has 1 to 20 carbon atoms, the alkenyl group preferably has 2 to 20 carbon atoms, and the cycloalkyl group has carbon atoms. The number is preferably 3 to 20, the cycloalkenyl group preferably has 3 to 20 carbon atoms, and the aryl group preferably has 6 to 20 carbon atoms.

Examples of the substituent that may be included in the substituent of R ⁵² include a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a phenyl group, Examples thereof include a carboxyl group, a carbonyl group, a sulfanyl group, a phosphino group, an amino group, and a nitro group.
The substituent represented by R ⁴ is not particularly limited, and examples thereof include a substituent represented by the following general formula (IV).

[In the formula (IV), R ¹ , R ² , R ³ and n are as defined in the general formula (I). In the formula, * represents a bond between —O— and R ⁴ of the compound represented by the general formula (I). ]
Examples of the substituent of the benzene ring in the general formula (I) include an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, an acyl group having 2 to 15 carbon atoms, and 6 carbon atoms. -14 aryl groups, carboxyl groups, hydroxyl groups, C2-C16 alkoxycarbonyl groups, halogen atoms, and the like. C1-C5 alkyl groups, phenyl groups, and halogen atoms are more preferable.

  The compound represented by the general formula (I) is not particularly limited as long as it has the structure, but for example, bis (hydroxyphenyl) fluorene represented by the following general formula (V) The compound obtained from a type epoxy compound can be mentioned. More specifically, a compound represented by the general formula (V) is used as a raw material to form an ethylenically unsaturated group-containing carbonyloxy group having 5 or more carbon atoms. Furthermore, the compound obtained by making 1 or more compounds chosen from polyhydric carboxylic acid, its anhydride, and the compound which has an isocyanate group react can be mentioned.

[In the formula (V), R ¹ , n, and the substituents which may be further included in the four benzene rings have the same meanings as in the formula (I). R ⁵ has the same meaning as R ¹ in formula (I). ]
Examples of the bis (hydroxyphenyl) fluorene forming the bis (hydroxyphenyl) fluorene type epoxy compound represented by the general formula (V) include 9,9-bis (4′-hydroxyphenyl) fluorene, 9 , 9-bis (4′-hydroxy-3′-
Methylphenyl) fluorene, 9,9-bis (4′-hydroxy-3 ′, 5′-dimethylphenyl) fluorene, 9,9-bis (4′-hydroxy-3′-methoxyphenyl) fluorene, 9,9- Bis (4′-hydroxy-3′-fluorophenyl) fluorene, 9,9-
Bis (4′-hydroxy-3′-chlorophenyl) fluorene, 9,9-bis (4′-hydroxy-3 ′, 5′-dichlorophenyl) fluorene, 9,9-bis (4′-hydroxy-)
3′-bromophenyl) fluorene, 9,9-bis (4′-hydroxy-3 ′, 5′-dibromophenyl) fluorene and the like. These bis (hydroxyphenyl) fluorene type epoxy compounds may be used alone or in combination of two or more.

The upper limit is not particularly limited as long as the carbon number of the ethylenically unsaturated group-containing carbonyloxy group formed in the bis (hydroxyphenyl) fluorene type epoxy compound represented by the general formula (V) is 5 or more. , Preferably 50, more preferably 20. When the curable composition of the present invention is used for a solder resist, the upper limit of the carbon number is more preferably 20, and 15 is particularly preferable. If the carbon number is less than the above range, when the curable composition is a cured product, the flexibility is insufficient and the adhesion to the substrate is inferior. On the other hand, if the carbon number is too large, the heat resistance is reduced. .
These ethylenically unsaturated group-containing carbonyloxy groups are preferably groups represented by the following general formula (II).

[In the formula (II), R ⁷ , R ⁸ and R ⁹ represent a hydrogen atom or a methyl group, and Y ¹ represents an arbitrary divalent group. In the formula, * indicates a bond with a methylene group generated by ring opening of the epoxy group of the bis (hydroxyphenyl) fluorene type epoxy compound. ]
Here, if the ethylenically unsaturated group-containing carbonyloxy group represented by the general formula (II) is formed as a result of a reaction using the compound represented by the general formula (V) as a raw material, The forming method is not limited. As the formation method, specifically, a method of reacting the compound represented by the general formula (V) with an ethylenically unsaturated group-containing carboxylic acid, or a carboxylic acid not containing an ethylenically unsaturated group first. After the reaction, a method of forming by a subsequent reaction can be exemplified.

Examples of the ethylenically unsaturated group-containing carboxylic acids include, for example, (meth) acrylic acid [in the present invention, “(meth) acrylic” means “acrylic” and / or “methacrylic”. . ) And lactone or polylactone, succinic anhydride, adipic anhydride, maleic anhydride, fumaric anhydride, itaconic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexa Saturated or unsaturated dicarboxylic anhydrides such as hydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, phthalic anhydride, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, polyethylene Glycol mono (meth) acrylate, glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate Half-esters obtained by reacting a (meth) acrylate derivative having one or more hydroxyl groups in one molecule, such as (meth) acrylates such as benzoate and dipentaerythritol penta (meth) acrylate, Saturated or unsaturated dicarboxylic anhydride, phenyl glycidyl ether, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 8,9-epoxy [bicyclo [4.3.0] non-3- Yl] (meth) acrylate, 8,9-epoxy [bicyclo [4.3.0] non-3-yl] oxymethyl (meth) acrylate and other half-esters obtained by reaction with unsaturated group-containing glycidyl compounds And the like. Among these, in the present invention, succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride and the like, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, Half-esters obtained by reacting pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and the like are particularly preferable. These may be used alone or in combination of two or more.

  The carboxylic acids not containing an ethylenically unsaturated group include saturated or unsaturated hydroxyl group-containing carboxylic acids such as lactic acid and dihydroxypropionic acid and anhydrides, oxalic acid, maleic acid, tetrahydrophthalic acid, phthalic acid, and tartaric acid. Saturated dicarboxylic acid and its anhydride are mentioned. Subsequently, a compound having a functional group that reacts with the generated hydroxyl group or carboxyl group is reacted to form an ethylenically unsaturated group-containing carbonyloxy group having 5 or more carbon atoms. Here, the compound having a functional group that reacts with a hydroxyl group or a carboxyl group is preferably a compound having an epoxy group, a carboxyl group, or an isocyanate group. Specifically, the above-described ethylenically unsaturated group-containing carboxylic acids, Examples include ethylenically unsaturated group-containing compounds such as unsaturated group-containing glycidyl compounds, but are not limited thereto.

  In addition, a bis (hydroxyphenyl) fluorene type epoxy compound represented by the above general formula (III) is used as a raw material, and an ethylenically unsaturated group-containing carbonyloxy group having 5 or more carbon atoms is formed thereon, and then further reacted. Examples of the carboxylic acid or anhydride thereof include oxalic acid, maleic acid, itaconic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, and phthalic acid. Saturated or unsaturated dicarboxylic acids such as acid anhydrides thereof, trimellitic acid and anhydrides thereof, pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, biphenyl ether tetracarboxylic acid, butane tetracarboxylic acid, etc. May be substituted fat Group or an aromatic tetracarboxylic acid and their anhydrides, and the like. Among these, dicarboxylic acids such as tetrahydrophthalic acid and phthalic acid and acid anhydrides thereof, trimellitic acid and anhydride thereof, tetracarboxylic acids such as pyromellitic acid, biphenyltetracarboxylic acid, and butanetetracarboxylic acid and acids thereof A dianhydride or the like is preferable as a curable composition because it is excellent in dissolution and removal of a non-image area at the time of alkali development, and is preferably a dicarboxylic acid such as tetrahydrophthalic acid or phthalic acid, and its acid anhydride, trimellitic acid and its anhydride. Particularly preferred are trivalent or lower carboxylic acids and their anhydrides.

Examples of the compound having an isocyanate group include butane isocyanate, 3-chlorobenzene isocyanate, cyclohexane isocyanate, organic monoisocyanates such as 3-isopropenoyl-α, α-dimethylbenzyl isocyanate, paraphenylene diisocyanate, 2,4-tolylene diisocyanate, Aromatic diisocyanates such as 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, tolidine diisocyanate, hexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate Aliphatic diisocyanate, isophorone diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate) Anate), alicyclic diisocyanates such as ω, ω′-diisocyanate dimethylcyclohexane, xylylene diisocyanate, aliphatic diisocyanates having an aromatic ring such as α, α, α ′, α′-tetramethylxylylene diisocyanate, lysine Ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, tris (isocyanate phenylmethane), tris Triisocyanates such as (isocyanate phenyl) thiophosphate, trimers thereof, water adducts, polyol adducts thereof and the like. Preferred are dimers and trimers of organic diisocyanates, most preferred are trimethylolpropane adducts of tolylene diisocyanate, trimers of tolylene diisocyanate, and trimers of isophorone diisocyanate. These may be used alone or in combination of two or more.

  In addition, as a compound represented by general formula (I) in this invention, it is preferable that an acid value is 30-150 mg * KOH / g, and it is still more preferable that it is 40-100 mg * KOH / g. Moreover, it is preferable that the polystyrene conversion weight average molecular weights by a gel permeation chromatography are 1,000-100,000, and it is still more preferable that it is 1,500-10,000.

  Further, if a specific method for synthesizing the compound represented by the general formula (I) in the present invention is given, for example, according to a conventionally known method described in Patent Document 4 or the like, specifically, the bis (hydroxy Phenyl) fluorene type epoxy compound is suspended or dissolved in an organic solvent such as methyl ethyl ketone, ethyl cellosolve acetate, butyl cellosolve acetate, tertiary amines such as triethylamine, benzyldimethylamine, tribenzylamine, or tetramethylammonium chloride, Quaternary ammonium salts such as methyltriethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, trimethylbenzylammonium chloride, phosphorus compounds such as triphenylphosphine, or triphenyls In the presence of a catalyst such as a stibine such as a bottle, in the presence of a thermal polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, or methylhydroquinone, the ethylenically unsaturated group-containing carboxylic acid is converted to one chemistry of the epoxy group of the epoxy compound. It is usually added in an amount of 0.8 to 1.5 chemical equivalents, preferably 0.9 to 1.1 chemical equivalents relative to equivalents, and is usually subjected to addition reaction at a temperature of 60 to 150 ° C, preferably 80 to 120 ° C. Subsequently, the polyvalent carboxylic acid or anhydride thereof is added in an amount that is usually 0.05 to 1.0 chemical equivalent to 1 chemical equivalent of the hydroxyl group generated in the reaction, and the reaction is performed under the above conditions. It can be manufactured by a method such as continuing.

[1-2] (A-2) Resin having a trisphenolmethane structure The curable composition of the present invention satisfies the physical property conditions described in [1-15] and / or [1-16] described below, In addition to the component (A-1) described in 1-1], or instead of the component (A-1), (A-2) a resin having a trisphenolmethane structure may be contained.
The resin having a trisphenol methane structure of the present invention is not particularly limited as long as the resin structure has a trisphenol methane structure. For example, an epoxy resin having a trisphenol methane structure and (meth) acrylic are used. Preferable examples include resins obtained by reacting acids and anhydrides thereof or reaction products of the ethylenically unsaturated group-containing carboxylic acids with the polyvalent carboxylic acids or anhydrides thereof.

Examples of the epoxy resin having a trisphenolmethane structure include “EPPN-501H”, “EPPN-501HY”, and “EPPN-502H” manufactured by Nippon Kayaku Co., Ltd.
Examples of the resin having a trisphenolmethane structure include “TCR1025”, “TCR1064”, and “TCR1286” manufactured by Nippon Kayaku Co., Ltd.
The amount per weight of the double bond of the component (A-1) and / or the component (A-2), which is a constituent element of the curable composition of the present invention, is a double bond equivalent; (double bond equivalent) = (Weight of compound (g))
/ (Number of moles containing double bond of compound), the more double bonds per unit weight, the smaller the double bond equivalent value. When the curable composition of the present invention is used for a spacer application, the total double bond amount (A) is preferably 550 or less, more preferably 400 or less, for improving the recovery rate and / or the elastic recovery rate. Most preferably, it is 350 or less.
In addition, it is preferable that the double bond amount as the whole curable composition of this invention is 200 or less, More preferably, it is 160 or less, Most preferably, it is 150 or less.
The double bond equivalent can be calculated by the above formula from the amount charged in the synthesis of the compound having an ethylenic double bond. In complex systems such as resist, the double bond equivalent of the solution is measured by a known method. Then, the solid content concentration of the resist is measured by a known method, and can be calculated by (double bond equivalent) = (resist double bond equivalent) × (solid content concentration).
[1-3] (B) Photopolymerization initiator and / or thermal polymerization initiator The curable composition of the present invention may further contain (B) a photopolymerization initiator and / or a thermal polymerization initiator. . The photopolymerization initiator (B) generates an active species such as a radical, an acid, or a base when the curable composition is irradiated with actinic rays, and is represented by the general formula (I). Compounds and active compounds that are used as necessary to bring the ethylenically unsaturated compound of component (C) described below into polymerization, such as acetophenones, benzophenones, hydroxybenzenes, thioxanthones, anthraquinones , Ketals, hexaarylbiimidazoles, titanocenes, halogenated hydrocarbon derivatives, organoborates, onium salts, sulfone compounds, carbamic acid derivatives, sulfonamides, triarylmethanols, etc. .

  Examples of the acetophenones include 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 1- Hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-trichloromethyl- (p-butylphenyl) ketone, α-hydroxy-2-methylphenylpropanone, α-aminoacetophenone described below, etc. Examples of benzophenones include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-carboxybenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, Michler's ketone, and the like. Examples of the roxybenzenes include 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-benzylbenzophenone, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 4-di-t- Butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate and the thioxanthones include, for example, thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2, 4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone and the like, and as anthraquinones, for example, 2-methylanthraquinone and the like, and as ketals, for example, benzyldimethyl ketal and the like, Each listed

Examples of the hexaarylbiimidazoles include 2,2′-bis (o-
Chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra (o, p-dichlorophenyl) biimidazole 2,2′-bis (o, p-dichlorophenyl) -4,4 ′, 5,5′-tetra (o, p-dichlorophenyl) biimidazole, 2,2′-bis (o-chlorophenyl)
-4,4 ', 5,5'-tetra (p-fluorophenyl) biimidazole, 2,2'-bis (o-chlorophenyl) -4,4', 5,5'-tetra (o, p-dibromo) Phenyl) biimidazole, 2,2′-bis (o-bromophenyl) -4,4 ′, 5,5′-tetra (o,
p-dichlorophenyl) biimidazole, 2,2′-bis (o-chlorophenyl) -4,
Examples thereof include 4 ′, 5,5′-tetra (p-chloronaphthyl) biimidazole. Among them, a hexaphenylbiimidazole compound is preferable, and a compound in which the o-position of the benzene ring bonded to the 2,2′-position on the imidazole ring is substituted with a halogen atom is more preferable. Particularly preferred are those in which the benzene ring bonded to the 4 ′, 5,5′-position is unsubstituted or substituted with a halogen atom or an alkoxycarbonyl group.

  Examples of the titanocenes include dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis (2,4-difluorophenyl), and dicyclopentadienyl titanium bis. (2,6-difluorophenyl), dicyclopentadienyl titanium bis (2,4,6-trifluorophenyl), dicyclopentadienyl titanium bis (2,3,5,6-tetrafluorophenyl), di Cyclopentadienyltitanium bis (2,3,4,5,6-pentafluorophenyl), di (methylcyclopentadienyl) titanium bis (2,6-difluorophenyl), di (methylcyclopentadienyl) titanium Bis (2,3,4,5,6-pentafluoro Eniru), dicyclopentadienyl titanium bis [2,6-difluoro-3- (1-pyrrolyl) phenyl], and the like. Of these, titanium compounds having a dicyclopentadienyl structure and a bisphenyl structure are preferred, and those in which the o-position of the bisphenyl ring is substituted with a halogen atom are particularly preferred.

  Examples of the halogenated hydrocarbon derivatives include halomethylated s-triazine derivatives, such as 2,4,6-tris (monochloromethyl) -s-triazine, 2,4,6-tris (dichloro). Methyl) -s-triazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2-n-propyl-4,6 -Bis (trichloromethyl) -s-triazine, 2- (α, α, β-trichloroethyl) -4,6-bis (trichloromethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) ) -S-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3,4-epoxyphenyl) -4,6 Bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- [1- (p-methoxyphenyl) -2,4-butadienyl] -4,6-bis (trichloromethyl) -s-triazine, 2-styryl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) ) -S-triazine, 2- (p-methoxy-m-hydroxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (pi-propyloxystyryl) -4,6-bis (Trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxynaphthyl) -4, -Bis (trichloromethyl) -s-triazine, 2- (p-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-ethoxycarbonylnaphthyl) -4,6-bis ( Trichloromethyl) -s-triazine, 2-phenylthio-4,6-bis (trichloromethyl) -s-triazine, 2-benzylthio-4,6-bis (trichloromethyl) -s-triazine, 2,4,6- Tris (dibromomethyl) -s-triazine, 2,4,6-tris (tribromomethyl) -s-triazine, 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2-methoxy- And halomethylated s-triazine derivatives such as 4,6-bis (tribromomethyl) -s-triazine, among which bis (trihalomethyl) -s -Triazines are preferred.

Examples of the organoborates include, for example, organoboron ammonium complexes, organoboron phosphonium complexes, organoboron sulfonium complexes, organoboron oxosulfonium complexes, organoboron iodonium complexes, organoboron transition metal coordination complexes, and the like. Examples of the organic boron anion include n-butyl-triphenyl boron anion, n-butyl-tris (2,4,6-trimethylphenyl) boron anion, n-butyl-tris (p-methoxyphenyl) boron anion, n-butyl-tris (p-fluorophenyl) boron anion, n-butyl-tris (m-fluorophenyl) boron anion, n-butyl-tris (3-fluoro-4-methylphenyl) boron anion, n-butyl- Tris (2,6-difluorophenyl) boron anion, n-butyl Tris (2,4,6-trifluorophenyl) boron anion, n-butyl-tris (2,3,4,5,6-pentafluorophenyl) boron anion, n-butyl-tris (p-chlorophenyl) boron anion Alkyl-triphenyl boron anions such as n-butyl-tris (2,6-difluoro-3-pyrrolylphenyl) -boron anion are preferable. Onium compounds such as cations are preferred, and organic ammonium cations such as tetraalkylammonium are particularly preferred.

  Examples of the onium salts include ammonium salts such as tetramethylammonium bromide and tetraethylammonium bromide, diphenyliodonium hexafluoroarsenate, diphenyliodonium tetrafluoroborate, diphenyliodonium p-toluenesulfonate, diphenyliodonium camphorsulfonate, dicyclohexyliodonium. Hexafluoroarsenate, dicyclohexyliodonium tetrafluoroborate, icyclohexyl salt such as dicyclohexyliodonium p-toluenesulfonate, dicyclohexyliodonium camphorsulfonate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium tetrafluoroborate, triphenyls Honiumu p- toluenesulfonate, triphenylsulfonium camphorsulfonate, tri-cyclohexyl hexafluoroarsenate, tri-cyclohexyl sulfonium tetrafluoroborate, tri-cyclohexyl sulfonium p- toluenesulfonate, sulfonium salts such as tri-cyclohexyl sulfonium camphorsulfonate, and the like.

  Examples of the sulfone compounds include bis (phenylsulfonyl) methane, bis (p-hydroxyphenylsulfonyl) methane, bis (p-methoxyphenylsulfonyl) methane, bis (α-naphthylsulfonyl) methane, and bis (β -Naphtylsulfonyl) methane, bis (cyclohexylsulfonyl) methane, bis (t-butylsulfonyl) methane, bis (sulfonyl) methane compounds such as phenylsulfonyl (cyclohexylsulfonyl) methane, phenylcarbonyl (phenylsulfonyl) methane, naphthylcarbonyl (phenyl) Sulfonyl) methane, phenylcarbonyl (naphthylsulfonyl) methane, cyclohexylcarbonyl (phenylsulfonyl) methane, t-butylcarbonyl (phenylsulfonyl) methane, phenyl Carbonyl (sulfonyl) methane compounds such as carbonyl (cyclohexylsulfonyl) methane, phenylcarbonyl (t-butylcarbonyl) methane, bis (phenylsulfonyl) diazomethane, bis (p-hydroxyphenylsulfonyl) diazomethane, bis (p-methoxyphenylsulfonyl) Diazomethane, bis (α-naphthylsulfonyl) diazomethane, bis (β-naphthylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (t-butylsulfonyl) diazomethane, phenylsulfonyl (cyclohexylsulfonyl) diazomethane, bis (sulfonyl) diazomethane compounds , Phenylcarbonyl (phenylsulfonyl) diazomethane, naphthylcarbonyl (phenylsulfonyl) diazomethane, Carbonyl (sulfonyl) diazomethane such as nylcarbonyl (naphthylsulfonyl) diazomethane, cyclohexylcarbonyl (phenylsulfonyl) diazomethane, t-butylcarbonyl (phenylsulfonyl) diazomethane, phenylcarbonyl (cyclohexylsulfonyl) diazomethane, phenylcarbonyl (t-butylcarbonyl) diazomethane Compounds and the like.

Examples of the carbamic acid derivatives include benzoyl cyclohexyl carbamate, 2-nitrobenzyl cyclohexyl carbamate, 3,5-dimethoxybenzyl cyclohexyl carbamate, 3-nitrophenyl cyclohexyl carbamate, and the sulfonamides thereof. For example, N-cyclohexyl-4-methylphenylsulfonamide, N-cyclohexyl-2-naphthylsulfonamide and the like, and triarylmethanols thereof include, for example, triphenylmethanol, tri (4-chlorophenyl) methanol and the like. , Respectively.

  Further, the thermal polymerization initiator of the component (B) constituting the curable composition of the present invention generates active species such as radicals when the curable composition is heated, and is represented by the general formula (I) An active compound that brings the ethylenically unsaturated compound of the component (C), which will be described later, to be used for polymerization, such as organic peroxides and azo compounds Etc.

  Examples of the organic peroxides include ketone peroxides such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, acetylacetone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, and 3,3,5-trimethylcyclohexanone peroxide. , Isobutyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, o-methylbenzoyl peroxide, m-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, m-toluoyl peroxide Diacyl peroxides such as t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide Id, p-menthane hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, 2,4,4-trimethylpentyl-2 -Hydroperoxides such as hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, 1,3 (or 1,4) -bis (t-butylperoxyisopropyl) Dialkyl peroxides such as benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3; 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) -3,3,5 Peroxyketals such as trimethylcyclohexane, 2,2-bis (t-butylperoxy) butane, 4,4-bis (t-butylperoxy) valeric acid-n-butyl ester, t-butylperoxyacetate, t-butyl peroxyoctoate, t-butyl peroxypivalate, t-butylperoxyneodecanoate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate Alkyl peresters such as di-t-butylperoxytrimethyladipate, t-butylperoxybenzoate, α-cumylperoxyneodecanoate, 2,4,4-trimethylpentylperoxyphenoxyacetate, di-2 -Ethylhexyl peroxydicarbonate, di-2-ethoxyethylper Xydicarbonate, diisopropylperoxydicarbonate, dimethoxyisopropylperoxydicarbonate, di-3-methoxybutylperoxydicarbonate, bis (3-methyl-3-methoxybutyl) peroxydicarbonate, t-butylperoxyisopropyl Examples thereof include peroxycarbonates such as carbonate, t-butyl peroxyallyl carbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, and acetylcyclohexylsulfonyl peroxydicarbonate.

Examples of the azo compounds include 1,1′-azobiscyclohexane-1
-Carbonitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (methylisobutyrate) Rate), α, α′-azobis (isobutyronitrile), 4,4′-azobis (4-cyanovaleric acid), and the like.

Among the photopolymerization initiators and / or thermal polymerization initiators of the above component (B), in the present invention, α-aminoacetophenone derivatives as acetophenones as photopolymerization initiators are preferable,
Those represented by the following general formula (VII) are particularly preferred.

[In the formula (VII), R ³⁵ represents an alkyl group which may have a substituent, an allyl group which may have a substituent, or a phenyl group which may have a substituent, R ³⁶ represents an alkyl group which may have a substituent, or an allyl group which may have a substituent, and R ³⁷ and R ³⁸ may each independently have a substituent. A good alkyl group, an allyl group optionally having substituent (s), or a phenyl group optionally having substituent (s), wherein R ³⁷ and R ³⁸ are linked to each other, or R ³⁷ or R ³⁸ And R ³⁵ or R ³⁶ may be linked to each other to form a cyclic structure, and the benzene ring may have a substituent. ]
Here, the alkyl group of R ³⁵ , R ³⁶ , R ³⁷ and R ^{38 in} the general formula (VII) is preferably an alkyl group having 1 to 15 carbon atoms, particularly 1 to 10 carbon atoms. Examples of the substituent in the alkyl group, allyl group, and phenyl group include an alkyl group, an alkoxy group, a hydroxyalkyl group, a hydroxyalkoxy group, an acetoxyalkoxy group, an alkoxyalkoxy group, an alkylcarbonylalkyl group, an alkylthio group, a haloalkyl group, A phenyl group, a halogen atom, etc. are mentioned. Also, in conjunction with R34 and R35 to each other, or, in conjunction with R ³⁷ or R ³⁸ and R ³⁵ or R ³⁶ with each other, as it is formed and has a cyclic structure, pyrrolidine, piperidine, piperazine, morpholine, oxazolidine , Pyridine and the like.

  In addition, examples of the substituent in the benzene ring include alkyl groups, hydroxy groups, alkoxy groups, allyloxy groups, phenoxy groups, benzoyl groups, silyloxy groups, mercapto groups, alkylthio groups, allylthio groups, cycloalkylthio groups, benzylthio groups, phenylthio groups, Examples include an alkylsulfonyl group, a phenylsulfonyl group, an alkylsulfinyl group, an alkylamino group, an allylamino group, a pyrrolidinyl group, a piperidinyl group, a piperazinyl group, a morpholinyl group, and a halogen atom, and the benzene ring forms a condensed ring. As the condensed ring, fluorenone, dibenzosuberone, indoline, quinoxaline, carbazole, phenazine, acridanone, benzodioxole, benzofuran, xanthene, xanthone, phenoxazine, Nzochiazoru, phenothiazines, and the like.

Specific examples of the α-aminoacetophenone derivative represented by the general formula (VII) above include the following compounds when classified according to the basic skeleton of the compound and exemplified for each carbon number. Particularly preferred are R ³⁵ and R ³⁶ each independently a methyl group, an ethyl group, or a benzyl group, and R ³⁷ and R ³⁸ are each a methyl group or are linked to each other to form a cyclic structure. And a benzene ring which is unsubstituted or has a methylthio group, a dimethylamino group or a morpholino group as a substituent, particularly preferably a compound having a morpholino group only at the p-position.

As propan-1-one classified into 3 carbon atoms of the basic skeleton, 1-phenyl-2-dimethylamino-2-methyl-3- (4-methylphenyl) -propan-1-one, 1-phenyl-2-one Dimethylamino-2-methyl-3- (4-methoxyphenyl) -propane-1-
ON, 1-phenyl-2-dimethylamino-2-methyl-3- (3,4-dimethoxyphenyl) -propan-1-one, 1-phenyl-2-dimethylamino-2-methyl-3- (4- Methylthiophenyl) -propan-1-one, 1-phenyl-2-dimethylamino-2-methyl-3- (4-fluorophenyl) -propan-1-one, 1-phenyl-2-dimethylamino-2-methyl -3- (2-chlorophenyl) -propan-1-one, 1-phenyl-2-dimethylamino-2-methyl-3- (4-chlorophenyl) -propan-1-one, 1-phenyl-2-dimethylamino 2-methyl-3- (4-bromophenyl) -propan-1-one, 1-phenyl-2-dimethylamino-2-methyl-3- (4-benzoylphenyl) -pro 1-one, 1-phenyl-2-dimethylamino-2-benzyl-propan-1-one, 1,3-diphenyl-2-dimethylamino-2-benzyl-propan-1-one, 1- (4 -Fluorophenyl) -2-dimethylamino-2-benzyl-propan-1-one, 1- (4-fluorophenyl) -2-dimethylamino-2-benzyl-3-phenyl-propan-1-one, 1- (4-Benzoylphenyl) -2-dimethylamino-2-benzyl-propan-1-one, 1- (4-methylthiophenyl) -2-morpholino-2-methyl-propan-1-one, 1- (4- Methylthiophenyl) -2-dimethylamino-2-methyl-3- (4-methylphenyl) -propan-1-one, 1- (4-methylthiophenyl) -2-dimethylamino 2-Methyl-3- (4-methoxyphenyl) -propan-1-one, 1- (4-methylthiophenyl) -2-dimethylamino-2-methyl-3- (3,4-dimethoxyphenyl) -propane -1-one, 1- (4-methylthiophenyl) -2-dimethylamino-2-methyl-3- (4-fluorophenyl) -propan-1-one, 1- (4-methylthiophenyl) -2-dimethyl Amino-2-methyl-3- (2-chlorophenyl) -propan-1-one, 1- (4-methylthiophenyl) -2-dimethylamino-2-methyl-3- (4-chlorophenyl) -propane-1- ON, 1- (4-methylthiophenyl) -2-dimethylamino-2-methyl-3- (4-bromophenyl) -propan-1-one, 1- (4-methylthiophenyl)- 2-Dimethylamino-2-methyl-3- (4-benzoylphenyl) -propan-1-one, 1,3-bis (4-methylthiophenyl) -2-dimethylamino-2-methyl-propan-1-one 1- (4-butylthiophenyl) -2-dimethylamino-2-benzyl-3-phenyl-propan-1-one, 1- (4-cyclohexylthiophenyl) -2-dimethylamino-2-benzyl-3 -Phenyl-propan-1-one, 1- (4-benzylthiophenyl) -2-dimethylamino-2-benzyl-propan-1-one, 1- (4-dimethylaminophenyl) -2-dimethylamino-2 -Benzyl-propan-1-one, 1- (4-dimethylaminophenyl) -2-dimethylamino-2-benzyl-3-phenyl-propan-1-one, -(4-morpholinophenyl) -2-dimethylamino-2- (2-chloropentenyl) -propan-1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2-benzyl-propane-1- ON, 1- (4-morpholinophenyl) -2-dimethylamino-2-benzyl-3-phenyl-propan-1-one, 1- (N-methylindoline-5-yl) -2-dimethylamino-2- Examples include benzyl-propan-1-one, 1- (N-butylphenoxazin-2-yl) -2-morpholino-2-benzyl-propan-1-one, and the like.

As butan-1-one classified into 4 carbon atoms of the basic skeleton, 1-phenyl-2-dimethylamino-2-benzyl-butan-1-one, 1- (4-methylphenyl) -2-dimethylamino-2 -Benzyl-butan-1-one, 1- (4-methoxyphenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- (3,5-dimethyl-4-methoxyphenyl) -2- Dimethylamino-2-benzyl-butan-1-one, 1- (3,4-dimethoxyphenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- (3,4,5-trimethoxy Phenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- (4-hydroxyphenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- [4- (2- Hide Kishietokishi) phenyl] -2-dimethylamino-2
Benzyl-butan-1-one, 1- (4-allyloxyphenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- (4-ethoxycarbonylmethoxyphenyl) -2-dimethylamino-2 -Benzyl-butan-1-one, 1- [4- (1,1,2-trimethylpropyldimethylsilyloxy) phenyl] -2-dimethylamino-2-benzyl-butan-1-one, 1- (4- Fluorophenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- (4-chlorophenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- (2,4-dichlorophenyl) ) -2-Dimethylamino-2-benzyl-butan-1-one, 1- (3,4-dichlorophenyl) -2-dimethylamino-2-benzyl-butane- -One, 1- (3,5-dichlorophenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- (4-bromophenyl) -2-dimethylamino-2-benzyl-butane-1- ON, 1- (4-mercaptophenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- (4-methylthiophenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- (4-methylthiophenyl) -2-dibutylamino-2-benzyl-butan-1-one, 1- (4-methylthiophenyl) -2-di (2-methoxyethyl) amino-2-benzyl-butane- 1-one, 1- [4- (2-methoxyethylthio) phenyl] -2-dimethylamino-2-benzyl-butan-1-one, 1- [4- (2-hydroxyethylthio) Enyl] -2-dimethylamino-2-benzyl-butan-1-one, 1- (4-octylthiophenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- (4-methylsulfonyl) Phenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- [4- (4-methylphenylsulfonyl) phenyl] -2-dimethylamino-2-benzyl-butan-1-one, 1- (4-benzenesulfonylphenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- (4-methylsulfinylphenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- (4-Aminophenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- (4-methylaminophenyl) -2-dimethylamino-2- Benzyl-butan-1-one, 1- (4-dimethylaminophenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- (4-dimethylaminophenyl) -2-dimethylamino-2- (4-Methylbenzyl) -butan-1-one, 1- (4-dimethylaminophenyl) -2-dimethylamino-2- (4-isopropylbenzyl) -butan-1-one, 1- (4-dimethylamino) Phenyl) -2-dimethylamino-2- (4-dodecylbenzyl) -butan-1-one, 1- (4-dimethylaminophenyl) -2-dimethylamino-2- (1-chlorohexenylmethyl) -butane- 1-one, 1- (4-dimethylaminophenyl) -2-dimethylamino-2- (2-pinen-10-yl) -butan-1-one, 1- (4-dimethyla No-2-methylphenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- (4-dimethylamino-3-ethylphenyl) -2-dimethylamino-2-benzyl-butane-1- ON, 1- (4-diethylaminophenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- (4-isopropylaminophenyl) -2-dimethylamino-2-butyl-butan-1-one 1- [4- (2-methoxyethylamino) phenyl] -2-dimethylamino-2-benzyl-butan-1-one, 1- [4- (3-methoxypropylamino) phenyl] -2-dimethylamino 2-benzyl-butan-1-one, 1- (4-acetylaminophenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- [4- (N Acetylmethylamino) phenyl] -2-dimethylamino-2-benzyl-butan-1-one, 1- [4- (N-acetyl-3-methoxypropylamino) phenyl] -2-dimethylamino-2-benzyl- Butan-1-one, 1- (4-piperidinophenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2-benzyl- Butan-1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2- (3,4-dimethylbenzyl) -butan-1-one, 1- (4-morpholinophenyl) -2-dimethylamino 2- (4-Ethylbenzyl) -butan-1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2- (4-isopropylbenzyl) -butane -1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2- (4-butylbenzyl) -butan-1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2- (4-isobutylbenzyl) -butan-1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2- (4-dodecylbenzyl) -butan-1-one, 1- (4-morpholinophenyl) 2-dimethylamino-2- (4-hydroxymethylbenzyl) -butan-1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2- (4-acetoxyethylbenzyl) -butane-1- ON, 1- (4-morpholinophenyl) -2-dimethylamino-2- (4-methoxybenzyl) -butan-1-one, 1- (4-morpholinophenyl) -2-di Tylamino-2- (4-butoxybenzyl) -butan-1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2- [4- (2-hydroxyethoxy) benzyl] -butan-1-one 1- (4-morpholinophenyl) -2-dimethylamino-2- [4- (2-methoxyethoxy) benzyl] -butan-1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2 -[4- (2- (2-methoxyethoxy) ethoxy) benzyl] -butan-1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2- [4- (2- (2-methoxy Ethoxy) ethoxycarbonyl) benzyl] -butan-1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2- [4- (2- (2- (2-methoxyethoxy) Ethoxycarbonyl) ethyl) benzyl] -butan-1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2- [4- (2-bromoethyl) benzyl] -butan-1-one, 1- ( 4-morpholinophenyl) -2-dimethylamino-2- [4- (2-diethylaminoethyl) benzyl] -butan-1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2-benzyl-butane -1-one-trifluoroacetate, 1- (4-morpholinophenyl) -2-dimethylamino-2-benzyl-butan-1-one-dodecylbenzenesulfonate, 1- (4-morpholinophenyl) -2-dimethylamino 2-Benzyl-butan-1-one-p-toluenesulfonate, 1- (4-morpholinophenyl) -2-dimethyl Amino-2-benzyl-butan-1-one-camphorsulfonate, 1- (4-morpholinophenyl) -2-diethylamino-2-benzyl-butan-1-one, 1- (4-morpholinophenyl) -2-di (2-methoxyethyl) amino-2-benzyl-butan-1-one, 1- (4-morpholinophenyl) -2-butylmethylamino-2-benzyl-butan-1-one, 1- (4-morpholinophenyl) ) -2-Butylmethylamino-2- (4-isopropylbenzyl) -butan-1-one, 1- (4-morpholinophenyl) -2-dibutylamino-2-benzyl-butan-1-one, 1- ( 4-morpholinophenyl) -2-benzylmethylamino-2-benzyl-butan-1-one, 1- (3-chloro-4-morpholinophenyl) -2- Methylamino-2-benzyl-butan-1-one, 1- [4- (2,6-dimethylmorpholin-4-yl) phenyl] -2-dimethylamino-2-benzyl-butan-1-one, 1- (1,4-Dimethyl-1,2,3,4-tetrahydroquinoxalin-6-yl) -2-dimethylamino-2-benzyl-butan-1-one, 1- (N-butylcarbazol-3-yl ) -2-dimethylamino-2-benzyl-butan-1-one, 1- (1,3-benzodioxol-5-yl) -2-dimethylamino-2-benzyl-butan-1-one, -(2,3-dihydrobenzofuran-5-yl) -2-dimethylamino-2-benzyl-butan-1-one, 1- (xanthen-2-yl) -2-dimethylamino-2-benzyl-butane- 1-on, -(2,3-dihydro-2,3-dimethylbenzothiazol-5-yl) -2-dimethylamino-2-benzyl-butan-1-one, 2- (2-dimethylamino-2-benzyl-butanoyl) -Fluorenone, 2- (2-dimethylamino-2-benzyl-butanoyl) -dibenzosuberone, 3,6-di (2-dimethylamino-2-benzyl-butanoyl) -9-butyl-carbazole and the like.

As pentan-1-one classified into 5 carbon atoms of the basic skeleton, 1- (4-morpholinophenyl) -2-dimethylamino-2-allyl-pentan-1-one, 1- (4-morpholinophenyl) -2 -Dimethylamino-2-benzyl-pentan-1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2- (2-isopropylbenzyl) -pentan-1-one, 1- (4-morpholinophenyl) ) -2-Butylmethylamino-2- (4-isobutylbenzyl) -pentan-1-one, 1- (4-morpholinophenyl) -2-butylmethylamino-2- (4-butoxybenzyl) -pentane-1 -ON etc. are mentioned.

Furthermore, as penten-1-one, 1-phenyl-2-dimethylamino-2-methyl-4-penten-1-one, 1-phenyl-2-dimethylamino-2-ethyl-4-penten-1-one 1-phenyl-2-dimethylamino-2-benzyl-4-penten-1-one, 1-phenyl-2-morpholino-2-methyl-4-penten-1-one, 1-phenyl-2-morpholino- 2-Benzyl-4-penten-1-one, 1,2-diphenyl-2-morpholino-4-penten-1-one, 1- (4-methylphenyl) -2-morpholino-2-methyl-4-pentene -1-one, 1- (4-dodecylphenyl) -2-morpholino-2-ethyl-4-penten-1-one, 1- (4-methoxyphenyl) -2-dimethylamino-2-ethyl-4- Nten-1-one, 1- (4-methoxyphenyl) -2-dibutylamino-2-methyl-4-penten-1-one, 1- (4-methoxyphenyl) -2-piperidino-2-ethyl-4 -Penten-1-one, 1- (4-methoxyphenyl) -2-oxazolidino-2-methyl-4-penten-1-one, 1- (4-methoxyphenyl) -2-morpholino-2-ethyl-4 -Penten-1-one, 1- (4-methoxyphenyl) -2-morpholino-2-phenyl-4-penten-1-one, 1- (3,4-dimethoxyphenyl) -2-morpholino-2-ethyl -4-penten-1-one, 1- [4- (2-methoxyethoxy) phenyl] -2-morpholino-2-methyl-4-penten-1-one, 1- [4- (2-methoxyethoxy) Feni ] -2-morpholino-2-ethyl-4-penten-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-morpholino-2-ethyl-4-penten-1-one, 1- (4-Isopropyloxyphenyl) -2-dimethylamino-2-benzyl-4-penten-1-one, 1- (4-butyloxyphenyl) -2-morpholino-2-ethyl-4-penten-1-one 1- [4- (2-allyloxyethoxy) phenyl] -2-morpholino-2-methyl-4-penten-1-one, 1- [4- (2-allyloxyethoxy) phenyl] -2-morpholino 2-ethyl-4-penten-1-one, 1- (4-trimethylsilyloxyphenyl) -2-morpholino-2-methyl-4-penten-1-one, 1- (4-fluorophenyl) ) -2-dimethylamino-2-methyl-4-penten-1-one, 1- (4-fluorophenyl) -2-dimethylamino-2-ethyl-4-penten-1-one, 1- (4- Fluorophenyl) -2-dimethylamino-2-benzyl-4-penten-1-one, 1- (4-fluorophenyl) -2-morpholino-2-methyl-4-penten-1-one, 1- (4 -Fluorophenyl) -2-morpholino-2-ethyl-4-penten-1-one, 1- (4-fluorophenyl) -2-morpholino-2-ethyl-4-methyl-4-penten-1-one, 1- (4-fluorophenyl) -2-morpholino-2-ethyl-5-methyl-4-penten-1-one, 1- (4-fluorophenyl) -2-morpholino-2-benzyl-4-pentene- 1-o 1- (3,4-dichlorophenyl) -2-dimethylamino-2-ethyl-4-penten-1-one, 1- (3,5-dichloro-4-methoxyphenyl) -2-morpholino-2-methyl -4-penten-1-one, 1- (4-bromophenyl) -2-morpholino-2-methyl-4-penten-1-one, 1- (4-bromophenyl) -2-morpholino-2-ethyl -4-penten-1-one, 1- (4-bromophenyl) -2-morpholino-2-tert-butyl-4-penten-1-one, 1- (4-methylthiophenyl) -2-dimethylamino- 2-methyl-4-penten-1-one, 1- (4-methylthiophenyl) -2-dimethylamino-2-ethyl-4-penten-1-one, 1- (4-methylthiophenyl) -2-dimethyl Amino- -Phenyl-4-penten-1-one, 1- (4-methylthiophenyl) -2-dimethylamino-2-benzyl-4-penten-1-one, 1- (4-methylthiophenyl) -2-piperidino- 2-ethyl-4-penten-1-one, 1- (4-methylthiophenyl) -2-morpholino-2-methyl-4-penten-1-one, 1- (4-methylthiophenyl) -2-morpholino- 2-ethyl-4-penten-1-one, 1- (4-methylthiophenyl) -2-morpholino-2-ethyl-4-methyl-4-penten-1-one, 1- (4-methylthiophenyl)- 2-morpholino-2-phenyl-4-penten-1-one, 1- (4-methylthiophenyl) -2-morpholino-2-benzyl-4-penten-1-one, 1- (4-ethylthio) Phenyl) -2-morpholino-2-ethyl-4-penten-1-one, 1- (4-isopropylthiophenyl) -2-morpholino-2-methyl-4-penten-1-one, 1- (4- Allylthiophenyl) -2-morpholino-2-ethyl-4-penten-1-one, 1- [4- (2-hydroxyethylthio) phenyl] -2-morpholino-2-methyl-4-pentene-1- ON, 1- [4- (2-hydroxyethylthio) phenyl] -2-morpholino-2-ethyl-4-penten-1-one, 1- [4- (2-hydroxyethylthio) phenyl] -2- Morpholino-2-propyl-4-penten-1-one, 1- [4- (2-hydroxyethylthio) phenyl] -2-morpholino-2-tert-butyl-4-penten-1-one, 1- [ 4- (2 Methoxycarbonylethylthio) phenyl] -2-morpholino-2-methyl-4-penten-1-one, 1- (4-methylsulfonylphenyl) -2-dimethylamino-2-ethyl-4-penten-1-one 1- (4-butylsulfinylphenyl) -2-dimethylamino-2-ethyl-4-penten-1-one, 1- [4- (4-methylphenylthio) phenyl] -2-morpholino-2-ethyl -4-penten-1-one, 1- [4- (4-methylphenylsulfonyl) phenyl] -2-morpholino-2-ethyl-4-methyl-4-penten-1-one, 1- (4-chlorophenyl) Thiophenyl) -2-dimethylamino-2-benzyl-4-penten-1-one, 1- (4-dimethylaminophenyl) -2-dimethylamino-2-methyl -4-penten-1-one, 1- (4-dimethylaminophenyl) -2-dimethylamino-2-ethyl-4-penten-1-one, 1- (4-dimethylaminophenyl) -2-dimethylamino 2-benzyl-4-penten-1-one, 1- (4-dimethylaminophenyl) -2-methylphenylamino-2-ethyl-4-penten-1-one, 1- (4-dimethylaminophenyl) 2- (pyrrolidin-1-yl) -2-methyl-4-penten-1-one, 1- (4-dimethylaminophenyl) -2-morpholino-2-methyl-4-penten-1-one, 1 -(4-Dimethylaminophenyl) -2-morpholino-2-ethyl-4-methyl-4-penten-1-one, 1- (4-dimethylaminophenyl) -2-morpholino-2-benzyl- 4-penten-1-one, 1- (4-dimethylaminophenyl) -2- (2,6-dimethylmorpholin-4-yl) -2-ethyl-4-penten-1-one, 1- (4- Diethylaminophenyl) -2-dimethylamino-2-benzyl-4-penten-1-one, 1- [4-bis (2-methoxyethyl) aminophenyl] -2-morpholino-2-methyl-4-pentene-1 -One, 1- (4-butylaminophenyl) -2-dibutylamino-2-methyl-4-penten-1-one, 1- (4-butylaminophenyl) -2-morpholino-2-methyl-4- Penten-1-one, 1- (4-dibutylaminophenyl) -2-morpholino-2-methyl-4-penten-1-one, 1- (4-diallylaminophenyl) -2-morpholino-2-methyl -4-penten-1-one, 1- [4- (pyrrolidin-1-yl) phenyl] -2-morpholino-2-methyl-4-penten-1-one, 1- (4-piperidinophenyl) 2-piperidino-2-methyl-4-penten-1-one, 1- [4- (piperazin-1-yl) phenyl] -2-dimethylamino-2-ethyl-4-penten-1-one, 1 -[4- (4-Methylpiperazin-1-yl) phenyl] -2-morpholino-2-methyl-4-penten-1-one, 1- [4- (N-methylpiperazin-1-yl) phenyl] 2- (N-methylpiperazin-1-yl) -2-methyl-4-penten-1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2-methyl-4-penten-1- ON, 1- (4-morpholinofeni ) -2-dimethylamino-2-ethyl-4-penten-1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2-isopropyl-4-penten-1-one, 1- (4- Morpholinophenyl)
2-dimethylamino-2-benzyl-4-penten-1-one, 1- (4-morpholinophenyl) -2-diethylamino-2-ethyl-4-penten-1-one, 1- (4-morpholinophenyl) ) -2-di (2-methoxyethyl) amino-2-ethyl-4-penten-1-one, 1- (4-morpholinophenyl) -2-butylmethylamino-2-methyl-4-penten-1- ON, 1- (4-morpholinophenyl) -2-allylmethylamino-2-ethyl-4-penten-1-one, 1- (4-morpholinophenyl) -2-diallylamino-2-ethyl-4-pentene -1-one, 1- (4-morpholinophenyl) -2-benzylmethylamino-2-ethyl-4-penten-1-one, 1- (4-morpholinophenyl) -2- (piperazine 1-yl) -2-ethyl-4-penten-1-one, 1- (4-morpholinophenyl) -2-morpholino-2-methyl-4-penten-1-one, 1- (4-morpholinophenyl) 2-morpholino-2-ethyl-4-penten-1-one, 1- (4-morpholinophenyl) -2-morpholino-2-ethyl-4-penten-1-one-dodecylbenzenesulfonate, 1- (4 -Morpholinophenyl) -2-morpholino-2-ethyl-4-methyl-4-penten-1-one, 1- (4-morpholinophenyl) -2-morpholino-2-benzyl-4-penten-1-one, 1- [4- (2,6-dimethylmorpholin-4-yl) phenyl] -2-morpholin-2-methyl-4-penten-1-one, 1- [4- (2,6-dimethylmorpholine) 4-yl) phenyl] -2- (2,6-dimethylmorpholin-4-yl) -2-ethyl-4-penten-1-one, 1- (N-butylindoline-5-yl) -2-morpholino 2-ethyl-4-penten-1-one, 1- (1,4-dibutyl-1,2,3,4-tetrahydroquinoxalin-6-yl) -2-morpholino-2-ethyl-4-pentene- 1-one, 1- (N-butylcarbazol-3-yl) -2-morpholino-2-ethyl-4-penten-1-one, 1- (5,10-dibutyl-5,10-dihydrophenazine-6 -Yl) -2-dimethylamino-2-methyl-4-penten-1-one, 1- (1,3-benzodioxol-5-yl) -2-morpholino-2-methyl-4-pentene- 1-one, 1- (benzofuran-3- Yl) -2-morpholino-2-ethyl-4-penten-1-one, 1- (benzofuran-6-yl) -2-morpholino-2-ethyl-4-penten-1-one, 1- (2, 3-Dihydrobenzofuran-5-yl) -2-morpholino-2-methyl-4-penten-1-one, 1- (N-methylphenothiazin-2-yl) -2-dimethylamino-2-allyl-4- Penten-1-one, 3,6-di (2-morpholino-2-methyl-4-pentenoyl) -carbazole, 2- (2-dimethylamino-2-allyl-4-pentenoyl) -acridanone, 2- (2 -Morpholino-2-methyl-4-pentenoyl) -xanthone, 2- (4-morpholinobenzoyl) -2-ethyl-N-methyl-1,2,3,6-tetrahydropyridine and the like.

  As hexane-1-one classified into 6 carbon atoms of the basic skeleton, 1- (4-methylthiophenyl) -2-morpholino-2-allyl-hexane-1-one, 1- (4-morpholinophenyl) -2- Dimethylamino-2-benzyl-hexane-1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2-benzyl-4,5,5-trimethyl-hexane-1-one, 1- (4- Morpholinophenyl) -2-butylmethylamino-2- (4-butylbenzyl) -hexane-1-one, 1- (4-morpholinophenyl) -2-dioctylamino-2- (4-methylbenzyl) -hexane- 1-one etc. are mentioned.

  Furthermore, as hexen-1-one, 1- (4-methylthiophenyl) -2-morpholino-2-ethyl-4-methyl-4-hexen-1-one, 1- (4-dimethylaminophenyl) -2- Dimethylamino-2,4,5-trimethyl-4-hexen-1-one, 1- (4-dimethylaminophenyl) -2-morpholino-2-ethyl-4-hexen-1-one, 1- (4- Morpholinophenyl) -2-morpholino-2-ethyl-4-hexen-1-one and the like.

As heptane-1-one classified into carbon number 7 of the basic skeleton, 1- (4-dimethylaminophenyl) -2-dimethylamino-2- [4- (2-methoxy) benzyl] -heptan-1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2-benzyl-heptan-1-one and the like.
Furthermore, as hepta-1,6-diene, 4-benzoyl-4-dimethylamino-hepta-1,6-diene, 4- (4-methoxybenzoyl) -4-dimethylamino-hepta-1,6-diene, 4- (4-methoxybenzoyl) -4-morpholino-hepta-1,6-diene, 4- (3,4-dimethoxybenzoyl) -4-dimethylamino-hepta-1,6-diene, 4- (4- Phenoxybenzoyl) -4-dimethylamino-hepta-1,6-diene, 4- (4-fluorobenzoyl) -4-dimethylamino-hepta-1,6-diene, 4- (4-fluorobenzoyl) -4- Morpholino-hepta-1,6-diene, 4- (4-methylthiobenzoyl) -4-dimethylamino-hepta-1,6-diene, 4- (4-methylthiobenzoyl) -4 Morpholino-hepta-1,6-diene, 4- (4-dimethylaminobenzoyl) -4-dimethylamino-hepta-1,6-diene, 4- (4-dimethylaminobenzoyl) -4-morpholino-hepta-1 , 6-diene, 4- (4-morpholinobenzoyl) -4-dimethylamino-hepta-1,6-diene, 4- (4-morpholinobenzoyl) -4-morpholino-hepta-1,6-diene, etc. It is done.

As octan-1-one classified into 8 carbon atoms of the basic skeleton, 1- (4-morpholinophenyl) -2-dimethylamino-2-benzyl-octane-1-one, 1- (4-morpholinophenyl) -2 -Dimethylamino-2- (4-dodecylbenzyl) -octane-1-one and the like.
When the curable composition of the present invention contains the compound represented by the general formula (I) and the photopolymerization initiator or / and thermal polymerization initiator of the component (B), The component (A) is preferably 20 to 95% by weight, more preferably 30 to 90% by weight, based on the total amount of the curable composition. Moreover, it is preferable that (B) component is 0.1 to 40 weight%, and it is still more preferable that it is 0.2 to 20 weight%. If the component (A) is too much or too little, and if the component (B) is too little, the curability as the curable composition tends to be insufficient, while if the component (B) is too much. , Background stains tend to occur during development.

[1-3] (C) Ethylenically unsaturated compound The curable composition of the present invention may further contain (C) an ethylenically unsaturated compound. The (C) component ethylenically unsaturated compound is preferably contained for the purpose of further improving the curability of the curable composition of the present invention. When the curable composition is irradiated with actinic rays or heated, the ethylenically unsaturated compound contains a photopolymerization initiator and / or a thermal polymerization initiator as the component (B). It is a compound having at least one radically polymerizable ethylenically unsaturated bond in the molecule that undergoes addition polymerization by the action of the system and, in some cases, crosslinks and cures.

  As the ethylenically unsaturated compound of component (C) in the present invention, a compound having one ethylenically unsaturated bond in the molecule, specifically, for example, (meth) acrylic acid, crotonic acid, isocrotonic acid, malein It may be an unsaturated carboxylic acid such as acid, itaconic acid, citraconic acid, and alkyl esters thereof, (meth) acrylonitrile, (meth) acrylamide, styrene, etc., but it is polymerizable, crosslinkable, and the exposed portion associated therewith And a compound having two or more ethylenically unsaturated bonds in the molecule from the viewpoint that the difference in developer solubility between the unexposed portion and the unexposed portion can be enlarged, and the unsaturated bond is (meth) acryloyl. Particularly preferred are acrylate compounds derived from oxy groups.

As the compound having two or more ethylenically unsaturated bonds in the molecule, typically, esters of unsaturated carboxylic acids and polyhydroxy compounds (hereinafter also referred to as ester (meth) acrylates), (meth) Acrylyloxy group-containing phosphates, urethane (meth) acrylates of hydroxy (meth) acrylate compounds and polyisocyanate compounds, and epoxy (meth) of (meth) acrylic acid or hydroxy (meth) acrylate compounds and polyepoxy compounds Examples include acrylates.

  Examples of esters of the unsaturated carboxylic acid and the polyhydroxy compound include the unsaturated carboxylic acid as described above, ethylene glycol, polyethylene glycol (addition number 2 to 14), propylene glycol, polypropylene glycol (addition number 2 to 2). 14), trimethylene glycol, tetramethylene glycol, hexamethylene glycol, trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol, and their ethylene oxide adducts, propylene oxide adducts, diethanolamine, triethanolamine, and other aliphatic groups Reaction product with polyhydroxy compound, specifically, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol, for example (Meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide addition tri (meth) acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, glycerol Propylene oxide-added tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate And similar crotonates, isocrotonates, maleates, itaconates, citraconates, and the like.

  Furthermore, as esters of the unsaturated carboxylic acid and the polyhydroxy compound, the unsaturated carboxylic acid as described above and an aromatic polyhydroxy compound such as hydroquinone, resorcin, pyrogallol, bisphenol F, bisphenol A, or ethylene oxide thereof. Reaction products with adducts, specifically, for example, bisphenol A di (meth) acrylate, bisphenol A bis [oxyethylene (meth) acrylate], bisphenol A bis [glycidyl ether (meth) acrylate], etc. A reaction product of an unsaturated carboxylic acid such as a heterocyclic polyhydroxy compound such as tris (2-hydroxyethyl) isocyanurate, specifically, for example, di (meta) of tris (2-hydroxyethyl) isocyanurate ) Acrylate, tri (me ) Acrylate, etc., or a reaction product of an unsaturated carboxylic acid, a polyvalent carboxylic acid and a polyhydroxy compound, such as a condensate of (meth) acrylic acid, phthalic acid and ethylene glycol, (meth) Examples include condensates of acrylic acid, maleic acid and diethylene glycol, condensates of (meth) acrylic acid, terephthalic acid and pentaerythritol, condensates of (meth) acrylic acid, adipic acid, butanediol and glycerin.

  The (meth) acryloyloxy group-containing phosphates are not particularly limited as long as they are phosphate compounds containing a (meth) acryloyloxy group. Among them, the following general formulas (VIIIa), (VIIIb), or ( Those represented by VIIIc) are preferred.

[In the formulas (VIIIa), (VIIIb) and (VIIIc), R ¹⁰ represents a hydrogen atom or a methyl group, p and p ′ are integers of 1 to 25, and q is 1, 2 or 3. ]
Here, p and p ′ are preferably 1 to 10, and particularly preferably 1 to 4, and specific examples thereof include, for example, (meth) acryloyloxyethyl phosphate, bis [(meth) acryloyloxyethyl] phosphate, (Meth) acryloyloxyethylene glycol phosphate and the like may be mentioned, and these may be used alone or as a mixture.

The urethane (meth) acrylates include, for example, hydroxy (meth) acrylate compounds such as hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, tetramethylolethane tri (meth) acrylate, hexamethylene diisocyanate, Aliphatic polyisocyanates such as aliphatic polyisocyanates such as 1,8-diisocyanate-4-isocyanate methyloctane, cyclohexane diisocyanate, dimethylcyclohexane diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, bicycloheptane triisocyanate , 4,4'-diphenylmethane diisocyanate, tris (isocyanatophenyl)
Examples thereof include a reaction product with an aromatic polyisocyanate such as thiophosphate, a heterocyclic polyisocyanate such as isocyanurate, and a polyisocyanate compound such as isocyanurate.

Among them, as the urethane (meth) acrylates, a compound having 4 or more urethane bonds [—NH—CO—O—] and 4 or more (meth) acryloyloxy groups in one molecule is preferable. Is obtained, for example, by reacting a compound having 4 or more hydroxyl groups in one molecule such as pentaerythritol and polyglycerin with a diisocyanate compound such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate. Compound (i-1) or a compound having two or more hydroxyl groups in one molecule, such as ethylene glycol, "Duranate 24A-100", "Duranate 22A-75PX", "Duranate" manufactured by Asahi Kasei Kogyo Co., Ltd. 21S-75E "," Duranai " 18H-70B "and other biuret types," Duranate P-301-75E "," Duranate E-402-90T "," Duranate E-405-80T ", etc. 1 molecule such as compound (i-2) obtained by reacting a compound having an isocyanate group, or compound (i-3) obtained by polymerizing or copolymerizing isocyanate ethyl (meth) acrylate or the like Compounds having 4 or more, preferably 6 or more isocyanate groups, such as “Duranate ME20-100” (i) manufactured by Asahi Kasei Kogyo Co., Ltd., pentaerythritol di (meth) acrylate, di Pentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipenta It is obtained by reacting a compound (ii) having one or more hydroxyl groups and two or more, preferably three or more (meth) acryloyloxy groups in one molecule, such as lithitol penta (meth) acrylate. be able to.

  Here, the molecular weight of the compound (i) is preferably 500 to 200,000, and particularly preferably 1,000 to 150,000. The molecular weight of the urethane (meth) acrylates as described above is preferably 600 to 150,000. Further, it preferably has 6 or more urethane bonds, particularly preferably 8 or more, more preferably 6 or more (meth) acryloyloxy groups, and particularly preferably 8 or more.

  In addition, such urethane (meth) acrylates include, for example, the compound (i) and the compound (ii) between the former isocyanate group and the latter hydroxyl group in an organic solvent such as toluene and ethyl acetate. It can be produced by a method of reacting at a molar ratio of 1/10 to 10/1 at 10 to 150 ° C. for about 5 minutes to 3 hours using a catalyst such as n-butyltin dilaurate as necessary. it can.

  In the present invention, among the urethane (meth) acrylates, those represented by the following general formula (IX) are particularly preferable.

[In the formula (IX), Ra represents a group having a repeating structure of an alkyleneoxy group or an aryleneoxy group and 4 to 20 oxy groups capable of bonding to Rb, and Rb and Rc are each independently a carbon. An alkylene group having a number of 1 to 10, Rd represents an organic residue having 1 to 10 (meth) acryloyloxy groups, Ra, Rb, Rc and Rd may have a substituent; x is an integer of 4 to 20, y is an integer of 0 to 15, and z is an integer of 1 to 15. ]
Here, as the repeating structure of the alkyleneoxy group of Ra in the formula (XI), for example, those derived from propylenetriol, glycerin, pentaerythritol and the like, and as the repeating structure of the aryleneoxy group, for example, pyrogallol , 1,3,5-benzenetriol and the like. Moreover, it is preferable that the carbon number of the alkylene group of Rb and Rc is respectively independently 1-5, and it is preferable that the (meth) acryloyloxy group in Rd is 1-7. Further, x is preferably 4 to 15, y is 1 to 10, and z is 1 to 10.

  Furthermore, as Ra, the following formula [wherein, k is an integer of 2 to 10. And Rb and Rc are each independently a dimethylene group, a monomethyldimethylene group or a trimethylene group, and Rd is particularly preferably represented by the following formula: .

  Moreover, as the epoxy (meth) acrylates, specifically, for example, (meth) acrylic acid, or a hydroxy (meth) acrylate compound as described above, (poly) ethylene glycol polyglycidyl ether, (poly) propylene Glycol polyglycidyl ether, (poly) tetramethylene glycol polyglycidyl ether, (poly) pentamethylene glycol polyglycidyl ether, (poly) neopentyl glycol polyglycidyl ether, (poly) hexamethylene glycol polyglycidyl ether, (poly) trimethylol Aliphatic polyepoxy compounds such as propane polyglycidyl ether, (poly) glycerol polyglycidyl ether, (poly) sorbitol polyglycidyl ether, phenol novolac polyepoxy Aromatic compounds such as brominated phenol novolac polyepoxy compounds, (o-, m-, p-) cresol novolac polyepoxy compounds, bisphenol A polyepoxy compounds, bisphenol F polyepoxy compounds, sorbitan polyglycidyl ethers And a reaction product with a polyepoxy compound such as a heterocyclic polyepoxy compound such as triglycidyl isocyanurate and triglycidyl tris (2-hydroxyethyl) isocyanurate.

  In addition to the above, other ethylenically unsaturated compounds include, for example, (meth) acrylamides such as ethylenebis (meth) acrylamide, allyl esters such as diallyl phthalate, vinyl group-containing compounds such as divinyl phthalate, Thioether bond-containing compounds in which the ether bond of the ether bond-containing ethylenically unsaturated compound is sulfurized with phosphorus pentasulfide or the like to convert it to a thioether bond to improve the crosslinking rate, and for example, Japanese Patent No. 3164407 and JP The polyfunctional (meth) acrylate compound and silica sol having a particle diameter of 5 to 30 nm (for example, isopropanol-dispersed organosilica sol (“IPA-ST” manufactured by Nissan Chemical Industries, Ltd.)), methyl ethyl ketone-dispersed organosilica sol ( “ME” manufactured by Nissan Chemical Co., Ltd. -ST "), methyl isobutyl ketone-dispersed organosilica sol (" MIBK-ST "manufactured by NISSAN CHEMICAL CO., LTD.)], Etc.] using an isocyanate group or a mercapto group-containing silane coupling agent. Examples include compounds in which the strength and heat resistance of a cured product are improved by reacting and bonding a silica sol with a saturated compound via a silane coupling agent.

  These ethylenically unsaturated compounds may be used alone or in combination of two or more. In the present invention, ester (meth) acrylates, (meth) acryloyloxy group-containing phosphates, or urethane (meth) acrylates are preferred as the ethylenically unsaturated compound of component (C) above, and ester (meth) Acrylates are particularly preferred, and among their ester (meth) acrylates, they contain polyoxyalkylene groups such as polyethylene glycol, polypropylene glycol, or polyethylene oxide adducts of bisphenol A, and contain two or more (meth) acryloyloxy groups. Particularly preferred are ester (meth) acrylates.

  In the curable composition of the present invention, the content of the ethylenically unsaturated compound as the component (C) is preferably 1 to 70% by weight, and 5 to 60% by weight with respect to the total amount of the curable composition. % Is more preferable. When the component (C) is less than the above range, the curability as the curable composition tends to be insufficient, whereas when it exceeds the range, the tackiness tends to be insufficient.

[1-4] (D) Epoxy Compound The curable composition of the present invention may further contain (D) an epoxy compound. Component (D) is an epoxy compound for the purpose of improving the heat resistance and chemical resistance of the cured product when the curable composition of the present invention is used for solder resist, overcoat, rib or spacer. , May be contained. The epoxy compound comprises a repeating unit of a so-called epoxy resin, a polyglycidyl ether compound obtained by reacting a polyhydroxy compound and epichlorohydrin, a polyglycidyl ester compound obtained by reacting a polycarboxylic acid compound and epichlorohydrin, and And compounds ranging from low molecular weight substances to high molecular weight substances, such as polyglycidylamine compounds obtained by reacting polyamine compounds and epichlorohydrin.

  Examples of the polyglycidyl ether compound include diglycidyl ether type epoxy of polyethylene glycol, diglycidyl ether type epoxy of bis (4-hydroxyphenyl), and diglycidyl ether of bis (3,5-dimethyl-4-hydroxyphenyl). Type epoxy, diglycidyl ether type epoxy of bisphenol F, diglycidyl ether type epoxy of bisphenol A, diglycidyl ether type epoxy of tetramethylbisphenol A, diglycidyl ether type epoxy of ethylene oxide added bisphenol A, phenol novolac type epoxy, cresol novolac These polyglycidyl ether compounds react with the remaining hydroxyl groups by reacting acid anhydrides or divalent acid compounds, etc. Or it may be obtained by introducing a sill group.

  Examples of the polyglycidyl ester compound include a diglycidyl ester type epoxy of hexahydrophthalic acid, a diglycidyl ester type epoxy of phthalic acid, and examples of the polyglycidyl amine compound include bis (4- Aminophenyl) methane diglycidylamine type epoxy, isocyanuric acid triglycidylamine type epoxy, and the like.

  In the curable composition of the present invention, the content of the epoxy compound as the component (D) is preferably 1 to 70% by weight, and 5 to 50% by weight with respect to the total amount of the curable composition. Is more preferable. When the component (D) is less than the above range, the curability as the curable composition tends to be insufficient. On the other hand, when the component is over the range, problems such as omission of non-image areas are liable to occur during development. .

[1-5] (E) Epoxy Curing Agent The curable composition of the present invention may further contain (E) an epoxy curing agent. The (E) component epoxy curing agent is preferably used together with the (D) component epoxy compound for the purpose of improving the curability of the curable composition. Examples of the epoxy curing agent for the component (E) include succinic anhydride, maleic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, 4 -Methyltetrahydrophthalic anhydride, 3-ethyltetrahydrophthalic anhydride, 4-ethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic acid Polyhydric carboxylic anhydrides such as anhydride, 3-ethylhexahydrophthalic anhydride, 4-ethylhexahydrophthalic anhydride, trimellitic anhydride, biphenyltetracarboxylic anhydride, tributylphosphine, triphenyl Organic phosphines such as phosphine and tris-2-cyanoethylphosphine, imidazo 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1- (2-cyanoethyl) -2-phenylimidazole, 1- (2-cyanoethyl) ) Imidazoles such as 2-ethyl-4-methylimidazole, dicyandiamide, benzylmethylamine, 4-methylbenzyl-N, N-dimethylamine, 4-methoxybenzyl-N, N-dimethylamine, 4-dimethylaminobenzyl Amine compounds such as -N, N-dimethylamine, 2,4,6-triamino-s-triazine, 2-vinyl-4,6-diamino-s-triazine, 2-vinyl-4,6-diamino-s -Triazine / isocyanuric acid adduct, 2,4-diamino-6-methacryloylo Amino-s-triazines such as ciethyl-s-triazine, 2,4-diamino-6-methacryloyloxyethyl-s-triazine / isocyanuric acid adduct, and quaternary ammonium salts such as benzyltrimethylammonium chloride and phenyltributylammonium chloride , Phosphonium salts such as tri-n-butyl-2,5-dihydroxyphenyl-phosphonium bromide, hexadecyltributylphosphonium chloride, etc. Among these, those having an —NH— group are preferred, and amine compounds and Amino-s-triazines are preferred, and dicyandiamide and 2,4,6-triamino-s-triazine are particularly preferred.
In the curable composition of the present invention, the content of the epoxy curing agent as the component (E) is 1% by weight or less based on the total amount of the curable composition from the viewpoint of temporal stability as the curable composition. It is preferable that it is 0.7 wt% or less.

[1-6] (F) Amino Compound The curable composition of the present invention may further contain (F) an amino compound. The amino compound (F) is preferably contained for the purpose of improving the heat resistance and chemical resistance of the cured product. Examples of the amino compound of component (F) include an amino compound having at least two methylol groups as functional groups and an alkoxymethyl group obtained by condensation-modifying an alcohol having 1 to 8 carbon atoms, such as melamine and formaldehyde. Melamine resin polycondensed, benzoguanamine resin polycondensed benzoguanamine and formaldehyde, glycoluril resin polycondensed glycoluril and formaldehyde, urea resin polycondensed urea and formaldehyde, melamine, benzoguanamine, glycol Examples thereof include resins obtained by copolycondensation of two or more types such as uril or urea and formaldehyde, and modified resins obtained by alcohol condensation modification of methylol groups of these resins. Among them, in the present invention, a melamine resin and a modified resin thereof are preferable, a modified resin having a methylol group modification ratio of 70% or more is more preferable, and a modified resin of 80% or more is particularly preferable.

As specific examples of amino compounds of these (F) components, as melamine resins and modified resins thereof, “Cymel” (registered trademark) 300, 301, 303, 350, 736, 738, 370, 771, 325 of Mitsui Cytec Co., Ltd. 327, 703, 701, 266, 267, 285, 232, 235, 238, 1141, 272, 254, 202, 1156, 1158, and “Nicarac” (registered trademark) E-2151, MW- from Sanwa Chemical Co., Ltd. 100LM, MX-750LM, as benzoguanamine resin and its modified resin, "Cymel" (registered trademark) 1123, 1125, 1128, and as glycoluril resin and its modified resin, "Cymel" (registered trademark) 1170, 1171, 1174, 1172 and “Nikarak” (registered trademark) MX-270, also, as a urea resin and a modified resin, Mitsui Cytec's "UFR" (registered trademark) 65,300, and "NIKALAC" (registered trademark) MX-290, and the like.
In the curable composition of the present invention, the content ratio of the amino compound of the component (F) is preferably 20% by weight or less, and preferably 10% by weight or less, based on the total amount of the curable composition. Further preferred.

[1-7] (G) Polymerization Accelerator The curable composition of the present invention may further contain (G) a polymerization accelerator. (G) The polymerization accelerator may be contained for the purpose of improving the polymerization initiation ability of the curable composition. As the polymerization accelerator of the component (G), an ester of an amino acid or a bipolar ion compound is preferable, and the ester or bipolar ion compound of the amino acid is preferably one represented by the following general formula (Xa) or (Xb).

[In the formulas (Xa) and (Xb), each of R ³⁹ and R ⁴⁰ independently has an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. An optionally substituted heterocyclic group or a hydrogen atom, R ⁴¹ and R ⁴² each independently represents an optionally substituted alkyl group or a hydrogen atom, and R ⁴³ represents a substituent. Represents an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or an aryl group that may have a substituent, and R ⁴⁴ may have a substituent. The alkyl group, the aryl group which may have a substituent, or the heterocyclic group which may have a substituent is shown, and s is an integer of 0-10. ]
Here, the alkyl groups of R ³⁹ , R ⁴⁰ , R ⁴¹ , R ⁴² , R ⁴³ , and R ⁴⁴ in formulas (Xa) and (Xb) preferably have 1 to 8 carbon atoms. More preferably, it is ~ 4. Examples of the alkenyl group for R ⁴³ include a vinyl group, allyl group, and isopropenyl group. Examples of the aryl group for R ³⁹ , R ⁴⁰ , R ⁴¹ , and R ⁴⁴ include a phenyl group and naphthyl group. Examples of the heterocyclic group of R ³⁹ , R ⁴⁰ , and R ⁴⁴ include a furyl group, a furanyl group, a pyrrolyl group, and a pyridyl group.

Examples of the substituent in the alkyl group and alkenyl group include an alkoxy group, an alkoxycarbonyl group, an alkenyloxy group, an alkenyloxycarbonyl group, a phenyl group, and a halogen atom. Examples of the substituent in the cyclic group include an alkyl group which may further have a substituent such as an alkoxy group or a phenyl group, an alkoxy group, an alkenyl group, an alkenyloxy group, an acyl group, an acyl group. , Also alkoxycarbonyl group, also phenoxy group,
Similarly, an alkylthio group, an alkylsulfonyl group, an aldehyde group, a carboxyl group, a hydroxyl group, a sulfo group, a nitro group, a cyano group, a halogen atom and the like can be mentioned.

In the present invention, in the amino acid ester or bipolar ion compound represented by the general formula (Xa) or (Xb), one of R ³⁹ and R ⁴⁰ in the formula (Xa) is a hydrogen atom and the other is A phenyl group which may have a substituent, R ⁴¹ and R ⁴² are both hydrogen atoms, and R ⁴³ may have an alkyl group which may have a substituent, or a substituent. A good phenyl group and an amino acid ester in which s is 0, 1, or 2, or R ³⁹ and R ^{40 in} formula (Xb) are both hydrogen atoms, or one of them has a substituent. R ⁴¹ and R ⁴² are both hydrogen atoms, R ⁴⁴ is an optionally substituted alkyl group, or an optionally substituted phenyl group, and s Is preferably an amino acid dipolar compound in which is 0, 1, or 2, and in the general formula (Xa), s 0, while the other is a phenyl group whose hydrogen atom R ³⁹ and R ^40, an ester of a certain N- phenylglycine R ⁴¹ and R ⁴² are both hydrogen atoms, especially, R ⁴³ is a benzyl group N- phenylglycine Bipolar of benzyl ester or N-phenylglycine in which s is 0, R ³⁹ , R ⁴⁰ , R ⁴¹ and R ⁴² are all hydrogen atoms and R ⁴⁴ is a phenyl group in the general formula (Xb) Ionic compounds are particularly preferred.

In the present invention, the polymerization accelerator of component (G) may further contain a polymerization accelerator other than the amino acid ester or the bipolar ion compound. Examples of the polymerization accelerator include 2- Mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4-triazole, 2-mercapto-4 (3H) -quinazoline, β-mercaptonaphthalene, ethylene glycol dithiopropionate Mercapto group-containing compounds such as trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopropionate, hexanedithiol, trimethylolpropane tristhioglyconate, pentaerythritol tetrakisthiopropionate, etc. Thiol compounds, N, N-dialkylaminobenzoic acid esters, N-phenylglycine or derivatives thereof such as ammonium salts and sodium salts thereof, phenylalanine or salts thereof such as ammonium and sodium salts, derivatives such as esters, etc. Examples include amino acids having an aromatic ring or derivatives thereof.
In the curable composition of the present invention, the content ratio of the polymerization accelerator of the component (G) is preferably 20% by weight or less, and preferably 10% by weight or less based on the total amount of the curable composition. Is more preferable.

[1-8] (H) Inorganic Filler The inorganic filler of component (H) used in the curable composition of the present invention may be contained for the purpose of improving the strength as a cured product. good. Examples of the inorganic filler of the component (H) include talc, silica, alumina, barium sulfate, magnesium oxide and the like.
In the curable composition of the present invention, the content of the inorganic filler as the component (H) is preferably 70% by weight or less, more preferably 50% by weight or less based on the total amount of the curable composition. Is more preferable.

[1-9] (I) Surfactant Further, the surfactant (I) used in the curable composition of the present invention is improved in coating property and developing property as a coating solution of the curable composition. For the purpose, etc., it may be contained. Specific examples include nonionic, anionic, cationic, amphoteric, and fluorine-based surfactants. More specifically, for example, as the nonionic surfactant, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene alkyl esters, Oxyethylene fatty acid esters, glycerin fatty acid esters, polyoxyethylene glycerin fatty acid esters, pentaerythritol fatty acid esters, polyoxyethylene pentaerythritol fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, sorbit Fatty acid esters, polyoxyethylene sorbite fatty acid esters and the like, and anionic surfactants include alkyl sulfonates, alkyl benzes. Sulfonates, alkyl naphthalene sulfonates, polyoxyethylene alkyl ether sulfonates, alkyl sulfates, alkyl sulfate esters, higher alcohol sulfates, aliphatic alcohol sulfates, polyoxyethylene alkyl ether sulfates, poly Oxyethylene alkylphenyl ether sulfates, alkyl phosphate esters, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkylphenyl ether phosphates, etc., and cationic surfactants include quaternary ammonium salts, imidazolines. Derivatives, amine salts and the like, and amphoteric surfactants include betaine-type compounds, imidazolium salts, imidazolines and amino acids.
In the curable composition of the present invention, the content of the surfactant as the component (I) is preferably 10% by weight or less, preferably 5% by weight or less, based on the total amount of the curable composition. Is more preferable.

[1-10] (J) Sensitizing dye Furthermore, the sensitizing dye of component (J) used in the curable composition of the present invention is contained for the purpose of improving the photosensitivity of the curable composition. Is preferred. As the sensitizing dye, it is a light-absorbing dye having an absorption maximum in a blue-violet region having a wavelength of 350 to 430 nm. Among them, dialkylaminobenzene compounds, pyromethene compounds, trihydroxypyrimidine derivatives, etc. System compounds are preferred.

The preferred dialkylaminobenzene compounds include, among others, dialkylaminobenzophenone compounds, dialkylaminobenzene compounds having a heterocyclic group as a substituent at a carbon atom in the p-position with respect to the amino group on the benzene ring, and benzene rings. Dialkylaminobenzene compounds having a substituent containing a sulfonylimino group at the carbon atom in the p-position with respect to the amino group above, and dialkylaminobenzene compounds having a carbostyryl skeleton are preferred.
As the dialkylaminobenzophenone-based compound, those represented by the following general formula (XI) are preferable.

[In formula (XI), R ¹¹ , R ¹² , R ¹⁵ , and R ¹⁶ each independently represents an alkyl group which may have a substituent, and R ¹³ , R ¹⁴ , R ¹⁵ , and R ¹⁶ each independently represents an alkyl group which may have a substituent, or a hydrogen atom, and R ¹¹ and R ¹² , R ¹¹ and R ¹³ , R ¹² and R ¹⁴ , R ¹⁵ and R ¹⁶ , R ¹⁵ and R ¹⁷ , and R ¹⁶ and R ¹⁸ may each independently form a nitrogen-containing heterocyclic ring. ]
Here, the carbon number of the alkyl group of R ¹¹ , R ¹² , R ¹⁵ , and R ¹⁶ in the formula (XI) and the carbon when R ¹³ , R ¹⁴ , R ¹⁷ , and R ¹⁸ are alkyl groups The number is preferably 1-6. Further, when forming a nitrogen-containing heterocyclic ring is preferably a 5- or 6-membered ring, R ¹¹ and R ^13, R ¹²
And R ¹⁴ , R ¹⁵ and R ¹⁷ , or R ¹⁶ and R ¹⁸ preferably form a 6-membered tetrahydroquinoline ring, and R ¹¹ , R ¹² , R ¹³ and R ¹⁴ , and / or R ^It is particularly preferred that ¹⁵ and R ¹⁶ , R ¹⁷ and R ¹⁸ form a julolidine ring. Furthermore, a tetrahydroquinoline ring having an alkyl group as a substituent at the 2-position or a julolidine ring containing the tetrahydroquinoline ring is particularly preferred.

Specific examples of the compound represented by the general formula (XI) include, for example, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, and
Examples include compounds having the following structure.

  In addition, the heterocyclic group in the dialkylaminobenzene compound having a heterocyclic group as a substituent at a carbon atom in the p-position with respect to the amino group on the benzene ring includes a nitrogen atom, an oxygen atom, or a sulfur atom. Alternatively, a 6-membered ring is preferable, a 5-membered ring having a condensed benzene ring is particularly preferable, and a compound represented by the following general formula (XII) is preferable.

[In Formula (XII), R ¹⁹ and R ²⁰ each independently represents an optionally substituted alkyl group, and R ²¹ and R ²² each independently represent a substituent. R ¹⁹ and R ²⁰ , R ¹⁹ and R ²¹ , and R ²⁰ and R ²² may each independently form a nitrogen-containing heterocyclic ring, , An oxygen atom, a sulfur atom, a dialkylmethylene group, an imino group, or an alkylimino group, and the benzene ring condensed to the heterocyclic ring may have a substituent. ]
Here, the carbon number of the alkyl group of R ¹⁹ and R ²⁰ in the formula (XII), and the carbon number when R ²¹ and R ²² are an alkyl group are preferably 1 to 6, and when forming a nitrogen heterocycle is preferably a 5- or 6-membered ring, is preferably R ¹⁹ and R ^21, R ²⁰ and R ²² form a tetrahydroquinoline ring of 6-membered ring, and R ¹⁹ It is particularly preferred that R ²⁰ , R ²¹ and R ²² form a julolidine ring. Furthermore, a tetrahydroquinoline ring having an alkyl group as a substituent at the 2-position or a julolidine ring containing the tetrahydroquinoline ring is particularly preferred. In addition, when X is a dialkylmethylene group, the alkyl group preferably has 1 to 6 carbon atoms, and when it is an alkylimino group, the alkyl group preferably has 1 to 6 carbon atoms.

  Specific examples of the compound represented by the general formula (XII) include 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, and 2- (p-dimethylaminophenyl). ) Benzo [4,5] benzoxazole, 2- (p-dimethylaminophenyl) benzo [6,7] benzoxazole, 2- (p-dimethylaminophenyl) benzothiazole, 2- (p-diethylaminophenyl) benzothiazole 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2- (p-dimethylaminophenyl) -3,3-dimethyl-3H-indole, 2- (p-diethylamino) Phenyl) -3,3-dimethyl-3H-indole, and Compounds of the serial structure.

  Examples of the dialkylaminobenzene compound other than the compound represented by the general formula (XII) having a heterocyclic group as a substituent at a carbon atom at the p-position with respect to the amino group on the benzene ring include: 2- (p-dimethylaminophenyl) pyridine, 2- (p-diethylaminophenyl) pyridine, 2- (p-dimethylaminophenyl) quinoline, 2- (p-diethylaminophenyl) quinoline, 2- (p-dimethylaminophenyl) ) Pyrimidine, 2- (p-diethylaminophenyl) pyrimidine, 2,5-bis (p-diethylaminophenyl) -1,3,4-oxadiazole, 2,5-bis (p-diethylaminophenyl) -1,3 , 4-thiadiazole and the like.

  Moreover, as the dialkylaminobenzene compound having a substituent containing a sulfonylimino group at the p-position carbon atom with respect to the amino group on the benzene ring, a compound represented by the following general formula (XIII) is preferable.

[In the formula (XIII), R ²³ and R ²⁴ each independently represents an optionally substituted alkyl group, and R ²⁵ and R ²⁶ each independently represent a substituent. also alkyl group, or a hydrogen atom, R ²³ and R ^24, R ²³ and R ^25, and each, independently of R ²⁴ and R ^26, may form a nitrogen-containing heterocycle, R ²⁷ Represents a monovalent group or a hydrogen atom, and R ²⁸ represents a monovalent group. ]
Here, the carbon number of the alkyl group of R ²³ and R ²⁴ in formula (XIII), and the carbon number when R ²⁵ and R ²⁶ are an alkyl group are preferably 1 to 6, and When forming a nitrogen heterocycle, it is preferably a 5- or 6-membered ring, but R ²⁵ and R ²⁶ are preferably hydrogen atoms. Examples of the monovalent group of R ²⁷ and R ²⁸ include an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkoxy group, an alkenyloxy group, an acyl group, an acyloxy group, an aryl group, an aryloxy group, Aralkyl group, arylalkenyl group, hydroxy group, formyl group, carboxyl group, carboxylic acid ester group, carbamoyl group, amino group, acylamino group, carbamate group, sulfonamido group, sulfonic acid group, sulfonic acid ester group, sulfamoyl group, alkylthio Group, imino group, cyano group, heterocyclic group and the like. Of these, R ²⁷ is preferably a hydrogen atom, and R ²⁸ is preferably an aryl group.
Further, as the dialkylaminobenzene compound having a carbostyril skeleton, those represented by the following general formula (XIV) are preferable.

[In the formula (XIV), R ²⁹ , R ³⁰ and R ³³ each independently represents an optionally substituted alkyl group, and R ³¹ and R ³² each independently represents a substituent. An alkyl group which may have, or a hydrogen atom, R ²⁹ and R ³⁰ , R ²⁹ and R ³¹ , and R ³⁰ and R ³² may each independently form a nitrogen-containing heterocycle; R ³⁴ represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or a hydrogen atom. ]
Here, the carbon number of the alkyl group of R ²⁹ , R ³⁰ , and R ³³ in formula (XIV), and the carbon number when R ³¹ , R ³² , and R ³⁵ are alkyl groups are 1-6. It is preferable that when a nitrogen-containing heterocycle is formed, a 5- or 6-membered ring is preferable, but R ³¹ and R ³² are preferably hydrogen atoms. R ³⁴ is preferably a phenyl group.

  As the sensitizing dye of the component (J), in the present invention, a dialkylaminobenzophenone compound represented by the general formula (XI), an amino group on the benzene ring represented by the general formula (XIII) A dialkylaminobenzene compound having a substituent containing a sulfonylimino group at the p-position carbon atom, or a dialkylaminobenzene compound having a carbostyryl skeleton represented by the general formula (XIV): Particularly preferred.

  In the curable composition of the present invention, the content of the sensitizing dye of the component (J) is preferably 0.01 to 20% by weight with respect to the total amount of the curable composition, More preferably, it is 10% by weight. If the component (J) is less than the above range, the photocurability as the curable composition tends to be insufficient, while if it exceeds the above range, background staining tends to occur during development.

Moreover, it is preferable that the curable composition of this invention has the maximum peak of spectral sensitivity in the wavelength range of 350-430 nm, and it is still more preferable to have the maximum peak of spectral sensitivity in the wavelength range of 390-430 nm. When having a maximum peak of spectral sensitivity in a wavelength range less than the above range, the sensitivity to laser light having a wavelength of 350 to 430 nm tends to be inferior as a photocurable composition, whereas, when having in a wavelength range exceeding the above range. Tends to be inferior in safe light under yellow light. The wavelength range of the maximum peak of these spectral sensitivities can be adjusted by appropriately selecting each component constituting the curable composition. In particular, the photopolymerization initiator and / or the thermal polymerization initiator of the component (B) And it can adjust with the kind and content of the sensitizing dye of (J) component.

  In the present invention, the maximum peak of spectral sensitivity is, for example, as described in detail in “Photopolymer Technology” (Akio Yamaoka, published by Nikkan Kogyo Shimbun, 1988, page 262), etc. Light spectrally divided from a light source such as a xenon lamp or a tungsten lamp using a photosensitivity image-forming material sample having a photocurable composition layer formed on the substrate surface is linearly exposed in the horizontal axis direction. In particular, the exposure intensity is set to change logarithmically in the vertical axis direction, and exposure is performed after irradiation, and then development processing is performed, whereby an image corresponding to the sensitivity of each exposure wavelength is obtained. The maximum energy in the spectral sensitivity curve obtained by calculating the exposure energy that can be formed from the image and plotting the wavelength on the horizontal axis and the reciprocal of the exposure energy on the vertical axis.

  In the curable composition of the present invention, when a blue-violet semiconductor laser is used as an exposure light source, the minimum exposure amount [S410] capable of forming an image at a wavelength of 410 nm is preferably 50 mJ / cm 2 or less, and 30 mJ / cm 2. More preferably, it is more preferably 20 mJ / cm 2 or less. When the minimum exposure amount [S410] exceeds the above range, although depending on the exposure intensity of the laser light source, the exposure time becomes long and the utility tends to be lowered. Although the lower limit of the minimum exposure [S410] is preferably as small as possible, it is usually 1 mJ / cm 2 or more.

The ratio [S410 / S450] of [S410] to the minimum exposure amount [S450 (mJ / cm @ 2)] capable of forming an image at a wavelength of 450 nm is preferably 0.1 or less, and is 0.05 or less. Is more preferable. If this ratio [S410 / S450] exceeds the above range, it tends to be difficult to achieve both the blue-violet laser sensitivity and the safelight property under a yellow lamp.
Further, the ratio [S450-650 (mJ / cm @ 2)] of the minimum exposure capable of forming an image at each wavelength of 450 nm to 650 nm to the minimum exposure [S450 (mJ / cm @ 2)] capable of forming an image at a wavelength of 450 nm. S450-650 / S450] is preferably more than 1. If this ratio [S450-650 / S450] is less than the above range, it tends to be difficult to achieve both blue-violet laser sensitivity and safe light performance under a yellow lamp.

  The minimum exposure amount [S410] capable of forming an image at a wavelength of 410 nm, the minimum exposure amount [S450] capable of forming an image at a wavelength of 450 nm, and the minimum exposure amount capable of forming an image at each wavelength of more than 450 nm and not more than 650 nm [ S450-650 (mJ / cm @ 2)] is obtained as the exposure energy capable of image formation calculated from the obtained image height in the measurement of the maximum peak of spectral sensitivity using the above-described spectral sensitivity measuring apparatus. The minimum exposure amount that can form an image under optimum development conditions determined by changing development conditions such as the type of developer, development temperature, development time, etc., and the optimum development condition is usually pH 11 A condition of immersing in an alkali developer of ˜14 at a temperature of 25 ° C. for 0.5 to 3 minutes is employed.

[1-11] (K) Other Alkali-Soluble Resin The alkali-soluble resin (K) used in the curable composition of the present invention may be contained as a binder of the curable composition. As the alkali-soluble resin, for example, (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylonitrile, (meth) acrylamide, maleic acid, styrene, vinyl acetate, vinylidene chloride, maleimide, etc. Examples of such polymers include acid-modified epoxy acrylates, polyamides, polyesters, polyethers, polyurethanes, polyvinyl butyrals, polyvinyl alcohols, polyvinyl pyrrolidones, and acetyl celluloses. Resins and acid-modified epoxy acrylates are preferred.

Specific examples of the carboxyl group-containing vinyl resin include (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid and other unsaturated carboxylic acids, and styrene. , Α-methylstyrene, hydroxystyrene, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, dodecyl (meth) acrylate , 2-ethylhexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, isobonyl (meth) acrylate, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycy Zir (meth) acrylate, benzyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N- (meth) acryloylmorpholine, (meth) acrylonitrile, (meth) acrylamide, N-methylol (meth) acrylamide, Examples thereof include copolymers with vinyl compounds such as N, N-dimethyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide, and vinyl acetate.

  Among these, a styrene- (meth) acrylate- (meth) acrylic acid copolymer is preferable, and 3-30 mol% of styrene, 10-70 mol% of (meth) acrylate, 10-60 mol% of (meth) acrylic acid. A copolymer consisting of 5 to 25 mol% of styrene, 20 to 60 mol% of (meth) acrylate, and 15 to 55 mol% of (meth) acrylic acid is particularly preferable. These carboxyl group-containing vinyl resins preferably have an acid value of 30 to 250 mg · KOH / g and a polystyrene-equivalent weight average molecular weight of 1,000 to 300,000.

  Furthermore, as the carboxyl group-containing vinyl resin, those having an ethylenically unsaturated bond in the side chain are suitable. Specifically, for example, allyl glycidyl ether, glycidyl (meth) acrylate is added to the carboxyl group-containing polymer. , Α-ethyl glycidyl (meth) acrylate, glycidyl crotonate, glycidyl isocrotonate, crotonyl glycidyl ether, itaconic acid monoalkyl monoglycidyl ester, fumaric acid monoalkyl monoglycidyl ester, maleic acid monoalkyl monoglycidyl ester, etc. Group epoxy group-containing unsaturated compound, or 3,4-epoxycyclohexylmethyl (meth) acrylate, 2,3-epoxycyclopentylmethyl (meth) acrylate, 7,8-epoxy [tricyclo [5.2.1. ] Dec-2-yl] An alicyclic epoxy group-containing unsaturated compound such as oxymethyl (meth) acrylate, 5 to 90 mol%, preferably about 30 to 70 mol% of the carboxyl group of the carboxyl group-containing polymer Reaction products obtained by reacting allyl (meth) acrylate, 3-allyloxy-2-hydroxypropyl (meth) acrylate, cinnamyl (meth) acrylate, crotonyl (meth) acrylate, methallyl (meth) acrylate, Compounds having two or more unsaturated groups such as N, N-diallyl (meth) acrylamide, or vinyl (meth) acrylate, 1-chlorovinyl (meth) acrylate, 2-phenylvinyl (meth) acrylate, 1- Propenyl (meth) acrylate, vinyl crotonate, vinyl (meth) a The ratio of the compound having two or more unsaturated groups such as chloramide and the unsaturated carboxylic acid such as (meth) acrylic acid or further unsaturated carboxylic acid ester to the whole compound having the unsaturated group. The reaction product etc. which were copolymerized so that it may become 10-90 mol%, preferably about 30-80 mol% are mentioned. Moreover, the reaction product of an epoxy group-containing polymer and an ethylenically unsaturated compound having a functional group capable of reacting with an epoxy group such as a carboxyl group or a hydroxyl group can also be mentioned.

The acid-modified epoxy acrylates can be obtained by further reacting a reaction product of an epoxy group-containing compound and an unsaturated group-containing carboxylic acid or its anhydride with a polybasic carboxylic acid or its anhydride (c). A compound. Furthermore, a resin in which an epoxy group-containing compound is further added to a part of the carboxyl group in the compound may be used. The production can be performed by a known method.

Examples of the epoxy group-containing compound include an epoxy compound described in JP-A-2001-174621 [a compound (a) having two or more epoxy groups in one molecule in the publication]. Bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol S type epoxy compound, biphenyl glycidyl ether, phenol novolac type epoxy compound, cresol novolac type epoxy compound, triglycidyl isocyanurate, alicyclic epoxy Examples of the compound include an epoxy compound having a polyadduct structure of a cyclic hydrocarbon compound having two or more unsaturated groups per molecule and a phenol, and a copolymerization type epoxy compound.
In the curable composition of the present invention, the content ratio of the alkali-soluble resin of the component (K) is preferably 70% by weight or less, and 40% by weight or less with respect to the total amount of the curable composition. Is more preferable.

[1-12] (L) Coloring Material When the curable composition of the present invention is used for a color filter or a black matrix, it is preferable to use a coloring material. Here, a coloring material means what colors the curable composition which concerns on this invention. As the coloring material, dyes and pigments can be used, but pigments are preferable from the viewpoint of heat resistance, light resistance and the like. As the pigment, various color pigments such as a blue pigment, a green pigment, a red pigment, a yellow pigment, a purple pigment, an orange pigment, a brown pigment, and a black pigment can be used. In addition to organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene, various inorganic pigments can be used. It is. Hereinafter, specific examples of usable pigments are indicated by pigment numbers. Terms such as “CI Pigment Red 2” mentioned below mean the color index (CI).

  Examples of red pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 17 , 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267 268, 269, 270, 271, 272, 273, 274, 275, 276. Of these, C.I. I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, more preferably C.I. I. Pigment red 177, 209, 224, 254.

Examples of blue pigments include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79. Of these, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3,
15: 4, 15: 6, more preferably C.I. I. Pigment blue 15: 6.

Examples of green pigments include C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55. Of these, C.I. I. And CI Pigment Green 7 and 36.
Examples of yellow pigments include C.I. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 17 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202 , 203, 204, 205, 206, 207, 208. Of these, C.I. I. Pigment yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, more preferably C.I. I. Pigment yellow 83, 138, 139, 150, 180.

  Examples of orange pigments include C.I. I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79. Of these, C.I. I. And CI pigment oranges 38 and 71.

  Examples of purple pigments include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50. Of these, C.I. I. Pigment violet 19, 23, more preferably C.I. I. And CI Pigment Violet 23.

  Moreover, when forming a black matrix using the curable composition of this invention, a black coloring material can be used. The black color material may be a single black color material or a mixture of red, green, blue and the like. These color materials can be appropriately selected from inorganic or organic pigments and dyes. In the case of inorganic and organic pigments, it is preferable to use the pigment dispersed in an average particle size of 1 μm or less, preferably 0.5 μm or less.

Color materials that can be mixed for preparing a black color material include Victoria Pure Blue (42595), Auramin O (41000), Catillon Brilliant Flavin (Basic 13), Rhodamine 6GCP (45160), Rhodamine B (45170). Safranin OK 70: 100 (50240), Erioglaucine X (42080), No. 120 / Lionol Yellow (21090), Lionol Yellow GRO (21090), Shimla First Yellow 8GF (21105), Benzidine Yellow 4T-564D (21095), Shimler First Red 4015 (12355), Lionol Red 7B4401 (15850), Fast Gen Blue TGR-L (74160), Lionol Blue SM (26150), Lionol Blue ES (Pigment Blue 15: 6), Lionogen Red GD (Pigment Red 168), Lionol Green 2YS (Pigment Green 36), etc. (The numbers in parentheses above indicate the color index (CI)).

  In addition, other pigments that can be used in combination are C.I. I. For example, C.I. I. Yellow pigments 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, C.I. I. Orange pigments 36, 43, 51, 55, 59, 61, C.I. I. Red pigments 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, C.I. I. Violet pigments 19, 23, 29, 30, 37, 40, 50, C.I. I. Blue pigment 15, 15: 1, 15: 4, 22, 60, 64, C.I. I. Green pigment 7, C.I. I. Examples thereof include brown pigments 23, 25, and 26.

Examples of the black color material that can be used alone include carbon black, acetylene black, lamp black, bone black, graphite, iron black, aniline black, cyanine black, and titanium black.
Among these, carbon black is preferable from the viewpoints of light shielding rate and image characteristics. Examples of carbon black include the following carbon black. Mitsubishi Chemical Corporation: MA7, MA8, MA11, MA100, MA100R, MA220, MA230, MA600, # 5, # 10, # 20, # 25, # 30, # 32, # 33, # 40, # 44, # 45 # 47, # 50, # 52, # 55, # 650, # 750, # 850, # 950, # 960, # 970, # 980, # 990, # 1000, # 2200, # 2300, # 2350, # 2400, # 2600, # 3050, # 3150, # 3250, # 3600, # 3750, # 3950, # 4000, # 4010, OIL7B, OIL9B, OIL11B, OIL30B, OIL31B, manufactured by Degussa: Printex3, Printex3OP, Printex30OP, Printex30OP , Printex40, Printex45, Pr ntex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, Printex L, Printex G, Printex P, Printex U, Printex V, PrintexG, SpecialBlack550, SpecialBlack350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBlack4, Color Black FW1, Color Black FW2, Color Black
FW2V, Color Black FW18, Color Black FW18, Color Black FW200, Color Black S160, Color
Black S170, manufactured by Cabot Corporation: Monarch120, Monarch280, Monarch460, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1100, Monarch1300, Monarch1400, Monarch4630, REGAL99, REGAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK PEARLS480, PEARLS130, VULCAN XC72R, ELFTEX-8, made by Colombian Carbon: RAVEN11, RAVEN14, RAVEN15, RAVEN16, RAV EN22RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN890H, RAVEN1000, RAVEN1020, RAVEN1040, RAVEN1060U, RAVEN1080U, RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000
As examples of other black pigments, titanium black, aniline black, iron oxide black pigments, and organic pigments of three colors of red, green, and blue can be mixed and used as black pigments.

In addition, barium sulfate, lead sulfate, titanium oxide, yellow lead, bengara, chromium oxide, and the like can also be used as the pigment.
These various pigments can be used in combination. For example, in order to adjust the chromaticity, a green pigment and a yellow pigment can be used in combination, or a blue pigment and a violet pigment can be used in combination.

The average particle size of these pigments is usually 1 μm, preferably 0.5 μm or less, more preferably 0.25 μm or less. Examples of dyes that can be used as the colorant include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.
Examples of the azo dye include C.I. I. Acid Yellow 11, C.I. I. Acid Orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Direct Yellow 12, C.I. I. Direct Orange 26, C.I. I. Direct Green 28, C.I. I. Direct Green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I. I. Reactive Black 5, C.I. I. Disperse Orange 5, C.I. I. Disperse thread 58, C.I. I. Disperse Blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Molded Red 7, C.I. I. Moldant Yellow 5, C.I. I. Examples thereof include Moldant Black 7.

Examples of anthraquinone dyes include C.I. I. Bat Blue 4, C.I. I. Acid Blue 40, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. Disper thread 60, C.I. I. Disperse Blue 56, C.I. I. Disperse Blue 60 etc. are mentioned.
In addition, examples of phthalocyanine dyes include C.I. I. Pad Blue 5 and the like are quinone imine dyes such as C.I. I. Basic Blue 3, C.I. I. Basic Blue 9 and the like are quinoline dyes such as C.I. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Disperse Yellow 64 and the like are nitro dyes such as C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Disperse Yellow 42 and the like.

  The proportion of the color material of the component (L) in the total solid content in the curable composition can usually be selected in the range of 1 to 70% by weight with respect to the total solid content in the curable composition. In this range, 10 to 70% by weight is more preferable, and 20 to 60% by weight is particularly preferable. When the ratio of the color material is too small, the film thickness with respect to the color density becomes too large, which adversely affects the gap control when the liquid crystal cell is formed. On the other hand, if the ratio of the color material is too large, sufficient image formability may not be obtained. In addition, the total solid content in the curable composition of the present invention is usually 10% by weight or more and 80% by weight or less.

A pigment derivative or the like may be added to improve the dispersibility of the pigment and improve the dispersion stability. As pigment derivatives, azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketopyrrolopyrrole, dioxazine Derivatives such as quinophthalone are preferable. Substituents of pigment derivatives include sulfonic acid groups, sulfonamide groups and quaternary salts thereof, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, amide groups, etc. directly on the pigment skeleton or alkyl groups, aryl groups, and complex groups. Examples thereof include those bonded via a ring group or the like, and a sulfonic acid group is preferable. Further, a plurality of these substituents may be substituted on one pigment skeleton. Specific examples of the pigment derivative include sulfonic acid derivatives of phthalocyanine, sulfonic acid derivatives of quinophthalone, sulfonic acid derivatives of anthraquinone, sulfonic acid derivatives of quinacridone, sulfonic acid derivatives of diketopyrrolopyrrole, and sulfonic acid derivatives of dioxazine. The addition amount of the pigment derivative is usually 0.1 to 30% by weight, preferably 0.1 to 20% by weight or less, more preferably 0.1 to 10% by weight, still more preferably 0.1 to 5% by weight based on the pigment. % Or less.

[1-13] (M) Dispersant and / or Dispersion Auxiliary In the case of using the curable composition of the present invention for a color filter or a black matrix, in particular, the color of the aforementioned component (L) When a pigment is used as the material, it is preferable to use a dispersant and / or a dispersion aid as the component (M) in order to improve the dispersibility of the pigment and the dispersion stability. Among these, it is particularly preferable to use a polymer dispersant as the pigment dispersant because it is excellent in dispersion stability over time. Examples of the polymer dispersant include a urethane dispersant, a polyethyleneimine dispersant, a polyoxyethylene alkyl ether dispersant, a polyoxyethylene glycol diester dispersant, a sorbitan aliphatic ester dispersant, and an aliphatic modified polyester. And the like, and the like. Specific examples of such a dispersant include trade names of EFKA (manufactured by EFKA Chemicals Beebuy (EFKA)), Disperbik (manufactured by BYK Chemie), Disparon (manufactured by Enomoto Kasei Co., Ltd.), SOLPERSE (manufactured by GENECA). ), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), polyflow (manufactured by Kyoeisha Chemical Co., Ltd.) and the like. These dispersants can be used alone or in admixture of two or more. The content of the pigment dispersant is usually 50% by weight or less, preferably 30% by weight or less in the solid content of the photosensitive coloring composition.

Further, as a dispersion aid, the compound represented by the general formula (I), (C) component ethylenically unsaturated compound, (D) epoxy compound, (K) other alkali-soluble resin, etc. It may be used for distributed processing.
[1-14] (N) Other Additives The curable composition of the present invention further includes various additives such as hydroquinone, p-methoxyphenol, 2,6-di-t-butyl-p-. Thermal polymerization inhibitor such as cresol, 2% by weight or less with respect to the curable composition, colorant comprising organic or inorganic dye / pigment is also 20% by weight or less, dioctyl phthalate, didodecyl phthalate, tricresyl phosphate, etc. 40% by weight or less of the plasticizer, 10% by weight or less of the sensitivity property improving agent such as tertiary amine or thiol, 30% by weight or less of the dye precursor, and 10% by weight or less of the silane coupling agent. You may contain in a ratio.

[1-15] Total deformation amount, displacement and elastic recovery rate under load, recovery rate The curable composition of the present invention has a total deformation amount of 1.35 μm or more in a load-unloading test with a microhardness meter. Alternatively, it is possible to form a cured product having a load N of 0.50 gf or less when the displacement under load is 0.25 μm and an elastic recovery rate of 50% or more and / or a recovery rate of 80% or more. It is a feature.

  For example, a spacer provided in a liquid crystal display device (hereinafter sometimes referred to as a “panel”) of a large-sized liquid crystal screen television is easily subjected to a load in the manufacturing process of the panel, and the total deformation amount of the spacer is large. Tend to be. In particular, in a large screen panel, the load tends to be uneven in each part. Even in such a case, the curable composition of the present invention is significant in that the cured product (spacer) has a high elastic recovery rate and / or high recovery rate.

Here, the load-unloading test by the micro altimeter is performed as follows.
Of the spacer patterns formed by [2-2] described later and a known method, one pattern having an upper cross-sectional area of 80 ± 10 μm ² is measured using a micro hardness tester.
The upper cross-sectional area of the spacer pattern means the following area. First, a vertical cross section passing through the central axis of the spacer pattern is profiled for one spacer pattern using an ultra-deep color 3D shape measurement microscope “VK-9500” manufactured by Keyence Corporation. The profile position is shown in FIG. Next, a straight line AA ′ parallel to the substrate surface in the spacer pattern graphic at a height of 90% of the height from the substrate surface of the profiled graphic (schematic diagram shown in FIG. 2) to the point Q at the highest position. Measure the length. The area of the circle having the diameter AA ′ is defined as the upper cross-sectional area of the spacer pattern.

As the micro hardness tester, Shimadzu Corporation (Shimadzu Dynamic Ultra Micro Hardness Tester DUH-W201S) is used.
The test conditions were a measurement temperature of 23 ° C. and a flat indenter with a diameter of 50 μm. A load was applied to the spacer at a constant speed (0.22 gf / sec). When the load reached 5 gf, the load was held for 5 seconds, and then the same speed. Unload at. From the load-displacement curve obtained from this test (schematic diagram shown in FIG. 3), the maximum displacement H [max], the final displacement H [Last], and the overload N (gf) when the displacement under load is 0.25 μm. Measure. The maximum displacement H [max] is defined as the total deformation amount.

The total deformation amount is preferably 1.4 μm or more, more preferably 1.5 μm or more, preferably 5 μm or less, more preferably 3 μm or less.
The load N when the displacement under load is 0.25 μm is preferably 0.45 gf or less, and preferably 0.1 gf or more.
If the total deformation amount is too large and / or the load N is too small, the elastic recovery rate and / or the recovery rate deteriorates. On the other hand, if the total deformation amount is too small and / or the load N is too large, the cured product cannot cope with load unevenness at the time of manufacturing the panel.

The elastic recovery rate and the recovery rate are calculated as follows based on the values measured by the load-unloading test using the micro altimeter.
Recovery rate (%) = H [last] / (pattern height before test) × 100
Elastic recovery rate (%) = (H [max] −H [last]) / H [max] × 100,
The recovery rate is preferably 85% or more, more preferably 90% or more.

The elastic recovery rate is preferably 60% or more, more preferably 80% or more.
If the recovery rate and / or the elastic recovery rate is too small, the cured product cannot cope with load unevenness during panel manufacture.
The composition of the curable composition of the present invention is not particularly limited as long as it has the above-described characteristics, and in particular, (A-1) the compound represented by the general formula (I) and / or Or (A-2) by having a compound having a trisphenolmethane structure.

[1-16] Bottom cross-sectional area and elastic recovery rate, recovery rate The curable composition of the present invention has a bottom cross-sectional area of 24.5 μm ² or less and an elastic recovery rate of 50% or more and / or recovery. It is characterized in that a cured product having a rate of 85% or more can be formed.
For example, a spacer provided for a screen panel of a mobile phone has a small bottom area so as not to damage an image because the pixel is small. On the other hand, a product such as a cellular phone is easily subjected to an impact during use or the like, so that a load is easily applied. Even in such a case, the curable composition of the present invention is significant in that the cured product (spacer) has a high elastic recovery rate and / or high recovery rate.

Here, the bottom cross-sectional area refers to a contact area of a cured product formed of the curable composition of the present invention such as a spacer with a substrate, and is measured by observing a spacer pattern with an optical microscope. The bottom cross-sectional area is preferably 20 μm ² or less, more preferably 15 μm ² or less, preferably 1 μm ² or more, and more preferably 5 μm ² or more.
If the bottom cross-sectional area is too large, it is not suitable for a panel such as a cellular phone with small pixels. On the other hand, if the bottom cross-sectional area is too small, a sufficient elastic recovery rate and / or recovery rate cannot be obtained.

The elastic recovery rate and recovery rate are calculated in the same manner as described above based on the values measured by the load-unloading test using the microhardness meter.
The recovery rate is preferably 90% or more.
The elastic recovery rate is preferably 60% or more, more preferably 80% or more.
If the recovery rate and / or elastic recovery rate is too small, the cured product cannot cope with a load such as an impact of the panel.
The composition of the curable composition of the present invention is not particularly limited as long as it has the above-described characteristics, and in particular, (A-1) the compound represented by the general formula (I) and / or Or (A-2) by having a compound having a trisphenolmethane structure.

[2] Method of using curable composition The curable composition of the present invention is a solder in printed wiring boards, liquid crystal display elements, plasma displays, large scale integrated circuits, thin transistors, semiconductor packages, color filters, organic electroluminescence, and the like. Form cured products such as resist films, coverlay films, and insulation coating layers of various electronic components, and cure color filter pixels, black matrix, overcoats, ribs, and spacers used in liquid crystal panels such as liquid crystal displays. Although it can be used by a known method in each application such as forming a product, the case where it is used as a solder resist and the case where it is used as a spacer will be described below.

[2-1] Use as a solder resist Normally, a curable composition dissolved or dispersed in a solvent is supplied onto a substrate on which a solder resist is to be provided in a film or pattern by a method such as coating. When the film is supplied after being dried, pattern formation is performed by a method such as photolithography in which exposure and development are performed as necessary. Alternatively, a curable composition previously prepared as a dry film resist material is supplied onto the substrate by a conventional method, and pattern formation is performed by a method such as photolithography in which exposure and development are performed if necessary. A solder resist layer is formed on the substrate by subjecting the film-like or pattern-like curable composition layer thus obtained to a heat curing treatment as necessary.

[2-1-1] Substrate As the substrate, the curable composition layer formed on the substrate is exposed to a laser beam or the like and developed, and the resulting image is subjected to soldering or the like as a resist A pattern such as a circuit or an electrode is formed on the surface, and may be a metal plate itself such as copper, aluminum, gold, silver, chromium, zinc, tin, lead, nickel, etc. , Epoxy resin, polyimide resin, bismaleimide resin, unsaturated polyester resin, phenol resin, melamine resin and other thermosetting resins, saturated polyester resin, polycarbonate resin, polysulfone resin, acrylic resin, polyamide resin, polystyrene resin, polyvinyl chloride Resin, polyolefin resin, thermoplastic resin such as fluorine resin, paper, glass, and aluminum It consists of inorganic materials such as na, silica, barium sulfate, calcium carbonate, or composite materials such as glass cloth base epoxy resin, glass nonwoven base epoxy resin, paper base epoxy resin, paper base phenol resin, etc. On the surface of an insulating support having a thickness of about 0.02 to 10 mm, the metal or a metal foil such as indium oxide, tin oxide, or indium oxide doped tin oxide is heated and pressure-bonded or laminated, or the metal is sputtered. A metal-clad laminate in which a conductive layer having a thickness of about 1 to 100 μm is formed by a method such as vapor deposition or plating is preferably used.

[2-1-2] Supply Method to Substrate When supplied onto a substrate in a state dissolved or dispersed in a solvent, a conventionally known method, for example, spin coating, wire bar coating, spray coating, dip coating, air Knife coating, roll coating, blade coating, screen coating, curtain coating, and the like can be used. The coating amount at that time is preferably 5 μm or more as a dry film thickness, more preferably 10 μm or more, from the viewpoints of image forming described later and processability such as soldering subsequent thereto, and more preferably 10 μm or more. In view of the above, it is preferably 200 μm or less, and more preferably 100 μm or less. The drying temperature at that time is, for example, about 30 to 150 ° C., preferably about 40 to 110 ° C., and the drying time is, for example, about 5 seconds to 60 minutes, preferably about 10 seconds to 30 minutes. It is done.

  In the case where a curable image forming material is produced by directly applying and drying the curable composition coating liquid, the curable composition formed on the substrate to be processed as described above. A protective layer is formed by applying a solution of polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide, methyl cellulose, carboxymethyl cellulose, hydroxymethyl cellulose, and the like on the layer to prevent polymerization inhibition by oxygen of the curable composition. May be formed.

  Moreover, when supplying as a dry film resist material on a board | substrate, it can carry out by a conventionally well-known method. Specifically, as a coating solution in which each of the above components is dissolved or dispersed in an appropriate solvent, it is coated on a temporary support film and dried, and the surface of the formed curable composition layer is coated with a coating film as necessary. By covering, it is a so-called dry film resist material or the like, and when the curable composition layer side of the dry film resist material is covered with the coating film, the coating film is peeled off and is applied onto the substrate to be processed. By laminating by a method such as heat laminating, it is supplied onto the substrate.

  As the temporary support film when used as the dry film resist material, a conventionally known film such as a polyethylene terephthalate film, a polyimide film, a polyamideimide film, a polypropylene film, or a polystyrene film is used. In that case, when those films have the solvent resistance and heat resistance necessary for the production of the dry film resist material, the curable composition coating solution is directly applied on the temporary support film. It can be applied and dried to produce a dry film resist material, and even if those films have low solvent resistance, heat resistance, etc., for example, polytetrafluoroethylene film, release film, etc. A curable composition layer is first formed on a film having releasability, and then a temporary support film having low solvent resistance or heat resistance is laminated on the layer, and then the film having releasability is peeled off. By doing so, a dry film resist material can also be produced.

The solvent used in the coating solution is not particularly limited as long as it has sufficient solubility for the components used and gives good coating properties. For example, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate Cellosolve solvents such as ethyl cellosolve acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol dimethyl ether, etc. Propylene glycol solvents, butyl acetate, amyl acetate, ethyl butyrate, butyl butyrate, diethyl oxalate, pyruvate Ester solvents such as ethyl, 2-hydroxybutyrate, ethyl acetoacetate, methyl lactate, ethyl lactate, methyl 3-methoxypropionate, alcohol solvents such as heptanol, hexanol, diacetone alcohol, furfuryl alcohol, cyclohexanone And ketone solvents such as methyl amyl ketone, highly polar solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and mixed solvents thereof, and those obtained by adding aromatic hydrocarbons to these. The use ratio of the solvent is usually in the range of about 1 to 20 times by weight with respect to the total amount of each component of the curable composition.

[2-1-3] Exposure Method The curable image forming material having a curable composition layer on a substrate to be processed is preferably irradiated with laser light or irradiated with a laser beam. Exposure is performed by scanning exposure as an exposure light source. At this time, when the protective layer or the like is provided, the protective layer or the like may be left as it is or after peeling. Moreover, when the curable composition layer is formed with the said dry film resist material, you may have a temporary support film, or after peeling.

  As the exposure light source, carbon arc lamp, mercury lamp, xenon lamp, metal halide lamp, fluorescent lamp, tungsten lamp, halogen lamp, and laser such as HeNe laser, argon ion laser, YAG laser, HeCd laser, semiconductor laser, ruby laser, etc. Although a light source is mentioned, the light source which generate | occur | produces the laser beam of a blue violet area | region with a wavelength range of 350-430 nm is especially preferable, and it is still more preferable that the center wavelength is about 405 nm. Specific examples include an indium gallium nitride semiconductor laser that oscillates at 405 nm.

The scanning exposure method using a laser light source is not particularly limited, and examples thereof include a plane scanning exposure method, an outer drum scanning exposure method, an inner drum scanning exposure method, and the like. The output light intensity is preferably 1 to 100 mW, more preferably 3 to 70 mW, the oscillation wavelength is preferably 390 to 430 nm, more preferably 400 to 420 nm, and the beam spot diameter is preferably 2 to 30 μm, more preferably 4 Scan exposure is performed at a scanning speed of ˜20 μm, a scanning speed of preferably 50 to 500 m / second, more preferably 100 to 400 m / second, and a scanning density of preferably 2,000 dpi or higher, more preferably 4,000 dpi or higher.
Moreover, the curable composition of this invention can form a cured layer on a board | substrate also by heating in presence of a thermal-polymerization initiator, without making the above-mentioned photocuring. As heating conditions in that case, the temperature is usually 80 to 250 ° C., preferably 100 to 200 ° C., usually 10 to 120 minutes, preferably 20 to 60 minutes.

[2-1-4] Development Method The development process after the exposure is preferably performed using an aqueous developer containing an alkali component and, if necessary, a surfactant. Examples of the alkali component include sodium silicate, potassium silicate, lithium silicate, ammonium silicate, sodium metasilicate, potassium metasilicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, Inorganic alkali salts such as dibasic sodium phosphate, tribasic sodium phosphate, dibasic ammonium phosphate, tribasic ammonium phosphate, sodium borate, potassium borate, ammonium borate, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, mono Isopropylamine, diisopropylamine, monobutylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine Organic amine compounds and the like, and used at a concentration of about 0.1 to 5 wt%.

Examples of the surfactant include the same surfactants as mentioned in the curable composition, and among them, nonionic, anionic, or amphoteric surfactants are preferable. Betaine type compounds are preferred. The surfactant is used in a concentration of preferably 0.0001 to 20% by weight, more preferably 0.0005 to 10% by weight, and particularly preferably 0.001 to 5% by weight.

Furthermore, the developing solution can contain an organic solvent such as isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol, if necessary. Further, the pH of the developer is preferably 9 to 14, and more preferably 11 to 14.
The development is usually about 10 to 50 ° C., more preferably 20 to 20 ° C., by a known development method such as immersing the image forming material in the developer or spraying the developer on the image forming material. It is performed at a temperature of about 40 ° C. for a time of about 5 seconds to 10 minutes. In addition, it is preferable to perform heat treatment at a temperature of, for example, about 140 to 160 ° C. in order to improve heat resistance and chemical resistance as a resist of an image formed as a cured product after development processing.

[2-2] Use as a spacer Usually, a curable composition dissolved or dispersed in a solvent is supplied onto a substrate on which a spacer is to be provided in a film or pattern by a method such as coating, and the solvent is dried. Then, when the film is supplied in the form of a film, pattern formation is performed by a method such as photolithography that performs exposure and development as necessary. Then, if necessary, a spacer is formed on the substrate by performing additional exposure or thermosetting treatment.

[2-2-1] Supplying Method to Substrate The curable composition of the present invention is usually supplied onto the substrate in a state dissolved or dispersed in a solvent. As the supply method, a conventionally known method such as a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, a spray coating method or the like can be used. Above all, according to the die coating method, the amount of coating solution used is greatly reduced, there is no influence of mist adhering to the spin coating method, and the generation of foreign matter is suppressed. To preferred. The coating amount varies depending on the application. For example, in the case of a spacer, the dry film thickness is usually in the range of 0.5 to 10 μm, preferably 1 to 8 μm, and particularly preferably 1 to 7 μm. It is also important that the dry film thickness or the height of the finally formed spacer is uniform across the entire substrate. When the variation is large, a nonuniformity defect occurs in the liquid crystal panel. Further, it may be supplied in a pattern by an inkjet method or a printing method.

[2-2-2] Drying method Drying after supplying the curable composition onto the substrate is preferably performed by a drying method using a hot plate, an IR oven, or a convection oven. Moreover, you may combine the reduced pressure drying method of drying in a reduced pressure chamber, without raising temperature. Drying conditions can be appropriately selected according to the type of solvent component, the performance of the dryer used, and the like. The drying time is usually selected in the range of 15 seconds to 5 minutes at a temperature of 40 to 130 ° C., preferably 50 to 110 ° C., depending on the type of solvent component, the performance of the dryer used, and the like. It is selected in the range of 30 seconds to 3 minutes.

[2-2-3] Exposure Method Exposure is performed by superimposing a negative mask pattern on the coating film of the curable composition and irradiating a UV or visible light source through this mask pattern. A scanning exposure method using laser light may be used. At this time, if necessary, exposure may be performed after an oxygen blocking layer such as a polyvinyl alcohol layer is formed in a deoxygenated atmosphere or on the photopolymerizable layer in order to prevent the sensitivity of the photopolymerizable layer from being reduced by oxygen. . The light source used for said exposure is not specifically limited. As the light source, for example, a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a fluorescent lamp, a lamp light source, an argon ion laser, a YAG laser, Examples include laser light sources such as excimer laser, nitrogen laser, helium cadmium laser, blue-violet semiconductor laser, and near infrared semiconductor laser. An optical filter can also be used when used by irradiating light of a specific wavelength.

[2-2-4] Development Method After performing the above exposure, an image pattern can be formed on the substrate by development using an aqueous solution containing an alkaline compound and, if necessary, a surfactant, or an organic solvent. This aqueous solution may further contain an organic solvent, a buffering agent, a complexing agent, a dye or a pigment.

  Alkaline compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate Inorganic alkaline compounds such as sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, mono-di- or triethanolamine, mono-di- or trimethylamine Mono-di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), co The organic alkaline compound such emissions and the like. These alkaline compounds may be a mixture of two or more.

  Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters, and alkylbenzene sulfonic acids. Examples include anionic surfactants such as salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinate esters, and amphoteric surfactants such as alkylbetaines and amino acids.

Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol and the like. The organic solvent can be used alone or in combination with an aqueous solution.
[2-2-5] Additional exposure and thermosetting treatment The substrate after development may be subjected to additional exposure by a method similar to the above-described exposure method, if necessary, or may be subjected to a thermosetting treatment. It is particularly preferable to perform a thermosetting treatment. The thermosetting treatment conditions at this time are selected such that the temperature is in the range of 100 to 280 ° C, preferably 150 to 250 ° C, and the time is in the range of 5 to 60 minutes.

Hereinafter, the curable composition of the present invention will be described with reference to specific examples for solder resists and spacers, but the present invention is limited to the following examples as long as the gist thereof is not exceeded. is not.
[1] Curable composition for solder resist Examples 1-3 and Comparative Examples 1-2
The following compounds (A1) to (A6) represented by the aforementioned general formula (I) and other compounds, (B1 to B4) component photopolymerization initiators, and (C1) component ethylenically unsaturated compounds , (D1) component epoxy compound, (E1) component epoxy curing agent, (H1-H2) component inorganic filler, (J1-J3) component sensitizing dye, and (X1) component other component, In addition to 100 parts by weight of propylene glycol monomethyl ether acetate at the blending ratio shown in Table 1, the coating solution was prepared by stirring at room temperature. Separately, a copper foil surface of a polyimide resin copper-clad laminate (thickness 1.5 mm, size 250 mm × 200 mm) bonded with a 35 μm thick copper foil is polished using “Scotch Bright SF” manufactured by Sumitomo 3M Limited. After washing with water and drying with an air stream, the surface is then preheated to 60 ° C. in an oven, and then the coating solution obtained above is dried on the copper foil of the copper clad laminate. Was applied to a thickness of 25 μm and dried in a hot air circulating drying oven at 80 ° C. for 30 minutes to prepare a photocurable image forming material.

(A1) Compound obtained by the following production example In a 500 ml four-necked flask, 231 g of 9,9-bis (4′-hydroxyphenyl) fluorene diepoxide (epoxy equivalent 231), 2-acryloyloxyethyl succinic acid (Acid value 260, “HOA-MS” manufactured by Kyoei Chemical Co., Ltd.) 216 g, triethylbenzylammonium chloride 0.45 g, and p-methoxyphenol 0.1 g were charged, and 90-100 ° C. while blowing air at a rate of 25 ml / min. Then, the solution is gradually heated to 120 ° C. to completely dissolve the solution in a cloudy state until the acid value reaches 0.8 KOH · mg / g. Stirring was continued for a period of time to obtain a colorless and transparent reaction product. Subsequently, after adding 20 g of cellosolve acetate to 447 g of the obtained reaction product, 38 g of 1,2,3,6-tetrahydrophthalic anhydride, 73.5 g of biphenyltetracarboxylic dianhydride, and bromide 1 g of tetraethylammonium was added, the temperature was gradually raised, and the mixture was reacted at 110 to 115 ° C. for 2 hours to obtain compound (A1).
The obtained compound had a weight average molecular weight of 3,500 and a double bond equivalent of 560.

(A2) Compound obtained by the following production example 200 parts by weight of succinic anhydride and 596 parts by weight of commercially available pentaerythritol triacrylate were added at 100 ° C. in the presence of 2.5 parts by weight of triethylamine and 0.25 parts by weight of hydroquinone. The polyfunctional acrylate having an acid value of 94 and consisting of 67 mol% of a polyfunctional acrylate having one carboxyl group and two or more acryloyl groups in one molecule and 33 mol% of pentaerythritol tetraacrylate A mixture was obtained. Compound (A2) was obtained in the same manner as in Production Example (A1) except that 597 g of this polyfunctional acrylate mixture was used instead of 216 g of 2-acryloyloxyethyl succinic acid. The obtained compound had a weight average molecular weight of 3,000 and a double bond equivalent of 210.

(A3) Compound obtained in the following production example In the production example of (A1), except that 70.5 g of biphenyltetracarboxylic dianhydride was used and 80.5 g of benzophenonetetracarboxylic dianhydride was used, Compound (A3) was obtained in the same manner as in the production example of (A1). The resulting compound has a weight average molecular weight of 3,
500 and the double bond equivalent was 189.

(A4) Compound obtained by the following production example In the production example of the above (A1), 9,9-bis (4'-) instead of 231 g of 9,9-bis (4'-hydroxyphenyl) fluorene diepoxide Compound (A4) was obtained in the same manner as in Production Example (A1) except that 231 g of the epoxidized product of hydroxy-3′-methylphenyl) fluorene was used. The obtained compound had a weight average molecular weight of 3,000 and a double bond equivalent of 187.

(A5; for comparative example) Compound obtained by the following production example In the production example of (A1), except that acrylic acid 72 g was used instead of 216 g of 2-acryloyloxyethyl succinic acid, In the same manner as in Production Example, compound (A5)
Got. The obtained compound had a weight average molecular weight of 3,200 and a double bond equivalent of 416.
(A6; for comparative example) Compound (A6) having the following constitutional repeating unit (acid value 100 mg KOH / g, weight average molecular weight 5,000, double bond equivalent 398, “PR-300J” manufactured by Showa Polymer Co., Ltd.)

(B1) 1- (4-methylthiophenyl) -2-morpholino-2-methyl-propan-1-one (B2) 2,4-diethylthioxanthone (B3) 2-hydroxy-4-n-octanoylbenzophenone (B4) ) 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole (C1) dipentaerythritol hexaacrylate (D1) o-cresol novolac type epoxy resin (epoxy value 216, “Epicoat 180S70” manufactured by Japan Epoxy Resin Co., Ltd.)
(E1) Dicyandiamide (H1) Barium sulfate (H2) Talc (J1) The following sensitizing dye (J2) The following sensitizing dye (J3) The following sensitizing dye

(X1) Phthalocyanine Green [1-1] High-pressure mercury lamp exposure sensitivity The exposure sensitivity of the photocurable image-forming material obtained above was measured by the method shown below, and the results are shown in Table 1.
Minimum exposure at which a step image is reproduced when the photocurable composition layer of the resulting image forming material is irradiated with a 1 kW ultra-high pressure mercury lamp and developed with a 1 wt% aqueous sodium carbonate solution at 30 ° C. for 80 seconds. The amount (mJ / cm ² ) was determined and used as the sensitivity.

[1-2] Adhesiveness to substrate Further, the obtained photocurable image-forming material was evaluated for the adhesiveness of the cured layer to the substrate to be processed and its heat resistance by the following method, and the results are shown in Table 1. It was shown to.
After irradiating the photocurable composition layer of the obtained image forming material with the minimum exposure amount obtained above by using a 1 kW ultra-high pressure mercury lamp to form a whole surface cured layer, the obtained cured layer was heated at 150 ° C. After heat-treating for 60 minutes, in accordance with JIS D0202, cuts are made with a cutter so as to form 100 grids at 1 mm intervals on the cured layer, and cellophane tape (manufactured by Nichiban Co., Ltd.) is placed on the cured layer. The number of peeled squares of the cured layer when the tape was attached and peeled off was measured and evaluated according to the following criteria.

A: The number of peeled cells in the cured layer is 0 out of 100 cells.
B: Of 100 squares, the number of peeled squares of the cured layer is 1 or more and less than 5.
C: Of 100 squares, the number of peeled squares of the cured layer is 5 or more and less than 10.
D: The number of peeled cells of the cured layer out of 100 cells is 10 or more.
[1-3] Heat resistance of adhesiveness After cutting with 100 cutters in the same manner as described above, flux (Tamura Kaken Co., Ltd.) is applied to the surface, and then 290 After being immersed in a solder bath at 0 ° C. for 30 seconds, the operation of returning to room temperature was repeated 6 times. Then, cellophane tape was stuck on the cured layer, and the number of peeled cells of the cured layer when the tape was peeled was measured in the same manner as described above, and evaluated according to the same criteria.

[1-4] Laser exposure sensitivity Example 4 (curable composition for solder resist: laser exposure)
About the photocurable image forming material produced in the same manner as in Examples 1 to 3, the laser exposure sensitivity was measured by the following method using laser light as the exposure light source, and the exposure light source was replaced with laser light. Evaluated the adhesion to the substrate and its heat resistance in the same manner as described above, and the results are shown in Table 1.
The photocurable composition layer of the obtained image forming material was fixed on an aluminum cylinder having a diameter of 7 cm, and a laser light source having a center wavelength of 405 nm and a laser output of 5 mW while changing the rotation speed at 10 to 100 revolutions per minute. (“NLHV500C” manufactured by Nichia Corporation) with an image plane illuminance of 2 mW and a beam spot diameter of 20 μm, scanning exposure while changing the beam scanning interval and scanning speed, and then a 1 wt% sodium carbonate aqueous solution at 30 ° C. Was sprayed as a developing solution to a pressure of 0.15 MPa, and spray development was performed for 1.5 times the minimum development time to reveal an image. With respect to the obtained image, an exposure amount required for reproducing a line width of 20 μm was obtained and set as sensitivity to a blue-violet laser.

[2] Curable composition for solder resist: dry film resist Examples 5 to 7
On a polyethylene terephthalate film (thickness 19 μm) as a temporary support film, an applicator is used to apply a dry film thickness of 25 μm, followed by drying in an oven at 90 ° C. for 5 minutes to form a photocurable composition layer A dry film resist material was prepared by laminating a polyethylene film (thickness 25 μm) as a coating film on the top and allowing it to stand for 1 day. Next, on the copper foil of the same copper-clad laminate as used in Examples 1 to 3, the obtained dry film resist material was peeled off the polyethylene film while using a hand-type roll laminator, By laminating at a roll temperature of 100 ° C., a roll pressure of 0.3 MPa, and a laminating speed of 1.5 m / min, a photocurable image forming material in which a photocurable composition layer was formed on a copper-clad laminate was produced.

  About the photocurable composition layer of the obtained photocurable image forming material, the laser exposure sensitivity was measured in the same manner as in Example 4, and the adhesion to the substrate and its heat resistance were evaluated. It is shown in Table 1.

[3] Curable composition for spacers Examples 8 to 14 and Comparative Examples 3 to 4
(A2), (A5) and the following compounds (A8) to (A12) represented by general formula (I) and other compounds, (B1) component polymerization initiator, (C1) and (C2) components The ethylenically unsaturated compound (F1), the amino compound (F1), the surfactant (I1), and the additive (N1) were added to 100 parts by weight of propylene glycol monomethyl ether acetate in the proportions shown in Table 2. In addition, the coating solution was prepared by stirring at room temperature. About the obtained coating liquid, storage stability was evaluated by the method shown below, and the results are shown in Table 2.

[3-1] Storage stability When the coating solution was sealed in a sample bottle and stored at 35 ° C. for 7 days, changes in viscosity and minimum development time before and after storage were measured and evaluated according to the following criteria. .
○: Change in viscosity is within ± 3%, and change in minimum development time is within ± 3%.
Δ: Change in viscosity exceeds ± 3%, but change in minimum development time is within ± 3%.

X: Change in viscosity is within ± 3%, but change in minimum development time exceeds ± 3%.
(A8) Compound obtained by the following production example In place of 38 g of 1,2,3,6-tetrahydrophthalic anhydride and 73.5 g of biphenyltetracarboxylic dianhydride, 1,2,3,6-tetrahydroanhydride Compound (A8) was obtained in the same manner as in Production Example (A2) except that 137 g of phthalic acid was used. The obtained compound had an acid value of 56, a weight average molecular weight of 2,620, and a double bond equivalent of 216.
(A9) Diglycidyl etherified compound of compound 9,9-bis (4′-hydroxyphenyl) fluorene obtained by the following production example (
Epoxy equivalent 231) 100 parts, reaction mixture of succinic anhydride and pentaerythritol triacrylate (acid number 90.5) 273.2 parts similar to that used in the production example of (A2), p-methoxyphenol 0 .19 parts, 7.4 parts of triphenylphosphine, and 368 parts of propylene glycol monomethyl ether acetate were charged in a reaction vessel and stirred at 90 ° C. until the acid value was 5 mg-KOH / g or less. It took 10 hours for the acid value to reach the target (acid value 1.0). Next, 6 parts of propylene glycol monomethyl ether acetate is added to 80 parts of the reaction solution obtained by the above reaction, 1.9 parts of hexamethylene diisocyanate and 0.01 part of dibutyltin dilaurate are added, and reacted at 90 ° C. for 3 hours. Further, 3.8 parts of trimellitic anhydride was added, reacted at 90 ° C. for 3 hours, acid value 52, a compound (A9) having a weight average molecular weight of 3,100 in terms of polystyrene measured by GPC and a double bond equivalent of 199.
) A solution was obtained.

(A10) Resin having a trisphenol methane structure (TCR 1286 manufactured by Nippon Kayaku Co., Ltd., acid value 101, double bond equivalent 315, diethylene glycol monoethyl ether acetate solution)
(A11) Compound obtained by the following production example (additional test of acrylic resin described in Synthesis Example 3 in JP-A-11-133600)
A flask equipped with a condenser and a stirrer was charged with 7 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol dimethyl ether. Subsequently, 10 parts by weight of styrene, 20 parts by weight of methacrylic acid, 45 parts by weight of glycidyl methacrylate, and 25 parts by weight of dicyclopentanyl methacrylate were charged and nitrogen was stirred. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (A11). The obtained polymer solution had a solid content concentration of 33%, and the weight average molecular weight of the polymer was 18,000.

(A12) A compound obtained by the following production example, instead of 38 g of 1,2,3,6-tetrahydrophthalic anhydride and 73.5 g of biphenyltetracarboxylic dianhydride, Shin Nippon which is tetracarboxylic dianhydride Compound (A12) was obtained in the same manner as in the production example of (A2) except that 57.5 g of Rikacid BT-100 manufactured by Rika Co., Ltd. and 43.8 g of 1,2,3,6-tetrahydrophthalic anhydride were used. It was. The obtained compound had an acid value of 55, a weight average molecular weight of 4450, and a double bond equivalent of 208.

(C2) (Meth) acryloyloxy group-containing phosphates represented by the above general formula (VIIIc) (KAYARAD PM21 manufactured by Nippon Kayaku Co., Ltd.)
(F1) Melamine resin and its modified resin (Nikarak E-2151 manufactured by Sanwa Chemical Co., Ltd.)
(I1) Fluorosurfactant (Megafac F475 manufactured by Dainippon Ink & Chemicals, Inc.)
(N1) Silane coupling agent (SH6040 manufactured by Toray Dow Corning)
Subsequently, the coating solution was applied onto the ITO film of the glass substrate having the ITO curtain formed on the surface by using a spinner, and then heated and dried on a hot plate at 80 ° C. for 3 minutes to form a coating film. Using the obtained coating film, each of nine circular openings having a diameter of 5 to 20 μm and a pattern mask having openings of 5 mm square or more, the exposure gap is 150 μm, and the intensity at 365 nm is 32 mW / cm ^2. Using an ultraviolet ray, the exposure was performed so that the exposure amount was 60 mJ / cm <2>. The ultraviolet irradiation at this time was performed under air. Next, spray development was carried out with a 0.1% aqueous potassium hydroxide solution at 23 ° C. for twice the minimum development time, followed by washing with pure water for 1 minute. Here, the minimum development time means a time during which the unexposed area is completely dissolved under the same development conditions. By these operations, the substrate with the spacer pattern formed by removing unnecessary portions is heated and cured in an oven at 230 ° C. for 30 minutes, and the height of the film portion formed in the opening of 5 mm square or more is about A plurality of spacer patterns of 4 μm and different bottom areas were obtained. The obtained spacer pattern was evaluated for adhesion and compression characteristics by the methods shown below, and the results are shown in Table 2.

[3-2] Adhesiveness Evaluation of adhesiveness was performed for Examples 8 to 11 and Comparative Examples 3 and 4.
With respect to spacer patterns having different bottom areas obtained from pattern masks having different mask opening diameters, the pattern height is 3 μm or more, and 8 or more patterns of 9 spacer patterns of the same size are formed. (In other words, the number of missing patterns among the nine patterns to be formed is 1 or less). The minimum pattern size is defined as adhesion, and the bottom area is shown in Table 2.

[3-3] Compression characteristics: Load-unloading test with micro hardness tester About the spacer pattern obtained above, the spacer pattern was measured using an ultra-deep color 3D shape measurement microscope “VK-9500” manufactured by Keyence Corporation. A longitudinal section through the central axis was profiled. The straight line AA ′ parallel to the substrate surface in the spacer pattern graphic at 90% of the height from the substrate surface of the profiled graphic (schematic diagram shown in FIG. 2) to the point Q at the highest position. The length was measured. Next, the area of a circle having a diameter of AA ′ was defined as the upper cross-sectional area of the spacer pattern. Among these, about one pattern whose upper cross-sectional area is 80 ± 10 μm ² , compression characteristics were evaluated by a load-unloading test using Shimadzu dynamic ultra-small hardness meter DUH-W201S. The test conditions were a measurement temperature of 23 ° C. and a flat indenter with a diameter of 50 μm. A load was applied to the spacer at a constant speed (0.22 gf / sec). When the load reached 5 gf, the load was held for 5 seconds, and then the same speed. The unloading method was used. From the load-displacement curve obtained from this test (schematic diagram is shown in FIG. 3), the maximum displacement H [max], final displacement H [Last], recovery rate (%) = H [last] / (before test) Pattern height) x 100, elastic recovery rate (%) = (H [max] -H [last]) / H [max] x 100, find the overload N (gf) when the displacement under load is 0.25μm The results are shown in Table 2.

[3-4] Evaluation of spacer characteristics (panel evaluation)
A liquid crystal cell was prepared by the following method, and the spacer characteristics were evaluated.
An electrode substrate A in which an ITO film is formed on one whole surface of each 2.5 cm non-alkali glass substrate (AN-100 manufactured by Asahi Glass Co., Ltd.) and a 2 mm width at the center of one surface of the 2.5 cm square glass substrate. An electrode B was prepared on which a 1 cm square ITO film connected with the takeout electrode was formed.
The curable composition shown in each example was applied on the electrode substrate A by spin coating, heated on a hot plate at 80 ° C. for 3 minutes, and a circular pattern having a bottom area of 80 μm ² in each portion of 1 cm in the center. Were exposed at an exposure gap of 150 μm using an exposure mask designed to be arranged at regular intervals of 30 / cm × 30 / cm = 900 in a grid pattern. The irradiation energy was 60 mJ / cm ² . Subsequently, development was performed using an aqueous potassium hydroxide solution, followed by washing with pure water and baking at 230 ° C. for 30 minutes in a hot air circulating furnace. The coating conditions were adjusted so that the spacer height after firing was 4 μm. In this way. An electrode substrate A having a spacer test pattern formed at the center was prepared.
Subsequently, an orientation film agent (Nissan Chemical Corporation Sun Ever 7492) was applied onto the electrode substrate A and the electrode substrate B by spin coating, and then dried on a hot plate at 110 ° C. for 1 minute, followed by hot air Heat at 200 ° C. for 1 hour in the circulation path to form a coating film having a thickness of 70 nm. After performing an alignment treatment using a rubbing machine, an epoxy resin-based sealant containing silica peas having a diameter of 4 μm is applied on the outer periphery of the surface of the electrode substrate B on which the alignment film has been applied. The surface on which the spacer test pattern is formed is placed so that the outer edge is shifted by 3 mm, and is heated at 180 ° C. for 2 hours without hot air circulation while being crimped. A liquid crystal (ZLI-4792 manufactured by Merck & Co., Inc.) was poured into the empty cell thus obtained, and the periphery was sealed with a UV curable sealant to prepare a test cell.
An AC voltage of 5 V and 60 Hz was applied to the obtained liquid crystal cell, and in-plane unevenness of the electro-optic response of the electrode forming portion was observed visually and with a microscope. The results are shown in Table 2. The case where there is no unevenness with the naked eye or the microscope is indicated as .largecircle., The case where unevenness is confirmed with the microscope which cannot be confirmed with the naked eye is indicated as .DELTA.

The curable composition of the present invention includes a printed wiring board, a liquid crystal display element, a plasma display, a large scale integrated circuit, a thin transistor, a semiconductor package, a color filter, a solder resist film and a coverlay film in organic electroluminescence, and various types of electrons. It is useful for forming an insulating coating layer of a part, and is particularly suitable for use in direct drawing with a laser beam. In addition, the curable composition of the present invention is useful as a curable composition for color filters, black matrices, overcoats, ribs and spacers used in liquid crystal panels such as liquid crystal displays.

It is a schematic diagram which shows the position to profile when a spacer pattern is seen from the top. It is a schematic diagram which shows the profile of the longitudinal cross-section of a spacer pattern. It is a schematic diagram which shows the load-displacement curve in the load-unloading test of a spacer.

Explanation of symbols

1 Spacer pattern 2 Center axis of spacer pattern 3 Profile position 4 Profile of spacer pattern longitudinal section 5 Height from substrate surface to highest position 6 Height 90% of height from substrate surface to highest position 7 Circle of upper section Diameter AA '

Claims (17)

A curable composition comprising a compound represented by the following general formula (I):

[In Formula (I), R < ¹ > shows the alkylene group which may have a substituent, or the arylene group which may have a substituent. R ² represents an ethylenically unsaturated group-containing carbonyloxy group having 5 or more carbon atoms, which may have a substituent. R ³ and R ⁴ each independently represents an arbitrary substituent. n is an integer of 0-10. The four benzene rings may further have a substituent. ] The curable composition according to claim 1, wherein R ² is a carbonyloxy group containing an ethylenically unsaturated group having 5 or more carbon atoms represented by the following general formula (II).

[In the formula (II), R ⁷ , R ⁸ and R ⁹ each independently represent a hydrogen atom or a methyl group, and Y ¹ represents an arbitrary divalent group. In the formula, * represents a bond between —CH ₂ — and R ² of the compound represented by the general formula (I). ] The curable composition according to claim 1 or 2, wherein R ³ is selected from a hydrogen atom, a substituent represented by the following formula (IIIa), and a substituent represented by (IIIb).

[In the formula (IIIa), R ⁵¹ represents an alkyl group which may have a substituent, an alkenyl group which may have a substituent, a cycloalkyl group which may have a substituent, or a substituent. The cycloalkenyl group which may have and the aryl group which may have a substituent are shown. ]

[In the formula (IIIb), R ⁵² represents an alkyl group which may have a substituent, an alkenyl group which may have a substituent, a cycloalkyl group which may have a substituent, or a substituent. The cycloalkenyl group which may have and the aryl group which may have a substituent are shown. ] The curable composition according to any one of claims 1 to 3, wherein R ⁴ is a substituent represented by the following general formula (IV).

[In the formula (IV), R ¹ , R ² , R ³ and n are as defined in the general formula (I). * In the formula is a general formula (
The bonding position of —O— and R ⁴ of the compound represented by I) is shown. ] The curable composition according to any one of claims 1 to 4, wherein the compound represented by the general formula (I) is a compound obtained from a bis (hydroxyphenyl) fluorene type epoxy compound. The compound represented by the general formula (I) forms an ethylenically unsaturated group-containing carbonyloxy group having 5 or more carbon atoms in a bis (hydroxyphenyl) fluorene type epoxy compound, and further a polyvalent carboxylic acid and its anhydride. The curable composition according to any one of claims 1 to 5, which is a compound obtained by reacting one or more compounds selected from compounds having an isocyanate group. Furthermore, the curable composition of any one of Claims 1 thru | or 6 containing the following (B) component.
(B) Photopolymerization initiator and / or thermal polymerization initiator Furthermore, the curable composition of any one of Claims 1 thru | or 7 containing the following (C) component.
(C) Ethylenically unsaturated compound Furthermore, the curable composition of any one of Claims 1 thru | or 8 containing the following (J) component.
(J) Sensitizing dye In a load-unloading test using a microhardness meter, the load N when the total deformation is 1.35 μm or more and / or the displacement at the time of loading is 0.25 μm is 0.50 gf or less, and the elastic recovery rate is 50 % And / or a cured product having a recovery rate of 80% or more can be formed. A curable composition capable of forming a cured product having a bottom cross-sectional area of 25 μm ² or less and an elastic recovery rate of 50% or more and / or a recovery rate of 85% or more.   The curable composition according to claim 10 or 11, further comprising a compound having a trisphenolmethane structure. In a load-unloading test using a microhardness meter, the load N when the total deformation is 1.35 μm or more and / or the displacement at the time of loading is 0.25 μm is 0.50 gf or less, and the elastic recovery rate is 50 The curable composition according to any one of claims 1 to 9, which can form a cured product having a recovery rate of 80% or more and / or a recovery rate of 80% or more. The curability according to any one of claims 1 to 10, which can form a cured product having a bottom cross-sectional area of 25 µm ² or less and an elastic recovery rate of 50% or more and / or a recovery rate of 85% or more. Composition.   Hardened | cured material formed using the curable composition of any one of Claims 1 thru | or 14.   A color filter having the cured product according to claim 15.   A liquid crystal display device having the cured product according to claim 15.

Images