KR20070024744A - Curable composition, cured object, color filter, and liquid-crystal display - Google Patents

Abstract

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. Also provided are: 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 cured object obtained from the composition. The curable composition contains a compound represented by the following general formula (I) [wherein R1 represents optionally substituted alkylene or optionally substituted arylene; n is an integer of 0 to 10; the four benzene rings may be further substituted; R2 represents carbonyloxy containing optionally substituted, C5 or higher, ethylenically unsaturated group; and R3 and R4 each independently represents any desired substituent]. ® KIPO & WIPO 2007

Description

Curable composition, cured product, color filter and liquid crystal display device {CURABLE COMPOSITION, CURED OBJECT, COLOR FILTER, AND LIQUID-CRYSTAL DISPLAY}

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram which shows the profile position 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.

3 is a schematic diagram showing a load-displacement curve in a load-unload test of a spacer.

1 to 3, reference numeral 1 denotes a spacer pattern, 2 denotes a medium axis of the spacer pattern, 3 denotes a profile position, 4 denotes a profile of a longitudinal cross section of the spacer pattern, 5 denotes a height from a substrate surface to a highest position, and 6 denotes a substrate surface. 90% of the height to the highest position, 7 represents the diameter AA 'of the circle on the top surface.

The present invention relates to a curable composition by light or heat, and more particularly, to a solder in a printed wiring board, a liquid crystal display device, a plasma display, a large scale integrated circuit, a thin transistor, a semiconductor package, a color filter, an organic electro luminescence, and the like. The present invention relates to a curable composition useful for forming a resist resist film, a cover ray film, and an insulating coating layer of various electronic components, and particularly suitable for use in direct imaging by laser light. .

Moreover, this invention is the curable composition for color filters, the black matrix, the overcoat, the rib, and the spacer used for liquid crystal panels, such as a liquid crystal display, the hardened | cured material formed using this, and the color with this A filter and a liquid crystal display device are related.

Conventionally, for example, in a printed wiring board, when soldering and wiring electronic components, soldering of circuit conductors is performed as a protective film that prevents the solder from adhering to unnecessary portions and prevents the circuit from being directly exposed to air. Forming a soldering resist on the surface except the part to be performed is performed. Lithography using a light sensitive image forming material (hereinafter sometimes referred to as an image forming material A) or the like is widely used for forming the solder resist.

An image forming material (A) means the dry film resist material which formed the photosensitive composition layer on the temporary support film, and covered the photosensitive composition layer surface with a coating film.

The lithographic method is performed in the following order. First, the photosensitive image forming material (henceforth an image forming material (B)) is produced by peeling the coating film of an image forming material (A) and laminating | stacking on a to-be-processed substrate. The image forming material (B) is also produced by applying and drying the coating liquid of the photosensitive composition directly on the substrate to be processed to form a photosensitive composition layer and, if necessary, covering the surface of the photosensitive composition layer with a protective layer.

Next, the photosensitive composition layer on the to-be-processed board | substrate of these image forming materials (B) is image-exposed through the mask film in which the circuit pattern was drawn. Then, the temporary support film or the protective layer is peeled off and developed using the difference in solubility in the developing solution of the exposed portion and the non-exposed portion to form a resist image corresponding to the circuit pattern. In addition, a circuit pattern drawn on the mask film is formed on the substrate by performing solder processing or the like on the substrate to be processed using this resist image as a resist.

On the other hand, by using laser light as an exposure light source in recent years, the laser direct drawing method of forming an image directly from digital information such as a computer without using a mask film can improve not only productivity but also resolution and position accuracy. In this regard, the use of laser light has also been actively studied in the lithography method.

By the way, as a laser light source, various light sources from an ultraviolet to an infrared region are known, but as a laser light source which can be used for image exposure, an argon ion laser and a helium neon in terms of output, stability, photosensitivity and cost, etc. The main focus is to emit light in the infrared region from visible regions such as lasers, YAG lasers, and semiconductor lasers. For example, the lithographic method using the argon ion laser of 488 nm of wavelengths, and the FD-YAG laser of 532 nm of wavelength has already come to practical use. In addition, with the recent remarkable advances in laser technology, semiconductor lasers capable of stably oscillating in the blue-violet region can be used.

However, the conventional photosensitive composition cannot be said to have sufficient sensitivity in the direct drawing method by laser light, and in particular, in the case of a blue-violet semiconductor laser, its output is low as compared with other visible regions and the like. It is the present situation that the sensitivity, developability, etc. of the photosensitive composition did not reach the level which can be put into practical use not only in the direct drawing method but also in the lithography method. For this reason, there is a strong demand for a solder resist material capable of laser exposure.

On the other hand, as a soldering resist for printed wiring boards, liquid resist inks are used from the viewpoint of high precision, high density, consideration for environmental problems, and the like, and as liquid resist inks for a long time, for example, α, β of epoxy resins. The reaction product of -unsaturated monocarboxylic acid addition product and dibasic carboxylic anhydride, the photocurable resist ink composition containing a photopolymerizable monomer, a photoinitiator, etc. are known.

Further, α, β-unsaturated monocarboxylic acid adducts of epoxy resins for the purpose of improving the sensitivity, developability of the photocurable photosensitive composition such as plating resists, etching resists or solder resists, and durability of the images formed thereby. The photosensitive composition containing alkali-soluble modified epoxy acrylate resin which added polyhydric carboxylic acid or its anhydride to this, and it laminated | stacked on a board | substrate as a dry film resist material, or apply | coated this composition coating liquid on a board | substrate, and dried and photosensitive Known image forming methods (e.g., see Patent Documents 1, 2 and 3) are developed by exposing an image forming material for a photoresist having a composition layer exposed to a high pressure mercury lamp or a visible or infrared laser. have.

In addition, a modified epoxy acrylate resin obtained by reacting a reaction product of a bis (hydroxyphenyl) fluorene type epoxy resin with (meth) acrylic acid with a polybasic carboxylic acid or an anhydride thereof for the purpose of increasing the soldering heat resistance and the like is used. A soldering resist resin composition is also known (for example, refer patent document 4).

However, while the photocurable compositions described in these still leave room for improvement in terms of sensitivity, they are inferior in adhesiveness with the substrate to be processed, in particular, as a solder resist or the like at high temperatures.

On the other hand, in the field of a liquid crystal display etc., when forming the color filter, black matrix, overcoat, rib, spacer, etc. which are used for a liquid crystal panel, the resin composition which consists of resin, a photopolymerizable monomer, a photoinitiator, etc. has been used. Various compositions have been proposed for the resin composition from the viewpoints of developability, pattern accuracy, adhesiveness, and the like, and as one of them, the resin contained in the resin composition for the purpose of forming a short time in the forming process and improving the yield. As a technique, the technique using the unsaturated group containing resin obtained by making the reaction material of an epoxy resin, unsaturated group containing carboxylic acid, or its anhydride further with polybasic carboxylic acid or its anhydride is disclosed (patent document 5). On the other hand, high curability and outstanding mechanical properties may be required for the resin composition for liquid crystal panels.

For example, a spacer (in this specification, a "spacer" is formed of a resin composition and represents a so-called columnar spacer, a photo spacer, etc.) is used for the purpose of maintaining a constant interval of a substrate in a liquid crystal panel. However, since the process of pressing a color filter and a board | substrate under high temperature, high pressure at the time of manufacture of a liquid crystal panel is carried out, the physical property that there is little deformation before and behind crimping | compression and a spacer function is maintained is required. That is, even if it was deformed by external pressure, it was necessary as a mechanical property of the resin composition for spacers in actual use environment to return to original shape, when the external pressure was removed. As what satisfy | fills this mechanical characteristic, the resin composition etc. which prescribed | regulated content of a polyfunctional acrylate monomer are proposed (patent document 6).

However, such spacers have the above mechanical properties, but also require pattern precision and adhesion. On the other hand, for the purpose of improving pattern accuracy and adhesion, it was not possible to form a resin composition having mechanical properties suitable for spacers simply by using the above-mentioned general unsaturated group-containing resin. In addition, although there is a demand for a soft spacer having a large amount of total deformation in the crimping process among the required mechanical properties, it is possible to form a soft spacer simply by using the above-described general unsaturated group-containing resin. Recovery after removal was insufficient and the deformation before and after crimping was large to withstand actual use.

[Patent Document 1] Japanese Patent Application Laid-Open No. 5-204150

[Patent Document 2] Japanese Unexamined Patent Publication No. 2000-147767

[Patent Document 3] Japanese Unexamined Patent Publication No. 2001-228611

[Patent Document 4] Japanese Patent Application Laid-Open No. 4-355450

[Patent Document 5] Japanese Unexamined Patent Publication No. 2001-174621

[Patent Document 6] Japanese Unexamined Patent Publication No. 2002-174812

Disclosure of the Invention

The present invention has been made in view of the above-described prior art, and therefore, an object of the present invention is to provide a curable composition having high sensitivity and excellent adhesiveness to a substrate to be processed and its heat resistance, particularly for soldering resists, and by laser light. It is to provide a curable composition suitable for use in direct drawing.

Further, another object of the present invention is to provide a curable composition for image formation, black matrix, overcoat, rib and spacer for color filters used in liquid crystal panels such as liquid crystal displays that solve the above problems.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining the said subject, the present inventors can achieve the said objective by containing a specific (especially characterized by having a C5 or more ethylenically unsaturated group containing carbonyloxy group) unsaturated group containing compound in a curable composition. It has been found that the present invention has been completed. That is, the gist of the present invention is as follows.

1. Curable composition containing compound represented by following General formula (I)

[In formula (I), R <^1> represents the alkylene group which may have a substituent, or the arylene group which may have a substituent, n is an integer of 0-10, and 4 benzene rings may have a substituent further. R ² represents a C5 or more ethylenically unsaturated group-containing carbonyloxy group which may have a substituent, and R ³ And R ⁴ each independently represent an optional substituent].

2. In the loading-unloading test by a microhardness tester, (i) the total deformation amount is 1.35 µm or more, the load N when the displacement under load is 0.25 µm or 0.50 gf or less, or the total deformation amount The load N when the displacement is 1.35 μm or more and the load is 0.25 μm or less, and (ii) the elastic recovery rate is 50% or more, the recovery rate is 80% or more, or the elastic recovery rate is 50% or more Curable composition which can form hardened | cured material whose recovery rate is 80% or more.

3. (i) A cured product having a bottom cross section of 25 µm ² or less and (ii) an elastic recovery rate of 50% or more, a recovery rate of 85% or more, or an elastic recovery rate of 50% or more and a recovery rate of 85% or more. Curable composition which can be formed.

4. Hardened | cured material formed using the curable composition of said 1 or 2.

5. Color filter which has hardened | cured material of 4 above.

6. Liquid crystal display device which has hardened | cured material of 4 above.

The present invention can provide a curable composition which is highly sensitive and excellent in adhesion to a substrate and its heat resistance, in particular, for a solder resist, and suitable for use in direct drawing by laser light.

Moreover, according to this invention, the curable composition for color filters, the black matrix, the overcoat, the rib, and the spacer used for liquid crystal panels, such as a liquid crystal display, which has high curability and outstanding mechanical characteristics can be provided.

To practice the invention  Best form for

Hereinafter, the present invention will be described in detail. In addition, the following description is an example of embodiment of this invention, This invention is not specified to these, unless the summary is exceeded.

[1] curable compositions

The curable composition of the present invention includes (A-1) a compound represented by the general formula (I) and / or a compound having the (A-2) trisphenol methane structure {hereinafter, collectively referred to as (A) component} It is characteristic to contain. Moreover, it is preferable to contain (B) photoinitiator and / or thermal polymerization initiator, and (C) ethylenically unsaturated compound further.

Moreover, when using the curable composition of this invention for soldering resists, overcoats, ribs, or a spacer, (D) epoxy compound, (E) epoxy hardener, (F) amino compound, (H) You may contain an inorganic filler. Moreover, when using the curable composition of this invention for a color filter or a black matrix, it is preferable to contain (L) colorant and (M) dispersing agent and / or a dispersal auxiliary agent further.

Moreover, when using the curable composition of this invention for a laser direct drawing method, it is preferable to contain (J) sensitizing dye further.

Moreover, as another structural requirement, (G) polymerization accelerator, (I) surfactant, (K) other alkali-soluble resin, (N) other additive, etc. are mentioned further.

Alternatively, in the curable composition of the present invention, in the load-unloading test by a microhardness tester described below, (i) the total deformation amount is 1.35 µm or more, or the load N when the displacement at load is 0.25 µm is 0.50 gf or less, Or when the total deformation amount is 1.35 μm or more, or when the displacement at load is 0.25 μm, the load N is 0.50 gf or less, and (ii) the elastic recovery rate is 50% or more, the recovery rate is 80% or more, or the elastic recovery rate is It is characterized by being able to form a cured product having a recovery rate of 50% or more and 80% or more.

Alternatively, the curable composition of the present invention has a bottom surface cross-sectional area of 25 µm ² or less, and (ii) an elastic recovery rate of 50% or more, a recovery rate of 85% or more, or an elastic recovery rate of 50% or more. Or a cured product having a recovery rate of 85% or more.

Hereinafter, each structural requirement of the curable composition of this invention is demonstrated.

[1-1] (A-1) A compound represented by formula (I)

The curable composition of this invention is characterized by containing the compound (A-1) represented by following General formula (I).

[In formula (I), R <^1> represents the alkylene group which may have a substituent, or the arylene group which may have a substituent, R <^2> represents the C5 or more ethylenically unsaturated group containing carbonyloxy group which may have a substituent, R ³ And R ⁴ each independently represent an arbitrary substituent, n is an integer of 0 to 10, and the four benzene rings may each independently have a substituent].

Here, the alkylene group of R ¹ is, that the number of carbon atoms is preferably a methylene group, an ethylene group, and propylene group, butylene group and more preferably 1 to 5, and the arylene group is preferably a carbon number of 6 to 10 And it is more preferable that it is a phenylene group. Especially, in this invention, it is preferable that it is an alkylene group. Moreover, as a substituent of these alkylene groups and an arylene group, a C1-C15 alkyl group etc. are mentioned, for example. In addition, n is an integer of 0-10, it is preferable that it is 0-5, and it is more preferable that it is 0-3. When n exceeds the said range, when a curable composition is made into hardened | cured material, the reduction of a film thickness etc. will arise as an image part at the time of image development, or heat resistance will fall.

Examples of the substituent group R ¹ may have include, for example, 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 and a phosphino group. A group, an amino group, a nitro group, etc. are mentioned.

Although carbon number of the ethylenically unsaturated group containing carbonyloxy group which may have a substituent of R <^2> is 5 or more, an upper limit in particular is not restrict | limited, Preferably it is 50, More preferably, it is 30. When using the curable composition of this invention for soldering resists, 20 is more preferable and 10 is especially preferable as an upper limit of carbon number.

Further, the ethylenically unsaturated group-containing carbonyloxy group of R ² is more preferably a group represented by the following general formula (II):

[In formula (II), R <^7> , R <^8> and R <^9>. Each independently represents a hydrogen atom or a methyl group, and Y ¹ Represents any divalent group. In the formula, * represents a bond of -CH ₂ -and R ² of the compound represented by the formula (I).

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

More preferably, the C1-C10 alkylene group which may have a substituent, and / or the C1-C10 arylene group which may have a substituent, and the bivalent group containing a carbonyloxy group are shown.

R ³ preferably represents a hydrogen atom, a substituent represented by the following formula (IIIa), and a substituent represented by (IIIb):

[In formula (IIIa), R <^51> represents the alkyl group which may have a substituent, the alkenyl group which may have a substituent, the cycloalkyl group which may have a substituent, the cycloalkenyl group which may have a substituent, and the aryl group which may have a substituent. ].

Herein, the alkyl group of R ⁵¹ preferably has 1 to 20 carbon atoms, the alkenyl group preferably has 2 to 20 carbon atoms, and the cycloalkyl group preferably has 3 to 20 carbon atoms, and cyclo The alkenyl group preferably has 3 to 20 carbon atoms, and the aryl group preferably has 6 to 20 carbon atoms.

Examples of the substituents R ⁵¹ may have include, for example, 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 carbonyl group, a sulfanyl group, A phosphino group, an amino group, a nitro group etc. are mentioned. Especially, it is preferable to have a carboxyl group:

[In 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, a cycloalkenyl group which may have a substituent, and an aryl group which may have a substituent. ].

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 preferably has 3 to 20 carbon atoms, and cyclo The alkenyl group preferably has 3 to 20 carbon atoms, and the aryl group preferably has 6 to 20 carbon atoms.

Examples of the substituents R ⁵² may have include, for example, 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 carbonyl group, a sulfanyl group, A phosphino group, an amino group, a nitro group etc. are mentioned.

The substituent represented by R ⁴ is not particularly limited, and examples thereof include a substituent represented by the following general formula (IV):

[In formula (IV), R <^1> , R <^2> , R <^3> and n have the same meaning as the thing in general formula (I), and * is -O- and R <^4> of the compound represented by general formula (I) Represents a combination of

Examples of the substituent on the benzene ring in the formula (I) include, for example, 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 an aryl having 6 to 14 carbon atoms. And a carboxyl group, a hydroxyl group, an alkoxycarbonyl group having 2 to 16 carbon atoms, a halogen atom, and the like, and an alkyl group having 2 to 5 carbon atoms, a phenyl group and a halogen atom are more preferable.

The compound represented by the general formula (I) is not particularly limited as long as it has the structure, and the production method thereof is, for example, a bis (hydroxyphenyl) fluorene type epoxy compound represented by the following general formula (V). The compound obtained by the above can be mentioned, More specifically, the compound represented by general formula (V) is used as a raw material, A C5 or more ethylenically unsaturated group containing carbonyloxy group is formed here, and a polyhydric carboxylic acid and its And compounds obtained by reacting at least one compound selected from any one of compounds having anhydrides and isocyanate groups:

[In formula (V), the substituent which may further have R <^1> , n and four benzene rings has the same meaning as the thing in Formula (I), respectively, R <^5> Has the same meaning as R ¹ in formula (I)].

As bis (hydroxyphenyl) fluorene which forms the bis (hydroxyphenyl) fluorene type epoxy compound represented by said Formula (V), for example, 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, etc. are mentioned. These bis (hydroxyphenyl) fluorene type epoxy compounds may be used independently or may use 2 or more types together.

The upper limit of the number of carbon atoms of the ethylenically unsaturated group-containing carbonyloxy group formed in the bis (hydroxyphenyl) fluorene type epoxy compound represented by the general formula (V) is not particularly limited, but is preferably 50, more preferably. Is twenty. When using the curable composition of this invention for soldering resists, 20 is more preferable and 15 is especially preferable as an upper limit of carbon number. When carbon number is less than the said range, when a curable composition is made into hardened | cured material, flexibility will fall and adhesiveness with respect to a board | substrate will fall, and when carbon number is too large, heat resistance will fall.

It is preferable that these ethylenically unsaturated group containing carbonyloxy group is group represented by following General formula (II):

[In formula (II), R <^7> , R <^8>. And R ⁹ represents a hydrogen atom or a methyl group, and Y ¹ represents any divalent group. In the formula, * represents a bond to a methylene group generated by ring opening of an epoxy group of a bis (hydroxyphenyl) fluorene type epoxy compound.

Here, if the ethylenically unsaturated group containing carbonyloxy group represented by the said General formula (II) is formed as a result by reaction using the compound represented by the said general formula (V) as a raw material, the formation method is not limited. . Specifically as the formation method, after the method of reacting ethylenically unsaturated group containing carboxylic acids with the compound represented by the said General formula (V), or the carboxylic acid which does not contain an ethylenically unsaturated group first, The method of forming by following reaction, etc. are mentioned.

As the ethylenically unsaturated group-containing carboxylic acids, for example, (meth) acrylic acid (in the present invention, "(meth) acryl" means "acryl" or / and "methacryl"). And reaction products of lactone or polylactone, succinic anhydride, adipic anhydride, maleic anhydride, fumaric anhydride, itaconic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydro anhydride Saturated or unsaturated dicarboxylic anhydrides such as phthalic acid, methylendomethylenetetrahydrophthalic anhydride, phthalic anhydride, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate , Polyethylene glycol mono (meth) acrylate, glycerin di (meth) acrylate, trimethylolpropanedi (meth) acrylate, pentaerythritoldi (meth (Meth) acrylate derivatives having one or more hydroxyl groups in one molecule such as (meth) acrylates such as acrylate, pentaerythritol tri (meth) acrylate and dipentaerythritol penta (meth) acrylate. Semiesters obtained by reacting the above, saturated or unsaturated dicarboxylic anhydrides as described above, phenylglycidyl 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) acrylic And semiesters obtained by reacting an unsaturated group-containing glycidyl compound such as a rate. Among them, in the present invention, succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, and the like, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate And the semi-esters obtained by making pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc. react are especially preferable. These may be used independently or may use 2 or more types together.

Moreover, as carboxylic acids which do not contain the ethylenically unsaturated group, saturation such as hydroxyl group-containing carboxylic acids such as lactic acid and dihydroxypropionic acid and its anhydrides, succinic acid, maleic acid, tetrahydrophthalic acid, phthalic acid and tartaric acid, or Unsaturated dicarboxylic acid and its anhydride are mentioned. Subsequently, the compound which has a functional group which reacts with the hydroxyl group and carboxyl group produced | generated is made to react, and a C5 or more ethylenically unsaturated group containing carbonyloxy group is formed. Here, as a compound which has a functional group which reacts with a hydroxyl group or a carboxyl group, the compound which has an epoxy group, a carboxyl group, and an isocyanate group is preferable, Specifically, the said ethylenically unsaturated group containing carboxylic acids and the said unsaturated group containing glycidyl Although ethylenically unsaturated group containing compounds, such as a compound, are mentioned, It is not limited to these.

In addition, a bis (hydroxyphenyl) fluorene type epoxy compound represented by the above formula (V) is used as a raw material, and a carbon 5 or more ethylenically unsaturated group-containing carbonyloxy group is formed therein, and then further reacted with polyvalent ( polybasic) As carboxylic acid or its anhydride, for example, succinic acid, maleic acid, itaconic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, phthalic acid, etc. Saturated or unsaturated dicarboxylic acids and their acid anhydrides, trimellitic acid and anhydrides thereof and pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, biphenylethertetracarboxylic acid, butanetetracarboxylic Aliphatic or aromatic tetracarboxylic acids and those acid anhydrides which may be substituted, such as an acid, etc. are mentioned.

Among them, tetracarboxylic acids such as dicarboxylic acids such as tetrahydrophthalic acid and phthalic acid and acid anhydrides thereof, trimellitic acid and anhydrides thereof, pyromellitic acid, biphenyltetracarboxylic acid, butanetetracarboxylic acid and the like Acid dianhydrides and the like are preferable because they are excellent in dissolving and removal properties of non-image portions during alkali development as curable compositions, and are preferable, such as dicarboxylic acids such as tetrahydrophthalic acid and phthalic acid, acid anhydrides thereof, trimellitic acid, and anhydrides thereof. The following carboxylic acid and its anhydride are especially preferable.

Moreover, as a compound which has this isocyanate group, organic monoisocyanate, paraphenylene diisocyanate, 2,4, such as butane isocyanate, 3-chlorobenzene isocyanate, cyclohexane isocyanate, 3-isopropenyl- (alpha), (alpha)-dimethylbenzyl isocyanate, etc. -Aromatic diisocyanates such as tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, tolidine diisocyanate, hexamethylene diisocyanate, 2,4 Aliphatic diisocyanates such as, 4-trimethylhexamethylene diisocyanate and dimer acid diisocyanate, isophorone diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), and alicyclic groups such as ω, ω'-diisocyanate dimethylcyclohexane Diisocyanate, xylene diisocyanate, α, α, α ', α'-tetra Aliphatic diisocyanates, lysine ester triisocyanates, 1,6,11- undecane triisocyanate, 1,8- diisocyanate-4-isocyanate methyl octane, 1,3,6 which have aromatic rings, such as methyl xylylene diisocyanate Triisocyanates, such as -hexamethylene triisocyanate, bicycloheptane triisocyanate, tris (isocyanate phenylmethane), and tris (isocyanate phenyl) thiophosphate, trimers, these water adducts, and these polyol adducts, etc. are mentioned. .

Preferred are dimers or trimers of organic diisocyanates, most preferred are trimethylolpropane adducts of tolylene diisocyanates, trimers of tolylene diisocyanates and trimers of isophorone diisocyanates. These may be used independently or may use 2 or more types together.

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

Moreover, the specific example of the compound represented by the general formula (I) in the present invention, for example, by the conventionally known method described in Patent Document 4, etc., specifically, the bis (hydroxyphenyl) fluorene The type epoxy compound is suspended or dissolved in organic solvents such as methyl ethyl ketone, ethyl cellosolve acetate, and butyl cellosolve acetate, and tertiary amines such as triethylamine, benzyldimethylamine and tribenzylamine or tetramethylammonium. Quaternary ammonium salts such as chloride, methyltriethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, trimethylbenzylammonium chloride, phosphorus compounds such as triphenylphosphine, or stibins such as triphenylstyrene; In the presence of, thermal polymerization of hydroquinone, hydroquinone monomethyl ether, methyl hydroquinone and the like Under the coexistence of the supporting agent, the ethylenically unsaturated group-containing carboxylic acids are usually added in an amount of 0.8 to 1.5 chemical equivalents, preferably 0.9 to 1.1 chemical equivalents, per one chemical equivalent of the epoxy group of the epoxy compound, and usually 60 to The reaction is carried out at a temperature of 150 DEG C, preferably 80 to 120 DEG C, and then the polyhydric carboxylic acid or its anhydride is usually 0.05 to 1.0 chemical equivalent to one chemical equivalent of the hydroxyl group generated in the reaction. It can be prepared by a method such as adding to and continuing the reaction under the above conditions.

[1-2] (A-2) Resin having a trisphenol methane structure

If the curable composition of this invention satisfy | fills the physical property conditions as described in [1-15] and / or [1-16] mentioned later, in addition to (A-1) component as described in [1-1] or (A-1) Instead of the component, the resin having a (A-2) trisphenol methane structure may be contained.

The resin having the trisphenol methane structure of the present invention is not particularly limited as long as it has a trisphenol methane structure in the resin structure. For example, an epoxy resin having a trisphenol methane structure, (meth) acrylic acid and its anhydride Or resin obtained by making the said polyhydric carboxylic acid or its anhydride react with reaction product with the said ethylenically unsaturated group containing carboxylic acid is mentioned as a preferable thing.

Here, the epoxy resin which has a trisphenol methane structure is Nippon Kayaku Co., for example. The manufacture "EPPN-501H", "EPPN-501HY", "EPPN-502H", etc. are mentioned.

As the resin having a trisphenol methane structure, for example, Nippon Kayaku Co. The manufacture "TCR1025", "TCR1064", "TCR1286", etc. are mentioned.

The amount per weight of the double bond of (A-1) component and / or (A-2) component which becomes a structural requirement of the curable composition of this invention is a double bond equivalent: (double bond equivalent) = (weight of a compound (g) ) / (Moles of double bond content of the compound), the more double bonds per unit weight, the smaller the value of the double bond equivalents. In the case where the curable composition of the present invention is used for spacer use, in order to improve the recovery rate and / or the elastic recovery rate, the total amount of double bonds (A) is preferably 550 or less, more preferably 400 or less, most preferably 350 It is as follows.

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 weight may be calculated by the above formula from the injection amount of the compound having an ethylenic double bond, and in a complex system such as a resist, the double bond equivalent weight of the solution is measured by a known method, and then the solid content concentration of the resist is known. It can also measure by the method of (double bond equivalent) = (double bond equivalent of resist) x (solid content concentration in resist).

[1-3] (B) Photopolymerization Initiator and / or Thermal Polymerization Initiator

The curable composition of this invention may contain the photoinitiator and / or the thermal polymerization initiator further. As the component (B), the photopolymerization initiator generates active species such as radicals, acids or bases when the curable composition is subjected to irradiation with active light, and is used as the compound represented by the above general formula (I) and as necessary. As an active compound which leads to the superposition | polymerization of the ethylenically unsaturated compound of (C) component to be mentioned, For example, acetophenones, benzophenones, hydroxybenzenes, thioxanthones, anthraquinones, ketals, hexaaryl ratio Imidazoles, titanocenes, halogenated hydrocarbon derivatives, organic boron salts, onium salts, sulfone compounds, carbamic acid derivatives, sulfonamides, triarylmethanols, and the like.

As the acetophenones, for example, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, and 1-hydroxy-1- ( p-dodecylphenyl) ketone, 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-trichloromethyl- (p-butylphenyl) ketone, α-hydroxy-2-methylphenyl Propanone, α-aminoacetophenone, and the like, and also benzophenones, for example, benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-carboxybenzophenone, 2 -Chlorobenzophenone, 4-bromobenzophenone, Michler ketone, etc., are also hydroxybenzenes, for example, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy Hydroxy-4-benzylbenzophenone, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate and the like In addition, as thioxanthones, for example, thioxanthone, 2-ethyl thioxanthone and 2-isopropyl thi Santon, 2, 4- dimethyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- diisopropyl thioxanthone, 2-chloro thioxanthone, etc. are also anthraquinones, For example, For example, 2-methyl anthraquinone etc. are ketals, For example, benzyl dimethyl ketal etc. are mentioned, respectively.

As the hexaarylbiimidazoles, for example, 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-dibromophenyl) biimidazole, 2,2'-bis (o -Bromophenyl) -4,4 ', 5,5'-tetra (o, p-dichlorophenyl) biimidazole, 2,2'-bis (o-chlorophenyl) -4,4', 5,5 '-Tetra (p-chloronaphthyl) biimidazole and the like. Among them, the hexaphenylbiimidazole compound is preferable, and it is more preferable that the o-position of the benzene ring bonded to the 2,2'-position on the imidazole ring is substituted with a halogen atom, and 4, on the imidazole ring It is particularly preferable that the benzene ring bonded at the 4 ', 5,5'-position is unsubstituted or substituted with a halogen atom or an alkoxycarbonyl group.

As the titanocene, for example, dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis (2,4-difluorophenyl) and dicyclo Pentadienyl titanium bis (2,6-difluorophenyl), dicyclopentadienyl titanium bis (2,4,6-trifluorophenyl), dicyclopentadienyl titanium bis (2,3,5, 6-tetrafluorophenyl), dicyclopentadienyltitaniumbis (2,3,4,5,6-pentafluorophenyl), di (methylcyclopentadienyl) titaniumbis (2,6-difluoro Phenyl), di (methylcyclopentadienyl) titaniumbis (2,3,4,5,6-pentafluorophenyl), dicyclopentadienyltitaniumbis [2,6-difluoro-3- (1 -Pyrrolyl) phenyl] etc. are mentioned. Among them, titanium compounds having a dicyclopentadienyl structure and a bisphenyl structure are preferable, and those in which the o-position of the bisphenyl ring is substituted with a halogen atom are particularly preferable.

Examples of the halogenated hydrocarbon derivatives include halomethylated s-triazine derivatives, for example, 2,4,6-tris (monochloromethyl) -s-triazine, 2,4,6 -Tris (dichloromethyl) -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-tri Azine, 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 (trichloro Rommethyl) -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)- 4,6-bis (trichloromethyl) -s-triazine, 2- (p-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-ethoxy Carbonylnaphthyl) -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-tri Halomethylated s- such as azine, 2-methyl-4,6-bis (tribromomethyl) -s-triazine and 2-methoxy-4,6-bis (tribromomethyl) -s-triazine Triazine derivatives are mentioned, A bis (trihalomethyl) -s-triazine is preferable among these.

Moreover, as the organic boron salts, for example, an organic boron ammonium complex, an organic boron phosphonium complex, an organic boron sulfonium complex, an organic boron oxosulfonium complex, an organic boron iodonium complex, an organic boron transition metal coordination The complex etc. are mentioned, As this organic boron anion, n-butyl- triphenyl boron anion, n-butyl- tris (2,4,6-trimethylphenyl) boron anion, n-butyl- tris is mentioned, for example. (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, n-butyl-tris (2,6-difluoro-3 -Pyrrolylphenyl) -borate Alkyl-triphenylboron anions, such as an anion, are preferable, and as an amphoteric ion, onium compounds, such as an ammonium cation, a phosphonium cation, a sulfonium cation, an iodonium cation, are preferable, and organic ammonium cations, such as tetraalkylammonium This is particularly preferred.

Moreover, as the onium salts, for example, ammonium salts such as tetramethyl ammonium bromide and tetraethyl ammonium bromide, diphenyl iodonium hexafluoroarsenite, diphenyl iodonium tetrafluoroborate, diphenyl ion Donium p-toluenesulfonate, diphenyl iodonium camphorsulfonate, dicyclohexyl iodonium hexafluoroarsenate, dicyclohexyl iodonium tetrafluoroborate, dicyclohexyl iodonium p-toluene Iodonium salts, such as sulfonate and dicyclohexyl iodonium camphorsulfonate, triphenyl sulfonium hexafluoroarsenate, triphenyl sulfonium tetrafluoroborate, triphenylsulfonium p-toluenesulfonate, triphenyl Sulfonium camphorsulfonate, tricyclohexyl sulfonium hexafluoroarsenate, tricyclohexyl sulfonium tetrafluoroborate, tri And sulfonium salts such as cyclohexylsulfonium p-toluenesulfonate and tricyclohexyl sulfonium camphor sulfonate.

Examples of the sulfone compounds include bis (phenylsulfonyl) methane, bis (p-hydroxyphenylsulfonyl) methane, bis (p-methoxyphenylsulfonyl) methane and bis (α-naph). Bis (sulfonyl) such as methylsulfonyl) methane, bis (β-naphthylsulfonyl) methane, bis (cyclohexylsulfonyl) methane, bis (t-butylsulfonyl) methane and phenylsulfonyl (cyclohexylsulfonyl) methane Methane compound, phenylcarbonyl (phenylsulfonyl) methane, naphthylcarbonyl (phenylsulfonyl) methane, phenylcarbonyl (naphthylsulfonyl) methane, cyclohexylcarbonyl (phenylsulfonyl) methane, t-butylcarbon Carbonyl (sulfonyl) methane compounds, bis (phenylsulfonyl) diazomethane, such as carbonyl (phenylsulfonyl) methane, phenylcarbonyl (cyclohexylsulfonyl) methane, and phenylcarbonyl (t-butylcarbonyl) methane , Bis (p-hydroxyphenylsulfonyl) diazomethane, bis (p-methoxyphenylsulfonyl) diazomethane, bis (α-naphthylsulfonyl) diazomethane, bis (β-naphthyl Ponyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (t-butylsulfonyl) diazomethane, phenylsulfonyl (cyclohexylsulfonyl) diazomethane, bis (sulfonyl) diazomethane Compound, Phenylcarbonyl (phenylsulfonyl) diazomethane, Naphthylcarbonyl (phenylsulfonyl) diazomethane, Phenylcarbonyl (naphthylsulfonyl) diazomethane, Cyclohexylcarbonyl (phenylsulfonyl) diazo Carbonyl (sulfonyl), such as methane, t-butylcarbonyl (phenylsulfonyl) diazomethane, phenylcarbonyl (cyclohexylsulfonyl) diazomethane, and phenylcarbonyl (t-butylcarbonyl) diazomethane A diazomethane compound etc. are mentioned.

Moreover, as the carbamic acid derivatives, for example, benzoylcyclohexyl carbamate, 2-nitrobenzylcyclohexyl carbamate, 3,5-dimethoxybenzyl cyclohexyl carbamate, 3-nitrophenylcyclo Hexyl carbamate and the like further include sulfonamides such as N-cyclohexyl-4-methylphenylsulfonamide, N-cyclohexyl-2-naphthylsulfonamide, and the like. As an example, triphenylmethanol, tri (4-chlorophenyl) methanol, etc. are mentioned, respectively.

In addition, the thermal polymerization initiator of (B) component which comprises the curable composition of this invention produces | generates active species, such as a radical, when a curable composition is heated, and is used if necessary and the compound represented by the said general formula (I) As an active compound which leads to superposition | polymerization the ethylenically unsaturated compound of (C) component mentioned later, organic peroxides, azo-type compounds, etc. are mentioned, for example.

As the organic peroxides, for example, methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, acetylacetone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, 3,3,5-trimethylcyclohexanone per Ketone peroxides such as oxides, isobutyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, o-methylbenzoyl peroxide, m-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide Diacyl peroxides such as oxides and m-toluoyl peroxides, t-butyl hydroperoxides, cumene hydroperoxides, diisopropylbenzene hydroperoxides, p-mentane hydroperoxides, 2,5-dimethylhexane-2 Hydroperoxides such as, 5-dihydroperoxide, 1,1,3,3-tetramethylbutylhydroperoxide, 2,4,4-trimethylpentyl-2-hydroperoxide, di-t-butylper Oxide, t-butyl cumyl peroxide, dicumyl peroxide, 1,3 (or 1,4) -bis (t-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy ) Dialkyl peroxides such as 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-trimethylcyclohexane, 2,2-bis (t-butylperoxy) butane, 4,4-bis (t-butylperoxy) valeric acid-n Peroxy ketals such as butyl ester, t-butyl peroxy acetate, t-butyl peroxy octoate, t-butyl peroxy pivalate, t-butyl peroxy neodecanoate, t-butyl peroxy-3 , 5,5-trimethylhexanoate, t-butylperoxylaurate, di-t-butylperoxytrimethyl adipate, t-butylperoxybenzoate, α-cumylperoxy neodecanoate, 2, Alkyl peresters such as 4,4-trimethylpentylperoxyphenoxyacetate, di-2-ethylhexyl peroxydicarbonate, di-2 Ethoxyethylperoxydicarbonate, diisopropylperoxydicarbonate, dimethoxyisopropylperoxydicarbonate, di-3-methoxybutylperoxydicarbonate, bis (3-methyl-3-methoxybutyl) peroxydicarbonate, Peroxy carbonates, such as t-butyl peroxy isopropyl carbonate, t-butyl peroxy allyl carbonate, bis (4-t-butyl cyclohexyl) peroxy dicarbonate, and acetyl cyclohexyl sulfonyl peroxy dicarbonate, etc. are mentioned. .

As the azo compounds, for example, 1,1'-azobiscyclohexane-1-carbonitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2 '-Azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (methylisobutyrate), 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 (B) component, in the present invention, α-aminoacetophenone derivatives as acetophenones of the photopolymerization initiator are preferable, and those represented by the following general formula (VII) are particularly preferable. :

[In 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, and 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 Each independently represent 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, and R ³⁷ And R ³⁸ are linked to each other, or R ³⁷ or R ³⁸ and R ³⁵ or R ³⁶ These may be connected to each other to form a cyclic structure, and the benzene ring may have a substituent.

Here, as an alkyl group of R <^35> , R <^36> , R <^37> and R <^{38> in} the said General formula (VII), it is preferable that it is C1-C15, especially 1-10. Moreover, as a substituent in an alkyl group, an allyl group, and a phenyl group, an alkyl group, an alkoxy group, a hydroxyalkyl group, a hydroxyalkoxy group, an acetoxy alkoxy group, an alkoxyalkoxy group, an alkylcarbonylalkyl group, an alkylthio group, a haloalkyl group, a phenyl group And halogen atoms. In addition, R ³⁴ With R ³⁵ Are connected to each other, or R ³⁷ or R ³⁸ and R ³⁵ or R ³⁶ Pyrrolidine, piperidine, piperazine, morpholine, oxazolidine, pyridazine, etc. are mentioned as a cyclic structure which is connected and formed mutually.

Moreover, as a substituent in a benzene ring, an alkyl group, a hydroxyl group, an alkoxy group, allyloxy group, phenoxy group, benzoyl group, silyloxy group, mercapto group, alkylthio group, allylthio group, cycloalkylthio group, benzyl tea Or phenylthio group, alkylsulfonyl group, phenylsulfonyl group, alkylsulfinyl group, alkylamino group, allylamino group, pyrrolidinyl group, piperidinyl group, piperazinyl group, morpholinyl group, halogen atom and the like. In addition, the benzene ring may form a condensed ring, and the condensed ring may include fluorenone, dibenzosuberon, indolin, quinoxaline, carbazole, phenazine, acridanone, benzodioxol, benzofuran, and xanthene. , Xanthone, phenoxadine, benzothiazole, phenothiazine and the like.

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

As propane-1-one classified into carbon number 3 of a basic skeleton, 1-phenyl- 2-dimethylamino- 2-methyl- 3- (4-methylphenyl)-propane- 1-one, 1-phenyl- 2-dimethylamino -2-methyl-3- (4-methoxyphenyl) -propane-1-one, 1-phenyl-2-dimethylamino-2-methyl-3- (3,4-dimethoxyphenyl) -propane-1- On, 1-phenyl-2-dimethylamino-2-methyl-3- (4-methylthiophenyl) -propane-1-one, 1-phenyl-2-dimethylamino-2-methyl-3- (4-fluoro Rophenyl) -propane-1-one, 1-phenyl-2-dimethylamino-2-methyl-3- (2-chlorophenyl) -propane-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) -propan-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-propane-1-one, 1- (4-benzoylphenyl) -2-dimethylamino-2-benzyl-propane-1-one, 1- (4-methylthio Phenyl) -2-morpholino-2-methyl-propane-1-one, 1- (4-methylthiophenyl) -2-dimethylamino-2-methyl-3- (4-methylphenyl) -propane-1- On, 1- (4-methylthiophenyl) -2-dimethylamino-2-methyl-3- (4-methoxyphenyl) -propan-1-one, 1- (4-methylthiophenyl) -2-dimethyl Amino-2-methyl-3- (3,4-dimethoxyphenyl) -propan-1-one, 1- (4-methylthiophenyl) -2-dimethylamino-2-methyl-3- (4-fluoro Phenyl) -propan-1-one, 1- (4-methylthiophenyl) -2-dimethylamino-2-methyl-3- (2-chlorophenyl) -propan-1-one, 1- (4-methylthio Phenyl) -2-dimethylamino-2-methyl-3- (4-chlorophenyl) -propan-1-one, 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-dimethyla No-2-methyl-propane-1-one, 1- (4-butylthiophenyl) -2-dimethylamino-2-benzyl-3-phenyl-propane-1-one, 1- (4-cyclohexylthiophenyl ) -2-dimethylamino-2-benzyl-3-phenyl-propane-1-one, 1- (4-benzylthiophenyl) -2-dimethylamino-2-benzyl-propane-1-one, 1- (4 -Dimethylaminophenyl) -2-dimethylamino-2-benzyl-propan-1-one, 1- (4-dimethylaminophenyl) -2-dimethylamino-2-benzyl-3-phenyl-propan-1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2- (2-chloropentenyl) -propane-1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2- Benzyl-propan-1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2-benzyl-3-phenyl-propan-1-one, 1- (N-methylindolin-5-yl ) -2-dimethylamino-2-benzyl-propan-1-one, 1- (N-butylphenoxazin-2-yl) -2-morpholino-2-benzyl-propan-1-one, etc. are mentioned. have.

As butan-1-one classified into carbon number 4 of a 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-tri Methoxyphenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- (4-hydroxyphenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- [4- (2-hydroxyethoxy) 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-dimethylami No-2-benzyl-butan-1-one, 1- (2,4-dichlorophenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- (3,4-dichlorophenyl) -2 -Dimethylamino-2-benzyl-butan-1-one, 1- (3,5-dichlorophenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- (4-bromophenyl)- 2-dimethylamino-2-benzyl-butan-1-one, 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-butan-1-one, 1- [4- (2-methoxyethylthio) phenyl] -2-dimethylamino-2-benzyl-butane- 1-one, 1- [4- (2-hydroxyethylthio) phenyl] -2-dimethylamino-2-benzyl-butan-1-one, 1- (4-octylthiophenyl) -2-dimethylamino- 2-benzyl-butan-1-one, 1- (4-methylsulfonylphenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- [4- (4-methylphenylsulfonyl) phenyl] 2-dimethylamino-2-benzyl-butan-1-one, 1- (4-benzenesul Nylphenyl) -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-dimethylaminophenyl) -2-dimethylamino-2- (4 -Dodecylbenzyl) -butan-1-one, 1- (4-dimethylaminophenyl) -2-dimethylamino-2- (1-chlorohexenylmethyl) -butan-1-one, 1- (4-dimethyl Aminophenyl) -2-dimethylamino-2- (2-pinene-10-yl) -butan-1-one, 1- (4-dimethylamino-2-methylphenyl) -2-dimethylamino-2-benzyl-butane -1-one, 1- (4-dimethylamino-3-ethylphenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- (4-diethylaminophenyl) -2-dimeth Methylamino-2-benzyl-butan-1-one, 1- (4-isopropylaminophenyl) -2-dimethylamino-2-butyl-butan-1-one, 1- [4- (2-methoxyethyl Amino) 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-morpholi Nophenyl) -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) -butan-1-one, 1- (4-morpholinophenyl)- 2-dimethylami 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) -butan-1-one, 1- (4 -Morpholinophenyl) -2-dimethylamino-2- (4-methoxybenzyl) -butan-1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2- (4-part Oxybenzyl) -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-dimethyl Amino-2- [4- (2- (2-methoxyethoxy) ethoxy) benzyl] -butan-1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2- [4 -(2- (2-methoxyethoxy) 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-butan-1- On-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-dimethylamino-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 -part Methylmethylamino-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-dimethylamino-2-benzyl-butane- 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, 1- (2,3-di Hydrobenzofuran-5-yl) -2-dimethylamino-2-benzyl-butan-1-one, 1- (xanthen-2-yl) -2-dimethylamino-2-benzyl-butan-1-one, 1 -(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) -diben Crude Veron, 3, 6-di (2-dimethylamino-2-benzyl- butanoyl) -9-butyl- carbazole, etc. are mentioned.

As pentan-1-one classified into carbon number 5 of a basic skeleton, 1- (4-morpholinophenyl) -2-dimethylamino-2-allyl-pentan-1-one and 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) -pentan-1-one etc. are mentioned.

In addition, as penten-1-one, 1-phenyl-2-dimethylamino-2-methyl-4-penten-1-one and 1-phenyl-2-dimethylamino-2-ethyl-4-penten-1-one , 1-phenyl-2-dimethylamino-2-benzyl-4-penten-l-one, 1-phenyl-2-morpholino-2-methyl-4-penten-l-one, 1-phenyl-2- Morpholino-2-benzyl-4-penten-l-one, 1,2-diphenyl-2-morpholino-4-penten-l-one, 1- (4-methylphenyl) -2-morpholino 2-methyl-4-penten-l-one, 1- (4-dodecylphenyl) -2-morpholino-2-ethyl-4-penten-l-one, 1- (4-methoxyphenyl) -2-dimethylamino-2-ethyl-4-penten-l-one, 1- (4-methoxyphenyl) -2-dibutylamino-2-methyl-4-penten-l-one, 1- (4 -Methoxyphenyl) -2-piperidino-2-ethyl-4-penten-1-one, 1- (4-methoxyphenyl) -2-oxazolidino-2-methyl-4-pentene-1- On, 1- (4-methoxyphenyl) -2-morpholino-2-ethyl-4-penten-l-one, 1- (4-methoxyphenyl) -2-morpholino-2-phenyl- 4-penten-l-one, 1- (3,4-dimethoxyphenyl) -2-morpholino-2-ethyl-4-penten-l-one, 1- [4- (2-methoxyethoxy ) Phenyl] -2-morpholino-2- Methyl-4-penten-l-one, 1- [4- (2-methoxyethoxy) phenyl] -2-morpholino-2-ethyl-4-penten-l-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-ether-4-penten-1- On, 1- (4-trimethylsilyloxyphenyl) -2-morpholino-2-methyl-4-penten-l-one, 1- (4-fluorophenyl) -2-dimethylamino-2-methyl- 4-penten-l-one, 1- (4-fluorophenyl) -2-dimethylamino-2-ethyl-4-penten-l-one, 1- (4-fluorophenyl) -2-dimethylamino- 2-benzyl-4-penten-l-one, 1- (4-fluorophenyl) -2-morpholino-2-methyl-4-penten-l-one, 1- (4-fluorophenyl)- 2-morpholino-2-ethyl-4-penten-l-one, 1- (4-fluorophenyl) -2-morpholino-2-ethyl-4-methyl-4-penten-l-one, 1- (4-fluorophenyl) -2-morpholino-2-ethyl-5-methyl-4-penten-l-one, 1- (4-fluorophenyl) -2-morpholino-2- Benzyl-4-penten-l-one, 1- (3,4-dichlorophenyl) -2-dimethylamino-2-ethyl-4-penten-l-one, 1- (3,5-dichloro-4-meth Methoxyphenyl) -2-morpholino-2-methyl-4-penten-l-one, 1- (4-bromophenyl) -2-morpholino-2-methyl-4-penten-l-one, 1- (4-bromophenyl) -2-morpholino-2-ethyl-4-penten-1-one, 1- (4-bromophenyl) -2-morpholino-2-t-butyl -4-penten-l-one, 1- (4-methylthiophenyl) -2-dimethylamino-2-methyl-4-penten-l-one, 1- (4-methylthiophenyl) -2-dimethylamino -2-ethyl-4-penten-l-one, 1- (4-methylthiophenyl) -2-dimethylamino-2-phenyl-4-penten-l-one, 1- (4-methylthiophenyl)- 2-dimethylamino-2-benzyl-4-penten-l-one, 1- (4-methylthiophenyl) -2-piperidino-2-ethyl-4-penten-l-one, 1- (4- Methylthiophenyl) -2-morpholino-2-methyl-4-penten-l-one, 1- (4-methylthiophenyl) -2-morpholino-2-ethyl-4-penten-l-one , 1- (4-methyl Ophenyl) -2-morpholino-2-ethyl-4-methyl-4-penten-1-one, 1- (4-methylthiophenyl) -2-morpholino-2-phenyl-4-pentene- 1-one, 1- (4-methylthiophenyl) -2-morpholino-2-benzyl-4-penten-l-one, 1- (4-ethylthiophenyl) -2-morpholino-2- Ethyl-4-penten-l-one, 1- (4-isopropylthiophenyl) -2-morpholino-2-methyl-4-penten-l-one, 1- (4-allylthiophenyl) -2 Morpholino-2-ethyl-4-penten-l-one, 1- [4- (2-hydroxyethylthio) phenyl] -2-morpholino-2-methyl-4-penten-l-one , 1- [4- (2-hydroxyethylthio) phenyl] -2-morpholino-2-ethyl-4-penten-l-one, 1- [4- (2-hydroxyethylthio) phenyl] -2-morpholino-2-propyl-4-penten-l-one, 1- [4- (2-hydroxyethylthio) phenyl] -2-morpholino-2-t-butyl-4- pentene -1-one, 1- [4- (2-methoxycarbonylethylthio) phenyl] -2-morpholino-2-methyl-4-penten-l-one, 1- (4-methylsulfonylphenyl ) -2-dimethylamino-2-ethyl-4-penten-l-one, 1- (4-butylsulfinylphenyl) -2-dimethylamino-2-ethyl-4-penten-l-one, 1- [ 4- (4-methylphenylthio) phenyl] -2-morpholino-2-ethyl-4-penten-l-one, 1- [4- (4-methylphenylsulfonyl) phenyl] -2-morpholino-2- Ethyl-4-methyl-4-penten-l-one, 1- (4-chlorophenylthiophenyl) -2-dimethylamino-2-benzyl-4-penten-l-one, 1- (4-dimethylaminophenyl ) -2-dimethylamino-2-methyl-4-penten-l-one, 1- (4-dimethylaminophenyl) -2-dimethylamino-2-ethyl-4-penten-l-one, 1- (4 Dimethylaminophenyl) -2-dimethylamino-2-benzyl-4-penten-l-one, 1- (4-dimethylaminophenyl) -2-methylphenylamino-2-ethyl-4-penten-l-one, 1- (4-dimethylaminophenyl) -2- (pyrrolidin-1-yl) -2-methyl-4-penten-1-one, 1- (4-dimethylaminophenyl) -2-morpholino- 2-methyl-4-penten-l-one, 1- (4-dimethylaminophenyl) -2-morpholino-2-ethyl-4-methyl-4-penten-l-one, 1- (4-dimethyl Aminophenyl) -2-morpholino-2-benzyl-4-penten-1-one, 1- (4-dimethylaminophenyl) -2- (2,6-dimethylmorpholin-4-yl) -2- Ethyl-4-penten-l-one, 1- (4-diethylaminophenyl) -2-dimethyl Mino-2-benzyl-4-penten-l-one, 1- [4-bis (2-methoxyethyl) aminophenyl] -2-morpholino-2-methyl-4-penten-l-one, 1 -(4-butylaminophenyl) -2-dibutylamino-2-methyl-4-penten-1-one, 1- (4-butylaminophenyl) -2-morpholino-2-methyl-4-pentene -1-one, 1- (4-dibutylaminophenyl) -2-morpholino-2-methyl-4-penten-l-one, 1- (4-diallylaminophenyl) -2-morpholino 2-methyl-4-penten-l-one, 1- [4- (pyrrolidin-l-yl) phenyl] -2-morpholino-2-methyl-4-penten-l-one, 1- (4-piperidinophenyl) -2-piperidino-2-methyl-4-penten-1-one, 1- [4- (piperazin-1-yl) phenyl] -2-dimethylamino-2- Ethyl-4-penten-l-one, 1- [4- (4-methylpiperazin-1-yl) phenyl] -2-morpholino-2-methyl-4-penten-l-one, 1- [ 4- (N-methylpiperazin-1-yl) phenyl] -2- (N-methylpiperazin-1-yl) -2-methyl-4-penten-1-one, 1- (4-morpholino Phenyl) -2-dimethylamino-2-methyl-4-penten-l-one, 1- (4-morpholinophenyl) -2-dimethylamino-2-ethyl-4-penten-l-one, 1- (4-morpholinophenyl)- 2-dimethylamino-2-isopropyl-4-penten-l-one, 1- (4-morpholinophenyl) -2-dimethylamino-2-benzyl-4-penten-l-one, 1- (4 -Morpholinophenyl) -2-diethylamino-2-ethyl-4-penten-l-one, 1- (4-morpholinophenyl) -2-di (2-methoxyethyl) amino-2- Ethyl-4-penten-l-one, 1- (4-morpholinophenyl) -2-butylmethylamino-2-methyl-4-penten-l-one, 1- (4-morpholinophenyl)- 2-allylmethylamino-2-ethyl-4-penten-l-one, 1- (4-morpholinophenyl) -2-diallylamino-2-ethyl-4-penten-l-one, 1- (4-morpholinophenyl) -2-benzylmethylamino-2-ethyl-4-penten-l-one, 1- (4-morpholinophenyl) -2- (piperazin-1-yl) -2 -Ethyl-4-penten-l-one, 1- (4-morpholinophenyl) -2-morpholino-2-methyl-4-penten-l-one, 1- (4-morpholinophenyl) -2-morpholino-2-ethyl-4-penten-l-one, 1- (4-morpholinophenyl) -2-morpholino-2-ethyl-4-penten-l-one-dodecyl Benzenesulfonate, 1- (4-morpholinophenyl) -2-morpholino-2-ethyl-4-methyl-4-penten-l-one, 1- (4 -Morpholinophenyl) -2-morpholino-2-benzyl-4-penten-l-one, 1- [4- (2,6-dimethylmorpholin-4-yl) phenyl] -2-morpholine -2-methyl-4-penten-l-one, 1- [4- (2,6-dimethylmorpholin-4-yl) phenyl] -2- (2,6-dimethylmorpholin-4-yl)- 2-ethyl-4-penten-l-one, 1- (N-butylindolin-5-yl) -2-morpholino-2-ethyl-4-penten-l-one, 1- (1,4 -Dibutyl-1,2,3,4-tetrahydroquinoxalin-6-yl) -2-morpholino-2-ethyl-4-penten-1-one, 1- (N-butylcarbazole-3 -Yl) -2-morpholino-2-ethyl-4-penten-l-one, 1- (5,10-dibutyl-5,10-dihydrophenazin-6-yl) -2-dimethylamino 2-methyl-4-penten-l-one, 1- (1,3-benzodioxol-5-yl) -2-morpholino-2-methyl-4-penten-l-one, 1- ( Benzofuran-3-yl) -2-morpholino-2-ethyl-4-penten-1-one, 1- (benzofuran-6-yl) -2-morpholino-2-ethyl-4-pentene -1-one, 1- (2,3-dihydrobenzofuran-5-yl) -2-morpholino-2-methyl-4-penten-l-one, 1- (N-methylphenothiazine- 2-yl) -2-dimethylamino-2-allyl-4-penten-l-one, 3,6-di (2-morpholi -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, etc. are mentioned.

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

In addition, as hexen-1-one, 1- (4-methylthiophenyl) -2-morpholino-2-ethyl-4-methyl-4-hexen-1-one and 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, etc. are mentioned.

As heptane-1-one classified into carbon number 7 of a 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, etc. are mentioned.

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-methylthio Benzoyl) -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. are mentioned.

As octane-1-one classified into carbon number 8 of a basic skeleton, 1- (4-morpholinophenyl) -2-dimethylamino-2-benzyl-octan-1-one and 1- (4-morpholinophenyl ) -2-dimethylamino-2- (4-dodecylbenzyl) -octan-1-one, etc. are mentioned.

When the curable composition of this invention contains the compound represented by the said General formula (I), and the photoinitiator and / or thermal-polymerization initiator of the said (B) component, the content rate of those each component is with respect to the whole quantity of a curable composition. (A) It is preferable that it is 20 to 95 weight%, and it is more preferable that it is 30 to 90 weight%.

Moreover, it is preferable that (B) component is 0.1-40 weight%, and it is more preferable that it is 0.2-20 weight%. When there are too many or too much (A) components, and too little (B) component, there exists a tendency for the sclerosis | hardenability as a curable composition to become inadequate, and when there are too many (B) components, background contamination is easy to generate | occur | produce at the time of image development. There is a tendency.

[1-3] (C) ethylenically unsaturated compound

The curable composition of this invention may contain the (C) ethylenically unsaturated compound further. It is preferable to contain the ethylenically unsaturated compound of (C) component for the purpose of further improving curability of the curable composition of this invention. The ethylenically unsaturated compound is additionally polymerized by the action of a polymerization initiation system comprising a photopolymerization initiator and / or a thermal polymerization initiator of component (B) when the curable composition is subjected to irradiation with actinic light or heated, In some cases, it is a compound which has at least one radically polymerizable ethylenically unsaturated bond in a molecule | numerator which crosslinks and hardens.

As an ethylenically unsaturated compound of (C) component in this invention, the compound which has one ethylenically unsaturated bond in a molecule | numerator, specifically, (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, Unsaturated carboxylic acids such as itaconic acid and citraconic acid, and alkyl esters thereof, (meth) acrylonitrile, (meth) acrylamide, styrene, and the like may be used, but may be polymerizable, crosslinkable, and thus developing solutions of exposed and non-exposed parts. It is preferable that it is a compound which has two or more ethylenically unsaturated bonds in a molecule | numerator from the point that the difference in solubility can be expanded, and the acrylate compound whose unsaturated bond originates in a (meth) acryloyloxy group especially desirable. As a compound which has two or more ethylenically unsaturated bonds in a molecule, typically, ester of unsaturated carboxylic acid and a polyhydroxy compound (henceforth ester (meth) acrylates), (meth) acryl Urethane (meth) acrylates with monooxy group-containing phosphates, hydroxy (meth) acrylate compounds and polyisocyanate compounds, and epoxy (meth) with (meth) acrylic acid or hydroxy (meth) acrylate compounds and polyepoxy compounds ) Acrylates and the like.

As ester of this unsaturated carboxylic acid and a polyhydroxy compound, For example, unsaturated carboxylic acid as mentioned above, ethylene glycol, polyethyleneglycol (additional number 2-14), propylene glycol, polypropylene glycol (additional number) 2-14), trimethylene glycol, tetramethylene glycol, hexamethylene glycol, trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol and their ethylene oxide adducts, propylene oxide adducts, diethanolamine, triethanolamine, etc. Reactant with an aliphatic polyhydroxy compound of, specifically, for example, ethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropanedi (meth ) Acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide Li (meth) acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, glycerol propylene oxide addition tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) ) Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like, and the same crotonate, isoctonate, maleate, Itaconate, citraconate, and the like.

Moreover, as ester of this unsaturated carboxylic acid and a polyhydroxy compound, Unsaturated carboxylic acid as mentioned above, aromatic polyhydroxy compounds, such as hydroquinone, resorcin, pyrogallol, bisphenol F, bisphenol A, or their ethylene oxide Reaction with an adduct, Specifically, for example, bisphenol A di (meth) acrylate, bisphenol A bis [oxyethylene (meth) acrylate], bisphenol A bis [glycidyl ether (meth) acrylate], etc. And a reaction product of such unsaturated carboxylic acid with a heterocyclic polyhydroxy compound such as tris (2-hydroxyethyl) isocyanurate, specifically, for example, tris (2-hydroxyethyl) iso Di (meth) acrylate and tri (meth) acrylate of cyanurate, and also the half of unsaturated carboxylic acid, polyhydric carboxylic acid, and polyhydroxy compound Water, specifically, the condensation product of (meth) acrylic acid, phthalic acid, and ethylene glycol, the condensation product of (meth) acrylic acid, maleic acid, and diethylene glycol, the (meth) acrylic acid, terephthalic acid, and pentaerythritol And condensates of (meth) acrylic acid, adipic acid, butanediol, and glycerin.

The (meth) acryloyloxy group-containing phosphate is not particularly limited as long as it is a phosphate compound containing a (meth) acryloyloxy group. Among them, the formula (VIIIa), (VIIIb) or (VIIIc) It is preferable to be displayed.

[In formula (VIIIa), (VIIIb), (VIIIc), R <^10> represents a hydrogen atom or a methyl group, p and p 'are an integer of 1-25, q is 1, 2 or 3.].

Here, it is preferable that p and p 'are 1-10, especially 1-4, As these specific examples, it is (meth) acryloyloxyethyl phosphate and bis [(meth) acryloyloxyethyl, for example. ] Phosphate, (meth) acryloyloxyethylene glycol phosphate, etc., These can be used individually or in mixtures, respectively.

Moreover, as the urethane (meth) acrylates, hydroxy (meth), such as hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, tetramethylol ethane tri (meth) acrylate, for example. ) Acrylic compound, aliphatic polyisocyanate, such as hexamethylene diisocyanate and 1,8- diisocyanate-4-isocyanate methyl octane, cyclohexane diisocyanate, dimethyl cyclohexane diisocyanate, 4,4'- methylene bis (cyclohexyl Alicyclic polyisocyanates such as isocyanate), isophorone diisocyanate, bicycloheptane triisocyanate, aromatic polyisocyanates such as 4,4'-diphenylmethane diisocyanate, tris (isocyanatephenyl) thiophosphate, isocyanurate Reactant with polyisocyanate compounds, such as heterocyclic polyisocyanate Etc. can be mentioned.

Especially, as urethane (meth) acrylates, the compound which has four or more urethane bond [-NH-CO-O-] and four or more (meth) acryloyloxy groups in 1 molecule is preferable, The compound Silver, for example, diamines such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate and tolylene diisocyanate in compounds having four or more hydroxyl groups in one molecule such as pentaerythritol and polyglycerol Asahi Kasei Kogyo Co. Ltd. is a compound having two or more hydroxyl groups in one molecule such as compound (i-1) or ethylene glycol obtained by reacting an isocyanate compound. Burette types such as `` DURANATE 24A-100 '', `` DURANATE 22A-75PX '', `` DURANATE 21S-75E '', `` DURANATE 18H-70B '', `` DURANATE P-301-75E '', `` DURANATE E-402-90T '', Compound (i-2) or isocyanate ethyl (meth) acrylate obtained by reacting a compound having three or more isocyanate groups in one molecule such as an adduct type such as "DURANATE E-405-80T" or the like is obtained. Specifically, For example, Asahi Kasei Kogyo Co., such as a compound which has four or more, preferably six or more isocyanate groups in 1 molecule, such as a compound (i-3). It can obtain by making "DURANATE ME200" manufacture and the compound (ii) which has 1 or more hydroxyl group and 2 or more, preferably 3 or more (meth) acryloyloxy group in 1 molecule.

Here, it is preferable that it is 500-200,000, and, as for the molecular weight of the said compound (i), it is especially preferable that it is 1,000-150,000. Moreover, it is preferable that the molecular weight of urethane (meth) acrylates as mentioned above is 600-150,000. Moreover, it is preferable to have 6 or more urethane bonds, It is especially preferable to have 8 or more, It is preferable to have 6 or more of (meth) acryloyloxy groups, It is especially preferable to have 8 or more.

In addition, such urethane (meth) acrylates have the molar ratio of the electron isocyanate group and the latter hydroxyl group to, for example, the compound (i) and the compound (ii) in an organic solvent such as toluene or ethyl acetate. It can be manufactured by the method of making it react at about 10 to 150 degreeC for 5 minutes-3 hours using catalysts, such as dilauric acid n-butyltin, as needed at a ratio of 10-10 / 1.

In this invention, it is especially preferable to represent with the following general formula (IX) among the said urethane (meth) acrylates.

[In Formula (IX), Ra has a repeating structure of an alkyleneoxy group or an aryleneoxy group, and also represents a group having 4 to 20 oxy groups which can be bonded to Rb, and Rb and Rc each independently represent 1 to 1 carbon. 10 represents an alkylene group, Rd represents an organic moiety having 1 to 10 (meth) acryloyloxy groups, each Ra, Rb, Rc and Rd may have a substituent, x is an integer of 4 to 20, y is an integer of 0-15, z is an integer of 1-15.

As a repeating structure of the alkyleneoxy group of Ra in said Formula (XI), what originates in propylene triol, glycerin, pentaerythritol, etc., for example, As a repeating structure of an aryleneoxy group, For example, pyrogallol, The thing derived from 1, 3- benzene triol etc. is mentioned, respectively. Moreover, it is preferable that carbon number of the alkylene group of Rb and Rc is 1-5 each independently, and it is preferable that the (meth) acryloyloxy group in Rd is 1-7. Moreover, it is preferable that x is 4-15, y is 1-10, and z is 1-10, respectively.

Moreover, as Ra, it is a following formula (wherein k is an integer of 2-10), and as Rb and Rc each independently, it is a dimethylene group, a monomethyldimethylene group, or trimethylene group, and Rd is a following formula Each is particularly preferred.

Moreover, as the epoxy (meth) acrylates, specifically, (meth) acrylic acid or the above-mentioned hydroxy (meth) acrylate compound, (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) hexa Aliphatic polyepoxy compounds, such as methylene glycol polyglycidyl ether, (poly) trimethylol propane polyglycidyl ether, (poly) glycerol polyglycidyl ether, and (poly) sorbitol polyglycidyl ether, phenol novolak poly Aromatics such as epoxy compounds, brominated phenol novolac polyepoxy compounds, (o-, m-, p-) cresol novolac polyepoxy compounds, bisphenol A polyepoxy compounds, bisphenol F polyepoxy compounds With polyepoxy compounds, such as a heterocyclic polyepoxy compound, such as a lypoxy compound, a sorbitan polyglycidyl ether, a triglycidyl isocyanurate, and a triglycidyl tris (2-hydroxyethyl) isocyanurate Reactants and the like.

Moreover, as other ethylenically unsaturated compound, (meth) acrylamides, such as ethylene bis (meth) acrylamide, allyl ester, such as diallyl phthalate, and vinyl groups, such as divinyl phthalate, are contained besides the above, for example. Compounds and thioether bond-containing compounds which improve the crosslinking rate by sulfiding ether bonds of ether-containing ethylenically unsaturated compounds with phosphorus penta sulfide or the like and converting them into thioether bonds, and for example, Japanese Patent No. 3164407 and Japanese Unexamined Patent Application Publication No. 9-100111 and the like, and a polyfunctional (meth) acrylate compound and a silica sol having a particle diameter of 5 to 30 nm [for example, isopropanol dispersed organosilica sol (manufactured by Nissan Chemical Co. IPA-ST ''), methyl ethyl ketone dispersed organosilicazol ("MEK-ST" manufactured by Nissan Chemical Co.), methyl isobutyl ketone dispersed organosilica (Nissan Chemical Co., Ltd. "MIBK-ST"), etc., by reacting a silica sol with an ethylenically unsaturated compound, such as a compound in which an isocyanate group or a mercapto group-containing silane coupling agent is reacted through a silane coupling agent The compound etc. which improved the strength and heat resistance as hardened | cured material by combining are mentioned.

The above ethylenically unsaturated compounds may be used alone, or two or more kinds may be used in combination. In the present invention, as the ethylenically unsaturated compound of the above (C) component, ester (meth) acrylates, (meth) acryloyloxy group-containing phosphates or urethane (meth) acrylates are preferable, and ester (meth) ) Acrylates are particularly preferable, and among the ester (meth) acrylates, (meth) acryloyl jade contains polyoxyalkylene groups such as polyethylene glycol, polypropylene glycol or a polyethylene oxide adduct of bisphenol A, and the like. Especially preferred are ester (meth) acrylates containing two or more time periods.

In the curable composition of this invention, it is preferable that it is 1-70 weight% with respect to whole quantity of a curable composition, and, as for the content rate of the ethylenically unsaturated compound of the said (C) component, it is more preferable that it is 5-60 weight%. If (C) component is less than the said range, there exists a tendency for sclerosis | hardenability as a curable composition to become inadequate, and when it exceeds the said range, there exists a tendency for adhesiveness to become inadequate.

[1-4] (D) Epoxy Compound

The curable composition of this invention may contain the (D) epoxy compound further. When using the curable composition of this invention for soldering resists, an overcoat, a rib, or a spacer, the epoxy compound of (D) component may contain for the purpose of the improvement of the heat resistance of a hardened | cured material, chemical-resistance, etc. As the epoxy compound, a polyglycidyl ether compound obtained by reacting a polyhydroxy compound constituting a repeating unit of an epoxy resin with epichlorohydrin, a polycarboxylic acid compound and polypoly obtained by reacting epichlorohydrin And compounds ranging from low molecular weight substances to high molecular weight substances such as glycidyl ester compounds and polyamine compounds and polyglycidylamine compounds obtained by reacting epichlorohydrin.

As this polyglycidyl ether compound, For example, the diglycidyl ether type epoxy of polyethyleneglycol, the diglycidyl ether type epoxy of bis (4-hydroxyphenyl), bis (3, 5- dimethyl) Diglycidyl ether type epoxy of 4-hydroxyphenyl), diglycidyl ether type epoxy of bisphenol F, diglycidyl ether type epoxy of bisphenol A, and diglycidyl ether type epoxy of tetramethylbisphenol A And diglycidyl ether epoxy of ethylene oxide addition bisphenol A, phenol novolac epoxy, cresol novolac epoxy and the like. These polyglycidyl ether compounds are acid anhydrides in the remaining hydroxyl group. A carboxyl group may be introduced by reacting a divalent acid compound or the like.

Moreover, as this polyglycidyl ester compound, For example, the diglycidyl ester type epoxy of hexahydrophthalic acid, the diglycidyl ester type epoxy of phthalic acid, etc. are further mentioned as the polyglycidyl amine compound. For example, the diglycidyl amine epoxy of bis (4-aminophenyl) methane, the triglycidyl amine epoxy of isocyanuric acid, etc. are mentioned, respectively.

In the curable composition of this invention, it is preferable that it is 1-70 weight% with respect to whole quantity of a curable composition, and, as for the content rate of the epoxy compound of the said (D) component, it is more preferable that it is 5-50 weight%. If (D) component is less than the said range, there exists a tendency for the sclerosis | hardenability as a curable composition to become inadequate, and when it exceeds the said range, there exists a tendency for problems, such as the omission of a non-image part, at the time of image development, to occur easily.

[1-5] (E) Epoxy Curing Agent

The curable composition of this invention may contain (E) epoxy hardening | curing agent further. It is preferable to use together, when the epoxy hardening | curing agent of (E) component contains the epoxy compound of (D) component for the purpose of the improvement of sclerosis | hardenability as a curable composition. As the epoxy curing agent of the component (E), for example, 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 anhydride, 3-ethylhexahydrophthalic anhydride, 4-ethylhexahydro Polyvalent carboxylic acid anhydrides such as phthalic anhydride, trimellitic anhydride and biphenyltetracarboxylic anhydride, organic phosphines such as tributylphosphine, triphenylphosphine and tris-2-cyanoethylphosphine, and Dazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1- (2-cyanoethyl) 2-phenylimidazole, 1- (2-hour Imidazoles such as anoethyl) -2-ethyl-4-methylimidazole, dicyandiamide, benzylmethylamine, 4-methylbenzyl-N, N-dimethylamine, 4-methoxybenzyl-N, N- Amine compounds such as dimethylamine and 4-dimethylaminobenzyl-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-methacryloyloxyethyl-s-triazine, 2,4-dia Quaternary ammonium salts such as amino-s-triazines such as mino-6-methacryloyloxyethyl-s-triazine and isocyanuric acid adducts, benzyltrimethylammonium chloride and phenyltributylammonium chloride; Phosphonium salts such as -butyl-2,5-dihydroxyphenyl-phosphonium bromide, hexadecyltributylphosphonium chloride, and the like, and the like, and among them, those having a -NH- group are preferable, and amine compounds and amino -s- Liao jinryu are preferred, dicyandiamide, 2,4,6-triamino--s- triazine Gene is particularly preferred.

In the curable composition of this invention, it is preferable that the content rate of the epoxy hardening | curing agent of the said (E) component is 1 weight% or less with respect to whole quantity of a curable composition, and is 0.7 weight in terms of aging stability as a curable composition. It is more preferable that it is% or less.

[1-6] (F) amino compounds

The curable composition of this invention can contain (F) amino compound further. It is preferable that the amino compound of (F) component contains for the purpose of the heat resistance of hardened | cured material, the improvement of chemical-resistance, etc. As an amino compound of this (F) component, the amino compound which has a methylol group as a functional group and at least two alkoxy methyl groups which C1-C8 alcohol condensation-modified is mentioned, For example, polycondensation of melamine and formaldehyde is carried out. Combined melamine resin, benzoguanamine resin polycondensed benzoguanamine and formaldehyde, glycoluril resin polycondensed glycoluril and formaldehyde, urea resin polycondensed urea and formaldehyde, melamine, benzoguanamine, And resins obtained by co-condensation of two or more kinds such as glycoluril or urea with formaldehyde, and modified resins obtained by alcohol condensation-modification of methylol groups of these resins. Especially, in this invention, melamine resin and its modified resin are preferable, the modified resin whose modification ratio of a methylol group is 70% or more is more preferable, and the modified resin which is 80% or more is especially preferable.

As a specific example of the amino compound of these (F) components, as a melamine resin and its modified resin, Mitsui Thytec Co. "THYMEL" (trademark) 300, 301, 303, 350, 736, 738, 370, 771, 325 , 327, 703, 701, 266, 267, 285, 232, 235, 238, 1141, 272, 254, 202, 1156, 1158 and NIKALACK (registered trademark) E-2151, MW-100LM by Sanwa Chemical Co. "THYMEL" (registered trademark) 1123, 1125, 1128, glycoluril resin and the modified resin "THYMEL" (registered trademark) 1170, 1171, 1174, 1172, and MX-750LM, a benzoguanamine resin, and its modified resin. "NIKALACK" (registered trademark) MX-270, urea resin and its modified resin include Mitsui Thytec Co. "UFR" (registered trademark) 65,300, "NIKALACK" (registered trademark) MX-290 and the like.

In the curable composition of this invention, it is preferable that it is 20 weight% or less with respect to whole quantity of a curable composition, and, as for the content rate of the amino compound of the said (F) component, it is more preferable that it is 10 weight% or less.

[1-7] (G) Polymerization Accelerator

The curable composition of this invention may contain (G) polymerization accelerator further. (G) The polymerization accelerator may be contained for the purpose of improving the polymerization starting ability of the curable composition. As the polymerization accelerator for the component (G), an ester of an amino acid or a dipolar ionic compound is preferable, and the ester or bipolar ionic compound of the amino acid is preferably represented by the following general formula (Xa) or (Xb).

[In Formulas (Xa) and (Xb), R ³⁹ and R ^40. Each independently represent an alkyl group which may have a substituent, an aryl group which may have a substituent, a heterocyclic group or a hydrogen atom which may have a substituent, and R ⁴¹ and R ⁴² each independently represent an alkyl group or a hydrogen atom which may have a substituent R ⁴³ represents an alkyl group which may have a substituent, an alkenyl group which may have a substituent or an aryl group which may have a substituent, and R ⁴⁴ represents an alkyl group which may have a substituent, an aryl group or substituent which may have a substituent The heterocyclic group which may have, and s is an integer of 0-10.

Here, as an alkyl group of R <^39> , R <^40> , R <^41> , R <^42> , R <^43> and R <^44> in Formula (Xa) and (Xb), it is preferable that carbon number is 1-8, It is more preferable that it is 1-4. Do. Moreover, as an alkenyl group of R <^43> , a vinyl group, an allyl group, an isopropenyl group, etc. are mentioned as an aryl group of R <^39> , R <^40> , R <^41> and R <^44> , for example, a phenyl group, a nap As a heterocyclic group of R <^39> , R <^40> and R <^{44> as} a methyl group etc., a furyl group, a furanyl group, a pyrrolyl group, a pyridyl group, etc. are mentioned, respectively, respectively.

Moreover, as a substituent in these alkyl groups and alkenyl groups, For example, an alkoxy group, an alkoxycarbonyl group, an alkenyloxy group, an alkenyloxycarbonyl group, a phenyl group, a halogen atom, etc., and also the substituent in those aryl groups, a heterocyclic group, etc. As an alkyl group which may have substituents, such as an alkoxy group and a phenyl group, for example, an alkoxy group, the same alkenyl group, the same alkenyloxy group, the same acyl group, the same acyloxy group, the same Alkoxycarbonyl groups, likewise phenoxy groups, likely alkylthio groups, likely alkylsulfonyl groups and aldehyde groups, carboxyl groups, hydroxyl groups, sulfo groups, nitro groups, cyano groups, halogen atoms and the like.

In the present invention, one of R ³⁹ and R ^{40 in} the formula (Xa) is a hydrogen atom and the other may have a substituent in the ester or a diionic compound of the amino acid represented by the above formula (Xa) or (Xb). Phenyl group, R ⁴¹ and R ⁴² Are all hydrogen atoms, R ⁴³ An alkyl group which may have this substituent or a phenyl group which may have a substituent, wherein s is 0, 1 or 2, an amino acid ester or R ³⁹ and R ⁴⁰ in formula (Xb) All are hydrogen atoms or one alkyl group which may have a substituent, both R ⁴¹ and R ⁴² are hydrogen atoms, R ⁴⁴ is an alkyl group which may have a substituent or a phenyl group which may have a substituent, and s is 0, 1 Or an amino acid bipolar ionic compound of 2, wherein in formula (Xa), s is 0, one of R ³⁹ and R ⁴⁰ is a hydrogen atom, the other is a phenyl group, and R ⁴¹ and R ⁴² are all hydrogen atoms; Esters of phenylglycine, among which R ⁴³ Is a benzyl group N- phenylglycine benzyl ester or s is ^{0, R 39, R 40,} R 41 and R ⁴² are both hydrogen atom in the general formula (Xb), R ⁴⁴ Particular preference is given to bipolar ion compounds of N-phenylglycine, wherein is a phenyl group.

Moreover, in this invention, as a polymerization accelerator of (G) component, polymerization accelerators other than the ester of the said amino acid or a bipolar ion compound can further be contained, As this polymerization accelerator, for example, 2- Mercaptobenzothiazole, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4-triazole, 2-mercapto-4 (3H) -quinazolin, β Mercapto-group-containing compounds such as mercaptonaphthalene, ethylene glycol dithiopropionate, trimethylolpropane tristyropropionate, pentaerythritol tetrakistioplopionate, hexanedithiol, trimethylol propane trithioglyco Polyfunctional thiol compounds such as nates and pentaerythritol tetrakistiopionionate, derivatives such as N, N-dialkylaminobenzoic acid esters, N-phenylglycine or salts such as ammonium salts and sodium salts, phenylalanine or its cancers Amino acids having a iodonium or aromatic ring derivatives such as salts, esters such as sodium salt, or there may be mentioned the derivatives and the like.

In the curable composition of this invention, it is preferable that it is 20 weight% or less with respect to whole quantity of a curable composition, and, as for the content rate of the polymerization accelerator of the said (G) component, it is more preferable that it is 10 weight% or less.

[1-8] (H) Inorganic Fillers

In addition, the inorganic filler of (H) component used for the curable composition of this invention may contain for the purpose of improvement of the strength as hardened | cured material, etc. As an inorganic filler of this (H) component, talc, silica, alumina, barium sulfate, magnesium oxide, etc. are mentioned, for example.

In the curable composition of this invention, it is preferable that it is 70 weight% or less with respect to whole quantity of a curable composition, and, as for the content rate of the inorganic filler of the said (H) component, it is more preferable that it is 50 weight% or less.

[1-9] (I) Surfactants

Moreover, the surfactant of (I) component used for the curable composition of this invention may contain for the purpose of the improvement of applicability | paintability, developability, etc. as a coating liquid of a curable composition. Specific examples thereof 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, polyoxy Ethylene 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, Sorbitol fatty acid esters, polyoxyethylene sorbitol fatty acid esters, and the like, and the anionic surfactants include alkyl sulfonates, alkylbenzene sulfonates, alkyl naphthalene sulfonates, polyoxyethylene alkyl ether sulfonates, alkyl sulfates, Alkyl sulfate ester salts, higher alcohol sulfuric acid Ether salts, aliphatic alcohol sulfate ester salts, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkylphenyl ether sulfates, alkyl phosphate ester salts, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkylphenyl ether phosphates, and the like. As the cationic surfactant, quaternary ammonium salts, imidazoline derivatives, amine salts, and the like, and as amphoteric surfactants, betaine-type compounds, imidazolium salts, imidazolines, and amino acids Etc. can be mentioned respectively.

In the curable composition of this invention, it is preferable that it is 10 weight% or less with respect to whole quantity of a curable composition, and, as for the content rate of surfactant of the said (I) component, it is more preferable that it is 5 weight% or less.

[1-10] (J) sensitizing pigment

Moreover, it is preferable to contain the sensitizing dye of (J) component used for the curable composition of this invention for the purpose of the improvement of the photosensitivity of a curable composition, etc. The sensitizing dye is a light absorbing dye having an absorption maximum in a blue-violet region having a wavelength of 350 to 430 nm, and is a dialkylaminobenzene compound in a dialkylaminobenzene compound, a pyrromethene compound, a trihydroxypyrimidine derivative, and the like. This is preferred.

As the preferable dialkylaminobenzene compound, a dialkylaminobenzophenone compound, a dialkylaminobenzene compound having a heterocyclic group as a substituent on a carbon atom at the p-position relative to an amino group on a benzene ring, and a benzene ring Preference is given to dialkylaminobenzene compounds having a substituent containing a sulfonylimino group at a carbon atom in the p-position relative to an amino group, and a dialkylaminobenzene compound having a carbostyryl skeleton.

As this dialkylamino benzophenone type compound, what is represented by following General formula (XI) is preferable.

[In Formula (XI), R <^11> , R <^12> , R <^15> and R <^16> may respectively independently represent the alkyl group which may have a substituent, and R <^13> , R <^14> , R <^15> and R <^16> may each independently have a substituent. 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 each independently represent a nitrogen-containing compound Can summon].

Here, it is preferable that carbon number of the alkyl group of R <^11> , R <^12> , R <^15> and R <^16> in Formula (XI) and carbon number when R <^13> , R <^14> , R <^17> and R <^18> are an alkyl group are 1-6. In addition, when forming a nitrogen-containing heterocycle, it is preferable that it is a 5 or 6 membered ring, and R ¹¹ and R ¹³ , R ¹² and R ¹⁴ , R ¹⁵ and R ¹⁷ or R ¹⁶ and R ¹⁸ are 6 membered rings of tetrahydroquinoline It is preferable to form a ring, and R ¹¹ , R ¹² , R ¹³ And R ¹⁴ and / or R ¹⁵ , R ¹⁶ , R ¹⁷ And R ¹⁸ preferably forms a dulolidine ring. Moreover, the tetrahydroquinoline ring which has an alkyl group as a substituent at 2-position, or the durolidine ring containing the tetrahydroquinoline ring is especially preferable.

As a specific example of a compound represented by the said general formula (XI), For example, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, and a compound of the following structure Can be mentioned.

The heterocyclic group in the dialkylaminobenzene compound having a heterocyclic group as a substituent on the carbon atom at the p-position relative to the amino group on the benzene ring is a 5 or 6 membered ring containing a nitrogen atom, an oxygen atom or a sulfur atom. It is preferable that the 5-membered ring having a condensed benzene ring is particularly preferred, and it is preferably represented by the following general formula (XII).

[Formula (XII) of, R ¹⁹ and R ²⁰ each independently represents an alkyl group which may have a substituent, R ²¹ and R ²² represents an alkyl group or a hydrogen atom which may have a substituent, each independently, R ¹⁹ and R ²⁰ , R ¹⁹ and R ²¹ and R ²⁰ and R ²² may each independently form a nitrogen-containing heterocycle, X represents an oxygen atom, a sulfur atom, a dialkylmethylene group, an imino group or an alkylimino group, and a heterocycle The benzene ring condensed on may have a substituent.

Here, it is preferable that carbon number of the alkyl group of R <^19> and R <^20> in Formula (XII) and carbon number when R <^21> and R <^22> is an alkyl group are 1-6, and when forming a nitrogen containing heterocycle, it is 5 or 6 It is preferable that it is a ring, and it is preferable that R <^19> and R <^21> , R <^20> and R <^{22> form} the 6-membered ring tetrahydroquinoline ring, and R <^19> , R <^2O> , R <^21> and R <^{22> form} a durolidine ring It is especially preferable to form. Moreover, the tetrahydroquinoline ring which has an alkyl group as a substituent at 2-position, or the durolidine ring containing the tetrahydroquinoline ring is especially preferable. Moreover, it is preferable that carbon number of the alkyl group when X is a dialkylmethylene group is 1-6, and it is preferable that carbon number of the alkyl group when an alkylimino group is 1-6.

As a specific example of a compound represented by the said general formula (XII), for example, 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, 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) benzoimidazole, 2- (p-diethylaminophenyl) benzoimidazole, 2- (p-dimethylaminophenyl) -3 And 3-dimethyl-3H-indole, 2- (p-diethylaminophenyl) -3,3-dimethyl-3H-indole and the compound having the following structure.

Moreover, as a dialkylaminobenzene type compound which has a heterocyclic group as a substituent at the carbon atom of p-position with respect to the amino group on a benzene ring other than the compound represented by the said general formula (XII), it is 2- (p-, for example). 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-diethyl Aminophenyl) -1,3,4-thiadiazole etc. are mentioned.

Moreover, it is preferable that it is represented by following General formula (XIII) as a dialkylamino benzene type compound which has a substituent which contains a sulfonyl imino group at the carbon atom of p-position with respect to the amino group on a benzene ring.

[In Formula (XIII), R <^23> and R <^24> respectively independently represents the alkyl group which may have a substituent, R <^25> and R <^26> Each independently represent an alkyl group or a hydrogen atom which may have a substituent, R ²³ and R ²⁴ , R ²³ and R ²⁵ and R ²⁴ and R ²⁶ may each independently form a nitrogen-containing heterocycle, and R ²⁷ is Monovalent group or hydrogen atom, and R ²⁸ represents monovalent group].

Wherein the carbon number of the alkyl groups of R ²³ and R ^{24 in} the formula (XIII) and R ²⁵ and R ²⁶ It is preferable that carbon number in this alkyl group is 1-6, and when forming a nitrogen-containing heterocycle, it is preferable that it is a 5 or 6 membered ring, but it is preferable that R <^25> and R <^26> are hydrogen atoms. As the monovalent group of R ²⁷ and R ²⁸ , for example, 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, aryl alkenyl group, hydroxy group, formyl group, carboxyl group, carboxylic acid ester group, carbamoyl group, amino group, acylamino group, carbamate group, sulfonamide group, sulfonic acid group, sulfonic acid ester group, sulfamoyl group, alkyl tea Ogi, imino group, cyano group, heterocyclic group, etc. are mentioned.

Among these, R ²⁷ is preferably a hydrogen atom, and R ²⁸ is preferably an aryl group.

Moreover, as a dialkylamino benzene-type compound which formed the carbostyryl frame | skeleton, what is represented by following General formula (XIV) is preferable.

[In Formula (XIV), R ²⁹ , R ³⁰ and R ³³ each independently represent an alkyl group which may have a substituent, and R ³¹ and R ³² each independently represent an alkyl group or hydrogen atom which may have a substituent, and R ²⁹ With R ³⁰ and R ²⁹ And R ³¹ and R ³⁰ and R ³² may each independently form a nitrogen-containing heterocycle, and R ³⁴ represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or a hydrogen atom.

Wherein the carbon number of the alkyl groups of R ²⁹ , R ³⁰ and R ^{33 in} the formula (XIV) and R ³¹ , R ³² and R ³⁵ It is preferable that carbon number when it is an alkyl group is 1-6, and when forming a nitrogen containing heterocycle, it is preferable that it is a 5 or 6 membered ring, but it is preferable that R <^31> and R <^32> are hydrogen atoms. In addition, R ³⁴ is preferably a phenyl group.

As a sensitizing dye of the above-mentioned (J) component, in this invention, the carbon of the p-position with respect to the dialkylamino benzophenone type compound represented by the said General formula (XI), and the amino group on the benzene ring represented by the said General formula (XIII) Particularly preferred is a dialkylaminobenzene compound having a substituent containing a sulfonylimino group at an atom, or a dialkylaminobenzene compound having a carbostyryl skeleton represented by the formula (XIV).

In the curable composition of this invention, it is preferable that it is 0.01-20 weight% with respect to whole quantity of a curable composition, and, as for the content rate of the sensitizing dye of the said (J) component, it is more preferable that it is 0.1-10 weight%. If (J) component is less than the said range, there exists a tendency for photocurability as a curable composition to become inadequate, and when it exceeds the said range, there exists a tendency for background contamination to arise at the time of image development.

Moreover, it is preferable that the curable composition of this invention has the maximum peak of a spectral sensitivity in the wavelength range of 350-430 nm, and it is more preferable to have the maximum peak of the spectral sensitivity in the wavelength range of 390-430 nm. When having the maximum peak of spectral sensitivity in the wavelength range below the said range, as a photocurable composition, there exists a tendency for the sensitivity with respect to the laser beam of wavelength 350-430 nm to fall, and when it exists in the wavelength range exceeding the said range, The safety light property under yellow light tends to fall.

On the other hand, when it exists in the wavelength range exceeding the said range, there exists a tendency for the safety light characteristic under yellow light to fall. Although the wavelength range of the maximum peak of these spectral sensitivity can be adjusted by selecting each component which comprises a curable composition suitably, especially the kind of the photoinitiator and / or thermal-polymerization initiator of (B) component, and the sensitizing dye of (J) component And content can be adjusted.

In the present invention, the maximum peak of the spectral sensitivity is described in detail in, for example, "Photopolymer Technology" (Tsugio Yamaoka, published by Nikkan Kogyo Shinbunsha, 1988, p. 262) and the like. The photocurable image forming material sample in which the layer was formed was subjected to light spectroscopically measured from a light source such as a xenon lamp or a tungsten lamp using a spectroscopic sensitivity measuring device. The exposure wavelength was linear in the horizontal axis direction and the exposure intensity was logarithmic in the vertical axis direction. By setting and changing the light to be irradiated, and then exposing and developing, an image corresponding to the sensitivity of each exposure wavelength is obtained, and the exposure energy that can be imaged is calculated from the height of the image, and the inverse of the exposure energy on the horizontal axis and the vertical axis is calculated. Point out the maximum peak in the spectral sensitivity curve obtained by plotting.

Moreover, in the curable composition of this invention, when a blue violet semiconductor laser is used as an exposure light source, it is preferable that the minimum exposure amount S410 which can form an image in wavelength 410nm is 50 mJ / cm <2> or less, It is more preferable that it is 30 mJ / cm <2> or less, It is 20mJ It is especially preferable that it is / cm <2> or less. When this minimum exposure amount [S410] exceeds the said range, although it changes with the exposure intensity of a laser light source, there exists a tendency for exposure time to become long and utility falls. On the other hand, although the minimum of this minimum exposure amount [S410] is so preferable that it is small, it is 1 mJ / cm <2> or more normally.

Further, it is preferable that the ratio [S410 / S450] to the minimum exposure amount [S450 (mJ / cm 2)] capable of forming an image at the wavelength of 450 nm of [S410] is 0.1 or less, and more preferably 0.05 or less. When this ratio [S410 / S450] exceeds the above range, there is a tendency that it is difficult to achieve safety light characteristics under blue violet laser photosensitivity and yellow light.

Further, the ratio [S450 to the minimum exposure amount [S450 (mJ / cm 2)] for image formation at wavelength 450 nm of the minimum exposure amount [S450-650 (mJ / cm 2)] for image formation at each wavelength of 450 nm or more and 650 nm or less in wavelength [S450] -650 / S450] is preferably more than one. When this ratio [S450-650 / S450] is less than the said range, it exists in the tendency to make it compatible with blue violet laser photosensitivity and the safety light characteristic under yellow light.

In addition, the minimum exposure amount [S410] that can be imaged at the wavelength of 410 nm, the minimum exposure amount [S450] that can be imaged at a wavelength of 450 nm, and the minimum exposure amount that can be imaged at each wavelength of 450 nm or more and 650 nm or less [S450-650 (mJ). / Cm 2)] is obtained as the image-formable exposure energy calculated from the image height obtained in the measurement of the maximum peak of the spectral sensitivity using the spectroscopic sensitivity measuring device described above, and the kind of the developing solution and the developing temperature at that time It means the minimum exposure amount which an image can be formed by the optimal image development conditions determined by changing image development conditions, such as image development time, As the optimal image development conditions, it is 0.5 to 14 at alkaline temperature of pH 11-14 normally at 25 degreeC. A condition of 3 minutes soaking is adopted.

[1-11] (K) other alkali-soluble resins

Alkali-soluble resin of (K) component used for the curable composition of this invention can be contained as a binder of a curable composition. As this alkali-soluble resin, (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylonitrile, (meth) acrylamide, maleic acid, styrene, vinyl acetate, vinylidene chloride, maleimide, etc. Single or copolymers thereof, acid-modified epoxy acrylates, polyamides, polyesters, polyethers, polyurethanes, polyvinyl butyral, polyvinyl alcohol, polyvinylpyrrolidone, acetyl cellulose and the like.

Among them, in view of alkali developability, carboxyl group-containing vinyl resins and acid-modified epoxy acrylates are preferable.

Specific examples of the carboxyl group-containing vinyl resin include unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, 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, isobornyl (meth) acrylate, hydroxymethyl (meth ) Acrylate, hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N- (meth) acryloyl Morpholine, (meth) acrylonitrile, ( Copolymers with vinyl compounds such as (e) acrylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide, vinyl acetate, and the like. Can be mentioned.

Among them, styrene- (meth) acrylate- (meth) acrylic acid copolymer is preferable, and it is composed of 3 to 30 mol% of styrene, 10 to 70 mol% of (meth) acrylate, and 10 to 60 mol% of (meth) acrylic acid. A copolymer is more preferable, and the copolymer which consists of 5-25 mol% of styrene, 20-60 mol% of (meth) acrylate, and 15-55 mol% of (meth) acrylic acid is especially preferable. Moreover, it is preferable that these carboxyl group-containing vinyl resins have an acid value of 30-250 mg.KOH / g, and the weight average molecular weights of polystyrene conversion are 1,000-300,000.

Moreover, as this carboxyl group-containing vinyl-type resin, what has an ethylenically unsaturated bond in a side chain is preferable, Specifically, for example, allyl glycidyl ether, glycidyl (meth) acrylate, (alpha) to a carboxyl group-containing polymer -Ethylglycidyl (meth) acrylate, glycidyl crotonate, glycidyl isocrotonate, crotonyl glycidyl ether, monoalkyl monoglycidyl ester of itaconic acid, monoalkyl monoglycidyl fumarate Aliphatic epoxy group-containing unsaturated compounds such as esters and monoalkyl monoglycidyl esters or 3,4-epoxycyclohexylmethyl (meth) acrylate, 2,3-epoxycyclopentylmethyl (meth) acrylate, 7,8 5-90 of the carboxyl group which a carboxyl group-containing polymer has alicyclic epoxy group containing unsaturated compounds, such as an epoxy [tricyclo [5.2.1.0] dec-2-yl] oxymethyl (meth) acrylate, %, Preferably the reaction product obtained by reacting about 30-70 mol%, allyl (meth) acrylate, 3-allyloxy- 2-hydroxypropyl (meth) acrylate, cinnamil (meth) acrylate, black Compounds having two or more unsaturated groups such as tonyl (meth) acrylate, metalyl (meth) acrylate, N, N-diallyl (meth) acrylamide, or vinyl (meth) acrylate, 1-chlorovinyl (meth) Compounds having two or more unsaturated groups such as acrylate, 2-phenylvinyl (meth) acrylate, 1-propenyl (meth) acrylate, vinyl crotonate, vinyl (meth) acrylamide, (meth) acrylic acid and the like Reaction products obtained by copolymerizing an unsaturated carboxylic acid or an unsaturated carboxylic acid ester into the entire compound having the former unsaturated group in an amount of 10 to 90 mol%, preferably about 30 to 80 mol%. Field Can be.

Moreover, the reaction product of an epoxy group containing polymer and ethylenically unsaturated compound which has a functional group which can react with epoxy groups, such as a carboxyl group or a hydroxyl group, is also mentioned.

Moreover, as this acid-modified epoxy acrylate, it is a compound obtained by making the reaction material of an epoxy group containing compound, an unsaturated group containing carboxylic acid, or its anhydride further react with polybasic carboxylic acid or its anhydride (c). Moreover, resin which added the epoxy group containing compound further to a part of carboxyl group in this compound may be sufficient. The manufacture can be performed by a well-known method.

As this epoxy group containing compound, the epoxy compound [compound (a) which has two or more epoxy groups in 1 molecule in the publication], etc. which are described in Unexamined-Japanese-Patent No. 2001-174621, etc. are mentioned, for example. Examples include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol S type epoxy compounds, biphenylglycidyl ethers, phenol novolac type epoxy compounds, cresol novolac type epoxy compounds, triglycidyl isocyanurate, and alicyclic compounds. The epoxy compound, the epoxy compound which has a polyaddition structure of the cyclic hydrocarbon compound which has 2 or more unsaturated groups per molecule, and a phenol, a copolymer type epoxy compound, etc. are mentioned.

In the curable composition of this invention, it is preferable that it is 70 weight% or less with respect to whole quantity of curable composition, and, as for the content rate of alkali-soluble resin of the said (K) component, it is more preferable that it is 40 weight% or less.

[1-12] (L) Colorant

When using the curable composition of this invention for a color filter or a black matrix, it is preferable to contain and use a color material. Here, a color material means coloring the curable composition which concerns on this invention. Although a dye pigment can be used as a coloring material, A pigment is preferable at the point of heat resistance, light resistance, etc. As the pigment, pigments of various colors such as blue pigments, green pigments, red pigments, yellow pigments, purple pigments, orange pigments, brown pigments and black pigments can be used.

In addition, various inorganic pigments can also be used as the structure, in addition to organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene and perylene. Hereinafter, the specific example of the pigment which can be used is shown by a pigment number. "C.I. Pigment Red 2 ", etc. mean a color index (C.I.).

As a red pigment, C.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, 179, 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. Among them, preferably C.I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, more preferably C.I. Pigment red 177, 209, 224, 254 is mentioned.

As a blue pigment, C.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. Among them, preferably C.I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, more preferably C.I. Pigment blue 15: 6.

As a green pigment, C.I. Pigment green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55. Among them, preferably C.I. Pigment green 7, 36 is mentioned.

As a yellow pigment, C.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, 173, 174 , 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203 , 204, 205, 206, 207, and 208.

Among them, preferably C.I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, more preferably C.I. Pigment yellow 83, 138, 139, 150, 180 is mentioned.

As an orange pigment, C.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. Especially, Preferably, C.I. Pigment oranges 38 and 71.

As a purple pigment, C.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. Among them, preferably C.I. Pigment violet 19, 23, more preferably C.I. Pigment violet 23 is mentioned.

Moreover, when forming a black matrix using the curable composition of this invention, a black color material can be used. The black color material may be a black color material alone or a mixture of red, green, blue, and the like. In addition, these color materials can be suitably selected from pigments and dyes of inorganic or organic. In the case of inorganic and organic pigments, it is preferable to disperse | distribute to an average particle diameter of 1 micrometer or less, Preferably it is 0.5 micrometer or less.

Examples of colorants that can be mixed to prepare black colorants include Victoria pure blue (42595), Oramine O (41000), Catylon brilliant flavine (Basic 13) , Rhodamine 6GCP (45160), Rhodamine B (45170), Safranine OK 70: 100 (50240), Erioglaucine X (42080), No.120 / Rionol Lionel Yellow (21090), Lionol Yellow GRO (21090), Simul First Yellow 8GF (21105), Benzidine Yellow 4T-564D (21095), Simulfast Thread 4015 ( 12355), Lionoled 7B 4401 (15850), Firstgen Blue TGR-L (74160), Lionol Blue SM (26150), Lionol Blue ES (Pigment Blue 15: 6), Lionol Red (Lionolgen red) GD (Pigment Red 168), Lionol Green 2YS (Pigment Green 36), etc. (The numbers in parentheses above mean a color index (CI)).

In addition, for other pigments usable in the mixture, for example, CI yellow pigments 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, CI Orange pigments 36, 43, 51, 55, 59, 61, C.I. Red pigments 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, C.I. Violet Pigments 19, 23, 29, 30, 37, 40, 50, C.I. Blue pigment 15, 15: 1, 15: 4, 22, 60, 64, C.I. Green pigment 7, C.I. Brown pigment 23, 25, 26 etc. are mentioned.

Moreover, carbon black, acetylene black, lamp black, this black, graphite, iron black, aniline black, cyanine black, titanium black etc. are mentioned as a black color material which can be used independently.

Among them, carbon black is preferable in view of light shielding rate and image characteristics. Examples of the carbon blacks include the following carbon blacks. Mitsubishi Chemical Corp. Manufacturing: 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, Degussa Co. Manufacturing: Printex3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, PrintexA, PrintexL, PrintexG, PrintexP, PrintexU, PrintexV, PrintexG, SpecialBlack550, SpecialBlack350, SpecialBlack250, SpecialBlack100, SpecialBlack100, SpecialBlack100 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, Cabot Co. Manufacture: Monarch120, Monarch280, Monarch460, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1100, Monarch1300, Monarch1400, Monarch4630, REGAL99, REGAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL400R, REGAL 640 XC72R, ELFTEX-8, Columbian Carbon Japan Ltd. Manufacturing: RAVEN11, RAVEN14, RAVEN15, RAVEN16, RAVEN22, RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN890H, RAVEN1000, RAVEN1020, RAVEN1040, RAVEN1060U, RAVEN1080U, RAVEN11, RAVEN250U, RAVEN250U RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000.

As an example of another black pigment, titanium black, aniline black, an iron oxide type black pigment, and red, green, and blue organic pigment of three colors can be mixed and used as a black pigment.

As the pigment, barium sulfate, lead sulfate, titanium oxide, yellow lead, iron red, chromium oxide, or the like can also be used.

These various pigments can also use many things together. For example, in order to adjust chromaticity, a green pigment and a yellow pigment can be used together as a pigment, or a blue pigment and a purple pigment can be used together.

Moreover, the average particle diameter of these pigments is 1 micrometer normally, Preferably it is 0.5 micrometer or less, More preferably, it is 0.25 micrometer or less. Examples of the dye that can be used as the colorant include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, methine dyes, and the like. .

As an azo dye, it is C.I. Acid Yellow 11, C.I. Acid orange 7, C.I. Acid Red 37, C.I. Acid Red 180, C.I. Acid Blue 29, C.I. Directred 28, C.I. Direct Red 83, C.I. Direct Yellow 12, C.I. Direct Orange 26, C.I. Direct Green 28, C.I. Direct Green 59, C.I. Reactive Yellow 2, C.I. Reactive Red 17, C.I. Reactive Red 120, C.I. Reactive black 5, C.I. Disperse Orange 5, C.I. Dispersed 58, C.I. Disperse Blue 165, C.I. Basic Blue 41, C.I. Basic Red 18, C.I. Mordant Red 7, C.I. Modern Yellow 5, C.I. Modern black 7 etc. are mentioned.

As an anthraquinone type dye, it is C.I. Batblue 4, C.I. Acid Blue 40, C.I. Acidgreen 25, C.I. Reactive Blue 19, C.I. Reactive Blue 49, C.I. Dispersed 60, C.I. Disperse Blue 56, C.I. Disperse Blue 60 etc. are mentioned.

In addition, as a phthalocyanine dye, it is C.I. As a quinone imine type dye, such as pad blue 5, For example, C.I. Basic Blue 3, C.I. Basic blue 9 and the like, quinoline dyes, for example, C.I. Solvent Yellow 33, C.I. Acid Yellow 3, C.I. Disperse yellow 64 and the like, as a nitro dye, for example, C.I. Acid Yellow 1, C.I. Acid orange 3, C.I. dispers yellow 42, etc. are mentioned.

The ratio of the color material of the (L) component in the total solid in a curable composition can be normally selected from 1 to 70 weight% with respect to the total amount of solid in a curable composition. In this range, 10-70 weight% is more preferable, and especially 20-60 weight% is especially preferable. When the ratio of the colorant is too small, the film thickness with respect to the color concentration becomes too large, adversely affecting the gap control during liquid crystal cell formation or the like. On the contrary, when there are too many ratios of a color material, sufficient image formability may not be obtained. In addition, the total solid in the curable composition of this invention is 10 weight% or more and 80 weight% or less normally.

Moreover, you may add a pigment derivative etc. in order to improve the dispersibility of a pigment, and to improve dispersion stability. Examples of the pigment derivative include azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perinone and diketopyrrolo. Although derivatives, such as a pyrrole system and a dioxazine system, are mentioned, Especially, a quinophthalone system is preferable. As the substituent of the pigment derivative, sulfonic acid group, sulfonamide group and quaternary salts thereof, phthalimide methyl group, dialkylaminoalkyl group, hydroxyl group, carboxyl group, amide group and the like are directly added to the pigment skeleton or alkyl group, aryl group, heterocyclic group The thing couple | bonded through etc. is mentioned, Preferably it is a sulfonic acid group. Moreover, these substituents can be substituted in multiple numbers in one pigment skeleton. Specific examples of the pigment derivatives 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, even more preferably 0.1 to 5% by weight or less based on the pigment.

[1-13] (M) dispersants and / or dispersing aids

In the case where the curable composition of the present invention is used for a color filter or a black matrix, in particular, when a pigment is used as the colorant of the component (L) described above, in order to improve the dispersibility of the pigment and to improve the dispersion stability, It is preferable to use a dispersing material and / or a dispersal auxiliary agent together as M) component. Especially, since a polymer dispersing agent is used especially as a pigment dispersant, since it is excellent in the dispersion stability with time, it is preferable. Examples of the polymer dispersant include urethane dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene glycol diester dispersants, sorbitan aliphatic ester dispersants, aliphatic modified polyester dispersants, and the like. Can be. Specific examples of such dispersants include EFKA (manufactured by FKA Chemical BV (EFKA)), Disperbik (manufactured by Big Chemir Co.), Disparon (manufactured by Hashimoto Kasei), SOLSPERSE (manufactured by Zenka Co.), KP (Shinetsu Chemical) Industry Co.), Polyflow (manufactured by Kyoeisha Chemical Co.), and the like. These dispersants can be used individually or in mixture of 2 or more types. Content of a pigment dispersant is 50 weight% or less normally in solid content of the photosensitive coloring composition, Preferably it is 30 weight% or less.

Moreover, as a dispersing adjuvant, you may select arbitrarily from the compound represented by General formula (I), the ethylenically unsaturated compound of (C) component, (D) epoxy compound, (K) other alkali solution resin, etc., and may use at the time of a dispersion process.

[1-14] (N) Other additives

The curable composition of the present invention further contains various additives such as hydroquinone, p-methoxyphenol, 2,6-di-t-butyl-p-cresol, and the like. 20% by weight or less of a coloring agent composed of an organic or inorganic dye pigment by weight or less, 40% by weight or less of a plasticizer such as dioctylphthalate, didodecyl phthalate, and tricresyl phosphate, tertiary amine, thiol, etc. 10 wt% or less of the same as the sensitivity characteristic improving agent, 30 wt% or less of the dye precursor, and 10 wt% or less of the silane coupling agent.

[1-15] Total strain, displacement under load, elastic recovery rate and recovery rate

In the load-unloading test by a microhardness tester of the curable composition of this invention, (i) the total strain amount is 1.35 micrometers or more, the load N when the displacement at the time of 0.25 micrometers is 0.50 gf or less, or the total strain amount 1.35 µm or more and the load N at a load of 0.25 µm is 0.50 gf or less, and (ii) the elastic recovery rate is 50% or more, the recovery rate is 80% or more, or the elastic recovery rate is 50% or more, and the recovery rate is It is a characteristic that the hardened | cured material which is 80% or more can be formed.

For example, a spacer used for a liquid crystal display device (hereinafter sometimes referred to as a "panel") of a large LCD screen TV tends to be subjected to a load in the manufacturing process of the panel, and the total amount of deformation of the spacer tends to increase. . In particular, in large panels, variations in load tend to occur at each part. The curable composition of the present invention is also significant in that the elastic recovery rate and / or recovery rate of the cured product (spacer) is high.

Here, the load-unloading test by the micro altimeter is performed as follows.

It is measured using a microhardness meter for one pattern whose top area is 80 +/- 10micrometer <^2> among the spacer patterns formed by [2-2] mentioned later or a well-known method.

The top area of a spacer pattern means the following areas. First, a profile of a longitudinal section through the medium axis of the spacer pattern was made using a super depth color 3D shape measurement microscope (Keyence Corp., VK-9500) for one spacer pattern. The profile position is shown in FIG.

Next, the length of the straight line AA 'parallel to the substrate surface in the figure of the spacer pattern at a height of 90% of the height from the substrate surface of the profiled figure (shown schematically in FIG. 2) to the point Q at the highest position is determined. Measure The area of the circle | round | yen which made AA 'the diameter is made into the upper end area of a spacer pattern.

Micro hardness tester is Shimazu Seisakusho Co. Ltd. Manufacture (Shimadzu Dynamic Ultra-micro hardness tester DUH-W201S) is used.

The test conditions were applied to the spacer at a constant speed (0.22 gf / sec) using a planar indenter having a measurement temperature of 23 ° C. and a diameter of 50 μm, and maintained at the point where the load reached 5 gf for 5 seconds. Unload at speed. From the load-displacement curve obtained in this test (shown schematically in FIG. 3), the maximum displacement H [max], the final displacement H [Last], and the load N (gf) when the displacement at load is 0.25 µm are measured. do. The maximum displacement H [max] is taken as the total deformation amount.

The total strain amount is preferably 1.4 µm or more, more preferably 1.5 µm or more, preferably 5 µm or less, and more preferably 3 µm or less.

The load N when the displacement at the time of loading is 0.25 μm is preferably 0.45 gf or less, and preferably 0.1 gf or more.

If the total strain is too large and / or the load N is too small, the elastic recovery rate and / or recovery rate deteriorate. On the other hand, when total amount of deformation is too small and / or when said load N is too large, hardened | cured material cannot respond to the deviation of the load at the time of panel manufacture.

In addition, an elastic recovery rate and a recovery rate are respectively computed as follows according to the value measured by the load-unload test with the said microhardness tester.

Recovery Rate (%) = H [last] / (Pattern Height before Test) × 100

Elastic recovery rate (%) = (H [max] -H [last]) / H [max] × 100,

Recovery rate becomes like this. Preferably it is 85% or more, More preferably, it is 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 variations in the load during panel production.

The curable composition of the present invention is not particularly limited as long as the curable composition has the above characteristics, and in particular, has a compound represented by the formula (A-1) and / or (A-2) trisphenol methane structure. It is achieved by having a compound.

[1-16] floor area, elastic recovery rate and recovery rate

Alternatively, the curable composition of the present invention is characterized by being capable of forming a cured product having a bottom surface cross-sectional area of 24.5 μm ² or less and having an elastic recovery rate of 50% or more and / or a recovery rate of 85% or more.

For example, a spacer used for a screen panel for a mobile telephone or the like has a small floor area so as not to damage an image because the pixels are small. On the other hand, products such as mobile telephones are easily subjected to a load because they are likely to be impacted upon use. The curable composition of the present invention is also significant in that the elastic recovery rate and / or recovery rate of the cured product (spacer) is high.

Here, a bottom surface cross-sectional area means the contact area with the board | substrate of the hardened | cured material formed with the curable composition of this invention, such as a spacer, and is measured by observing the spacer pattern by 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 panels such as mobile phones with small pixels. On the other hand, if the bottom surface area is too small, sufficient elastic recovery rate and / or recovery rate cannot be obtained.

In addition, an elastic recovery rate and a recovery rate are calculated similarly to the above according to the value measured by the load-unload test with the said microhardness tester.

Recovery rate becomes like this. Preferably it is 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 may not cope with the load during manufacture of the panel.

The curable composition of the present invention is not particularly limited as long as the curable composition has the above characteristics, and in particular, has a compound represented by the formula (A-1) and / or (A-2) trisphenol methane structure. It is achieved by having a compound.

[2] use of curable composition

The curable composition of the present invention is insulated from solder resist films, coverlay films, and various electronic components in printed wiring boards, liquid crystal display devices, plasma displays, large-scale integrated circuits, thin transistors, semiconductor packages, color filters, organic electro luminescence, and the like. It can be used by a well-known method in each use, such as forming hardened | cured material, such as a coating layer, or hardened | cured material, such as a pixel of a color filter used for liquid crystal panels, such as a liquid crystal display, a black matrix, an overcoat, a rib, and a spacer. However, the case where it is used especially as a soldering resist and the case where it is used as a spacer is demonstrated below.

[2-1] Use as Solder Resist

Usually, when a curable composition dissolved or dispersed in a solvent is supplied in a film form or a pattern form by coating or the like on a substrate on which a solder resist is to be formed, the solvent is dried and then supplied in a film form. According to the above, a pattern is formed by a method such as photolithography which performs exposure-development. Or the curable composition made into the dry film resist material previously is supplied on a board | substrate by a regular method, and a pattern is formed by methods, such as photolithography which expose-develops as needed. Thus, the soldering resist layer is formed on the board | substrate by performing a thermosetting process with respect to the film-form or pattern-form curable composition layer obtained as needed.

[2-1-1] substrate

As the substrate, a pattern such as a circuit, an electrode, or the like is formed on the surface of the curable composition layer formed thereon by soldering the exposed image as a resist by exposing and developing with a laser beam or the like. The metal plate itself, such as aluminum, gold, silver, chromium, zinc, tin, lead, nickel, may be sufficient, for example, epoxy resin, polyimide resin, bismaleimide resin, unsaturated polyester resin, phenol resin, melamine Resins such as thermoplastic resins such as thermosetting resins, saturated polyester resins, polycarbonate resins, polysulfone resins, acrylic resins, polyamide resins, polystyrene resins, polyvinyl chloride resins, polyolefin resins, and fluorine resins such as resins, paper and glass And inorganic or glass cloth-based epoxy resins such as alumina, silica, barium sulfate, calcium carbonate, and glass nonwoven fabric groups. It consists of composite materials, such as an epoxy resin, a paper-based epoxy resin, and a paper-based phenol resin, and the said metal or indium oxide, tin oxide, indium-doped tin oxide etc. on the surface of the insulating support body whose thickness is about 0.02-10 mm. Metal-coated laminates having a conductive layer having a thickness of about 1 to 100 μm are preferably used by a method such as heating, crimping, or laminating a metal foil such as a metal oxide of a metal oxide. .

[2-1-2] Supply Method to Substrate

When supplied onto a substrate in a dissolved or dispersed state in a solvent, conventionally known methods such as rotary coating, wire bar coating, spray coating, dip coating, air knife coating, roll coating, blade coating, screen coating and curtain Application | coating etc. can be used. In that case, it is preferable that it is 5 micrometers or more as a dry film thickness, It is more preferable that it is 10 micrometers or more in terms of processability, such as image formation mentioned later and solder processing etc. which are mentioned later, 200 micrometers in terms of a sensitivity etc. It is preferable that it is the following, and it is more preferable that it is 100 micrometers or less.

As the drying temperature at that time, for example, about 30 to 150 ° C, preferably about 40 to 110 ° C, and as the drying time, for example, about 5 seconds to 60 minutes, preferably 10 seconds to 30 minutes. Minutes are adopted.

Moreover, when a curable image forming material is produced by directly applying and drying the said curable composition coating liquid, it superposes | polymerizes with the oxygen of a curable composition on the said curable composition layer formed on the said to-be-processed substrate as mentioned above. In order to prevent the inhibitory action, a protective layer may be formed by applying a solution of polyvinyl alcohol, polyvinylpyrrolidone, polyethylene oxide, methyl cellulose, carboxymethyl cellulose, hydroxymethyl cellulose, or the like to dry.

Moreover, when supplied on a board | substrate as a dry film resist material, it can carry out by a conventionally well-known method. Specifically, it is apply | coated on a temporary support film as a coating liquid which melt | dissolved or disperse | distributed each said component in the suitable solvent, and it is made to dry, and if necessary, covers the surface of the formed curable composition layer with a coating film, what is called a dry film resist material, etc. When the curable composition layer side of this dry film resist material is covered with the coating film, it is supplied on a board | substrate by peeling the coating film and laminating | stacking on a to-be-processed substrate by methods, such as a heating lamination.

As a temporary support film in the case of being used by the dry film resist material etc., conventionally well-known films, such as a polyethylene terephthalate film, a polyimide film, a polyamideimide film, a polypropylene film, a polystyrene film, are used, for example. do. In that case, when those films have solvent resistance, heat resistance, etc. which are necessary at the time of preparation of a dry film resist material, the curable composition coating liquid can be apply | coated directly on these temporary support films, and it can dry and produce a dry film resist material, Even if these films have low solvent resistance, heat resistance, or the like, for example, a curable composition layer is first formed on a film having releasability, such as a polytetrafluoroethylene film or a release film, and then the solvent resistance is formed on the layer. A dry film resist material can also be produced by laminating | stacking the temporary support film with low heat resistance, etc., and peeling off the film which has mold release property after that.

The solvent used in the coating liquid is not particularly limited as long as it has sufficient solubility in the used component and imparts good coating properties. For example, methyl cellosolve, ethyl cellosolve, methyl cellosolve Cellosolve solvents such as acetate and 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, and propylene glycol monobutyl Propylene glycol-based solvents such as ether acetate and dipropylene glycol dimethyl ether, butyl acetate, amyl acetate, ethyl butyrate, butyl butyrate, diethyl oxalate, ethyl pyruvate, ethyl-2-hydroxybutyrate, ethyl acetoacetate, and methyl lactate Ethyl lactate, methyl 3-methoxypropionate, etc. Ester solvents, alcohol solvents such as heptanol, hexanol, diacetone alcohol, furfuryl alcohol, ketone solvents such as cyclohexanone, methyl amyl ketone, dimethylformamide, dimethylacetamide, N-methylpyrroli High polar solvents, such as a ton, these mixed solvents, what added aromatic hydrocarbon to these, etc. are mentioned. The use ratio of a solvent is the range of about 1 to 20 times by weight ratio with respect to the total amount of each component of a curable composition normally.

[2-1-3] Exposure Method

And the curable image forming material which has a curable composition layer on a to-be-processed board | substrate exposes the curable composition layer by light irradiation or heating, Preferably it exposes by scanning-exposing a laser beam as an exposure light source. At this time, when it has the said protective layer etc., the state which has the protective layer etc. may be sufficient, or may be after peeling. Moreover, when the curable composition layer is formed of the said dry film resist material, it may be a state which has a temporary support film, or may be after peeling.

As the exposure light source, laser light sources such as carbon arc lamp, mercury lamp, xenon lamp, metal halide lamp, fluorescent lamp, tungsten lamp, halogen lamp and HeNe laser, argon ion laser, YAG laser, HeCd laser, semiconductor laser, ruby laser and the like Although the light source which produces | generates the laser beam of the blue-purple region of wavelength range 350-430 nm is especially preferable, it is more preferable that the center wavelength is about 405 nm. Specifically, an indium gallium nitride semiconductor laser which vibrates 405 nm, etc. are mentioned.

In addition, the scanning exposure method by a laser light source is not specifically limited, For example, a planar scanning exposure system, an outer drum scanning exposure system, an inner drum scanning exposure system, etc. are mentioned, As a scanning exposure condition, a laser is given. The output light intensity of is preferably 1 to 100 mW, more preferably 3 to 70 mW, vibration wavelength, preferably 390 to 430 nm, more preferably 400 to 420 nm, beam spot diameter, preferably 2 to 30 µm, more preferably 4 to 20 µm, scanning speed, preferably 50 to 500 m / sec, more preferably 100 to 400 m / sec, scanning density, preferably 2,000 dpi or more, more preferably Scan exposure as 4,000 dpi or more.

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 photocuring mentioned above. As heating conditions at that time, the temperature of 80-250 degreeC normally, Preferably it is 100-200 degreeC, Usually, 10 to 120 minutes, Preferably time for 20 to 60 minutes is employ | adopted.

[2-1-4] Developing Method

In addition, the development process after the exposure is preferably performed using an aqueous developer containing an alkali component and a surfactant as necessary. As the alkali component, for example, sodium silicate, potassium silicate, lithium silicate, ammonium silicate, sodium metasilicate, potassium metsilicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, diphosphate Inorganic alkali salts such as sodium, trisodium phosphate, diammonium phosphate, triammonium phosphate, sodium borate, potassium borate and ammonium borate, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, tri Organic amine compounds such as ethylamine, monoisopropylamine, diisopropylamine, monobutylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, and the like. It is used at a concentration of about weight percent.

Moreover, as surfactant, the same surfactant as what was mentioned in the said curable composition is mentioned, Among these, nonionic, anionic, or amphoteric surfactant is preferable, and amphoteric surfactant, especially a betaine type compound are preferable. Do.

The surfactant is preferably used at a concentration of 0.0001 to 20% by weight, more preferably 0.0005 to 10% by weight, particularly preferably 0.001 to 5% by weight.

Moreover, the developing solution can contain organic solvents, such as isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol, as needed. In addition, the pH of the developer is preferably set to 9-14, more preferably 11-14.

In addition, the development is usually performed by a known developing method such as immersing the image forming material in the developing solution or spraying the developing solution in the image forming material, preferably about 10 to 50 ° C, more preferably 20 to 40 ° C. It is performed at a temperature of about 5 seconds to about 10 minutes. Moreover, in order to improve the heat resistance, chemical resistance, etc. as a resist of the image formed as hardened | cured material after image development processing, it is preferable to heat-process at temperature of about 140-160 degreeC, for example.

[2-2] Use as a spacer

Usually, when the curable composition melt | dissolved or dispersed in the solvent is supplied in the form of a film or a pattern by the method of application | coating etc. on the board | substrate to which a spacer is to be formed, and after drying a solvent, it is supplied in a film form, As needed, a pattern is formed by methods, such as photolithography which performs exposure development. Thereafter, if necessary, spacers are formed on the substrate by performing further exposure or thermosetting.

[2-2-1] Supply Method to Substrate

The curable composition of this invention is normally supplied on a board | substrate in the state dissolved or dispersed in the solvent. As a supply method, it can carry out by a conventionally well-known method, for example, a spinner method, a wire bar method, a flow coat method, a die coat method, a roll coat method, a spray coat method, etc. Among them, the die coating method is preferable from a comprehensive point of view such that the amount of coating liquid used is greatly reduced, and there is no influence of mist or the like adhered when the spin coating method is used. Although application amount changes with a use, For example, in the case of a spacer, it is 0.5-10 micrometers normally as a dry film thickness, Preferably it is 1-8 micrometers, Especially preferably, it is the range of 1-7 micrometers. It is also important that the dry film thickness or the height of the finally formed spacer is uniform throughout the substrate. If the deviation is large, nonuniform defects are caused in the liquid crystal panel. Moreover, you may supply in a pattern form by the inkjet method, the printing method, etc.

[2-2-2] drying method

It is preferable that the drying after supplying a curable composition on a board | substrate is based on the drying method using a hotplate, an IR oven, and a convection oven. Moreover, you may combine the pressure reduction drying method which dries in a pressure reduction chamber, without raising a temperature. The conditions for drying can be suitably selected according to the kind of solvent component, the performance of the dryer to be 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 30 seconds to a temperature of 50 to 110 ° C., depending on the type of the solvent component, the performance of the dryer to be used, and the like. It is selected in the range of 3 minutes.

[2-2-3] exposure method

Exposure is performed by superimposing a negative mask pattern on the coating film of curable composition, and irradiating a light source of an ultraviolet-ray or visible light through this mask pattern. Moreover, the scanning exposure system by a laser beam may be sufficient. At this time, in order to prevent the fall of the sensitivity of the photopolymerizable layer by oxygen as needed, exposure may be performed after forming oxygen blocking layers, such as a polyvinyl alcohol layer, in a deoxidation atmosphere or on a photopolymerizable layer. The light source used for the said exposure is not specifically limited. Examples of the light source include lamp sources such as xenon lamps, halogen lamps, tungsten lamps, high pressure mercury lamps, ultrahigh pressure mercury lamps, metal halide lamps, medium pressure mercury lamps, low pressure mercury lamps, carbon arc and fluorescent lamps, and argon ion lasers and YAG lasers. And laser light sources such as excimer laser, nitrogen laser, helium cadmium laser, blue violet semiconductor laser, and near infrared semiconductor laser. When irradiating and using the light of a specific wavelength, an optical filter can also be used.

[2-2-4] Developing Method

After performing the said exposure, an image pattern can be formed on a board | substrate by the image development which uses the aqueous solution or organic solvent containing an alkaline compound and surfactant as needed. The aqueous solution may further contain an organic solvent, a buffer, a complexing agent, a dye or a pigment.

As an alkaline compound, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium silicate, potassium silicate, sodium metsilicate, sodium phosphate, potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate Inorganic alkaline compounds such as sodium dihydrogen phosphate, potassium dihydrogen phosphate and ammonium hydroxide, mono-, di- or triethanolamine, mono-, di- or trimethylamine, mono-, di- or triethylamine, mono- Or organic alkaline compounds such as diisopropylamine, n-butylamine, mono-, di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), and choline. 2 or more types of mixtures may be sufficient as these alkaline compounds.

As surfactant, For example, Nonionic surfactant, such as polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene alkyl ester, sorbitan alkyl ester, monoglyceride alkyl ester, Anionic surfactants, such as alkylbenzene sulfonate, alkylnaphthalene sulfonate, alkyl sulfate, alkyl sulfonate, and sulfosuccinic acid ester salt, an amphoteric surfactant, such as alkylbetaines and amino acids, are mentioned.

As an organic solvent, isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol, etc. are mentioned, for example. The organic solvent can be used alone or in combination with an aqueous solution.

[2-2-5] further exposure and thermosetting

The substrate after development may be subjected to further exposure by the same method as the above exposure method as necessary, or may be subjected to a thermosetting treatment. It is preferable to perform a thermosetting process especially. The thermosetting treatment conditions at this time are selected in the range of 100 to 280 ° C, preferably in the range of 150 to 250 ° C, and the time is selected in the range of 5 to 60 minutes.

EXAMPLE

In the following, 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 not limited to the following examples without departing from the gist thereof.

[1] curable compositions for soldering resists

Examples 1-3 and Comparative Examples 1-2

The compound represented by the said general formula (I) of the following (A1)-(A6) component, another compound, the photoinitiator of (B-1-B-4) component, the ethylenically unsaturated compound of (C-1) component, The epoxy compound of (D1) component, the epoxy hardening | curing agent of (E1) component, the inorganic filler of (H1-H2) component, the sensitizing dye of (J1-J3) component, and the other component of (X1) component are shown in Table 1 The coating solution was prepared by adding 100 parts by weight of propylene glycol monomethyl ether acetate in a blending ratio and stirring at room temperature.

Separately, the surface of the copper foil of the copper clad laminated substrate (thickness 1.5 mm, size 250 mm x 200 mm) of the polyimide resin which bonded the copper foil of 35 micrometers in thickness was made into Sumitomo 3M Co. After using "Scotch Brite SF", the product was polished and washed with water, dried by air flow, and the surface was cleaned, and then preheated to 60 ° C in an oven, the coating liquid obtained above on the copper foil of the copper clad laminate. Was applied so as to have a dry film thickness of 25 μm, and dried at 80 ° C. for 30 minutes in a hot air circulation drying furnace to prepare a photocurable image forming material.

(A1) The compound obtained by the following manufacture examples

231 g of diepoxide (epoxy equivalent 231) of 9,9-bis (4'-hydroxyphenyl) fluorene, 2-acryloyloxyethyl succinate (acid value 260, manufactured by Kyoei Chemical Co.) `` HOA-MS '') 216 g, 0.45 g of triethylbenzyl ammonium chloride and 0.1 g of p-methoxyphenol were added thereto, heated and dissolved at 90 to 100 DEG C while blowing air at a rate of 25 ml / min, and the solution was clouded. The solution was gradually heated to 120 ° C. in a state of complete dissolution, and then the solution containing the transparent mucus was continuously heated and stirred for 8 hours until the acid value became 0.8 KOH · mg / g to obtain a colorless transparent reaction product. Subsequently, 20 g of cellosolve acetate was added to and dissolved in 447 g of the obtained reaction product. Then, 38 g of 1,2,3,6-tetrahydrophthalic anhydride, 73.5 g of biphenyl tetracarboxylic dianhydride, and 1 g of tetraethylammonium bromide were added. And the temperature was gradually raised to react at 110 to 115 ° C for 2 hours to obtain a compound (A1). The weight average molecular weight of the obtained compound was 3,500, and the double bond equivalent was 560.

(A2) Compound obtained by the following Preparation Example

200 parts by weight of succinic anhydride and 596 parts by weight of commercially available pentaerythritol triacrylate are reacted at 100 ° C for 5 hours in the presence of 2.5 parts by weight of triethylamine and 0.25 parts by weight of hydroquinone, thereby yielding at least one carboxyl group in one molecule. The polyfunctional acrylate mixture of the acid value 94 containing 67 mol% of polyfunctional acrylate which has acryloyl group, and 33 mol% of pentaerythritol tetraacrylate was obtained. Compound (A2) was obtained by the same method as the preparation example of (A1), except that 597 g of a polyfunctional acrylate mixture was used instead of 216 g of 2-acryloyloxyethyl succinic acid. The weight average molecular weight of the obtained compound was 3,000, and the double bond equivalent was 210.

(A3) Compound obtained by the following Preparation Example

In the production example of (A1), the compound (A3) was prepared in the same manner as in the production example of (A1), except that 80.5 g of benzophenone tetracarboxylic dianhydride was used instead of 73.5 g of biphenyl tetracarboxylic dianhydride. ) The weight average molecular weight of the obtained compound was 3,500, and the double bond equivalent was 189.

(A4) Compound obtained by the following Preparation Example

In the preparation of the above (A1), diepoxide of 9,9-bis (4'-hydroxy-3'-methylphenyl) fluorene instead of 231 g of 9,9-bis (4'-hydroxyphenyl) fluorene Except having used 231g, the compound (A4) was obtained by the same method as the manufacturing example of said (A1). The weight average molecular weight of the obtained compound was 3,000, and the double bond equivalent was 187.

(A5; for comparative example) Compound obtained by the following preparation example

In the production example of (A1), the compound (A5) was obtained by the same method as the production example of (A1), except that 72 g of acrylic acid was used instead of 216 g of 2-acryloyloxyethyl succinic acid. The weight average molecular weight of the obtained compound was 3,200, and the double bond equivalent was 416.

(A6; for comparative example)

Compound (A6) having the following structural repeating unit (acid value 100 mgKOH / g, weight average molecular weight 5,000, double bond equivalent weight 398, Showa Kobunshi Co. make "PR-300J")

(B1) 1- (4-methylthiophenyl) -2-morpholino-2-methyl-propan-1-one

(B2) 2,4-diethyl thioxanthone

(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 216, manufactured by Japan Epoxy Resin Co. `` Epicoat 180S70 '')

(E1) dicyandiamide

(H1) barium sulfate

(H2) talc

(J1) the following sensitizing dyes

(J2) the following sensitizing dyes

(J3) the following sensitizing dyes

(X1) phthalocyanine green

[1-1] high pressure mercury lamp exposure sensitivity

About the photocurable image forming material obtained above, exposure sensitivity was measured by the method shown below, and the result was shown in Table 1.

The minimum exposure amount (mJ / cm 2) at which a step image is reproduced when a 1 kW ultrahigh pressure mercury lamp is irradiated to the photocurable composition layer of the obtained image forming material and developed at 30 ° C. for 80 seconds using a 1 wt% sodium carbonate aqueous solution. Was measured as the sensitivity.

[1-2] Adhesion to Substrates

Moreover, about the obtained photocurable image forming material, the adhesiveness with respect to the to-be-processed board | substrate of the hardened layer and its heat resistance were evaluated by the method shown below, and the result was shown in Table 1.

After irradiating the photocurable composition layer of the obtained image forming material with the minimum exposure amount calculated | required above using the 1 kW ultrahigh pressure mercury lamp, and forming a front hardening layer, after heat-processing the obtained hardened layer at 150 degreeC for 60 minutes, it conforms to JISD0202. Cut through the cutter so as to form 100 grids at 1 mm intervals on the cured layer, and attach a cellophane tape (manufactured by Nichiban Co.) on the cured layer to measure the peeled grid number of the cured layer when the tape was peeled off. The following criteria evaluated.

A: The number of peeling grid | lattices of a hardened layer is 0 among 100 grids.

B: The number of peeling grid | lattices of a hardened layer among 100 grids is one or more and less than five.

C: The number of peeling grid | lattices of a hardened layer among 100 grids is five or more and less than ten.

D: The number of peeling grids of a hardened layer is 10 or more among 100 grids.

[1-3] Adhesive Heat Resistance

In the same way as above, the cutter was cut into 100 grid shapes, and then the flux (manufactured by Tamura Kaken Co.) was applied to the surface, and then immersed in a solder bath at 290 ° C. for 30 seconds, and then returned to room temperature. The turning operation was repeated 6 times. Then, the cellophane tape was stuck on the hardened layer, the peeling grid | lattice of the hardened layer at the time of peeling the tape by the same method as the above was measured, and it evaluated by the same reference | standard.

[1-4] Laser Exposure Sensitivity

Example 4 (Curable composition for solder resist: laser exposure)

About the photocurable image forming material produced by the method similar to Examples 1-3, the laser exposure sensitivity was measured by the method shown below using a laser beam as an exposure light source, and the exposure light source was changed into the laser beam except that The adhesiveness to the board | substrate and its heat resistance were evaluated by the same method, and the result was shown in Table 1. A laser light source having a center wavelength of 405 nm and a laser output of 5 mW while fixing the photocurable composition layer of the obtained image forming material on an aluminum cylinder having a diameter of 7 cm and varying the rotation speed at 10 to 100 rpm (manufactured by Nichia Chemical Industry Co., Ltd. "NLHV500C"). Using 2 mW of image surface roughness and a beam spot diameter of 20 µm, scanning exposure while varying the beam scanning interval and scanning speed, and then spraying a 30 wt.% 1% by weight aqueous solution of sodium carbonate as a developing solution to 0.15 MPa, The image was expressed by spray development at a time of 1.5 times the minimum development time. With respect to the obtained image, the exposure dose required to reproduce the line width of 20 µm was determined and determined as the sensitivity to the blue violet laser.

[2] curable compositions for soldering resists: dry film resists

Examples 5-7

On a polyethylene terephthalate film (thickness 19 μm) as a temporary supporting film, an applicator was used to apply a dry film thickness of 25 μm, dried in an oven at 90 ° C. for 5 minutes, and on the formed photocurable composition layer, a coating film The dry film resist material was produced by laminating | stacking polyethylene film (25 micrometers in thickness) as it and leaving to stand for 1 day. Subsequently, on the peeling surface of the obtained dry film resist material on the same copper foil of the copper clad laminated board as used in Examples 1-3, while peeling the polyethylene film, the roll temperature is 100 degreeC using a hand-rolled laminator, The photocurable image forming material in which the photocurable composition layer was formed on the copper-clad laminated substrate was produced by laminating | stacking at roll pressure 0.3 Mpa, and lamination speed 1.5 m / min.

About the photocurable composition layer of the obtained photocurable image forming material, laser exposure sensitivity was measured by the method similar to Example 4, and also the adhesiveness to the board | substrate and its heat resistance were evaluated, and the result was shown in Table 1.

[3] curable compositions for spacers

Examples 8-14, Comparative Examples 3-4

(A2), (A5) and the compound represented by general formula (I) of following (A8)-(A12) component, the other compound, the polymerization initiator of (B1) component, ethylenic of (C1) and (C2) component The unsaturated compound, the amino compound of the component (F1), the surfactant of the component (I1) and the additive of the component (N1) were added to 100 parts by weight of propylene glycol monomethyl ether acetate at the blending ratios shown in Table 2, and stirred at room temperature, A coating liquid was prepared. About the obtained coating liquid, storage stability was evaluated by the method shown below, and the result was 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, the change in viscosity and minimum developing time before and after storage were measured and evaluated based on the following criteria.

○: Viscosity change is within ± 3%, and minimum development time is within ± 3%.

(Triangle | delta): Although a viscosity change exceeds ± 3%, the change of minimum developing time is within ± 3%.

X: The change in viscosity is within ± 3%, but the change in minimum developing time is more than ± 3%.

(A8) The compound obtained by the following manufacture example

Production example of (A2) above except that 137 g of 1,2,3,6-tetrahydrophthalic anhydride was used instead of 38 g of 1,2,3,6-tetrahydrophthalic anhydride and 73.5 g of biphenyltetracarboxylic dianhydride. The compound (A8) was obtained by the same method as the above. The acid value of the obtained compound was 56, the weight average molecular weight was 2,620, and the double bond equivalent was 216.

(A9) The compound obtained by the following manufacture example

100 parts of diglycidyl etherate (epoxy equivalent 231) of 9,9-bis (4'-hydroxyphenyl) fluorene, the same succinic anhydride and pentaerythritol triacrylic acid as used in the preparation of (A2) above Reaction mixture with acid rate (acid value 90.5) 273.2 parts, p-methoxyphenol 0.19 part, triphenylphosphine 7.4 part, propylene glycol monomethyl ether acetate 368 parts were put into a reaction container, and the acid value was 5 mg-KOH / g at 90 degreeC. Stir until it became below. It took 10 hours for the acid value to reach the goal (acid value 1.0). Subsequently, 6 parts of propylene glycol monomethyl ether acetate were added to 80 parts of reaction liquids obtained by the above reaction, 1.9 parts of hexamethylene diisocyanate and 0.01 part of dibutyl tin dilaurate were added to react at 90 ° C for 3 hours, and further 3.8 parts of trimellitic anhydride were added and reacted at 90 degreeC for 3 hours, and the compound (A9) solution which has a weight average molecular weight of 3100 and the double bond equivalent of 199 of polystyrene conversion measured by acid value 52 and GPC was obtained.

(A10) Resin having a trisphenol methane structure (TCR1286 manufactured by Nippon Kayaku Co., acid value 101, 315 double bond equivalents, diethylene glycol monoethyl ether acetate solution)

(A11) The compound obtained by the following manufacture example (The test of the acrylic resin of the synthesis example 3 in Unexamined-Japanese-Patent No. 11-133600 further).

In a flask equipped with a cooling tube and a stirrer, 7 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol dimethyl ether were added. 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 added, and the mixture was gradually stirred after purging with nitrogen. The temperature of the solution was raised to 70 ° C, and this temperature was maintained for 5 hours to obtain a polymer solution containing a copolymer (A11). Solid content concentration of the obtained polymer solution was 33%, and the weight average molecular weight of the polymer was 18,000.

(A12) The compound obtained by the following manufacture example

Instead of 38 g of 1,2,3,6-tetrahydrophthalic anhydride and 73.5 g of biphenyltetracarboxylic dianhydride, manufactured by New Japan Chemical, tetracarboxylic dianhydride, 57.5 g of RIKACID BT-100, 1,2,3,6 Compound (A12) was obtained by the same method as the preparation example of (A2), except that 43.8 g of tetrahydrophthalic anhydride was used. The acid value of the obtained compound was 55, the weight average molecular weight was 4450, and the double bond equivalent was 208.

(C2) (meth) acryloyloxy group-containing phosphates represented by the general formula (VIIIc) (KAYARAD PM21 manufactured by Nippon Kayaku Co.)

(F1) melamine resin and its modified resin (NIKALAC E-2151 manufactured by Sanwa Chemical Co.)

(I1) Fluorine-based surfactant (MegaFAX F475 manufactured by DaiNippon Ink Chemical Industry Co.)

(N1) Silane coupling agent (SH6040 manufactured by Toray Dow Corning Co.)

Subsequently, after apply | coating the said coating liquid using the spinner on the ITO film | membrane of the glass substrate in which the ITO film | membrane was formed on the surface, it heat-dried at 80 degreeC for 3 minutes on the hotplate, and formed the coating layer. The exposure amount was 150 micrometers of exposure gap using the pattern mask which has 9 circular openings of diameter 5-20 micrometers, and the opening of 5 mm or more in width | variety to the obtained coating layer using the ultraviolet-ray with an intensity of 32 mW / cm <2> at 365 nm. It exposed so that it might become 60mJ / cm <2>. Ultraviolet irradiation at this time was performed under air. Subsequently, spray development was carried out with 23% of 0.1% aqueous potassium hydroxide solution for 2 times the minimum development time, followed by 1 minute washing with pure water. Here, the minimum development time means a time at which the unexposed part is completely dissolved under the same development conditions. By these operations, the board | substrate with which a spacer pattern was formed by removing an unnecessary part was heated and hardened | cured at 230 degreeC for 30 minutes in oven, The film part formed in the opening part of 5 mm or more in width | variety is about 4 micrometers, and the bottom area is A plurality of different spacer patterns were obtained. About the obtained spacer pattern, adhesiveness and compression characteristics were evaluated by the method mentioned later, and the result was shown in Table 2.

[3-2] Adhesiveness

Adhesive evaluation was performed about Examples 8-11 and Comparative Examples 3 and 4.

For spacer patterns having different bottom areas obtained from pattern masks having different mask opening diameters, the pattern height is 3 占 퐉 or more, and at least 8 of the nine spacer patterns of the same size are formed (that is, 9 to be formed). Table 2 shows the bottom area of each of the two patterns with the missing pattern) and the minimum pattern size as the adhesiveness.

[3-3] Compression characteristics: Load-unload test by micro hardness tester

About the spacer pattern obtained above, the longitudinal cross section which passed the intermediate axis of a spacer pattern was profiled using the super depth color 3D shape measurement microscope (Keyence Corp., VK-9500). The length of the straight line AA 'parallel to the board | substrate surface in the figure of a spacer pattern at the height of 90% of the height from the board | substrate surface of the profiled figure (shown the schematic diagram in FIG. 2) to the point Q of the highest position was measured. Next, the area of the circle | round | yen which made AA 'the diameter was made into the upper end area of a spacer pattern.

Among them, the upper load area with a 80 ± 10㎛ ² pattern, Shimadzu dynamic hardness meter DUH-W201S second minute for 1 - were evaluated for compressive properties by unloading test. The test conditions were applied to the spacer at a constant rate (0.22 gf / sec) at a constant rate (0.22 gf / sec) using a planar indenter having a measurement temperature of 23 ° C. and a diameter of 50 μm, held at the point where the load reached 5 gf for 5 seconds, and then continued at the same speed. It was made by the method of subtracting. From the load-displacement curve obtained in this test (shown schematically in FIG. 3), the maximum displacement H [max], final displacement H [Last], recovery rate (%) = H [last] / (pattern height before test) × 100, elastic recovery rate (%) = (H [max] -H [last]) / H [max] × 100, and the load N (gf) when the displacement at the time of loading is 0.25 micrometer was calculated | required, and it is shown in Table 2.

[3-4] Evaluation of spacer characteristics (panel evaluation)

The liquid crystal cell was produced by the method shown below, and the spacer characteristic was evaluated.

Electrode substrate A and electrode substrate B were manufactured.

The former was a 2.5 cm wide alkali free glass substrate (Asahi glass, AN-100) coated with an ITO layer on one side of the front surface, while the latter was coated with a 1 cm wide ITO layer with a 2 mm wide interconnection electrode at the center of one side. It was the same glass substrate of 2.5 cm in width.

The curable composition (manufactured by each example) was applied onto the electrode substrate A by spin coating, and heated on a hot plate at 80 ° C. for 3 minutes, and the bottom area was 80 at the center (area 1 square centimeter). 900 circular patterns having a μm ² were exposed on the lattice (30 pieces / cm × 30 pieces / cm) with an exposure gap of 150 μm using an exposure mask designed side by side at equal intervals. The irradiation energy was 60 mJ / cm 2. Subsequently, it developed using the potassium hydroxide aqueous solution, wash | cleaned with pure water, and heated at 230 degreeC in hot-air circulation furnace for 30 minutes. Coating conditions were adjusted so that the spacer height after heating might be 4 micrometers. In this way, the electrode substrate A in which the test pattern of the spacer was formed in the center part was prepared.

Subsequently, an alignment film agent (SUNEVER 7492, manufactured by Nissan Chemical Industries, Ltd.) was applied to the electrode substrate A and the electrode substrate B by spin coating, and then dried at 110 ° C. on a hot plate for 1 minute, followed by 200 in a hot air circulation path. It heated at 1 degreeC for 1 hour, and formed the coating layer of film thickness 70nm. After carrying out the alignment treatment using a rubbing machine, an epoxy resin sealant containing silica beads having a diameter of 4 μm is applied using a dispenser on the outer circumference of the surface on which the alignment film of electrode substrate B is applied. With respect to the surface on which the spacer test pattern of the electrode substrate A was formed, the substrate was heated at 180 ° C. for 2 hours in a hot air circulation path with the outer edges facing each other so as to be shifted by 3 mm.

A liquid crystal (ZLI-4792, manufactured by Merck & Co.) was injected into the empty cell thus obtained, and the periphery was sealed with a UV curable sealant to prepare a test cell.

AC voltage (5V, 60Hz) was added to the obtained liquid crystal cell, and the electro-optical reaction of the electrode formation part was observed visually and a microscope. The cells were evaluated according to the following criteria.

(Circle): When a nonuniformity is not recognized even by a naked eye and a microscope.

(Triangle | delta): When it cannot confirm visually but a nonuniformity is confirmed by a microscope

X: When non-uniformity is confirmed visually

The results are shown in Table 2.

Although the present invention has been described in detail using specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope of the invention.

This application is based on the JP Patent application (Application No. 2003-380666) of an application on November 11, 2003, The whole content is integrated by reference.

The curable composition of the present invention is insulated from solder resist films, coverlay films, and various electronic components in printed wiring boards, liquid crystal display devices, plasma displays, large-scale integrated circuits, thin transistors, semiconductor packages, color filters, organic electro luminescence, and the like. It is useful for forming the coating layer, and is particularly suitable for use in direct drawing by laser light.

Moreover, the curable composition of this invention is useful as a curable composition for color filters, a black matrix, an overcoat, a rib, and a spacer used for liquid crystal panels, such as a liquid crystal display.

Claims (7)

A curable composition containing an ethylenically unsaturated group and a carboxyl group-containing compound, wherein in the loading-unloading test by a microhardness tester, (i) when the total strain is 1.35 µm or more, or the displacement at load is 0.25 µm. When the load N is 0.50 gf or less, or the total strain is 1.35 μm or more and the displacement at load is 0.25 μm, the load N is 0.50 gf or less, and (ii) the elastic recovery rate is 50% or more, or the recovery rate is Curable composition characterized in that it can form a cured product of 80% or more, or the elastic recovery rate is 50% or more and the recovery rate is 80% or more. A curable composition containing an ethylenically unsaturated group and a carboxyl group-containing compound, wherein in a load-unloading test by a microhardness tester, (i) the bottom surface cross section is 25 µm ² or less, and (ii) the elastic recovery rate is 50% or more, or the recovery rate. The curable composition which can form the hardened | cured material which is 85% or more, or 50% or more of elastic recovery rate, and 85% or more of recovery rate. The curable composition according to claim 1 or 2, further comprising a compound having a trisphenol methane structure. The curable composition according to claim 1 or 2, wherein the total amount of double bonds in the composition is 200 or less. Hardened | cured material formed using the curable composition of Claim 1 or 2. The color filter which has a hardened | cured material of Claim 5. The liquid crystal display device which has the hardened | cured material of Claim 5.

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