TW200530279A - Curable composition, cured product, color filter and liquid crystal display device - Google Patents

Abstract

A curable composition having high sensitivity and excellent in adhesion to a substrate and heat resistance thereof, particularly, a curable composition suitable to use in direct imaging by a laser light used for a solder resist, as well as a curable composition and a curing product thereof for color filters, black matrixes, overcoats, ribs and spacers, used, for example, in liquid crystal panels of liquid crystal displays having high curability and excellent mechanical characteristics, the curable composition containing a compound represented by the following formula (I): in which R1 represents an alkylene group which may have a substituent, or an arylene group which may have a substituent, n is an integer of from 0 to 10, four benzene rings may further have a substituent, R2 represents an ethylenically unsaturated group-containing carbonyloxy group of 5 or more carbon atoms which may have a substituent, and R3 and R4 each represents independently an optional substituent.

Description

200530279 IX. Description of the invention: [Technical field to which the invention belongs] The present invention relates to a hardenable composition using light or heat. More specifically, it relates to a printed wiring board, a liquid crystal display element, a plasma display device, and a large-scale product. Fields such as bulk circuits, thin transistors, semiconductor packages, color filters, organic electric field light emitting devices, etc. are useful in the formation of solder masks, cover films, and insulation coatings for various electronic parts, especially when using lightning The light directly describes the hardening composition suitable for use in the day. Furthermore, the present invention relates to a hardenable composition used in a liquid crystal panel of a liquid crystal display device or the like to function as a color filter, a black substrate, an overcoat, a rib, and a spacer, and uses the hardenable composition. The hardened material formed by the object, and the color filter and the liquid crystal display device having the hardened object. [Prior art] Conventionally, for example, when a printed wiring board is soldered to electronic parts and wired, it is necessary to prevent the adhesion of the solder to parts that do not need to be soldered, and to prevent the direct exposure of the circuit to air. A method of providing a solder resist layer on a surface other than the soldered portion of the circuit conductor is implemented. For the formation of this solder resist, a photolithographic method using a photosensitive day image forming material (hereinafter sometimes referred to as a day image forming material (A)) or the like is widely used. The day image forming material (A) refers to a dry film photoresist formed by forming a photosensitive composition layer on a temporary support film and then covering the surface of the photosensitive composition layer with a coating film. 6 326 \ Patent Specification (Supplement) \ 94-03 \ 93134393 200530279 Photolithography is performed in the following order. First, a coating film of a day image forming material (A) is peeled off and laminated on a substrate to be processed to form a photosensitive day image forming material (hereinafter sometimes referred to as a day image forming material (B)). The image forming material (B) can also be directly coated on the substrate to be processed with a coating solution of a photosensitive composition, dried to form a photosensitive composition layer, and the photosensitive composition is covered with a protective layer if necessary. The surface of the layer is prepared. Next, the photosensitive composition layer of these daytime image forming materials (B) on the substrate to be processed is subjected to portrait exposure through a photomask film on which a circuit pattern is drawn. Then, the temporary supporting film or protective layer is peeled off, and the difference in the solubility of the developing solution between the exposed portion and the non-exposed portion is used to perform a development process to form a photoresist image corresponding to the circuit pattern. Then, under the photoresist day image serving as a photoresist, a soldering process or the like is applied to the substrate to be processed, thereby forming a circuit pattern drawn on the photomask film on the substrate. On the other hand, recently, there is a direct laser daylighting method, which uses laser light as an exposure light source, thereby using a photomask to form a daylight image directly from digital information, such as a computer. The improvement of the nature can also be used to improve the image and position accuracy, and it has attracted attention. Following this, the photolithography technology is also actively studying the use of laser light. Next, as the laser light source, various light sources in the ultraviolet to infrared field are known. However, regarding the laser light source that can be used for day image exposure, argon ions are based on the viewpoints of output, stability, photosensitivity, and cost. Lasers, helium-neon lasers, YAG lasers, and semiconductor lasers that emit light that can be seen into the infrared field become its main force, such as the use of argon ion lasers with a wavelength of 4 8 8 η, wavelengths of 5 3 2 nm The FD-YAG laser photolithography method has reached 326 \ Patent Specification (Supplement) \ 94-03 \ 9313β93 200530279 into practical use. Furthermore, due to the remarkable progress of laser technology in recent years, semiconductor lasers that can stably oscillate in the blue-violet field have also become available. However, in the case of a conventional photosensitive composition using direct drawing method of laser light, its sensitivity may not be sufficient, especially in the case of blue-violet semiconductor laser, its output is lower than other visible fields, etc. Therefore, the corresponding photosensitivity The sensitivity and developability of the composition are not only in the direct tracing method, but also in the photolithography method. The actual level has not yet reached the practical level. Therefore, there is a great need for a solder resist material that is likely to achieve laser exposure. On the other hand, as a solder resist layer for a printed wiring board, a liquid photoresist ink is used from the viewpoints of high accuracy, high density, and environmental considerations, and as the liquid photoresist ink, for example, , A photocurable photoresist ink (the reaction product of an α, / 3 -unsaturated monocarboxylic acid adduct of an epoxy resin and a dicarboxylic acid anhydride, a photopolymerizable monomer, and a photopolymerization initiator containing epoxy resin) has been known for a long time. . Furthermore, a photosensitive composition is known, which is formed by improving the sensitivity and developability of a light-curing and sexy photo-sensitive composition used in a resist layer, a 14-resist photoresist layer, or a solder resist layer, and the like. For the purpose of improving the durability of the day image, etc., a modified solubility ring containing a polycarboxylic acid or its anhydride added to an epoxy resin α, / 3 -unsaturated monoweilic acid adduct is included. Those who have oxyacrylic acid baking ester resin and use the composition as a dry film photoresist material and laminate it on the substrate, or apply the coating solution of the composition on the substrate and allow it to dry, thus forming A daylight image forming method for a daylight image forming material having a photosensitive composition layer by exposing it with a high-pressure mercury lamp or visible laser or infrared laser to perform a development process (for example, refer to Patent Document 1, Patent Document 2, and 8 326 \ Patent Specification (Supplement) \ 94-03 \ 93134393 200530279 Literary Literature 3) and so on. In addition, a solder resist resin composition is also known. In order to improve soldering heat resistance, a reaction product of bis (hydroxybenzene) fluorene type epoxy resin and (fluorenyl) acrylic acid is further used to further react with polycarboxylic acid. A modified epoxy acrylate resin obtained by reacting its acid anhydride or its anhydride (for example, refer to Patent Document 4). However, the photo-hardenable compositions described in these documents still have room for improvement in terms of sensitivity, and they are closely adhered to the substrate to be processed, especially when they are used as solder resists and are exposed to high temperatures. Poor sex. In the field of liquid crystal display devices and the like, when forming color filters for liquid crystal panels, black substrates, coatings, ribs, and spacers, resins, photopolymerizable monomers, and photopolymerization have been used. Resin composition composed of agents. From the viewpoints of developability, pattern accuracy, and adhesiveness, various compositions of resin compositions have been proposed. One of the proposals is to reveal a short time in the formation step and increase the productivity. Next, as the resin contained in the resin composition, an unsaturated group-containing resin obtained by further reacting an epoxy resin with an unsaturated group-containing carboxylic acid or its anhydride with a polycarboxylic acid or its anhydride ( Patent Document 5). On the other hand, a resin composition for a liquid crystal panel is sometimes required to have high hardenability or excellent mechanical properties. For example, a spacer (in this specification, the "" spacer "means a so-called" columnar spacer "," photosensitive spacer ", etc. formed of a resin composition) is a liquid crystal panel, and holds two substrates. For users with a certain interval, the spacers are deformed before and after being pressurized due to the pressure step of the color filters and substrates under high temperature and pressure when manufacturing LCD panels. 9 326 \ Patent Specification (Supplementary Document) ) \ 94-03 \ 93] 34393 200530279, while maintaining the physical properties of the spacer function. That is, it is required that the resin composition for a spacer in a practical use environment has a mechanical property, and even if it is deformed by external pressure, it can be restored to its original shape when the external pressure is removed. In order to satisfy this mechanical characteristic, a resin composition or the like that specifies the content of a polyfunctional acrylate monomer is proposed (Patent Document 6). However, such spacers are required to have not only the above-mentioned mechanical characteristics, but also pattern accuracy and adhesion. On the other hand, when the purpose of improving pattern accuracy and adhesion is to simply use the unsaturated group-containing resin described above, it is not possible to form a resin composition having mechanical properties suitable for a spacer. In addition, because of the required mechanical characteristics, the total deformation amount during a pressing step is large, that is, the requirement for a soft spacer, and for this reason, when only the above unsaturated group-containing resin is used, a simple soft interval can be formed. However, the recovery after removing the external pressure is not sufficient, and the deformation before and after the pressure is large, that is, it is not a practically durable thing. [Patent Document 1] Japanese Patent Laid-Open No. 5-2 0 4 1 50 [Patent Document 2] Japanese Patent Laid-Open No. 2 0 0-1 4 7 7 6 7 [Patent Document 3] Japanese Patent Special Open 2 0 0 1-2 2 8 6 1 1 [Patent Document 4] Japanese Patent Laid-open No. 4-3 5 5 4 50 0 [Patent Document 5] Japanese Patent Laid-Open 2 0 0 1-1 7 4 6 2 Publication No. 326 \ Patent Specification (Supplement) \ 94-03 \ 93134393 10 200530279 [Patent Document 6] Japanese Patent Laid-Open No. 2 0 0 2-1 7 4 8 1 [Summary of the Invention] The present invention In view of the invention created by the facts of the foregoing conventional technologies, an object of the present invention is to provide a hardenable composition having high sensitivity and excellent adhesion to a substrate to be processed and excellent heat resistance. A hardenable composition suitable for use in solder mask applications and suitable for direct drawing using laser light. Moreover, another object of the present invention is to provide a liquid crystal panel used in a liquid crystal display device or the like which solves the above-mentioned problems, for use in day image formation of color filters, for use in black substrates, for use in coatings, Curable composition used for ribs and spacers. As a result of intensive research on the above-mentioned subject by the inventors of the present case, it was found that when the curable composition contains a specific unsaturated group-containing compound (especially characterized by having an ethylenically unsaturated group-containing carbonyloxy group having 5 or more carbon atoms), By virtue of the fact that it is possible to achieve the above object, the present invention has been completed. That is, the gist of the present invention is as follows. 1. A curable composition containing a compound represented by the following general formula (I)

[In the formula (I), R1 represents an alkylene group which may have a substituent, or an alkylene group which may have a substituent of 11 326 \ Patent Specification (Supplement) \ 94-03 \ 93134393 200530279, and η is 0 to 10 Integer, 4 benzene rings may further have a substituent, R2 represents an ethylenically unsaturated group-containing carbonyloxy group having 5 or more carbon atoms, and R3 and R4 each independently represent an optional substituent]. 2. Regarding the load-except load test using a micro hardness tester, the load N when the total deformation amount is 1.35 // Π1 or more and / or the load displacement is 0.25 // m is 0.5 gf or less, A hardenable composition characterized by a hardened material having an elastic recovery rate of 50% or more and / or a recovery rate of 80% or more. 3. A hardening composition characterized by forming a hardened product with a bottom cross-sectional area of 25 // m2 or less, an elastic recovery rate of 50% or more, and / or a recovery rate of 85% or more. 4. A hardened product formed by using the hardenable composition described in 1 or 2 above. 5. A color filter having the hardened material according to the above 4. 6. A liquid crystal display device having the cured product according to the above 4. The present invention can provide a hardening composition having high sensitivity and excellent adhesion to a substrate and excellent heat resistance. The composition is particularly suitable for use in a solder resist layer and is suitable for using laser light. Directly describe the hardening composition used in the day. Furthermore, according to the present invention, it is possible to provide a liquid crystal panel used in a liquid crystal display device or the like with high hardening property and excellent mechanical properties to serve as a color filter, a black substrate, an overcoat layer, a rib, and a spacer. Hardening composition. [Embodiment] The present invention will be described in detail below. According to another, the following description is an example of the implementation of the present invention. As long as the present invention does not exceed its gist, it is not specified in 12 326 \ Patent Specification (Supplement) \ 94-03 \ 93〗 34393 200530279 content. [1] Sclerosing composition The sclerosing composition of the present invention contains a compound represented by the general formula (I) and / or (A-2) a compound having a phenol pinane structure {the following are It is characterized by (A) component}. Furthermore, it is preferable to further contain (B) a photopolymerization initiator and / or a thermal polymerization initiator, and (C) an ethylenically unsaturated compound. When the hardenable composition of the present invention is used for a solder resist, an overcoat, a rib, or a spacer, it further contains (D) an epoxy compound and (E) an epoxy hardener. Agents, (F) amine compounds, (ii) inorganic fillers may also be used. Furthermore, when the curable composition of the present invention is used for a color filter application or a black matrix application, it is preferable to further contain (L) a color material and (M) a dispersant and / or a dispersing aid. Agent. Furthermore, in the case where the curable composition of the present invention is used in a laser direct tracing method, it is preferable to further contain (J) a sensitizing dye. Further, as other constituent elements, (G) a polymerization accelerator, (I) a surfactant, (K) other soluble resins, (N) other additives, and the like are further mentioned. Alternatively, the hardenable composition of the present invention is about a load-except load test using a micro hardness tester described later, so that the total deformation can be 1. 3 5 // m or more and / or the displacement at the load is 0.25 // The load N at m is 0.50 gf or less, and a hardened product having an elastic recovery rate of 50% or more and / or a recovery rate of 80% or more is characterized. Alternatively, the hardenable composition of the present invention can form a bottom surface as described later 13 326 \ Patent Specification (Supplement) \ 94-03 \ 93134393 200530279 The cross-sectional area is 25 μm2 or less, and the elastic recovery rate is 50% It is characteristic that the above and / or the recovery rate is more than 85%. Hereinafter, each component of the curable composition of the present invention will be described. [1-1] (A-1) Compound represented by general formula (I) The curable composition of the present invention is characterized by containing the compound (A-1) represented by general formula (I): R2-CH2 -CH-CH2- (0R1) -0

⑴ [In the formula (I), R1 represents an alkylene group which may have a substituent, or an arylene group which may have a substituent, and R2 represents a carbonyl group containing an ethylenically unsaturated group having 5 or more carbon atoms which may have a substituent. Oxygen, R3 and R4 each independently represent an optional substituent, η is an integer of 0 to 10, and four benzene rings may further have a substituent]. Here, it is preferable that the elongation group of R 1 is an elongation group having 1 to 5 carbon atoms, and the fluorenyl group, ethylenyl group, propylenyl group, and butylene group are more preferable, and The radical is preferably an arylene group having 6 to 10 carbon atoms, and a phenylene group is more preferable. Especially in the present invention, alkylene is preferred. Examples of the substituent of such an alkylene group or an alkylene group include an alkyl group having 1 to 15 carbon atoms. Furthermore, η is an integer from 0 to 10, preferably from 0 to 5, and more preferably from 0 to 3. When η is outside the above range, when the curable composition becomes a cured product, a reduction in the film thickness of the daytime image portion or the like occurs during development, or a reduction in heat resistance occurs. 14 326 \ Patent Specification (Supplement) \ 94-03 \ 93134393 200530279 is a "possible" substituent of R1, and examples thereof include a hydrogen atom, a halogen atom, a hydroxyl group, and an alkyl group having 1 to 10 carbon atoms. , Alkenyl, phenyl, phenyl, amine, amine, amine, nitro, etc., having 2 to 10 carbon atoms. Regarding the carbonyloxy group containing an ethylenically unsaturated group which may have a substituent in R2, the number of carbon atoms may be 5 or more. The upper limit is not particularly limited, but 50 is preferred, and 30 is further preferred. good. In the case where the hardenable composition of the present invention is used for a solder resist, the upper limit of the number of carbon atoms is more preferably 20, and particularly preferably 15. Furthermore, it is more preferable when the carbonyloxy group containing an ethylenically unsaturated group of R2 is a group represented by the following general formula (Π). R9 [丨 r7 \ ^ \ yk ^ \ 〇 / * (11) R8 [In formula (II), R7, R8, and R9 each independently represent a hydrogen atom or a methyl group, and Y1 is an optional divalent group. In the formula, * Represents a bond between -CH2- and R 2 of a compound represented by the general formula (I)] It is also preferable that Y1 represents an alkylene group which may have a substituent or / and an aromatic group which may have a substituent And the divalent group of carbonyloxy. More preferably, Y 1 represents an alkylene group having 1 to 10 carbon atoms which may have a substituent or an alkylene group having 1 to 10 carbon atoms which may have a substituent and a carbonyloxy group. 2-valent base. R3 preferably represents a substituent represented by the following formula (Ilia), and 15 326 \ Patent Specification (Supplements) \ 94-03 \ 931343 shown in (Illb) 200530279 There are 3 to 20 carbon atoms, 2 to 1 0 nitrate groups [Formula (based on the base or a carbon substituted group on the dilute base. One C one R51

In Ilia), R51 represents an alkyl group which may have a substituent, a diluent group which may have a substituent, a cycloalkyl group which may have a substituent, and an aryl group which may have a substituent. Therefore, the alkyl group of R51 is preferably one having 1 to 20 carbon atoms, the alkyl group of R51 is preferably one having 2 to 20 carbon atoms, and the cycloalkyl group of R51 is preferably one having 3 to 20 carbon atoms. Preferably, the cycloalkenyl group of R51 has a carbon number, and the aryl group of R51 has a carbon number of 6 to 20. Each substituent of R51 "may have a substituent" includes, for example, a hydrogenogen halogen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having a carbon atom number, a phenyl group, a carboxyl group, a carbonyl group, and a sulfonamide. Group, phosphine group, amine group, etc. Among them, those having a carboxyl group are preferred. 〇 II H (fflb)-C-N-R 52

In Illb), R52 represents an alkyl group which may have a substituent, a diluent group which may have a substituent, a cycloalkyl group which may have a substituent, and an aryl group which may have a substituent. Here, the alkyl group of R5 2 is preferably one having 1 to 20 carbon atoms, the alkyl group of R5 2 is preferably one having 2 to 20 carbon atoms, and the cycloalkyl group of R5 2 is 3 having atomic number 3 It is preferred to be 20 or more. The cycloalkenyl group of R52 has a carbon number of 16 326 \ Patent Specification (Supplement) \ 94-03 \ 93134393 200530279 3 to 2 0 is preferred. The aryl group of R 5 2 is to have 6 to 20 carbon atoms are preferred. Each substituent of R52 "may have a substituent." Examples include hydrogens, halogen atoms, hydroxyl groups, alkyl groups having 1 to 10 carbon atoms, and carbon atoms 2. ~ 10 of alkenyl, phenyl, carboxyl, carbonyl, sulfonyl, phosphino, aminonitro, etc. The substituent represented by R4 is not particularly limited, and examples thereof include the substituent represented by the following general formula (IV). R2 — CH2 —CH—CH2— (OR1) „One

I 〇αν) ι R 3 [In the formula (IV), the definitions of R1, R2, R3, and η are the same as those defined by the general formula (I), and * in the formula (IV) represents the general formula (I) -0-bonded to the compound] Examples of the substituent of the benzene ring in the general formula (I) include an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, 2 to 1 5 carbon atoms, fluorenyl group, 6 to 14 carbon atoms, aryl group, Wei group, warp group, 2 to 3 carbon atoms, alkoxycarbonyl group, halogen atom, etc., among which 1 to 5 carbon atoms Alkylphenyl and i prime atoms are more preferred. It is a compound represented by the general formula (I), as long as it has a structure, and there is no particular limitation on the production method. For example, a bis (hydroxybenzene) hydrazone type represented by the following general formula (V) is mentioned. More specifically, the compound obtained by the epoxy compound includes a compound represented by the general formula (V) as a raw material, and an ethylenically unsaturated group-containing carbonyloxy group having 5 or more carbon atoms is formed. Since 326 \ Patent Specification (Supplement) \ 94-03 \ 93134393 17 the original number of R4 is 16 and the original value is 200530279 carboxylic acid, its anhydride, and one or more compounds containing isocyanate group. The resulting compound.

[In formula (V), the substituents that R1, η, and the four benzene rings may further have are the same as those defined by formula (I), and the definition of R5 is the same as that of R1 of formula (I)]. Examples of the bis (hydroxybenzene) fluorene that forms the bis (hydroxybenzene) fluorene type epoxy compound represented by the aforementioned formula (V) include, for example, 9,9-bis (4'-hydroxybenzene) buckwheat, 9 , 9-Bis (4, -Cyclo-3, -Benzene) pyrene, 9,9-Bis (4, -Cyclo-3,, 5, -Xylene), 9,9-Bis (4'-hydroxyl) -3'_methoxyphenyl) pyrene, 9,9-bis (4'-hydroxy-3'-fluorobenzene) buckwheat, 9,9_bis (4'-hydroxy-3 benzene) pyrene, 9, 9- Bis (4, -hydroxy-3 ', 5'-dichlorobenzene) pyrene, 9,9-bis (4'_hydroxy-3'-bromobenzene) buckwheat, 9,9-bis (4'-hydroxy-3) ', 5'-dibromobenzene) buckwheat and so on. These bis (hydroxybenzene) fluorene type epoxy compounds may be used alone or in combination of two or more kinds. The ethylenically unsaturated group-containing carbonyloxy group formed from the bis (hydroxybenzene) fluorene type epoxy compound represented by the aforementioned general formula (V) has no particular upper limit when the number of carbon atoms is 5 or more. Restricted, but 50 is better and 20 is even better. In the case where the hardenable composition of the present invention is used for the purpose of a solder resist, the upper limit of the number of carbon atoms is more preferably 20, and 15 is particularly suitable. If the number of carbon atoms is less than the above range, when the hardenable composition becomes a hardened material, the flexibility is insufficient, which makes it dense to the substrate. 326 \ Patent Specification (Supplement) \ 94-03 \ 93134393 18 200530279 The properties are low, and if the number of carbon atoms is too high, the heat resistance is reduced. These ethylenically unsaturated carbonyloxy groups are preferably those represented by the following general formula (I I).

(Π) [In the formula (II), R7, R8, and R9 represent a hydrogen atom or a methyl group, Y1 is an optional divalent group, and * in the formula represents an epoxy resin of a bis (hydroxybenzene) type epoxy compound. Bond formed by a fluorenyl group generated by ring opening of a radical] Here, the ethylenically unsaturated carbonyloxy group represented by the above general formula (II) is mainly a compound represented by the aforementioned general formula (V) If it is formed as a result of carrying out the reaction under the raw material, there is no restriction on the formation method. Specific examples of the formation method include a method of reacting a compound represented by the general formula (V) with an ethylenically unsaturated group-containing carboxylic acid, or firstly reacting a compound without an ethylenically unsaturated group with a carboxylic acid. After the reaction, a method such as subsequent formation is used. Examples of the ethylenically unsaturated group-containing carboxylic acids include (fluorenyl) acrylic acid [also, in the present invention, "(fluorenyl) acrylic acid" means "acrylic acid" or / and "methacrylic acid" ] The reaction product with lactone or polylactone, from saturated or unsaturated dicarboxylic anhydride (such as succinic anhydride, adipic anhydride, maleic anhydride, fumaric anhydride, itaconic anhydride, tetrahydrophthalic anhydride , Fluorenyl tetrahydrophthalic anhydride, hexahydrophthalic anhydride, fluorenyl hexahydrophthalic anhydride, fluorenyl and fluorenyl tetrahydrophthalic anhydride, phthalic anhydride, etc.) and (fluorenyl) acrylic acid derivative reaction 19 326 \ Patent Instruction (Supplement) \ 94-03 \ 93134393 200530279 Half esters obtained, in which the (fluorenyl) acrylate derivative is based on (fluorenyl) acrylate [such as (fluorenyl) hydroxyethyl acrylate, (曱Hydroxypropyl acrylate 6 purpose, hydroxybutyl (fluorenyl) acrylate, polyethylene glycol mono (fluorenyl) acrylate, glycerol di (fluorenyl) acrylate, trihydroxymethylpropane di (methyl) Acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (fluorenyl) propene Esterates, di (pentaerythritol) penta (meth) acrylate, etc.], etc., which have more than one hydroxyl group in one molecule, are composed of the aforementioned saturated or unsaturated dicarboxylic anhydride and benzene glycidol, ( Methyl) glycidyl glycidyl ester, 3,4- (fluorenyl) epoxy cyclohexylfluorenyl acrylate, 8,9-(fluorenyl) acrylic epoxy [bicyclo [4 · 3 · 0] non-3- Esters, esters of 8,9 mono (fluorenyl) acrylic epoxy [bicyclo [4. 3 · 0] non-3 -yl] oxymethyl, etc., and half esters obtained by reacting unsaturated glycidyl compounds, etc. . Among them, succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, and the like with hydroxyethyl (fluorenyl) acrylate, hydroxypropyl (fluorenyl) acrylate, hydroxybutyl (fluorenyl) acrylate, and pentaerythritol triol. Semi-esters obtained by the reaction of (fluorenyl) acrylate and di (pentaerythritol) penta (fluorenyl) acrylate are particularly suitable. These compounds may be used alone or in combination of two or more kinds. In addition, as the carboxylic acids which do not contain an ethylenically unsaturated group, there may be mentioned hydroxy-containing carboxylic acids such as lactic acid and dihydroxypropionic acid and anhydrides thereof, such as succinic acid, maleic acid, and tetrahydrophthalic acid. Or phthalic acid, tartaric acid and other saturated or unsaturated dicarboxylic acids and their anhydrides. Then, a compound having a functional group reactive with the generated hydroxyl or carboxyl group is reacted to form an ethylenically unsaturated group-containing carbonyloxy group having 5 or more carbon atoms. Here, the compound having a functional group having reactivity to a hydroxyl group or a carboxyl group is preferably a compound having an epoxy group, a carboxyl group, and an isocyanate group. To this end, specific examples include the aforementioned ethylenic unsaturated 20 326 \ Patent Instruction (Supplement) \ 94-03 \ 93134393 200530279 and unsaturated carboxylic acids, unsaturated glycidyl compounds and other ethylenically unsaturated compounds, but they are not restricted by these compounds. Furthermore, the bis (hydroxybenzene) buckwheat type epoxy compound represented by the general formula (V) is used as a raw material to form an ethylenically unsaturated group-containing carbonyloxy group having 5 or more carbon atoms, and then further The object of the reaction is the polycarboxylic acid or its anhydride, and examples thereof include saturated or unsaturated dicarboxylic acids (such as succinic acid, maleic acid, itaconic acid, tetrahydrophthalic acid, fluorenyltetrahydrophthalic acid, Hexahydrophthalic acid, fluorenylhexahydrophthalic acid, methyl and fluorenyltetrahydrophthalic acid, phthalic acid, etc.) and their anhydrides, trimellitic acid and its anhydride, and substituted aliphatic or aromatic tetra Carboxylic acids (such as pyromellitic acid, diphenyltetracarboxylic acid, diphenyl ketone tetracarboxylic acid, biphenyltetracarboxylic acid, biphenyl ether tetracarboxylic acid, butane tetracarboxylic acid, etc.) and their anhydrides. Among them are dicarboxylic acids such as tetrahydrophthalic acid and phthalic acid and their anhydrides, trimellitic acid and its anhydride, pyromellitic acid, biphenyltetracarboxylic acid, butanetetracarboxylic acid, etc. Tetracarboxylic acids and their acid dianhydrides are preferred because the obtained hardenable composition has excellent dissolution and removal properties in non-day-to-day image portions during alkali development, especially dicarboxylic acids such as tetrahydrophthalic acid and phthalic acid and Trivalent or lower carboxylic acids and anhydrides thereof, such as acid anhydrides, trimellitic acid and anhydrides thereof, are particularly suitable. Examples of the isocyanate group-containing compound include butyl isocyanate, 3-isocyanochlorophenyl ester, cyclohexyl isocyanate, and 3-isocyanoisopropene 醯 -α, α_di Organic monoisocyanates such as fluorenyl benzyl ester, such as p-phenylene diisocyanate, 2, 4- fluorenyl phenyl diisocyanate, 2, 6-fluorenyl phenyl diisocyanate, 4, 4'-diphenylmethane diisocyanate, naphthalene _ 1, 5-diisocyanate, biphenylaniline isocyanate and other aromatic diisocyanates, such as hexamethylene diisocyanate, 2,4,4 -trimethylene hexamethylene diisocyanate, dimer fatty acid diisocyanate 21 326 \ Patent Specification (Supplement) \ 94-03 \ 93134393 200530279 Aliphatic diisocyanates such as esters, such as isophorone diisocyanate, 4, bisphosphonium bis (cyclohexyl isocyanate), ω, ω '-di Cycloaliphatic diisocyanates such as isocyanate dioxane, such as diphenylene diisocyanate α, α ', α'-tetrakisylene diphenylene diisocyanate, etc., aliphatic diisocyanates having a ring, such as triisocyanate Cyanate cyanate, 1,6 undecane triisocyanate, 1,8 -diisocyanate- Tri-esters of 4-isocyanate pinane, 1,3,6-hexamethylenetriisocyanate, dicycloheptane triisocyanate, cyanate phenylmethane), ginseng (isocyanatephenyl) thiophosphate, and their Among terpolymers, water adducts, and polyhydric alcohol adducts thereof, dimers and trimers of organic diisocyanate are preferred, and tris (hydroxymethyl) propane adduct of diisocyanate and toluene Trimers of diisocyanate and trimers of isophorone diisocyanate are most suitable. The compounds may be used alone or in combination of two or more kinds. According to the invention, the compound represented by the general formula (I) of the present invention preferably has 30 to 150 mg · KOH / g, and more preferably 40 to 100 mg · KOH / g. The weight-average molecular weight of polystyrene in terms of gel permeation chromatography can be 1,000 to 100,000, and more preferably 1,500 to 10,000. Further, specific examples of the synthesis of the compound represented by the general formula (I) of the present invention include, for example, the conventionally known methods described in the aforementioned Patent Document 4 and the like, and specifically, the aforementioned bis (hydroxybenzene) fluorene Type epoxy compounds are suspended and dissolved in organic solvents such as fluorenyl ethyl ketone, 2-ethoxyethanol ethyl acetate, 2-ethoxy ethyl acetate, etc. In this regard, tertiary amines (such as triethylamine, amidine , Tribenzylamine, etc.) or quaternary ammonium salts (such as vaporized tetramethylammonium chloride, triethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium gasification, vaporized triammonium benzylamine, etc.) 326 \ Patent Specification (Supplements) \ 94 · 03 \ 93134393 22 4, — cyclohexyl, a, aromatic, 11-kisocene, "isoisocyanate, etc." For those acid values of benzoate, the best method is to use or Butyl benzyl difluorenyl or phosphorus 200530279 compounds (such as triphenylphosphine, etc.) or catalysts (such as triphenylphosphonium, etc.) in the presence of catalysts, and in the presence of hydroquinone, hydroquinone monomethyl ether, fluorenyl hydroquinone With the coexistence of a thermal polymerization inhibitor, the chemical equivalent of 1 to the epoxy compound epoxy group is usually 0.8 to 1.5 chemical equivalents (to 0.9 to 1.1 The amount is better) Add the aforementioned ethylenically unsaturated carboxylic acids, and perform the addition reaction at a temperature of usually 60 to 150 ° C (preferably 80 to 120 ° C), and then, relative to It can be produced by adding 1 chemical equivalent of the basic group produced by the aforementioned reaction, and adding the aforementioned polycarboxylic acid or its anhydride in the usual 0.05 to 1.0 chemical equivalent, and continuing the reaction under the aforementioned conditions. [1-2] (A-2 ) Resin having a phenol methane structure If the hardenable composition of the present invention satisfies the physical property conditions described in [1-1 5] and / or [1-1 6] described below, it contains in addition to the material contained in [1-1] In addition to the component (A-1), or in place of the component (A-1), a resin containing (A-2) having a phenolphenol methane structure may be included. As the resin having a phenolphenol pane structure in the present invention, The resin structure is not particularly limited if it has a p-phenol-methane structure. For example, the resin structure having a p-phenol-methane structure and epoxy resin (meth) acrylic acid and its anhydride or the above-mentioned ethylenic properties are not limited. The product obtained by the reaction of saturated carboxylic acids. The resin obtained by the reaction of the acid anhydride is a preferable resin. Here, examples of the resin having a phenol-pentane structure include "EPPN-501H", "EPPN-501HY", and "EPPN-501HY" manufactured by Nippon Kayaku Co., Ltd. EPPN- 5 0 2 H ”, etc. In addition, as the resin having a p-phenol-pentane structure, for example, 23 326 \ Patent Specification (Supplement) \ 94-03 \ 93134393 200530279 manufactured by Nippon Kayaku Co., Ltd. "TCR1025", "TCR1064", "TCR1286_, etc. If the component (A-1) and / or the component (A-2) serves as a constituent element of the hardenable composition of the present invention, the double bond amount per unit weight can be double bond equivalent (ie, double bond equivalent) = (weight of the compound) (G)) / (the number of moles of the compound containing double bonds), that is, the more double bonds per unit weight, the smaller the double bond equivalent value. In the case where the curable composition of the present invention is used for a spacer application, in order to improve the recovery rate and / or the elastic recovery rate, the total amount of double bonds (A) is preferably 5 50 or less, and 400 or less. It is more preferable, and the most suitable is less than 3 50. Further, the amount of double bonds in the entire hardenable composition of the present invention is preferably 200 or less, more preferably 160 or less, and most preferably 150 or less. The double bond equivalent is based on the compounding amount of the compound with ethylenic double bond during the synthesis, and it can also be calculated according to the above formula, or in a complex system such as photoresist, using conventional methods to measure the double bond equivalent of the solution , The solid content concentration of the photoresist can be measured by a conventional method, and it can be calculated according to (double bond equivalent) = (double bond equivalent of the photoresistance) X (solid content concentration). [1-3] (B) Photopolymerization initiator and / or thermal polymerization initiator The curable composition of the present invention may further contain (B) a photopolymerization initiator and / or a thermal polymerization initiator. The photopolymerization initiator of the component (B) is an active compound that generates active species such as radicals, acids, or bases when the hardening composition is irradiated with active light, causing polymerization of the compound represented by the general formula (I). And those using an ethylenically unsaturated compound of the component (C) described later as needed, for example, acetophenones, diphenylketones, hydroxybenzenes, thiophenones, anthraquinones, Ketals, hexaaryl biimidazoles, dicene 24

326 \ Patent Specification (Supplement) \ 94-03 \ 93134393 200530279 Titanium, halogenated hydrocarbon derivative, organic borate, rust salt, sulfone compound, amino acid derivative, sulfonamide, triaryl Methyl alcohols and so on. Examples of the acetophenones include 2,2-diethoxyacetophenone, 2,2-dioxo-2-acetophenone, 1-hydroxy-cyclohexanone, and 1-hydroxy-1 -(P-dodecylbenzene) ketone, 1-hydroxy-1-fluorenylethyl- (p-cumene) ketone, 1-trichlorofluorene- (p-butylphenone) ketone, hydroxy-2-fluorene Phenylacetone, α-amine acetophenone, etc. to be described later, and diphenyl ketones include, for example, diphenyl ketone, 2-methyldiphenyl ketone, 3-methyldiphenyl ketone, and 4- Perylene diphenyl ketone, 2-carboxydiphenyl ketone, 2-chlorodiphenyl ketone, 4-bromodiphenyl ketone, Michelin and the like, and further, hydroxybenzenes, for example, 2- Trans-4-n-octyloxydiphenylphosphonium, 2-trans-4-benzyl diphenyl ketone, 2- (2-trans-5-toluene) benzenetrisigma, 4-2 tertiary butylbenzene 3,5 -Third butadiene 4-hydroxybenzoate, etc., and further, sulfur. Examples of ketones include thioxanthone, 2-ethylthiosigma ketone, 2-isopropylthiosigma ketone, 2,4-dimethylthiosigma ketone, and 2,4-diethyl Thiophanone, 2,4-diisopropylsulfur. Examples of ketones, 2-chloro-thio ° ketones, and anthraquinones include 2-fluorenylanthraquinone and the like, and further examples of ketals include benzylbisacetal and the like. Examples of the hexaarylbiimidazoles include 2,2'-bis (o-phenylene) -4,4 ', 5,5'-tetrabenzimidazole, and 2,2'-bis (ortho) Gas benzene) -4,4 ', 5,5'-tetra (o, p-dichlorobenzene) biimidazole, 2,2'-bis (o-p-dichlorobenzene) -4,4', 5, 5'-tetrakis (o-, p-dichlorobenzene) biimidazole, 2,2'-bis (o-chlorobenzene) -4,4 ', 5,5'-tetrakis (p-fluorobenzene) biimidazole, 2,2 '-Bis (o-chlorobenzene) -4,4', 5,5'-Tetra (o-, p-dibromobenzene) biimidazole, 2,2'-bis (o-bromobenzene) -4,4 ', 5 , 5'-tetrakis (o-p-diphenylene) biimidazole, 2,2'-bis (o-phenylbenzene) -4, 4 ', 5,5'-tetrakis (p-naphthalene) biimide 25 326 \ Patent Specification (Supplement) \ 94-03 \ 93134393 200530279 azole and so on. Among them, hexabenzimidazole compounds are more preferred, especially those in which the ortho position of the benzene ring (bonded to the 2, 2′-position of the imidazole ring) is substituted with a _ prime atom, and those bonded to the imidazole ring are more preferred. The -4,4 ', 5,5' position of the benzene ring has no substituent or is substituted with a ii element atom or an oxygen atom. Examples of the titanocene include titanium dicyclopentadiene chloride, biphenyldicyclopentadiene titanium, bis (2,4-difluorobenzene) dicyclopentadiene titanium, and bis ( 2,6-difluorobenzene) titanium dicyclopentadiene, bis (2, 4, 6-trifluorobenzene) titanium dicyclopentadiene, bis (2, 3, 5, 6-tetrafluorobenzene) bicyclo Pentadiene titanium, bis (2, 3, 4, 5, 6-pentafluorobenzene) titanium dicyclopentadiene, bis (2, 6-difluorobenzene) di (fluorenylcyclopentadiene) titanium, bis (2,3, 4, 5, 6-pentafluorobenzene) di (fluorenylcyclopentadiene) titanium, bis [2,6-difluoro-3-(1-pyrrole) benzene] dicyclopentadiene titanium Wait. Among them, a titanium compound having a dicyclopentadiene structure and a biphenyl structure is preferable, and a halogen atom substituted at the ortho position of the biphenyl ring is particularly suitable. Examples of the iS-derived hydrocarbon derivatives include halogenated symmetric tri-tillage derivatives, and examples include 2,4,6-symbol (monochloroform) symmetrical tri-tillage, 2, 4, 6 -Symmetric (two gas tritium) symmetrical three-cultivation, 2,4,6 -Shen (three gas tritium) symmetrical three-cultivation well, 2 -Tanji-4, 6-double (three gas tritium) symmetrical three-cultivation, 2 -positive Propane-4, 6-bis (trifluoromethyl) symmetrical three-sigma wells, 2- (α, α, / 3-trichloroethyl) -4,6-bis (trichlorohydrazone) symmetrical tri-tillage, 2-phenyl -4,6 -Bis (trichloromethane) symmetrical triple wells, 2-(p-methoxyphenyl) -4,6 -bis (trigas tritium) symmetrical triple tillers, 2-(3,4-epoxybenzene )-4,6 -bis (trifluoromethyl) symmetrical three ploughing, 2-(para-gas benzene)-4,6-bis (trichloromethyl) symmetrical three wells, 2-[1-(p-monofluorene oxybenzene) ) A 2,4 pentadiene] a 4,6-double (three gas tritium) symmetrical three ploughing, 2-styrene-4,6-double (three gas tritium) symmetrical three ploughing, 2-(p-a Oxystyrene) -4,6 -bis (trifluoromethyl) symmetrical Misaki, 2-(p-fluorene oxygen-m-hydroxyphenylethyl 26 326 \ Patent Specification (Supplement) W-03 \ 93134393 200530279ene) _ 4 , 6-Bis (trichlorohydrazone) symmetrical three , 2-(p-isopropyloxystyrene)-4,6-bis (trichlorohydrazone) symmetrical three-cultivation, 2-(p-toluene)-4,6 -bis (tri-gas trioxide) symmetrical three-cultivation, 2 -(P-Pyridoxine) -4,6 -bis (trichloropyrene) symmetrical tri-tillage, 2- (p-ethoxynaphthalene) -4,6 -bis (trichloropyridine) symmetric tri-tillage, 2- ( P-ethoxycarbonylnaphthalene) -4,6-bis (trichlorohydrazone) symmetrical three. Well, 2-phenylthio-4,6-bis (trichloroarsine) symmetrical three-sigma well, 2-benzylthio-4,6-bis (trichloroarsine) symmetrical three-degree well, 2,4,6 -ginseng ( Dibromomethyl) Symmetrical three-cultivation, 2,4,6 -Shen (tribromofluorene) Symmetrical three-zero well, 2-Methyl-4,6-bis (tribromofluorene) Symmetrical three-cultivation, 2-Methoxy-4 , 6-Bis (tribromofluorene) symmetric trihalo, etc., halogenated symmetric trisigma well derivatives, of which bis (tri-methyl) symmetric tris17 wells are preferred. Examples of the organic borate include organic boron ammonium complex, organic boron complex, organic boron complex, organic borate complex, organic boron complex, organic Boron transition metal coordination complexes, etc., whose organic boron anions are, for example, n-butyl-tribenzyl boron anion, n-butyl-ginseng (2,4,6-triphenylbenzene) boron anion, n-butyl-ginseng (p-- Phenoxybenzene) boron anion, n-butyl-shen (p-fluorobenzene) boron anion, n-butyl-shen (meta-fluorobenzene) boron anion, n-butan-shen (3-fluoro-4-benzene) boron anion, N-butyl-ginseng (2, 6-difluorobenzene) boron anion, n-butyl-ginseng (2, 4, 6-trifluorobenzene) boron anion, n-butyl-ginseng (2, 3, 4, 5, 6-5) Fluorobenzene) boron anion, n-butyl-ginseng (p-chlorobenzene) boron anion, n-butyl ginseng (2,6-difluoro-3- ° than 17 each benzene) pentyl anion, etc. Preferably, it is a counter cation, and rust compounds such as ammonium cation, sulfonium cation, sulfonium cation, and sulfonium cation are preferred, and organic ammonium cations such as tetraalkylammonium are particularly suitable. In addition, the anchor salts include, for example, ammonium salts such as tetraammonium bromide, tetrabromide 27 326 \ Patent Specification (Supplement) \ 94-03 \ 93134393 200530279 ethyl ammonium, such as hexafluoroarsenic Acid diphenylhydrazone, diphenylhydrazone tetrafluoroborate, diphenylhydrazone p-toluenesulfonate, diphenylhydrazone camphorsulfonate, dicyclohexamethane hexafluoroarsenate, dicyclohexafluorene tetrafluoroborate, p-toluenesulfonic acid Dicyclohexamidine, dicyclohexamethane di camphorsulfonate, and other sulfonium salts, such as triphenylarsine hexafluoroarsenate, triphenyliridium tetrafluoroborate, triphenylarsine p-toluenebenzenesulfonate, triphenylarsine camphorsulfonate, Tricyclohexanium hexafluoroarsinate, tricyclohexanium tetrafluoroborate, tricyclohexanene p-toluenesulfonic acid shovel, camphor sulfonic acid tricyclohexanine, etc. Examples of the stone wind compounds include, for example, bis (benzite scutellaria) arsenic, bis (p-hydroxybenzenesulfonium sulfonium) oxane, bis (p-hydroxyphenylsulfonium sulfonium) oxane, Bis (α-naphthalenesulfonyl) methane, bis (dot-naphthalenesulfonyl) methane, bis (cyclohexylsulfonium) methane, bis (tertiary butanesulfonyl) methane, benzenesulfonium (cyclohexylsulfonium) Bis (sulfofluorene) pinane compounds such as oxane, such as benzenecarbonyl (benzenesulfonyl) methane, naphthylcarbonyl (benzenesulfonyl) fluorene, benzenecarbonyl (naphthylsulfonyl) fluorene, cyclohexylcarbonyl (benzenesulfonyl) Carbonyl compounds such as oxane, tert-butanecarbonyl (benzenesulfonium) oxane, phenylcarbonyl (cyclohexylsulfonium) oxane, phenylcarbonyl (third butylcarbonyl) methane, such as bis ( Benzenesulfonium) diazomethane, bis (p-hydroxybenzenesulfonyl) diazomethane, bis (p-methoxybenzenesulfonyl) diazomethane, bis (α_naphthalenesulfonyl) diazomethane, Bis (/ 3-naphthalenesulfonium) diazomidine, bis (cyclohexylsulfonium) diazine, bis (tertiary butanesulfonyl) diazine, benzenesulfonium (cyclohexylsulfonium) diazide Bis (sulfofluorene) diazonium compounds such as benzenecarbonyl (benzenesulfonium) Diazomethane, naphthalenecarbonyl (benzenesulfonium) diazomethane, benzenecarbonyl (naphthalenesulfonium) diazomethane, cyclohexylcarbonyl (benzenesulfonium) diazomethane, tert-butylcarbonyl (benzenesulfonium) Carboxy (sulfohydrazone) diazopine compounds such as azepine, benzenecarbonyl (cyclohexylsulfonium) diazomethane, benzenecarbonyl (tertiary butylcarbonyl) diazopine and the like. In addition, for the amino acid derivatives, for example, benzamidine amino acid 28 326 \ Patent Specification (Supplement) \ 94-03 \ 93134393 200530279 cyclohexyl acetate, 2-nitrobenzylamine formic acid cyclohexyl Vinegar, cyclohexyl 3,5-dioxobenzylamine, cyclohexyl 3-nitroaniline, and the like. Examples of the sulfonamides include N-cyclohexyl-4 -benzene. Sulfonamide, N-cyclohex-2-naphthylsulfonamide and the like, and examples of the triarylfluorenols include triphenylfluorenol and tris (4-chlorobenzene) methanol. Furthermore, the thermal polymerization initiator that constitutes the component (B) of the curable composition of the present invention is an active compound that generates active species such as radicals when the curable composition is heated, resulting in the general formula (I). Polymerization of a compound and polymerization of an ethylenically unsaturated compound using the component (C) described later as needed. Examples of the thermal polymerization initiator include organic peroxides and azo compounds. Examples of the organic peroxides include fluorenyl ethyl ketone peroxide, fluorenyl isobutyl ketone peroxide, acetone acetone peroxide, cyclohexanone peroxide, and fluorenyl cyclohexanone peroxide. , 3,3,5-trimethylcyclohexanone peroxide, such as isobutyl peroxide, 3,3,5-trimethylcyclohexanone peroxide, phenylhydrazine peroxide, orthoperoxide Dihydrazyl peroxides such as -fluorenylphenylhydrazone, m-phenylazine peroxide, 2,4-dioxophenylazine peroxide, m-phenylazine peroxide, etc. Butyl, cumene hydroperoxide, dicumene hydroperoxide, p-cap of hydroperoxide, 2, 5-dihydroperoxy 2,5-difluorenylhexane, 1,1,3,3 -Hydrogen peroxides such as tetramethylbutyl hydroperoxide, 2,4,4 -trimethylpentyl hydroperoxide, such as di-third butyl peroxide, third butyl isopropyl peroxide Benzene, dicumyl peroxide, 1,3 (or 1,4) -bis (third butyl peroxycumene) benzene, 2, 5-difluorene-2, 5-di (third butyl peroxy) Peroxide of hexane, 2, 5 -dimethyl-2, 5-bis (third butyl peroxy) hexyne-3, etc. 29 326 \ Patent said Books (Supplements) \ 94-03 \ 93134393 200530279 Dialkyls, such as 1,1-bis (third butyperoxy) cyclohexane, 1,1_bis (third butyperoxy) -3, 3 Peroxal ketals such as, 5-trimethylcyclohexane, 2,2-bis (third-butperoxy) butane, 4,4-bis (third-butperoxy) n-butyl valerate, such as Tertiary butyl peroxyacetate, tertiary butyl peroxyoctanoate, tertiary butyl peroxytrimethylacetate, tertiary butyl peroxyneodecanoate, peroxy-3,5, 5 -trimethylhexanoate Tert-butyl acid, tert-butyl peroxylaurate, tert-butyl peroxytrimethyl adipate, tert-butyl peroxybenzoate, α-cumyl peroxyneodecanoate Alkyl peroxy esters such as 2,4,4-trimethylpentyl peroxyphenoxyacetate, such as di-2-ethylhexyl peroxydicarbonate, di-2 -ethoxy peroxydicarbonate Ethyl ester, diisopropyl peroxydicarbonate, diisopropyl peroxydicarbonate, di-3 -methoxybutyl peroxydicarbonate, bis (3-fluorenyl-3 -fluorene peroxydicarbonate) Oxybutyl ester), tert-butyl peroxyisocarbonate, tert-butyl peroxyallylic carbonate, bis (4-tert-butylcyclohexyl) peroxydicarbonate, sulfo Peroxocarbonate, such as osmium peroxodicarbonate and cyclohexyl ester. Examples of the azo-based compounds include 1,1'-azobiscyclohexane-1-chai, 2,2'-azobis (2,4-dimethylfluoronitrile), and 2 ， 2 " Ethylbis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (fluorenyl isobutyric acid), α, α'-azobis (iso Butyronitrile), 4,4'-azobis (4-cyanovaleric acid), etc. Among the above-mentioned photopolymerization initiators and / or thermal polymerization initiators of the component (B), the α-amine acetophenone derivatives of acetophenones, which are preferably photopolymerization initiators according to the present invention, are particularly described below. The formula (VII) is particularly suitable. 30 326 \ Patent Specification (Supplement) \ 94-03 \ 93134393 200530279

r35 I 36 \ rrR ㈤ 11 A-r38 R37 [In the formula (VII), R35 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 R36 means that it may have a substituent. Alkyl group or allyl group which may have a substituent, R37 and R38 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 R37 and R38 are connected to each other Or, R37 or R38 and R35 or R36 may be connected to each other to form a cyclic structure, and the benzene ring may have a substituent]. Here, the alkyl groups of R35, R36, R37, and R38 in the general formula (VII) are preferably those having 1 to 15 carbon atoms (particularly 1 to 10). Examples of the substituents on the alkyl, allyl, and phenyl include alkyl, alkoxy, hydroxyalkyl, hydroxyalkoxy, ethoxyalkoxy, and alkoxyalkoxy. , Alkylcarbonylalkyl, alkylthio, haloalkyl, phenyl, halogen atom, and the like. Further, as a ring structure in which R37 and R38 are connected to each other, or R37 or R38 and R35 or R36 are connected to each other, a ratio of bite and hexahydro may be mentioned. Specific bite, hexahydropi ratio. Wells, forests, mouths, etc. σ is determined by σ. Equal to π. In addition, examples of the substituent on the benzene ring include an alkynyl group, a meridyl group, an alkoxy group, a roasted propoxy group, a phenoxy group, a phenylfluorenyl group, an oxalyloxy group, a weyl group, and a thio group. , Roasted propylthio, cyclosulfanyl, benzylthio, phenylthio, sulfanyl, benzenesulfonyl, alkanesulfinyl, alkylamino, allylamino, pyrrolidinyl, hexahydro ° Specific σ-based group, hexahydropyridyl U well group, morpholinyl group, halogen atom, etc. Furthermore, 31 326 \ Patent Specification (Supplement) \ 94-03 \ 93134393 200530279 The benzene ring can also form a condensed ring as this condensation Examples of the ring include field ketone, dibenzocycloheptanone, indoline, sigma-line, carbazo, phenone, acrida η ο ne, benzodiazepine, benzoσ Furan, glutathione, ° ketone, phenoxazine, benzothiazole, phenothiazine, etc. As the α-amine acetophenone derivative represented by the above-mentioned general formula (VII), the specific compounds are classified according to the basic skeleton of the compounds, and when exemplified by the number of carbon atoms, the following compounds are mentioned, and among them, particularly preferred R35 and R36 each independently represent a methyl group, an ethyl group, or a benzyl group, and R "and R38 each represent a methyl group or a morpholinyl group connected to each other in a cyclic structure, and has no substituent on the benzene ring or has 曱Compounds in the case of a thio group, a diamido group, or a morpholinyl group are particularly suitable for compounds having a morpholinyl group only in the para position. As for a propane-1 ketone having 3 carbon atoms classified as a basic skeleton, it may be Examples include 1-phenyl-2-dimethylamine-2-fluorenyl-3- (4-fluorenyl) propane-1-one, 1-phenyl-2-dimethylamine_2-fluorenyl-3- (4-Methoxybenzene) propane-1-one, 1-phenyl-2-dimethylamine-2-fluorenyl-3-(3,4-dioxobenzene) propane-1-one, 1-benzene 2-dimethylamine-2-fluorenyl-3-(4-fluorenylthiophenyl) propan-1-one, 1-phenyl-2-difluorenamine-2 -methyl-3- (4- Fluorobenzene) propane-1-one, 1-phenyl-2-difluorenamine- 2-fluorenyl-3-(2-gasbenzene) propan-1-one, 1-phenyl_2-difluorenamine -2- 3- (4-chlorobenzene) propane_1-one, 1-phenyl-2-difluorenamine-2-fluorenyl 3- (4-bromobenzene) propane-1-one, 1-phenyl -2-dioxamine-2-methyl-3-(4-benzylbenzene) propane-1-one, 1-phenyl-2-dimethylamine-2-benzyl-propane-1-one, 1,3-diphenyl-2-difluorenamine-2-benzyl-propan-1-yl, 1- (4-fluorobenzene) -2-diamidamine-2-benzyl-propane-1- Ketone, 1- (4-fluorobenzene) -2-difluorenamine-2-benzyl-3-phenyl-propan-1-one, 1_ (4-phenylbenzyl) -2-difluorenamine-2 -Benyl-Propane- 1- 32 326 \ Patent Specification (Supplement) \ 94-03 \ 93134393 200530279 Ketones, 1-(4 -fluorenylthiobenzene) -2 -morpholine-2 -fluorenylpropane-1- Ketones, 1-(4 -fluorenylthiobenzene) -2-difluorenamine-2 -fluorenyl-3- (4-toluene) propane-1-one, 1- (4 -fluorenylthiobenzene) -2-difluorene Amine-2-fluorenyl-3- (4-fluorenylbenzene) propane-1-one, 1- (4-fluorenylthiobenzene) -2 -difluorenamine-2 -methyl-3-(3,4- Dioxobenzene) propane-1 -one, 1- (4-fluoranthiobenzene) -2 -dimethylamine-2-methyl-3-(4_fluorobenzene) propane-1 -one, 1- ( 4-Azathiobenzene) -2-diamine-2-methyl_3- (2_chlorobenzene) propan-1-one, 1- (4-Azathiobenzene) -2-diamine-2 -Methyl-3-(4-chlorobenzene) propane-1 -Ketone, 1- (4-fluorenylthiobenzene) -2 -dioxamine-2-methyl- 3- (4-bromobenzene) propane-1-one, 1- (4-fluorenylthiobenzene) -2 Dimethylamine 2-methyl-3-(4-benzyl with benzene) propane-1_one, 1,3-bis (4-methylthiobenzene) 2-dimethylamine 2-methylpropane- 1 monoketone, 1- (4-butylthiobenzene) _2-dimethylamine-2-benzylphenyl-propan-1-one, 1- (4-cyclohexylthiobenzene)-2-dihydrazine- 2-benz-3-phenyl-propan-1-one, 1- (4-benzylthiobenzene) -2-difluorenamine-2-benzyl-propane-1-one, 1- (4-difluorene Aminebenzene) -2-diamidamine-2-benzyl-propane-1-one, 1- (4-diamidinobenzene) -2-diamidamine-2_benzyl-3-phenyl-propane-1 -Ketone, 1_ (4-morpholinobenzene) -2-dimethylamine-2-(2-Pentapentene) propane-1-one, 1- (4-morpholinene) -2-dioxamine-2 -Benyl-Propane-1-8 Iso, 1- (4-morphsyllinene)-2-Difluorenamine-2-section-3 -Phenyl-Propane-1-copper, 1- (N_曱 Dihydro ° Introducing sigma-5-yl)-2-diamidamine-2-benzyl-propan-1-one, 1-(N-butene sigma -2 -yl) -2-? Porphyrin-2 -benzyl-propane-1-one and the like. Examples of butane-1 -ones having 4 carbon atoms classified as a basic skeleton include phenylphenyl-2-dioxamine-2-fyl-butane-1-one, and bis (4-benzophenone). ) -2-Difluorenamine_2-benzyl-butane-1-one, 1- (4-methoxybenzene) -2-difluorenamine-2 -benzyl-butan-1-one, 1- (3,5 -Difluorene-4 -fluorenylbenzene) _2-difluorenamine-2-benzyl-butane-1-one, 1- (3,4-dimethoxyphenyl) -2-difluorenamine -2-benzyl-33 326 \ Patent Specification (Supplement) \ 94-03 \ 93134393 200530279 Butane-1-one, 1- (3,4,5-trioxophenyl) -2-dioxamine- 2-benzyl-butane is the same as 1- (4-benzyl) -2-dioxamine-2-benzyl_butan-1-one, 1- [4- (2-ethoxy) benzene] 2-Diamidamine-2-benzyl-butan-1-one, 1- (4-allyloxybenzene) -2-dimethylamine-2-benzyl-butane-1_one, 1- (4-ethoxycarbonylfluorenoxybenzene) -2-difluorenamine-2-benzyl-butane-1-one, [4- (1,1,2-trimethylpropylpropyldihydrazyloxy) Benzene] -2-diamine-2-benzyl-butane-1-one, 1- (4-1benzene) -2-difluorenamine-2-benzyl-butanyl-I-pyridine, 1 -(4-Chlorobenzene) -2-diamidoamine-2-benzyl-butane-1-one, 1- (2, 4-dichlorobenzene) -2-dimethylamine-2-benzyl-butane Burn 1-one, 1-( 3,4-dichlorobenzene) -2-diamine- 2 -benzyl-butane-1-one, 1- (3,5-dichlorobenzene) -2-difluorenamine-2-benzyl- Butane-1-one, 1- (4-benzyl) -2-dioxamine-2 -benzyl-butan-1-one, 1-(4-weiphenyl) -2-dimethylamine-2 -Benzyl-butane-1-one, 1- (4-sulfenylthiobenzene) -2 -dioxamine-2-benzyl-butan-1--1-, 1- (4-fluorenylthiobenzene) -2 -Difluorenylamine-benzyl-butan-1-one, 1- (4-methylthiobenzene) -2 -bis (2-methoxyethyl) amine-2-benzyl-butane-1-one, 1 -[4- (2-methoxyethylthio) benzene] _2-diamidamine-2-benzyl-butane-1-one, 1- [4- (2-hydroxyethylthio) benzene] -2-di Fluorenamine-2-benzyl-butane-1-one, 1- (4-octylthiobenzene) -2-dimethylamine-2-benzyl-butan-1-one, 1- (4- vermiculite Scutellaria benzene)-2-Dimethylamine-2-benzyl-butane-1-one, 1-[4- (4-Benzenesulfenylhydrazone) benzene]-2-dimethylamine- 2-benzyl- Butan-1 -S I, 1- (4-Benzylxanthrenebenzene) -2-difluorenamine-2-benzyl-butane-1-one, 1- (4-fluorenylsulfenylbenzene)- 2-Diamidino-2-benzyl-butane-1_one, 1- (4-aminebenzene) -2 -diamidamine_2-benzyl-butan-1-one, 1- (4- Amidobenzene) -2-diamidamine-2 -benzyl-butane-1-one, 1- (4-dimethylaminephenyl) -2-diamidamine- 2-benzyl-butane-1-one, 1- (4-diamidophenyl) -2-dioxamine- 2- (4-methylf) butane-1-one, 1- (4-di Amine Benzene)-2- 326 \ Patent Specification (Supplement) \ 94-03 \ 93134393 34 200530279 Diamine-2- (4-isopropylbenzyl) butane-1-one, 1-(4-dihydrazone Amine benzyl) -2 -diamidamine-2-(4-dodecylbenzyl) butane-1-one, 1- (4-diamidinophenyl) -2-diamidamine-2- (1-aircap Diene) butane-1-one, di (4-diamidobenzene) -2-dioxamine-2-(2-pinene-10-yl) butane-1-one, 1- (4- Dimethylamine-2-methylbenzene) -2-dimethylamine-2-benzyl-butane-1-one, 1- (4-dimethylamine-3 -ethylbenzene) -2-dimethylamine-2 -Benzyl-butan-1-one, 1- (4-diethylaminebenzene) -2-dimethylamine-2-benzyl-butan-1 -S, 1- (4-isopropylaminebenzene) 2-dioxamine-2 -butyl-butane-1-one, 1- [4- (2-fluorenylethylamine) benzene] -2-dimethylamine-2 -benzyl-butane-1 -Ketone, 1- [4- (3-oxopropylamine) benzene] -2-dioxanamine-2-benzyl-butyrate 8 iso, 1- (4-ethylamine phenyl) -2-dioxamine 2-benzyl-butan-1-one, 1-[4- (N-ethylammoniummethylamine) benzene] -2-dimethylamine-2-benzyl-butane-1-one, 1- [ 4- (N_Ethyl-3-oxopropylamine) benzene] -2-difluorene -2-benzyl-butan-1-one, 1- (4-hexahydropyridylbenzene) -2-difluorenamine-2-benzyl-butane-1-one, 1-(4-morpholinobenzene ) 2-Diamine-2-benzyl-butane-1 -one, 1 _ (4-morpholinobenzene) -2-dimethylamine-2- (3,4_dimethylform) butyrate_ 1-8 same, 1- (4_morpholinyl) -2-difluorenamine-2- (4-ethylidene) butan-1_one, 1_ (4_morpholinphenyl) -2-difluorene Amine-2- (4-isopropylbenzyl) butane-1-one, 1- (4-morpholinobenzene) -2-difluorenamine-2- (4-butane) butane-1-one, 1 -(4-morpholinebenzene) -2-dimethylamine-2-(4-isobutylf) butane-1-one, 1- (4-morpholinebenzene) -2-diamidamine-2- ( 4-dodecyl) 1-S isocyanate, 1- (4 -morphine) -2-diamine-2-(4_ by selenium) butane-1-one, 1- (4 -Morpholine benzene) -2_dihydrazine- 2- (4-ethylammonium ethyl) butane-1-8 iso, 1- (4- morpholine benzene) -2-dimethylamine-2- (4 -Heptazone) Butanone, 1- (4-morpholine benzene)-2-Dimethylamine-2- (4-butoxo) butan-1-1S, 1- (4-morpholine benzene) -2-Diamidamine-2- [4- (2-hydroxyethoxy) benzyl] butane_; 1-35 326 \ Patent Specification (Supplement) \ 94-03 \ 93134393 200530279 Ketone, 1-(4 _ Morpholine benzene) -2 -diamine-2-[4-(2 -Fluorenylethoxy) benzyl] butane-1 -one, 1-(4-morpholinobenzene) -2 -dioxamine-2-[4-(2-(2 -methoxyethoxy) ethoxy) Section] Butan-1-, 1- (4-morphobenzene) -2-dimethylamine-2-[4-(2-(2-(oxoethoxy) ethoxycarbonyl) benzyl] butane- 1-ketone, 1- (4-morpholinobenzene) -2-dimethylamine-2- [4- (2- (2- (2- (2-oxoethoxy) ethoxycarbonyl) ethyl) benzyl] Ding Shaowan -1-¾, 1- (4-Mr. Stilbene) -2-dioxamine-2- [4- (2- ,; stinky)) Ding Shaowan_1-8 Same as 1- (4 ••. Lin benzene) _2-dimethylamine_2_ [4_ (2 · diethylamineethyl) benzyl] butane-1-one, 1- (4-morpholinobenzene) -2 -dimethylamine-2-benzyl- Butane-1-one-trifluoroacetic acid S, 1- (4-morpholinobenzene) -2-difluorenamine-2-benzyl-butane-1-fluorene-f * , 1- (4-morpholine) -2-dioxamine-2-benzyl-butyrate- 1-keto-p-toluenesulfonate, 1- (4-morpholinebenzene) -2 -dimethyl Amine-2 -benzyl-butan-1 -one-keto camphor lutein S, 1-(4-morpholinyl)-2 -diethylamine-2 -benzyl-butane-1-one, 1_ (4 -morpholinobenzene) _2 -bis (2-oxoethyl) amine-2-benzyl-butane-1-one, 1-(4-morpholinebenzene) -2 -butylmethylamine-2 -benzyl -Butane-1 -one, 1- (4-methyl. Lin benzene) -2-butylamidamine-2- (4-isopropylidene) butan-1-one, 1- (4-methyl σ lin Benzene)-2 -dibutylamine-2 -benzyl-butane-1 -one, 1-(4-Molyl benzene) -2-f fluoramine-2-f-yl-butane-1-one, 1- (3-Ga-4-morpholinylbenzene) -2-difluorenamine-2-benzyl-butan-1-one, 1- [4-(2,6-dimethylmorpholin-4-yl ) Benzene]-2-dimethylamine-2-benzyl-butyrate_1-fluorene, 1-(1,4-difluorene-1,2,3,4-tetrahydrofluorene slogan. Lin_6 —based )One 2 -Dimethylamine-2 -benzyl-butyro-1-S is the same as 1- (N-butylα card σ sitting —3-yl) -2 * ~ dimethylamine_2_benzyl-butan- Same as 1-3, 1- (1,3-benzodiamidino-5-yl) -2-dimethylamine-2-benzyl-butane-1-one, 1- (2, 3-dihydrobenzene Benzofuran-5-yl) -2-difluorenylamine-2-benzyl-butane-1-one, 1- (grutan-2-yl) _2-difluorenamine- 2-benzyl-butane- 1-S Iso, 1- (2,3-dihydro-2,3_ difluorene 36 326 \ Patent Specification (Supplement) \ 94-03 \ 93134393 200530279 Benzothiazol-5-yl) -2-difluorenamine -2-benzyl-butane-1-one, 2- (2-difluorenamine-2 -benzylbutanyl) fluorenone, 2- (2-dioxamine-2 -benzylbutylfluoren) dibenzo ring Gengxitong, 3,6-bis (2-diamidoamine-2-benzylbutyrazine) -9-butyl-17 card ° wait. Regarding the five-carbon pentyl group which is classified as a basic skeleton _ 1-0¾ 'Examples include 1- (4-Mo ° benzene) -2-dimethylamine dilute propyl-pyrene-1-pyrene, 1 -(4 -Momalylin benzene)-2_dimethylamine-benzyl-pentan-1 -Xitong, 1_ (4-morpholinyl) -2_ difluorenamine_2- (2-isopropylidene) Pentamyl-1-one, 1- (4-morpholinyl) -2 ~~ butylammonamine-2-(4-isobutylidene) pentane-1 -one, 1-(4-morpholinobenzene) -2-Butylamidin-2- (4-butoxybenzyl) pentan-1-one, etc. Examples of the pentene-1-one include 1-phenyl-2-difluorenamine-2-methyl-4-pentane-1-fluorene and 1-phenyl-2-difluorenamine-2. -Ethyl-4-pentane-1 -one, 1-phenyl-2-diamine-2benzyl-4-pentene-1-one, 1-phenyl-2 -morpholine-2-methyl Methyl-4-pentane-1-one, 1-phenyl-2-morpholin-2-benz-4-pentene-1-one, 1,2-diphenyl-2-morpholin-4-pentene 1-one, 1- (4-toluene) -2-? Lin-2 -methyl-4-penten-1-one, 1- (4-dodecylbenzene)-2-morpholin-2-ethyl-4 -pentan-1-one, 1_ (4_ Fluorenylbenzene) -2 -difluorenamine_2-ethyl-4-pentan-1-one, 1- (4 -fluorenylbenzene) -2 -dibutylamine-2 -fluorenyl-4-pentene 1-one, 1- (4-fluorenoxybenzene) _2-hexahydropyridine-2 -ethyl-4 -pentene- ;! -Ketone, 1- (4--oxobenzene) _2-1 ^. Sigma-2-methyl-4-pentane-1-8 iso, 1- (4-methoxyphenyl) -2-morpholin-2-ethyl-4-penten-1-one, 1- (4-Methoxybenzene) -2-morpholine-2 -phenyl-4-penten-1-one, 1- (3,4-dioxophenyl)-2-morpholine-2-ethyl- 4-penten-1-one,!-[4- (2- (oxoethoxy) benzene] -2-morpholin-2-amidino-4-penten-1-one, 1- [4- (2-Methoxyethoxy) benzene] -2-morpholine-2-ethyl-4-pentan-1-one, 1- [4_ (2-Ethoxy) benzene] -2 -morpho- 2-Ethyl-4-pentane-1- 326 \ Patent Specification (Supplement) \ 94-03 \ 93134393 37 200530279 Painting same, 1- (4 ~ isopropyloxybenzene) -2-dioxamine_2- Benzene-4-pentane-1_S, 1- (4-butoxybenzene) -2 -morpholine-2 -ethyl-4-penten-1-one, 1- [4- (2-allyloxy Ethoxy) benzene] -2-morpholin-2 -fluorenyl-4-pentane_1-8, 1- [4- (2-dilute propoxyethoxy) benzene] -2 -morpholine-2 -Ethyl-4-penten-1-one, 1- (4-trimethylsilyloxybenzene) -2 -morpholin-2-methyl-4 -pentan-1_one, 1- (4- Fluorobenzene) -2-dimethylamine-2_methyl-4_fluorene-1-3 iso, 1- (4_fluorobenzene) -2-diamine-2 -ethyl_4-fluorene- Same as 1-3, 1- (4-fluorobenzene) -2 -dimethylamine-2 ~ Noble dilute-1_, same as 1- (4-fluorobenzene) -2-morphine-2- 曱4-pentan-1-one, benzene) -2-morpholin-2-ethyl-4-penten-1-one, 1- (4-fluorophenyl) -2-morpholine-2-ethyl 4-Amidino-4-penten-1-one, BU (4-fluorobenzene) -2-morpholin-2-ethyl-5-amidino-4-penten-1-one, 1- ( 4-Fluorobenzene) -2 -morpholine-2-benzyl-4 -pentene-:!-One, 1- (3,4-dichlorobenzene) -2-difluorenamine-2-ethyl-4- Pentene-1-one, BU (3,5-dichloro_4-fluorenylbenzene 2-morpholin-2-fluorenyl-4-pentene-1-one, 1- (4-benzene) -2 -Mo. Lin-Methyl ~~ 4- 戍 dilute-1-S isopropyl, 1- (4-one; benzene) -2 -morpholine-2 -ethyl-4 pentene-1 -one, 1- (4-Bromobenzene) -2 -morpholine-2 -Third-butane-4 -Pentamidine-1_ 嗣, 1_ (4_methylthiobenzene) -2-dimethylamine-2-fluorenyl-4 -pentyl Diluted 1-one, 1- (4_fluorenylthiophene) -2-difluorenamine-2-ethyl-4-pentan-1-one, 1- (4-fluorenylthiophene) -2-difluorene Amine-2-phenyl-4-penten-1-one, bu (4-methylthiobenzene) -2-dimethylamine-2-benzyl-4-penten-1-one, 1- (4-fluorene Thiobenzene) -2-hexahydropyridine-2 -ethyl-4 -pentene-1 -one, 1-(4-methylthiobenzene)-2 -morpholine-2 -methyl-4 -pentene-bu Ketone, 1- (4-fluorenylthiophene) -2-morpholine-2-ethyl-4-pentene-1 -one, 1- (4 -fluorenylthiophene) -2 -morpholine-2 -Ethyl-4 -methyl-4 -penten-1-one, 1-(4 -fluorenylthiobenzene)-2 -morpholine-2 -phenyl-4 -pentene-; 1 -one, 1- (4 -Methylthiobenzene) -2 -Mo Lin-2 -Knot-4 -Ethylene Diluted-1-8 Same, 1-(4 -Ethylthiobenzene) -2 -Mo Lin-2-38 326 \ Patent Instruction (Supplement) \ 94-03 \ 93134393 200530279 Ethyl-4-pentene-1_one, 1- (4-isopropylthiobenzene) -2 -morpholine-2-fluorenyl- 4-pentane- Is 1-S the same as 1- (4-dilute thiosulfene) _2-? Lin-2-ethyl-4-pentan-1-one, 1-[4-((2-hydroxyethylthio) benzene] -2 -morpholine-2 -fluorenyl-4-pentene_1 -one, 1-[4-(2-hydroxyethylthio) benzene] _ 2 -morpholine-2 -ethyl-4 -pentene-1 -one, 1- [4- (2-hydroxyethylthio) benzene] -2 -Morpholine-2 -propyl-4-penten-1-one, bu [4-(2-hydroxyethylthio) benzene] -2 -morphap-2 -tertiary butan-4 -pentene-1- Ketone, Bu [4-(2 -fluorenyloxycarbonylthio) benzene]-2 -morpholine-2 -fluorenyl-4 -pentene-1 -one, 1- (4-fluorenylsulfonylbenzene) -2- Diamine-2-ethyl-4-pentene-1-S with 1- (4-butanesulfenylbenzene) -2-difluorenamine-2-ethyl-4-pentene-1-one , 1- [4- (4-Benzenethio) benzene] -2 -morpholine-2-ethyl-4-penten-1-one, 1-[4_ (4-xanthazol yellow) benzene] -2-? ° Lin-2-ethyl-4-fluorenyl-4-pentan-1-one, 1- (4-chlorophenylthiobenzene) -2-difluorenamine-2-benzyl-4-pentyl En-1-one, 1- (4-dimethylaminebenzene) -2-diamine-2methyl-4-penten-1-one, 1- (4-diamineaminebenzene) -2- Dimethylamine-2 -ethyl-4-pentene M-one, 1- (4-dimethylamine benzene) -2 -dimethylamine-2 -section-4 -pentan-1- 8 the same, 1- (4-Dimethylamine benzene) -2 -Dibenzylamine-2 -ethyl-4 -pentene-1-one;!-(4-dimethylamine benzene ) -2- (pyrrolidin-1-yl) -2 -fluorenyl-4-penten-1-one, 1_ (4-dimethylaminebenzene) -2 -morpholine-2-methyl-4-pent En-1-one, 1- (4-diamidobenzene) -2_morpholin-2-ethyl-4 -fluorenyl-4-pentene-1 1-8 iso, 1- (4-diamine Benzene)-2-Mokoulin 2-Section 1-4-pentaene-1-one ketone, 1-(4-diamidinophenyl) -2- (2,6-diamimorpholin-4-yl)- 2-ethyl-4-pentene-; 1-one, 1- (4-diethylaminephenyl) -2-difluorenamine- 2-benzyl-4-pentene-1-one, 1-[4- Bis (2-methoxyethyl) aminebenzene] -2 -morpholin-2-fluorenyl-4-penten-1-one, 1-(4-butylaminephenyl) -2-dibutylamine-2-fluorene 4-Penten-1-one, 1- (4-butylaminebenzyl) -2-morpholin-2-amidino-4-penten-1-one, 1- (4-dibutylaminebenzene) 2-? 39 326 \ Patent Specification (Supplement) \ 94-03 \ 93134393 200530279 Porphyrin-2-amidino-4-penten-1-one, 1- (4-diallylamine benzene) -2-? Porphyrin-2-methyl-4-pentene-1 -one, 1-[4-((pyrrolidin-1 -yl) benzene] -2 -morpholin-2 -fluorenyl-4-penten-1-one , 1- (4-hexahydropyridylbenzene) -2-hexahydropyridine-2-methyl_4-pentan-1-S, 1- [4- (hexahydro ° ratio 0 well_1-yl) Benzene] _2-diamidamine-2-ethyl-4-penten-1-one, 1- [4 -(4-methylhexahydro-1-yl) benzene] -2-morpholin-2-fluorenyl-4-penten-1-one, 1- [4- (N-fluorenylhexahydropyridine Phen-1-yl) benzene] -2- (N-methylhexahydropyridine-1-yl) -2-methyl-4-penten-1-one, 1- (4-morpholinobenzene) -2 -Difluorenamine-2 -fluorenyl-4 -pentene-1 -one, 1-(4-morpholinobenzene) _2 -difluorenamine-2-ethyl-4-pentan-1-one, 1-(4- ?. Lin benzene)-2-Dimethylamine-2-isopropyl-4-pentene-1-one, 1- (4-morpholinebenzene) -2-dimethylamine- 2-benzyl-4-pentene-1 -Ketone, 1- (4-morpholinebenzene) -2-diethylamine-2-ethyl-4-penten-1-one, 1- (4-morpholinene) -2 -bis (2-methyl Oxyethyl) amine-2_ethyl-4-pentan-1-S isocyanate, 1_ (4-morphobenzene) _2-butylmethylamine-2-methyl-4-pentan-1-enamine, 1- (4_? Lin benzene) 2-dipropanamide-2-ethyl-pentan-1-one, 1_ (4-morphobenzene) -2-dicumylamine-2-ethyl-4 -Pentane_1-S isopropyl, 1_ (4-morpholinyl) -2 -benzylamine-2-ethyl-4-pentene-;!-One, 1- (4_morpholinyl) -2 -(Hexahydropyridine-1-yl)-2-ethyl-4 -pentene-1 -one, 1-(4-morpholinobenzene)-2 -morpholine-2 -methyl-4- Ethyl -1-8, 1- (4-morpholinyl) -2-morphine- 2-ethyl-4_pentan-1--8, 1- (4-morpholinyl) -2_ Morin-2-ethylpyrene-1 -one-dodecylsulfonate, 1-(4-morpholinobenzene) -2 -morpholine-2 -ethyl-4 -fluorenyl-4-pentyl -1-¾, 1_ (4-morpholinyl) _2-morpholine-2-benz-4-pentene_1-one, 1- [4-(2, 6-dioxomorpholin-4-yl ) Benzene] -2 -morpholin-2-amidino-4-pentene-1 -one, 1-[4-(2, 6 -difluorene? -4 -yl) benzene] -2-(2,6 -dihydrazone ° Lin-4 -yl) -2 -ethyl-4-fluorene-1-S iso, 1- (1 ^ 1_but 11 13--5-yl) -2- 40 326 \ Patent Specification (Supplement) W-03 \ 93134393 200530279 Morpholine-2 -ethyl-4-penten-1-one, 1- (1,4- Dibutyl-1,2, 3, 4 Porphyrin-6-yl) -2 -morpholine-2 -ethyl-4 -pentene-1 -one, 1-(N -3 -yl) -2-? Porphyrin-2 -ethyl-4 -penten-1-one, 1- (5 ,: -5,10-dihydrophen ° Qin-6-yl)-2-dimethylamine-2-fluorenyl-4 -Pentylene (1,3-benzodiocene-5 -yl) -2 -morpholine-2 -methyl-4 -pentene 1-(benzobenzyl-3-yl) _2- ?. Lin-2-ethyl-4-pyrene-1-S homo-sigma-6-yl) -2-morpholin-2-ethyl-4-pentane, 1- (2 benzofuran-5 -Yl) -2 -morpholin-2-amidino_4-penten-1-one, 1: 1-thiazin-2-yl) -2-difluorenamine-2-allyl-4-pentene- 1-one, 3, morpholine-2 -methyl-4 -pentenefluorene) carbazole, 2-(2 -diamidamine-2 -enenefluorene) acridone, 2-(2 -morpholine- 2-methyl-4 -pentene 醯)-° ketomorpholine benzamidine) _ 2-ethyl-N -methyl-1,2,3,6-tetrahydropyridine etc. are classified as basic skeleton Hexane with 1 to 6 carbon atoms and 1- (4-pyridinethiobenzene) -2-morpholine-2-allyl-hexane-1-one, benzenebenzene) -2-diamine Benzene-hexano-1-one, 1- (4- ?. Linben)-2 -2-section-4, 5, 5-trimethylhexyl-1-one, 1- (4-morpholinobenzene ) -2 amine-2- (4-butylbenzyl) hexane-1-one, 1- (4-morpholinobenzene) -2-dioctylmethylbenzyl) hexane-1-one, and the like. In addition, for the same purpose, 1- (4-fluorenylthiobenzene) -2 -ethyl-4 -fluorenyl-4 -hexen-1-one, 1- (4-diaminoaminebenzene)- 2--2,4,5_triamidine-4 -hexan-1-one, 1- (4-diamidobenzene)-2 -ethyl_4-hexanone -1-3 same, 1-( 4-morpholinyl) -2-morpholin-2-ethyl-1-one and the like. About heptane with 7 carbon atoms that is classified as the basic skeleton-; 1-326 \ Patent Specification (Supplement) \ 94-03 \ 93134393 41 -Tetrahydroquinone-butadiene Kawa 1 0-Dibutyl_ 1 1 Identical, -1-8, and benzene (benzene, 3-dihydro (N-methylphen 6-bis (2-propan- 4-pentane, 2- (4- ί〇ketone), can we give (4 _? Lyme-dimethylamine-butyl hydrazone c -2- (4-morpholin- 2--dimethylamine 4 wood-2 _-4-hexenone, for example 200530279 to produce 1-(4-dimethyl Amine benzene) -2-diamidamine- 2- [4- (2- -oxo) benzyl] heptane-bu g, 1-(4-? Σ linbenzene) -2 -dimethylamine-2 _ section -Heptane-1 -one, etc. In addition, as hept-1,6-diene, 4-benzidine-4-difluorenamine-hepta-1,6-diene, 4- (4- Dioxophenylhydrazone) -4-dioxamine-heptan-1,6-diene, 4- (4-oxophenylhydrazone) -4-morpholine-heptan-1,6-diene, 4- (3,4-Dioxobenzidine) -4-dioxamine-heptan-1,6-diene, 4- (4-phenoxybenzidine) _4-dioxamine-heptane-1,6 -Diene, 4- (4-fluorophenylhydrazone) -4-diamidamine-heptan-1,6-diene, 4- (4-fluorobenzidine) -4 -morpholine-hept-1, 6-diene, 4- (4-methylthiobenzidine) -4-difluorenamine-heptan-1,6-diene 4-(4-methylthiophenylhydrazone) _4-morpholine-heptan-1,6-diene, 4- (4-diamidoaminephenylhydrazone) _4-diamidamine-heptan-1,6-di Ene, 4- (4-diamidophenylphenylhydrazone) -4 -morpholine-heptan-1,6-diene, 4- (4-morpholinophenylhydrazone) _ 4-dimethylamine-heptan-1 , 6-diene, 4- (4-morpholine benzamidine) -4-morpholine-heptan-1,6-diene, etc. Regarding octane-1 with 8 carbon atoms classified as the basic skeleton Examples of ketones include 1- (4-morpholinyl) _2-difluorenamine- 2-benzyl-octane-1-one, 1- (4-morpholinlin) -2-dimethylamine-2 -(4-section-2)-octane-1-ketone, etc. The curable composition of the present invention contains the compound represented by the general formula (I) and the photopolymerization initiator of the component (B) or / and heat In the case of a polymerization initiator, the content ratio of these components is preferably 20 to 95% by weight, and more preferably 30 to 90% by weight relative to the total amount of the curable composition. Further, The component (B) is preferably from 0.1 to 40 wt%, and more preferably from 0.2 to 2 wt%. When the component (A) is too much or too little, the component (B) is too small Hardening composition It tends to be insufficient in hardenability, and if the component (B) is too much, substrate staining is liable to occur when the image is displayed. [1-3] (C) Ethylene unsaturated compound The curable composition of the present invention may further contain (C) an ethylenically unsaturated compound. The ethylenically unsaturated compound of the component (C) is preferably contained for the purpose of further improving the hardenability of the hardenable composition of the present invention. The ethylenically unsaturated compound has at least one free-radically polymerizable ethylenically unsaturated bond in the molecule, so that when the hardenable composition is irradiated with active light or heated, it includes photopolymerization by the aforementioned component (B). The addition or polymerization of the initiator or / and the polymerization initiator of the thermal polymerization initiator may cause cross-linking and hardening. The ethylenically unsaturated compound of the component (C) of the present invention is a compound having one ethylenically unsaturated bond in the molecule, and specifically, for example, (fluorenyl) acrylic acid, crotonic acid, isocrotonic acid, and cis Unsaturated carboxylic acids such as oxalic acid, itaconic acid, citraconic acid, and their alkyl esters, (fluorenyl) acrylonitrile, (fluorenyl) acrylamide, styrene, etc. may be used. From the viewpoints of cross-linkability and the possibility of widening the difference in solubility of the developer between the exposed and non-exposed parts, a compound having two or more ethylenically unsaturated bonds in the molecule is preferred, and a (fluorenyl) group Acrylate compounds derived from unsaturated bonds of acrylic acid are particularly suitable. It is a compound having two or more ethylenically unsaturated bonds in the molecule. Representative examples include esters (hereinafter, also referred to as esters- (fluorenyl groups) formed from unsaturated carboxylic acids and polycyclic compounds. ) Acrylic esters), Phosphonic esters containing (fluorenyl) acryloxy, and urethane (fluorenyl) acrylates formed from hydroxy (meth) acrylate compounds and polyisocyanate compounds with 43 326 \ Patent Specification (Supplement) \ 94-03 \ 93134393 200530279 and epoxy (fluorenyl) acrylates formed from (fluorenyl) acrylic or hydroxy (fluorenyl) acrylate compounds and polyepoxides. Examples of the esters formed from the unsaturated carboxylic acid and a polyhydric compound include, for example, the aforementioned unsaturated carboxylic acid and an aliphatic polyhydric compound [polyol (such as ethylene glycol, polyethylene glycol ( Addition number 2 to 14), propylene glycol, polypropylene glycol (addition number 2 to 14), trimethylene glycol, tetramethylene glycol, hexamethylene glycol, tris (hydroxyamidine) propane, glycerol, pentaerythritol, Dipentaerythritol and its ethylene oxide adducts, propylene oxide adducts, diethanolamine, triethanolamine, etc.), specifically, for example, ethylene glycol di (fluorenyl) acrylate, di (ethyl Diol) di (fluorenyl) acrylate, propylene glycol di (fluorenyl) acrylate, tri (hydroxymethyl) propane di (fluorenyl) acrylate, tri (hydroxymethyl) propane tri (fluorenyl) acrylate, tri ( Hydroxyl) propane ethylene oxide addition tri (fluorenyl) acrylate, glycerol di (fluorenyl) acrylate, glycerol tri (fluorenyl) acrylate, glycerol propylene oxide addition tri ( Fluorenyl) acrylate, pentaerythritol di (fluorenyl) acrylate, pentaerythritol tri Fluorenyl) acrylate, pentaerythritol tetra (fluorenyl) acrylate, di (pentaerythritol) penta (fluorenyl) acrylate, di (pentaerythritol) hexa (fluorenyl) acrylate, etc., and the same crotonic acid ester, isocrotonic acid Esters, maleic acid esters, itaconic acid esters, citraconic acid esters, and the like. In addition, examples of the esters formed from the unsaturated carboxylic acid and the polyhydric compound include the unsaturated polyacids and aromatic polycyclic compounds (such as hydroquinone, resorcin, gallophenol, and bisphenol). F, bisphenol A, etc.) or a reactant formed by an ethylene oxide adduct thereof, and specific examples thereof include bisphenol A di (meth) acrylate, bisphenol A bis [oxyethylene (fluorenyl) Acrylate], bisphenol A bis [glycidyl ether (fluorenyl) propionate], etc., furthermore, as the aforementioned unsaturated 44 326 \ Patent Specification (Supplement) \ 94-03 \ 93134393 200530279 carboxylic acid Reactants formed with heterocyclic polyhydroxy compounds (such as ginseng (2-hydroxyethyl) isoisocyanurate, etc.), for example, ginseng (2-hydroxyethyl) isoisocyanurate two (Fluorenyl) acrylate, tris (fluorenyl) acrylate, etc. In addition, as a reactant formed by an unsaturated carboxylic acid, a polycarboxylic acid, and a polyhydroxy compound, specific examples include (meth) acrylic acid, Condensate of phthalic acid and ethylene glycol, formed by (fluorenyl) acrylic acid, maleic acid, and diethylene glycol The condensate of (meth) acrylic acid, the condensate of formed phthalic acid and pentaerythritol, a condensate (Yue-yl) acrylic acid, adipic acid, butanediol, and glycerin formed of. In addition, as the (fluorenyl) acrylic alkoxy group-containing phosphates, the phosphoric acid ester compounds mainly containing (meth) acryl alkoxy groups are not particularly limited, but the following general formula (VIII) A), (VIII b), or (VIII c) is preferred.

Rl0s H2C = C—c—0— (CH2) p—0 R10 〇 H2C = C—C—0— (CH2CH2O)] υ I—⑽) 3-q (Via) Q Η u —⑽) 3_q (Wb) R10 0 p- (OH) 3-q (Vlllc) H2C = C—C—0— (CH2CH2O) p — [〇C (= 0) CH2CH2CH2CH2CH2] p * — [[Formula (VIIIa), (VIIIb), ( In VIIIc), R1Q represents a hydrogen atom or a fluorenyl group, p and p 'are integers of 1 to 25, and q is 1, 2, or 3]. Here, p and ρ ′ are preferably 1 to 10, and 1 to 4 are particularly suitable. As specific examples of these compounds, for example, phosphoric acid (fluorenyl) propenyloxyethyl 326 \ Patent Specification (Supplementary Pieces) \ 94-03 \ 93134393 45 200530279 esters, bis [(fluorenyl) propenyloxyethoxylates], phosphoric acid (fluorenyl) propenyloxyethylene glycol esters, etc. These compounds are used alone or in mixtures Can be used. In addition, as the amino fluorenyl (fluorenyl) acrylates, for example, a hydroxy (fluorenyl) acrylate compound [such as (fluorenyl) acrylic acid, methacrylic acid (meth) acrylate) Esters, tetrahydroxyamidoethane tri (meth) acrylate, etc.] and polyisocyanate compounds [such as aliphatic polyisocyanates (such as hexamethylene diisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, etc.) ), Alicyclic polyisocyanates (such as cyclohexane diisocyanate, difluorene cyclohexane diisocyanate, 4, 4 '-fluorene bis (cyclohexyl isocyanate), isophorone diisocyanate, dicycloheptane triisocyanate, etc. ), The reaction of aromatic polyisocyanates (such as 4,4'-diphenylmethane diisocyanate, thiophosphate (isocyanate phenyl ester), etc.), heterocyclic polyisocyanates (such as isoisocyanurate, etc.), etc.] product. Especially for amino phosphonate (fluorenyl) acrylates, there are 4 or more amino phosphonate bonds [-NH-C0-0-] and 4 or more (meth) acrylic acid in one molecule. Phenoxy compounds are preferred. The compound is, for example, compound (i-1), which is composed of a compound having four or more hydroxyl groups (such as pentaerythritol, polyglycerol, etc.) and a diisocyanate compound (such as hexamethylene dioxane) in one molecule. Isocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, fluorene diisocyanate, etc.); or compound (i-2), which is a compound having two or more hydroxyl groups in one molecule (such as ethyl Diols, etc.) and compounds with three or more isocyanate groups in one molecule (such as "DURANATE24A-100", "DURANATE22A-75PX" by Asahi Kasei Corporation,

"DURANATE21S-75E", "DURANATE18H-70B" and other biuret types, such as Asahi Kasei Industrial Products "DURANATEP-301-75E", "DURANATE 46 326 \ Patent Specification (Supplement) \ 94-03 \ 93134393 200530279 E -402-90T "," DURANATEE-405-80T "and other adducts; or compound (i-3) obtained by polymerization or copolymerization of (meth) acrylic acid isocyanate One of them has four or more (preferably six or more) isocyanate-based compounds. Specifically, for example, Asahi Kasei Corporation's product "DURANATE ME20-100" (i) and one molecule has one or more hydroxyl groups And 2 or more (preferably 3 or more) (fluorenyl) propenyloxy compounds (ii) (such as pentaerythritol di (meth) acrylate, di (pentaerythritol) tri (meth) acrylate, di (Pentaerythritol) tetra (fluorenyl) acrylate, di (pentaerythritol) penta (fluorenyl) acrylate, etc.) can be reacted to obtain the compound. Here, the molecular weight of the aforementioned compound (i) is preferably from 500 to 2 0,0 0, and particularly preferably from 1,0 0 to 1,50,0 0. In addition, as the aforementioned amino sulfonate (fluorenyl) acrylic esters, the molecular weight thereof is preferably from 60 to 150,0 0. Furthermore, those having six or more urethane bonds are preferable, and those having eight or more are particularly suitable. Those having six or more (fluorenyl) propenyloxy groups are more preferable, and those having eight or more are particularly suitable. In addition, for such urethane (fluorenyl) acrylates, for example, the aforementioned compound (i) and the aforementioned compound (ii) are used in an organic solvent (such as toluene or ethyl acetate). The ratio of the molar ratio of the isocyanate group of the former to the molar ratio of the hydroxyl group of the latter is 1/1 0 to 1 0/1. If necessary, a catalyst such as n-butyltin dilaurate is used at a temperature of 10 to 150 ° C. It can be produced by a method of reacting for a period of time ranging from 5 minutes to 3 hours. With regard to the present invention, among the amino sulfonate (meth) acrylates, those represented by the following general formula (I X) are particularly suitable. 47 326 \ Patent Specification (Supplement) W-03 \ 93134393 200530279

Ra

b R ov

d-R ο1 OHC1 HN _ c R HN-OHC

X

[In formula (IX), Ra represents an overlying structure of an alkoxy group or an aryleneoxy group, and has 4 to 20 groups which can be bonded to Rb, and Rb and Rc each independently represent a carbon number of 1 to 10 is an alkylene group, and R d represents an organic residue having 1 to 10 (fluorenyl) propanyloxy groups. Ra, Rb, Rc, and Rd may each have a substituent, and x is 4 to 20 Integer, y is an integer from 0 to 15, and z is an integer from 1 to 15]. Here, examples of the repeating structure of the oxyalkylene group of R a in the formula (IX) include structures derived from glycerol, glycerol, pentaerythritol, and the like. Examples include structures derived from gallophenol, 1,3,5-benzenetriol and the like. In addition, as for the carbon number of the alkylene group of Rb and Rc, each of them is preferably 1 to 5, and the number of (fluorenyl) propenyloxy groups of Rd is preferably 1 to 7. Furthermore, X is preferably 4 to 15, y is preferably 1 to 10, and z is preferably 1 to 10. In addition, R a is particularly suitable as shown by the following formula [wherein k is an integer of 2 to 10], and Rb and Rc each independently form a dimethylene group, a monomethylenediene group, or a trimethylene group. The base is particularly suitable, and Rd is particularly suitable as shown by the following formula. 48 326 \ Patent Specification (Supplement) \ 94-03 \ 93134393 200530279

Ra; —CH2— (| H—CH 「0 士 〇 QI 0 ch2 -0-CH2 卞 CH2-OQ ch2 I ^ 0 IQ 0-o-ch2-ch- {ch2-oq) 2 (but, q is- c—ch = ch2) Furthermore, as the epoxy (fluorenyl) acrylate, specifically, for example, (fluorenyl) acrylic acid or the aforementioned hydroxy (fluorenyl) acrylate compound and polyhydric Epoxy compounds [such as aliphatic polyepoxides (such as (poly) ethylene glycol polyglycidyl ether, (poly) propylene glycol polyglycidyl ether, (poly) tetramethylene glycol polyglycidyl ether, (poly) penta Polymethylene glycol polyglycidyl ether, (Poly) neopentyl glycol polyglycidyl ether, (Poly) hexamethylene glycol polyglycidyl ether, (Poly) tri-methyl propylene glycol polyglycidyl ether, (Poly) Glycerol polyglycidyl ether, (poly) glucosyl polyglycidyl ether, etc.); aromatic polyepoxides (such as phenol-type phenolic resin polyepoxy compounds, brominated phenol-type phenolic resin polyepoxy compounds, (ortho -, M-, p-) phenol-type phenolic resin polyepoxides, bisphenol A polyepoxides, bisphenol F polyepoxides, etc.); miscellaneous Reaction products formed by polyepoxides of the formula (such as sorbitol polyglycidyl ether, triglycidyl isoisocyanurate, triglycidyl (2-hydroxyethyl) isoisocyanurate, etc.) Wait.

Q

Q 0 CH, 0 CH,

Rd; — 0-CH2-C-CH2-〇-CH2-p-CH2-0-Q CH〇 CH2

0 I Q

0 IQ 326 \ Patent Specification (Supplement) \ 94-03 \ 93134393 49 200530279 In addition, as other ethylenically unsaturated compounds, in addition to the foregoing, for example, (fluorenyl) acrylamide (such as Ethylene bis (fluorenyl) acrylamide, etc.), allyl esters (such as diallyl phthalate, etc.), vinyl-containing compounds (such as g-diacetate, etc.), thioether bond compounds Type (the ether bond of an ethylenically unsaturated compound containing an ether bond is vulcanized by phosphorus pentasulfide, etc. to become a thioether bond to increase the crosslinking speed), and for example, Japanese Patent No. 3 1 6 4 4 0 7 JP-A-2009 and JP-A-Hei 9 _ 1 0 0 1 1 1 etc. described in the publication of a polyfunctional (fluorenyl) valeric acid S compound and a dioxolol having a particle size of 5 to 30 nm [for example, iso Propanol-dispersed Organic Silica Sol (Nissan Chemical Co., Ltd. product "IPA-ST"), methyl ethyl ketone-dispersed Organic Silica Sol (Nissan Chemical Co., Ltd. product "M EK-ST"), fluorenyl isobutyl ketone Dispersed organic silica sol (say, MIBK-ST, a product of Sanko Chemical Co., Ltd., etc.) An ester-based or sulfonyl-based silane coupling agent is combined with a compound such as an ethylenically unsaturated compound by reacting the silica sol with the silane coupling agent to increase the strength or heat resistance of the cured product. Compounds and so on. The above ethylenically unsaturated compounds may be used singly or in combination of two or more kinds. In the present invention, as the ethylenically unsaturated compound of the above component (C), there are ester- (fluorenyl) acrylates, (fluorenyl) -acrylic hydroxyloxy phosphates, or aminophosphonates ( Fluorenyl) acrylates are preferred, of which ester- (meth) acrylates are particularly suitable, and ester- (fluorenyl) acrylates contain, for example, polyethylene glycol, polypropylene glycol, or bisphenol A Polyoxyalkylenes, such as polyethylene oxide adducts, and esters ((fluorenyl) acrylate) containing two or more (fluorenyl) propylene fluorenyloxy groups are more preferred. In the curable composition of the present invention, the ethylenic content of the aforementioned component (C) is 326 \ Patent Specification (Supplement) \ 94-03 \ 93134393 50 200530279 and the compound content ratio is relative to the total amount of the curable composition. It is preferably 1 to 70 wt%, and more preferably 5 to 60 wt%. If the content of the component (C) is less than the above range, the hardenability of the hardenable composition tends to be insufficient, and if it exceeds the above range, the viscosity tends to be insufficient. [1-4] (D) Epoxy Compound The curable composition of the present invention may further contain (D) an epoxy compound. The epoxy compound of the component (D) is used in the case where the hardenable composition of the present invention is used for solder resist, overcoat, rib, or spacer applications, and improves the heat resistance or chemical resistance of the hardened material. Or for other purposes. Examples of the epoxy compound include a polyglycidyl ether compound obtained by reacting a polyhydric compound constituting a so-called epoxy unit with an epichlorohydrin and a polyglycidyl ether obtained by reacting a polycarboxylic acid compound and epichlorohydrin. The ester compound and the polyglycidylamine compound obtained by the reaction of the polyamine compound and epihydric alcohol are compounds from low molecular weight to high molecular weight. Examples of the polyglycidyl ether compound include diglycidyl ether epoxy compounds of polyethylene glycol, diglycidyl ether epoxy compounds of bis (4-hydroxybenzene), and bis (3,5- Dipyridine-4 -hydroxybenzene) diglycidyl ether type epoxy compound, double hope F diglycidyl ether type epoxy compound, double hope A diglycidyl ether type epoxy compound, tetrafluoride bisphenol A Diglycidyl ether type epoxy compound, ethylene oxide bisphenol A diglycidyl shout type epoxy compound, phenol type phenol resin type epoxy compound, phenol type 6 phenol resin type epoxy compound, etc. These polyglycidyl ether compounds are those in which a carboxyl group is introduced by the reaction of a remaining hydroxyl group with an acid anhydride or a divalent acid compound, etc. 51 326 \ Patent Specification (Supplement) \ 94-03 \ 93134393 200530279. Examples of the polyglycidyl ester compound include diglycidyl-type epoxy compounds of phthalic acid and diglycidyl-type epoxy compounds of phthalic acid. Further, as the polyglycidyl amine compound, a polyglycidylamine compound may be used. Examples thereof include diglycidylamine compounds of bis (4-aminophenyl) methane and triglycidylamine compounds of uric acid and the like. In the curable composition of the present invention, the epoxy content rate of the component (D) is more preferably 1 to 70 wt%, and more preferably 5 to 50% by weight based on the total amount of the curable composition. If the content of the component (D) is less than the above range, the hardenability of the hardenable composition tends to be insufficient, and if it is in a large range, it may easily cause [1-5] (E) rings such as poor whitening of the non-day image part during development. The oxygen hardener further contains (E) epoxy resin in the curable composition of the present invention. The epoxy hardener of the component (E) is preferably used together with the epoxy compound containing the component (D) for the purpose of improving the hardenability and composition or other purposes. As the epoxy hardener of the component (E), for example, polycarboxylic acid anhydrides (such as succinic anhydride, maleic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, 4 -Fluorenyltetraanhydride, 3-ethyltetrahydrophthalic anhydride, 4-ethyltetrahydrophthalic anhydride, hexahydrophthalophthalone 3-fluorenylhexahydrophthalic anhydride, 4-fluorenylhexahydrophthalic anhydride, 3-ethylhexade Anhydride, 4-ethylhexahydrophthalic anhydride, trimellitic anhydride, biphenyltetracarboxylic organic phosphines (such as tributylphosphine, triphenylphosphine, gins-2-cyanoethylphosphine, etc.); imid 4 , 2-Amidino sigma, 2-Ethyl sigma, 2-Ethyl-4-methylaminobenzimidazole, 4-phenylimidazole, 1- (2-cyanoethyl) -2-benzene Glycidazole, 326 \ Patent Specification (Supplement) \ 94-03 \ 93134393 52, hexahydroglyceride esters, for example, isocyanate compounds are preferred, and Wai is in the above-mentioned problems. The chemical agent is also the case where the substance is hard (Anhydride, phthalic anhydride, murine anhydride, etc.); L type (such as mouth sitting, 2-1- (2-200530279 cyanoethyl) -2 -ethyl-4 -methylimidazole, etc.); amine compounds (Such as I amine, 4-benzyl-N, N-dioxamine, 4-oxenyl benzyl —N, N-diamidoamine-N, N-diamidoamine, etc.); amine symmetrical three ° wells (such as 2, 4, 6-tri17 wells, 2-acetal-4,6-diamine Symmetrical three-degree well, 2-Ethylene-4,6-three-degree well • Isocyanuric acid adduct, 2, 4-diamine-6-methacrylic acid three-degree well, 2, 4-diamine-6 -Smallyl propylene, ethoxylated tri-tillage, foreign matter, etc.); quaternary ammonium salts (such as vaporized benzyltrimethylammonium, gasification, etc.); phosphonium salts (such as tri-n-butyl bromide-2,5- Dihydroxybenzidine, butyl chloride, etc.), among them, those with -N Η-groups are preferred, and aminated amines are preferred, especially cyanoguanidine, 2,4,6-triamine Symmetric fit. In the hardenable composition of the present invention, the content ratio of the ring of the component (E) is based on the stability of the hardenable composition over time with respect to the total amount of the hardenable composition, preferably 1 wt% or less, and The following is further preferred. [1-6] (F) amine compound The curable composition of the present invention further contains (F) amine. The amine compound of the component (F) is preferably contained in the composition for the purpose of improving the chemical resistance of the cured product or other purposes. Examples of the 4 compounds include amination of alkoxymethyl groups modified by an alcohol condensation having at least two hydroxyl groups having 1 to 8 hydroxyl groups serving as functional groups. Examples include polycondensation of melamine and formaldehyde. The obtained tri-lipid is acetylene 326 \ Patent Specification (Supplement) \ 94-03 \ 93134393 53 made from polycondensed guanamine resin of Benzoguanamine and acetic acid, and polycondensation of acetylene urea and formaldehyde. , Benzyl methyl, 4-dihydrazine triamine symmetric diamine symmetric oxyethyl symmetric cyanuric acid plus phenyltributylammonium hexadecyl tri-complexes and three ° well special oxygen hardeners, taking 0 · 7 wt% The compound is also heat-resistant or resistant (F) to the amine group obtained through carbonation, such as a phenylurea resin obtained from a melamine tree, 200530279 a urea resin obtained by the polycondensation of gland and osmic acid, selected from the group consisting of melamine and benzene Resin obtained by copolymerization and condensation of two or more kinds of guanamine, acetylene urea, urea, etc. with formaldehyde, and modified resin in which the hydroxymethyl group of these resins is modified by alcohol condensation. Among them, in terms of the present invention, melamine resins and modified resins thereof are preferred, and modified resins having a hydroxyfluorenyl modification ratio of 70% or more are further preferred, and modified resins of 80% or more are more preferred. Quality resins are particularly suitable. Regarding specific examples of the amine compound of this component (F), melamine resins and modified resins thereof include "THYMEL" (registered trademark) 300, 301 '303, 350, 736, 738, 370, 771 of Mitsui Thytec Corporation. '325, 327, 703, 701, 266, 267' 285, 232, 235, 238, 1141, 272, 254, 202, 1156, 1158, and "NIKALACK_ (registered trademark) E-2151, MW of Sanwa Chemical Company" -100LM, MX-750LM, and benzoguanamine resin and modified resins thereof include "THYMEL" (registered trademark) 1 1 23, 1 1 2 5, 1 1 2 8 and further, acetylene urea resin and Examples of the modified resin include "THYMEL" (registered trademark) 1170, 1171, 1174, 1172, and "NIKALACK" (registered trademark) M X-2 70, and furthermore, urea resins and modified resins can be cited Mitsui Thytec's "UFR" (registered trademark) 65, 300, and "NIKALACK" (registered trademark) MX-290, etc. In the curable composition of the present invention, the content rate of the amine compound of the component (F) is preferably 20 wt% or less, and more preferably 10 wt% or less with respect to the total amount of the curable composition. [1-7] (G) polymerization accelerator The hardening composition of the present invention may further contain (G) a polymerization accelerator. The polymerization accelerator of the component (G) is initiated to improve the polymerization of the hardenable composition. 54 326 \ Patent Specification (Supplement) \ 94-03 \ 93134393 200530279 Series agent rapid addition polymerization (N) / G / (\ divided into HaiC It may also contain the acid amine δδ of other bifunctional or esters, which is better than the acid amines of the compound dipole or diester, as shown below.) / B X Γ \ Or Ν) / a X / (\

R——N—R 9 3 o 4

R——c——R I—i 4 2 4

OM

〇1 Me- s \ / 2 CH 3 4

a X

-4 4 R

——R 9 3 o 4

R——c—R I—I 4 2 4

CH 01 o = c- s

b X

[In the formulae (Xa) and (Xb), R39 and R4 ° each independently represent a substituent which may have a substituent, an aryl which may have a substituent, a heterocyclic group which may have a substituent or a hydrogen atom, and R41 and R42 each Independently represents an alkyl group or a hydrogen atom which may have a substituent, R43 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 R44 represents an alkyl group which may have a substituent, may An aryl group having a substituent or a heterocyclic group which may have a substituent, s is an integer of 0 to 10] 0 Here, R39, R4 °, R41, R42, R43, and R43 in the formulae (Xa) and (Xb), and The alkyl group of R4 4 is preferably one having 1 to 8 carbon atoms, and more preferably 1 to 4 carbon atoms. Examples of the alkenyl group of R43 include vinyl, allyl, and isopropenyl, and examples of the aryl group of R39, R4 °, R41, and R44 include phenyl and naphthyl. In addition, the heterocyclic groups of R39, R4 °, and R44 include, for example, furyl (fury 1), furyl (furany 1), pyrrolyl, and n-phenylene. In addition, as the substituents on the alkyl and alkenyl groups, for example, alkoxy 55 326 \ Patent Specification (Supplement) \ 94-03 \ 93134393 200530279 oxygen, alkoxycarbonyl, alkenyl, and alkenyl Examples of the substituents on the aryl group and the heterocyclic group include a carbonyl group, a phenyl group, and a halogen atom. Examples thereof include an alkyl group and an alkoxy group which may have a substituent such as an alkoxy group and a phenyl group. , Alkenyl, alkenyl, fluorenyl, fluorenyl, alkenyloxycarbonyl, phenoxy, alkylthio, alkylsulfanyl blue, and acid groups, retarders, warp groups, acid groups, wall groups, cyano groups Base, halo atoms, etc. In the present invention, in the ester or bipolar ionic compound of the amino acid represented by the aforementioned general formula (X a) or (X b), one of R39 and R4Q in the formula (Xa) is a hydrogen atom and another One is a phenyl group which may have a substituent, R41 and R42 are both hydrogen atoms, R43 is an alkyl group which may have a substituent or a phenyl group which may have a substituent, and s is an amino ester of 0, 1, or 2 Or R39 and R4 ° in formula (Xb) are both hydrogen atoms or one of them is an alkyl group which may have a substituent, R41 and R42 are hydrogen atoms, R44 is an alkyl group which may have a substituent or may have The phenyl group of the substituent is preferably an amine bipolar ion compound in which s is 0, 1, or 2; wherein s in the aforementioned general formula (Xa) is 0, and one of R39 and R4 ° is a hydrogen atom and the other One is phenyl, and N-aniline acetate when R41 and R42 are both hydrogen atoms (especially N-aniline benzyl acetate when R 4 3 is benzyl) is particularly suitable, or s in formula (Xb) A bipolar ion compound of N-phenylaminoacetic acid when R39, R4 °, R41, and R42 are all hydrogen atoms and R4 4 is a phenyl group is particularly suitable. In addition, in the present invention, a polymerization accelerator that further contains a polymerization accelerator other than the aforementioned amino acid ester or bipolar ion compound as the component (G) may be used. Examples of the polymerization accelerator include sulfonamide-containing compounds. Base compounds (such as 2- benzobenzopyrene sigma, 2-benzobenzo sigma, 2-benzobenzo sigma, 3-succino-1,2, 4 -trisigma, 2 -sparse- 4 (3 Η)-noisy sitting. Lin, / 3-selenium naphthalene, ethylene glycol disulfide 56 326 \ Patent Specification (Supplement) \ 94-03 \ 93134393 200530279 Propionate, trishydroxypropylpropane ginseng ( Thiopropionate), pentaerythritol (thiopropionate), etc.); polyfunctional thiol compounds (such as hexanedithiol, trihydroxymethylpropane ginseng (thioglycolate), pentaerythritol (thiopropionic acid) (Esters), etc.); amino acids or derivatives thereof having aromatic rings (such as N, N-dialkylamine benzoate, N-aniline acetic acid or derivatives thereof such as ammonium and sodium salts, phenylpropylamine) Acid or its derivative such as ammonium, sodium salt, ester, etc.). In the curable composition of the present invention, the content of the polymerization accelerator of the aforementioned component (G) is preferably 20 wt% or less with respect to the total amount of the curable composition, and more preferably 1 wt% or less. good. [1-8] (i) Inorganic filler In addition, the inorganic filler of the component (ii) used in the curable composition of the present invention may be contained for the purpose of improving the strength of the cured product or other purposes. Examples of the inorganic filler of the component (i) include talc, silicon dioxide, sulphur oxide, barium sulfate, and oxide lock. In the curable composition of the present invention, the content rate of the inorganic filler of the aforementioned component (i) is preferably 70 wt% or less, and more preferably 50 wt% or less with respect to the total amount of the curable composition. good. [1-9] (I) Surfactant Further, the surfactant (I) of the component (I) used in the curable composition of the present invention improves the coatability and developability of the curable composition as a coating liquid, or It may be contained for other purposes. To this end, specific examples include nonionic, anionic, cationic, amphoteric, and fluorine-based surfactants. More specifically, examples of the nonionic surfactant include polyoxyethylene alkyl ethers, polyoxyethylene ethyloxypropyl alkyl ethers, and polyoxyethylene 326 \ Patent Specification ( (Supplements) \ 94-03 \ 93134393 57 200530279 Alkyl alkyl phenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene fatty acid esters, glycerol fatty acid esters, polyoxyethylene ethyl glycerine Fatty acid esters of fatty acids, Fatty acid esters of pentaerythritol, fatty acid esters of polyoxyethylene pentaerythritol, fatty acid esters of sorbitol, fatty acid esters of polyoxyethylene sorbitol, fatty acid esters of glucosyl alcohol, polyoxylates Ethyl glucosyl fatty acid esters, and the anionic surfactants include alkyl sulfonates, alkyl benzene sulfonates, alkyl naphthalene sulfonates, and polyoxyethylene Alkyl ether sulfonates, alkyl sulfates, alkyl sulfates, higher alcohol sulfates, aliphatic alcohol sulfates, polyoxyalkylene ether ethers, polyoxylates Ethyl alkyl phenyl ether sulfates, alkyl phosphate salts, polyoxyalkyl ether ether phosphates Polyoxyalkylene phenyl ether phosphates, etc. In addition, the cationic surfactants include quaternary ammonium salts, imidazolium derivatives, amine salts, etc. Furthermore, the amphoteric Examples of the surfactant include beet-type compounds, imida ζ 1 μm salts, mi sigmaline, amino acids, and the like. In the curable composition of the present invention, the content ratio of the surfactant of the aforementioned component (I) is preferably 10 wt% or less, and more preferably 5 wt% or less with respect to the total amount of the curable composition. . [1-10] (J) Sensitizing dye In addition, the sensitizing dye of the component (J) used in the hardenable composition of the present invention is preferably contained in order to improve the sensitivity of the hardenable composition or for other purposes. Inside the composition. The sensitizing dye is a light-absorbing dye having a maximum absorption (value) in a blue-violet region with a wavelength of 350 to 43 Onm, and examples thereof include dialkylamine benzene compounds. Than the subliminal compounds, trihydroxy. Close-biting derivatives, etc., 58 326 \ Patent Specification (Supplement) \ 94-03 \ 93134393 200530279 Among them, two :): Phenylamine benzene compounds are preferred. Among the preferred dialkylamine benzene-based compounds, especially the dialkylamine phenyl ketone-based compounds, the carbon atom in the para position (based on the amine group on the benzene ring) has a heterocyclic group as a substituent A dialkylamine benzene-based compound, a dialkylamine benzene-based compound having a carbon atom in the para position (based on the amine group on the benzene ring) having a sulfoimino group-containing substituent, and 2- The bisquinolamine benzene compound having a hydroxyquinoline skeleton is preferred. The dialkylamine diphenyl ketone compound is preferably one represented by the following general formula (X I).

(XI) [In the formula (XI), R11, R12, R15, and R16 each independently represent an alkyl group which may have a substituent, and R13, R14, R17, and R18 each independently represent an alkyl group or a hydrogen atom which may have a substituent. And R11 and R12, R11 and R13, R12 and R14, R15 and R16, R15 and R17, and R16 and R18 each independently form a nitrogen-containing heterocyclic ring]. Here, the number of carbon atoms of the alkyl group of R11, R12, R15, and R16 in formula (XI) and the number of carbon atoms of R13, R14, R17, and R18 when they are alkyl groups are all from 1 to 6. Better. Furthermore, in the case of forming a nitrogen-containing heterocyclic ring, it is preferable to form a 5 or 6 ring chain, and R11 and R13, R12 and R14, R15 and R17, or R16 and R 18 to form a 6-chain tetrahydroquinoline ring. It is preferred to form R11, R12, R13, and R14. (D u r ο 1 i d i n e) ring or / and R 15, R 16, 59 326 \ Patent Specification (Supplement) \ 94-03 \ 93134393 200530279 R 17, and R 18 are preferred. In addition, tetrahydroquine having an alkyl group at the 2-position as a substituent is used. Ringwood, or containing the tetrahydroquine. Ring of pyrimidine ring is particularly suitable. Specific examples of the compound represented by the general formula (XI) include 4, 4'-bis (diamidine) diphenyl ketone, 4, 4'-bis (diethylamine) diphenyl ketone, And compounds of the following structures.

Furthermore, the heterocyclic group in a dialkylamine benzene-based compound having a heterocyclic group as a substituent at a carbon atom at the para position of the (amino group on the p-benzene ring) contains a nitrogen atom, an oxygen atom, or The 5 or 6 ring chain of a sulfur atom is preferable, and the 5 ring chain having a condensed benzene ring is particularly suitable, and it is preferably one represented by the following general formula (XII). 326 \ Patent Specification (Supplement) \ 94-03 \ 93134393 60 200530279

[In formula (XII), R19 and R2G each independently represent an alkyl group which may have a substituent, R21 and R22 each independently represent an alkyl group or a hydrogen atom which may have a substituent, and R19 and R2 °, R19 and R21, and R2G and Each group of R22 may independently form a nitrogen-containing heterocyclic ring, X represents an oxygen atom, a sulfur atom, a dialkylfluorenylene group, an imino group, or an alkylimino group, and the benzene ring condensed on the heterocyclic ring has a substitution Base also]. Here, the number of carbon atoms of the alkyl group of R19 and R2G in the formula (XII) and the number of carbon atoms when R21 and R2 2 are alkyl groups are preferably 1 to 6. Moreover, in the case of forming a nitrogen-containing heterocyclic ring, it is best to form a 5 or 6 ring chain, and R19 and R2] or RU and R22 to form a tetrahydroquinoline ring of 6 ring chain is preferred, especially R19, R2 °, R21, and R22 form a pyrrolidine ring. In addition, a tetrahydrofluorene ring having a thio group at the 2-position as a substituent, or a pyridine ring containing a tetrahydrohasyl ring ring is particularly suitable. The number of carbon atoms of the alkyl group when X is a dialkylmethylene group is preferably 1 to 6, and the number of carbon atoms of the alkyl group when the alkylimine group is 1 to 6 is preferable. Specific examples of the compound represented by the general formula (XII) include, for example, 2- (p-dioxamine) benzoxazole, 2- (p-diethylaminephenyl) benzoxazole, and 2- (P-Dimethylamine benzene) benzene [4,5] benzoxazole, 2- (p-dimethylaminebenzene) benzene [6,7] benzoxazole, 2- (p-dimethylaminebenzene) Benzothiazole, 2- (p-diethylaminebenzene) benzothiazole, 2- (p-dioxamine) benzimidazole, 2- (p-diethylamine 61 326 \ Patent Specification (Supplement) \ 94 -03 \ 93134393 200530279 Aminobenzene) benzimidazole, 2-(p-dioxamine) -3,3 -difluorene-3 fluorene -indole, 2- (p-diethylaminebenzene) -3,3 -Di 曱 -3! 1- ° sigma and compounds of the following structure.

In addition, as the dialkylamine benzene-based compound having a heterocyclic group as a substituent at a carbon atom at the para position of the (amino group on the p-benzene ring), in addition to the compound represented by the aforementioned general formula (XII), 2- (p-dimethylaminebenzene) pyridine, 2- (p-diethylaminebenzene) pyridine, 2- (p-dimethylaminebenzene) quinoline, 2- (p-diethylaminebenzene) quinoline , 2- (p-dimethylaminebenzene) pyrimidine, 2- (p-diethylaminebenzene) pyrimidine, 2,5-bis (p-diethylaminebenzene) -1,3,4-pyridinediazole, 2 , 5-bis (p-diethylaminebenzene) -1,3,4-thiadiazole, etc. In addition, as for the dialkylamine benzene-based compound having a sulfoimino group-containing substituent at a carbon atom in the para position of the (amino group on the p-phenylene ring), one represented by the following general formula (XIII) .

326 \ Patent Specification (Supplement) \ 94-03 \ 93134393 62 200530279 [In the formula (XIII), R23 and R24 each independently represent an alkyl group which may have a substituent, and R25 and R26 each independently represent an alkyl group which may have a substituent. Or a hydrogen atom, and each of R23 and R24, R23 and R25, and R24 and R26 may independently form a nitrogen-containing heterocyclic ring, R2 7 represents a monovalent group or a hydrogen atom, and R2 8 represents a monovalent group. Here, the number of carbon atoms of the alkyl group of R23 and R24 in formula (XIII) and the number of carbon atoms when R25 and R2 6 are alkyl groups are preferably from 1 to 6, and furthermore, when a nitrogen-containing heterocyclic ring is formed In this case, it is preferable to form a 5 or 6 ring chain, but R25 and R26 are preferably hydrogen atoms. Examples of the monovalent group of R 2 7 and R 2 8 include alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkoxy, alkenyl, fluorenyl, fluorenyl, aryl, Aryloxy, aralkyl, arylalkenyl, hydroxy, fluorenyl, carboxyl, carboxylate, amine, amine, amine, amine, amine, sulfonyl, sulfonyl Acid groups, sulfonate groups, sulfamoyl groups, alkylthio groups, imino groups, and heterocyclic groups. Among them, a hydrogen atom is preferred at R27, and an aryl group is preferred at R2 8. The dialkylamine benzene-based compound having a 2-hydroxyquinoline skeleton is preferably represented by the following general formula (X I V).

[In formula (XIV), R29, R3G, and R33 each independently represent an alkyl group which may have a substituent 63 326 \ Patent Specification (Supplement) \ 94 · 03 \ 93134393 200530279, and R31 and R32 each independently represent a substituent An alkyl group or a hydrogen atom, and each of R29 and R3 °, R29 and R31, and R3 ° and R32 may independently form a nitrogen-containing heterocyclic ring. R34 represents an alkyl group which may have a substituent, and an aromatic group which may have a substituent. Radical or hydrogen atom. ] Here, the carbon number of the alkyl group of R29, R3G, and R33 in formula (XIV) and the carbon number of R31, R3 2, and R3 5 when they are alkyl groups are preferably 1 to 6, and In the case of forming a nitrogen-containing heterocyclic ring, it is preferable to form a 5 or 6 ring chain, but R 31 and R 3 2 are preferably hydrogen atoms. Moreover, R3 4 is preferably a phenyl group. Among the sensitizing dyes of the above-mentioned component (J), in the present invention, the dialkylaminodiphenylδ homologue compound represented by the aforementioned general formula (XI) and the aforementioned general formula (X II I) A dialkylamine benzene compound having a sulfoimino group-containing substituent at a carbon atom at the para position of the (amino group on the p-benzene ring), or a 2-hydroxy group formed by the aforementioned general formula (XIV) A dialkylamine benzene-based compound having a quinoline skeleton is particularly suitable. In the hardenable composition of the present invention, the content ratio of the sensitizing dye of the above-mentioned component (J) is preferably 0.001 to 20 wt%, and 0.1 to 0.1% of the total amount of the hardenable composition. ~ 10% by weight is further preferred. If the content of the component (J) is smaller than the above range, the photocurability of the curable composition tends to be insufficient, and if it is larger than the above range, the substrate fouling tends to easily occur during development. Furthermore, the hardening composition of the present invention preferably has an extremely large value of its spectral sensitivity in the wavelength range of 350 to 430 nm, and more preferably exists in the wavelength range of 390 to 430 nm. If the maximum peak of the spectral sensitivity exists in a range smaller than the above-mentioned wavelength range, the sensitivity of the photocurable composition to laser light with a wavelength of 350 to 430 nm will be inferior, and if the spectral sensitivity is 64 326 \ Patent Specification (Supplement) \ The maximum peak of 94-03 \ 93134393 200530279 exists in the wavelength range larger than the above-mentioned range, which results in a tendency of poor safety light properties under yellow light. Regarding the wavelength range of the maximum peak value of these spectral sensitivities, it is possible to adjust the above-mentioned wavelength range by appropriately selecting each component constituting the hardenable composition. In particular, the photopolymerization initiator and / or heat of the component (B) can be used. Selection of the type and content of the polymerization initiator and the sensitizing dye of the component (J) is adjusted. Also, in the present invention, the maximum peak of the spectral sensitivity refers to the following maximum peak, that is, your J Shikou "photo polymer · technology" (by Yamaoka Yafu, published in the Nikkan Kogyo Shimbun in 1988) , Page 2 6 2), etc., under the use of a spectroscopic sensitivity measuring device, the light split from a light source such as a xenon lamp or tungsten lamp can be linearly changed in the horizontal axis direction at the exposure wavelength and the exposure intensity can be adjusted at The logarithmic change of the vertical axis direction is set to irradiate a photocurable day image forming material sample (a photocurable composition layer is formed on the surface of the substrate). After exposure, a development process is performed to obtain a wavelength according to each exposure. The daylight image of the sensitivity is calculated from the height of the image. The exposure energy that may form a daylight image is calculated. The wavelength is plotted on the horizontal axis and the inverse number of the exposure energy is plotted on the vertical axis. That is the above-mentioned maximum peak. In addition, regarding the hardening composition of the present invention, when a blue-violet semiconductor laser is used as the exposure light source, the minimum exposure amount [S 4 1 0] at which a day image may be formed at a wavelength of 4 10 nm is 50. m J / c m2 or less is preferred, 30 m J / c m2 or less is further preferred, and 20 m J / c m2 or less is particularly suitable. When the minimum exposure amount [S 4 1 0] is larger than the foregoing range, although it varies depending on the exposure intensity of the laser light source, there is a tendency to cause a longer exposure time and reduce the practicality. 65 326 \ Patent Specification (Supplement) \ 94-03 \ 93134393 200530279. Press again, the smaller the lower limit of the minimum exposure [S 4 1 0] is, the better, it is usually 1 m J / c m2 or more. In addition, the ratio [54 10/3 4 5 0] of the aforementioned [S410] and the minimum exposure amount [54 5 0 (11 ^ / 〇: 1112)] that may form a day image at a wavelength of 450 nm is 0.1 or less. It is preferably, and more preferably 0.05 or less. If this ratio [S410 / S450] is higher than the aforementioned range, it is difficult to have both blue-violet laser sensitivity and safety light characteristics under yellow light. Furthermore, it is preferable that the minimum exposure amount [S 4 5 0-6 5 0 (mJ / cm2)] at which the daytime image can be formed at each wavelength greater than 450nm and below 650nm and that the daylight image can be formed at a wavelength of 450nm The minimum exposure [S450 (mJ / cm2)] ratio [S450-650 / S450] is greater than 1. If this ratio [S450-650 / S450] is below the aforementioned range, blue-violet laser sensitivity will result. It is difficult to combine the safety light with the yellow light. According to the above, the minimum exposure amount [S410] that may form a day image at a wavelength of 410 nm, the minimum exposure amount that may form a day image at a wavelength of 450 nm [S450], and each wavelength that is greater than 450 ηπ and less than 650 nm may be formed The minimum exposure of the day image [S 4 5 0-6 5 0 (mJ / cm2)] is the measurement of the maximum peak value of the spectral sensitivity performed by the spectrophotometer, and the height of the obtained day image can be obtained. The calculated exposure energy that is likely to form a day image has the meaning that the minimum exposure energy that can form a book image is determined by the optimal development conditions determined by the development conditions such as the type of developer, development temperature, and development time at the time. For this optimal development condition, a condition of impregnating 0.5 to 3 minutes at a temperature of 2 5 t in an alkali developing solution of P 1 1 to 1 4 is generally adopted. [1-1 1] (K) Other alkali-soluble resins 326 \ Patent Specification (Supplement) \ 94_〇3 \ 93134393 66 200530279 The components (K) alkali-soluble resins used in the hardenable composition of the present invention are based on It may be contained as a binder of the curable composition. Examples of the alkali-soluble resin include (fluorenyl) acrylic acid, (fluorenyl) acrylate, (fluorenyl) acrylonitrile, (fluorenyl) acrylamide, maleic acid, styrene, and vinyl acetate. Homopolymers or copolymers of vinylidene chloride, butylene diimide, etc .; acid-modified epoxy acrylates, polyamides, polyesters, polyethers, polyurethanes, polyamines Among vinyl butyraldehyde, polyvinyl alcohol, polyvinyl pyrrolidone, acetocellulose, and the like, from the viewpoint of alkali developability, a carboxyl group-containing vinyl resin and an acid-modified epoxy acrylate are more suitable. Specific examples of the carboxyl group-containing vinyl resin include unsaturated carboxylic acids (such as (fluorenyl) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, maleic anhydride, itaconic acid) Acid, citraconic acid, etc.) and ethylene compounds (such as styrene, α-fluorenylstyrene, hydroxystyrene, fluorene (fluorenyl) acrylate, ethyl (fluorenyl) acrylate, propyl (meth) acrylate, (Fluorenyl) butyl acrylate, amyl (meth) acrylate, hexyl (meth) acrylate, dodecyl (meth) acrylate, 2-ethylhexyl acrylate (fluorenyl) acrylic acid, (fluorenyl) acrylic acid Dicyclopentyl ester, adamantyl (fluorenyl) acrylate, isoxulin (meth) acrylate, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, ( (Methenyl) benzyl acrylate, (Methenyl) N, N -diamidinoethyl ester, N-(Methenyl) acrylic morpholine, (Meth) acrylonitrile, (Methenyl) acrylamide, N- Hydroxyl (fluorenyl) acrylamide, Ν, Ν-bis (fluorenyl) acrylamide, Ν, Ν- Yue amine acetate (Yue-yl) acrylamide, vinyl acetate, etc.) copolymers. Among them, styrene- (meth) acrylate- (fluorenyl) acrylic acid copolymer is better than 67 326 \ Patent Specification (Supplement) \ 94-03 \ 93134393 200530279, so as to bake 3 ~ 30ml% of styrene. The copolymer composed of (fluorenyl) acrylic acid ester 10 to 70 mol%, and (fluorenyl) propionic acid 10 to 60 m ο 1% is further preferred, and 5 to 25 ml of styrene is baked. Copolymers composed of 20% to 60% by mole of (fluorenyl) acrylic acid and 15% to 5 5 m ο 1% of (fluorenyl) propionic acid are particularly suitable. In addition, these carboxyl group-containing vinyl resins preferably have an acid value of 30 to 250 Hi g · KOH / g, and a polystyrene-equivalent weight average molecular weight of 1,000 to 300,000. The carboxyl-containing vinyl resin preferably has an ethylenically unsaturated bond in a side chain. Specific examples thereof include, for example, an aliphatic epoxy-containing unsaturated compound for a carboxyl-containing polymer ( Such as dilute glycidyl ether, (fluorenyl) glycidyl acrylate, α-ethyl glycidyl (meth) acrylate, glycidyl crotonic acid, glycidyl isocrotonate, glycidyl ether , Itaconic acid monoalkyl monoglycidyl ester, fumaric acid monoalkyl monoglycidyl ester, maleic acid monoalkyl monoglycidyl ester, etc.) or alicyclic epoxy-containing group Unsaturated compounds (such as 3,4-epoxycyclohexylfluorenyl (fluorenyl) acrylate, 2,3-epoxycyclopentylfluorenyl (meth) acrylate, 7,8-epoxy (fluorenyl) acrylate [ Tricyclic [5 · 2 · 1 · 0] dec-2 -yl] oxymethyl ester, etc.), based on 5 to 90 mol% of the carboxyl group of the carboxyl group-containing polymer (preferably 30 to 70 m ο 1%) Reaction products obtained by reaction to a certain degree, and compounds having two or more unsaturated groups (such as (fluorenyl) propylene) Allyl ester, 3-allyloxy-2-hydroxypropyl (fluorenyl) acrylate, cinnamyl (fluorenyl) acrylate, crotyl (fluorenyl) acrylate, fluorenyl allyl (fluorenyl) acrylate, N, Ν-diallyl (fluorenyl) acrylamide, etc.) or other compounds having more than two unsaturated groups (such as (fluorenyl) vinyl acrylate, (fluorenyl) 1-vinyl acrylate, (、 Base) acrylic acid 2-benzyl vinyl ester, (fluorenyl) acrylic acid 1-68 326 \ Patent Specification (Supplement) \ 94-03 \ 93134393 200530279 Propylene ester, vinyl crotonic acid, ethylene (meth) acrylamide, etc.) With unsaturated carboxylic acids (such as (fluorenyl) acrylic acid, etc.) or further with unsaturated carboxylic acid esters, the ratio of the unsaturated group-containing compounds in the whole may be 1 0 ~ 9 0 m ο 1% (with 3 0 ~ 80 m 〇1% is preferred) to copolymerize the reaction products. Furthermore, the reaction products of an ethylenic compound and a compound containing an epoxy group-containing polymer and a functional group (e.g., carboxyl group, hydroxyl group, etc.) that react with an epoxy group can also be mentioned. The acid-modified epoxy acrylate is a compound obtained by further reacting an epoxy group-containing reaction product with an unsaturated group-containing carboxylic acid or an acid anhydride thereof with a polybasic acid or an acid anhydride (c) thereof. Furthermore, a resin obtained by adding an epoxy group-containing compound to a part of the carboxyl group of the compound may be manufactured by a conventional method. Examples of the epoxy group-containing compound include the epoxy compounds described in Japanese Patent Publication Nos. 2000-1 to 7 4 6 2 1. [According to the publication, the epoxy compound has two or more epoxy groups. The compound (a)] can be specifically bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol S oxygen compound, biphenyl glycidyl ether, phenolic phenolic resin type epoxy resin, and phenolic system. A phenolic epoxy compound, a triglyceride isocyanurate, an alicyclic epoxy compound, and an additive structure composed of a cyclic hydrocarbon compound having more than one unsaturated group per molecule and phenols Epoxy compounds, copolymerized epoxy compounds, and the like. In the curable composition of the present invention, the content of the alkali-soluble fat of the above-mentioned component (K) is preferably 70 wt%, and further less than 40 wt% with respect to the total amount of the curable composition. good. 326 \ Patent Specification (Supplements) \ 94-03 \ 93134393 69 Saturated before it became available with unsaturated carboxylic acids. It is listed in JP 1 of the following two types of polymerizable trees of cyclic hydrated hydrazone. Compared with 200530279 [1 _ 1 2] (L), the hardening composition of the present invention is used for color filters or black substrates. In this case, it is best to use it with a color material. Here, the color material is a material which colors the curable composition according to the present invention. Dyes and pigments can be used as the coloring material, and pigments are preferred from the viewpoints of heat resistance and light resistance. As the pigment, pigments of various colors such as blue pigment, green pigment, red pigment, yellow pigment, purple pigment, orange pigment, brown pigment, and black pigment can be used. In addition, in addition to its structure, it is possible to use azo-based systems, photocyanine-based systems, quinacrid οne-based systems, benzimid σ-based ketone systems, iso, σ-done-based systems, two 4 σ-well systems, In addition to organic pigments such as indanthrene and a1, b 1-dibenzoanthracene (Pery 1 ene), various inorganic pigments may be used. Hereinafter, specific examples of usable pigments are indicated by pigment numbers. The meaning of C.I. in the terms "C.I.Pigment Red 2" and the like listed below is the Color Index. Examples of red pigments include 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 '5 7: 2, 58: 4' 60, 63, 63: 1, 63: 2, 64, 6 4 ·· 1 , 68, 69, 8 Bu 81], 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 10 Bu 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, 326 \ Patent Specification (Supplement) \ 94-03 \ 93134393 70 200530279 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, 263 264, 265, 266, 267, 268, 269, 270 271, 272,273,274,275,276. Among them, CI Pigment Red 48: 1 '122, 168, 177, 202, 206, 207, 209, 224, 2 4 2, 2 5 4 are more preferable, and those who are more preferable include C.I.Pigment Red 1 7 7, 2 0 9, 224, 254 ° Blue pigments can be cited as C.I.Pigment Blue 1, 1: 2, 9, 1 4, 1, 15, 15: 1, 15, 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, 6 6 > 67, 68, 71, 72, 73, 74, 75, 76, 78., 79. Among them, C. I. Pigment Blue 1 5, 1 5 ·· 1, 1 5: 2, 1 5: 3, 1 5 ·. 4, 1 5: 6 are more preferable, and further more For the better, CI Pigment Blue 15: 6 can be cited. Examples of green pigments include C. I. Pigment Green 1, 2, 4, 7, 8, 10, 1, 3, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54 Among them, 55 ° is preferable. For example, C.I. Pigment Green 7, 3 6 is mentioned. Examples of yellow pigments include 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, 1 01 > 104, 105, 108, 109, 110, 111, 116, 117, 1 1 9 > 120, 126' 127 > 127: 1 ^ 128, 129, 133, 134 > 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 326 \ Patent Specification (Supplement) \ 94-03 \ 93134393 71 200530279 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, 19 1: 1 ^ 19 2, 193, 194, 195, 196, 197, 198, 199, 2 0 0, 2 0 2, 2 0 3, 2 0 4, 2 0 5 , 2 0 6, 2 0 7, 2 0 8. Among them, C. I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 1 5 5, 1 8 0, 1 8 5 can be cited as the better, and more preferably, C. I. Pigment Yellow 8 3, 138, 139, 150, 180 ° Orange pigments include C. I. Pigment Orange 1, 2, 5, 1, 3, 1, 6, 1, 7, 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, 7 7, 7 8, 7 9. Among them, C. I. Pigment Orange 3 8, 71 is preferable. Examples of purple pigments include 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, 3, 32, 37, 39, 42, 44, 47, 49, 50. Among them, C. I. Pigment Violet 19, 2 3 is preferred, and C. I. Pigment Violet 23 ° is further preferred, and the hardening composition of the present invention is used. When a black matrix is formed under the object, a black color material can be used. As the black color material, a black color material alone or a mixed color material such as red, green, and blue may be used. Furthermore, for these color materials, an inorganic or organic pigment or dye can be appropriately selected. In the case of inorganic and organic pigments, it is preferable to use them in a state of being dispersed in an average particle size of 1 // m or less (preferably 0.5 or less // m). As a color material that may be mixed for the preparation of black color material, 326 \ Patent Specification (Supplement) \ 94-03 \ 93134393 72 200530279 Victoria Pure Blue (42595), A uramine 0 (4 1 0 0 0), Catilon Brilliant Flavin (basic 13), Rhodamine

6GCPC 4 5 1 6 0), Rhodamine B (4 5 1 7 0), safranine OK 7 0: 1 0 0 (5 0 2 4 0) > Eriog1 aucine X (4 2 0 8 0) ^ No. 120 / Liοηo1 Ye11ow (2 1 0 9 0), Liο ηo1 Yellow GR0 (2 1 0 9 0), Simu1 ar First Yellow 8GF (21105), Benzidine Yellow 4T-564D (21095), Simular First Red 4015 (12355), Lionol Red 7B 4401 (15850), Firstgen Blue TGR-L (74160), Lionol Blue SM (26150), Lionol Blue ES (Pigment Blue 15: 6), Lionolgen Red GD (Pigment Red 168), Lionol Green 2YS (Pigment Green 36) Wait. Press again, the number in the above brackets is the color index (C · I ·). In addition, regarding other pigments that may be mixed and used, C.I. is represented by numbers, for example, C.I., yellow pigment 2 0, 2 4, 8 6, 9 3, 1 0 9, 110, 117, 125, 137, 138, 147 '148, 153, 154, 166, C · I · Orange Pigment 3 6, 4 3, 5 1, 5 5, 5 9, 6 1, C · I · Red Pigment 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, CI purple pigment 19, 2 3, 2 9, 3 0, 3 7, 4 0, 50, C · I · blue pigment 15, 15: 1, 15: 4, 2 2, 6 0, 6 4, C · I. Green pigment 7, C · I · brown pigment 2 3, 2, 5, 2 6 and so on. Examples of the black color material that may be used alone include carbon black, acetylene black, lamp black, bone black, graphite, iron black, nigrosine, cyanine black, and titanium black. Among these black color materials, 326 \ patent specification (supplement) \ 94_〇3 \ 93134393 73 200530279 carbon black is preferable from the viewpoints of light shielding rate and image characteristics. Examples of the carbon black include carbon black as described below. MA7, MA8, ΜΗ, 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, Printex3 made by Iron Bone Sand Company, Printex30P, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, Printex L, Printex G, Printex P, Printex U 'Printex V' PrintexG, Specia 1B1 ack 5 5 0, SpecialBlack , SpecialBlack250, SpecialBlacklOO, SpecialBlack6, SpecialBlack5, SpecialBlack4, Color Black FW1, Color Black FW2, Color Black FW2V > Color Black FW18, Color Black FW18, Color Black FW200, Color Black S160, Color Black S1 70, Monarchl 20, Monarch280, Monarch460, Monarch800, Monarch880, Monarch900, MonarchlOO, MonarchllOO, Monarch 1 3 0 0, Monarchl400, Monarch4630, REGAL99, REGAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL250 REGAL400R, REGAL55R0, REGAL660R, BLACK PEARL S480, PEARLS130, VULCAN XC72R > ELFTEX-8, RAVEN11, RAVEN14, RAVEN15, RAVEN16, 326 manufactured by Columbia Carbon Corporation \ Patent Specification (Supplement) \ 94-03 \ 93134393 74 200530279 RAVEN22, RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN 8 9 0 H, RAVEN 1 0 0 0, RAVEN 1 0 2 0, RAVEN 1 0 4 0, RAVEN 1 0 6 0 U , RAVEN 1 0 8 0 U, RAVEN1 1 70 > RAVEN1190U, RAVEN 1 2 5 0, RAVEN 1 5 0 0, RAVEN 2 0 0 0, RAVEN 2 5 0 0 U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000 ° For examples of other black pigments, titanium black, aniline black, iron oxide black And red, green, blue organic pigments of three colors are mixed to be used as a black pigment. Further, as the pigment, barium sulfate, lead sulfate, titanium oxide, yellow lead, iron red, chromium oxide, and the like can be used. These various pigments may be used in combination of two or more kinds. For example, for the purpose of adjusting chromaticity, the pigment may be combined with a green pigment and a yellow pigment, or a combination of a blue pigment and a purple pigment. Furthermore, the average particle diameter of these pigments is usually 1 // m or less, preferably 0 · 5 // m or less, and more preferably 0.2 5 // m or less. Examples of dyes that can be used as color materials include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, Secondary perylene dyes. Examples of the azo dye include C. I. Acid Yellow 11 1, C. I. Acid Orange 7, C · I · Acid Red 3 7, C. I. Acid Red 1 80, C. I. Acid Blue 2 9, C. I. Direct Red 2 8, C. I. Direct Red 8 3, C. I. Direct Yellow 1 2, C. I. Direct Orange 2 6, C · I · Direct Green 2 8, C. I. Direct Green 5 9, C. I. Active Yellow 2, C. I. Active 75 32 < 5 \ Patent Specification (Supplement) \ 94-03 \ 93134393 200530279 Red 1 7, C. I. Active Red 1 2 0, C. I. Reactive Black 5, C. I. Disperse Orange 5, C. I. Disperse Red 5 8, C. I. Disperse Blue 1 6.5, C. I. Receptive Blue 4 1, C. I · Experimental Red 18, C. I. Mordant Red 7, C. I. Mordant Yellow 5, C. I. Mordant Black 7, etc. Examples of the anthraquinone dye include C. I. osmium blue 4 > C. I. acid blue 40, C. I. acid green 25, C. I. reactive blue 19, and C. I. reactive blue 4 9. C. I. Disperse Red 60, C. I. Disperse Blue 5 6, C. I. Disperse Blue 60 and so on. In addition to the above, examples of phthalocyanine dyes include C.I. osmium blue 5, and examples of quinone imine-based dyes include C. I. basic blue 3, C. I. basic blue 9, and the like. Examples of the sigma forest dyes include C. I. Solvent Yellow 3 3, C. I. Acid Yellow 3, C. I. Disperse Yellow 6 4 and the like, and examples of nitro dyes include C. I. Acid. Yellow 1, C.I. Acid Orange 3, CI Disperse Yellow 4 2 and the like. The proportion of the color material of the component (L) in the total solid content of the hardenable composition is usually relative to the total solid content of the hardenable composition and can be selected within a range of 70 wt%. Within this range, 10 to 70 wt% is further preferred, and 20 to 60 wt% is particularly suitable. If the ratio of the color material is too low, the film thickness of the color density becomes too large, and it has a bad influence on the gap control when the liquid crystal cell is converted. Conversely, if the ratio of the color materials is too high, sufficient image formability may not be obtained in some cases. In addition, the total solid content in the curable composition of the present invention is usually 10% by weight or more and 80% by weight or less. Furthermore, in order to improve the dispersibility and dispersion stability of the pigment, pigment derivatives and the like may be added. Examples of the pigment derivative include azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, quinophthalone-based, isoindolinone-based, dioxin ° well-based, anthraquinone-based, and indanes Yan, Yan, etc. of forest system, a 1, b 1 -dibenzoanthracene system, pery η ne, diketone, pyrene, pyrene and pyrrole, σ well system such as two degrees 76 326 \ Patent Specification (Supplement) \ 94-03 \ 93134393 200530279, among which quinophthalone pigment derivatives are preferred. Examples of the substituent of the pigment derivative include pigments such as sulfonic acid group, sulfonamido group and its fourth-order salt, phthaloiminofluorenyl group, dialkylaminoalkyl group, hydroxyl group, carboxyl group, and fluorenylamino group. Those in which the skeleton is bonded directly or through an alkyl group, an aryl group, a heterocyclic group and the like, among which a sulfonic acid group is preferred. Further, these substituents may be substituted in plural in one pigment skeleton. Specific examples of the pigment derivative include sulfonic acid derivatives of phthalocyanine, sulfonic acid derivatives of quinophthalone, sulfonic acid derivatives of quinone, sulfonic acid derivatives of quinacridone, and diketopyrrolopyrrole Sulfonic acid derivatives such as sulfonic acid derivatives of di 唠 σ wells. The amount of pigment derivative added is based on the amount of pigment, usually 0 ·:! ~ 3 0 wt%, preferably 0.1 ~ 2 0 wt%, and 0 ·:! ~ 1 0 wt% is further compared Good, and more preferably 0.1 to 5 wt%. [： 1-1 3] (Μ) Dispersant and / or dispersing aid In the case where the curable composition of the present invention is used for a color filter application or a black matrix application, especially when a pigment is used as the aforementioned component ( In the case of a color material of L), in order to improve the dispersibility and dispersion stability of the pigment, it is preferable to use a dispersant and / or a dispersing aid together as a component (M). In particular, it is preferable to use a high molecular dispersant as a pigment dispersant because it exhibits excellent dispersion stability over time. Examples of the high-molecular dispersant include aminoamidate-based dispersants, polyethyleneimine-based dispersants, polyoxyethyleneethylether-based dispersants, polyoxyethylene glycol diester-based dispersants, and sorbitan. Sugar alcohol aliphatic ester-based dispersant, aliphatic modified polyester-based dispersant, and the like. Specific examples of this kind of dispersant include "EFKA" (manufactured by FKA Chemical BV), "Disperbik" (manufactured by BigChemir Co.), "DISPARL0N" (manufactured by Kusumoto Chemical Co., Ltd.), "S0LSPERSE" (77 326 made by Zeneka Co. \ Patent Specification (Supplement) \ 94-03 \ 93134393 200530279), "KP" manufactured by Shin-Etsu Chemical Co., Ltd., "Polyflow" (Kyoeisha Chemical Co., Ltd. ) Manufactured) etc. These dispersants can be used alone or in combination of two or more. The content of the pigment dispersant in the solid content of the photosensitive coloring composition is usually 50 wt% or less, and preferably 30 wt% or less. In addition, as the dispersing aid, compounds represented by the general formula (I), ethylenically unsaturated compounds of the component (C), epoxy compounds of the component (D), and other alkali-soluble resins of the component (K), etc. After optional, it can also be used at the time of dispersion processing. [1-1 4] (N) According to other additives, the hardenable composition of the present invention may further contain various additives. For example, the hardenable composition contains a thermal polymerization inhibitor at a ratio of 2 wt% or less ( (Such as hydroquinone, p-fluorenol, 2,6-tert-butyl-p-phenol, etc.), containing a coloring agent composed of organic or inorganic dyes and pigments at a ratio of 20 wt% or less, according to Contains plasticizers (such as dioctyl phthalate, dilauryl phthalate, cresol phosphate, etc.) at a ratio of less than 40 wt%, and sensitivity improving agents (such as a grade 3 amine or Thiol, etc.), the pigment precursor is contained at a ratio of 30 wt% or less, and the silane coupling agent is contained at a ratio of 10 wt% or less. [1-1 5] Total deformation, displacement and elastic recovery rate under load, recovery rate The hardening composition of the present invention is about a load-except load test using a micro hardness tester, which can form a type with a total deformation of 1 . 3 5 # m or more and / or the load when the displacement is 0.25 // m load N is 0.50gf or less, and the elastic recovery rate is 50% or more and / or the recovery rate is 80% or more of the hardening Things are characteristic. 326 \ Patent Specification (Supplement) \ 94-03 \ 93134393 78 200530279 For example, the spacers supplied to the LCD display device (hereinafter 'referred to as "panel") of a large LCD daytime television are in the manufacturing process of the panel Due to the load, the total deformation of the spacer tends to increase. Furthermore, unevenness in the load of each part is apt to occur in the large daylight panel. The hardenable composition of this invention also exhibits a high degree of hardening of the rice separator even in this case.) The elastic recovery rate and / or recovery rate, even if it is valuable at this point, press the load-except load test using a micro hardness tester. It is as follows. Regarding a spacer pattern formed by [2_2] described later or a conventional method, a pattern having an upper cross-sectional area of 80 ± 10 μm2 was used, and measurement was performed using a microhardness. The cross-sectional area above the spacer pattern refers to the following area. First, regarding a spacer pattern, a longitudinal cross-section through the center axis of the spacer pattern under the "V K-9500" of the ultra-deep color 3D shape measuring microscope using the Keyence Corporation. The locations depicted are in Figure 1. Secondly, from the surface of the drawn figure (the schematic diagram of which is shown in FIG. 2) to 90% of the height of the highest position point Q is parallel to the substrate surface (the substrate surface in the pattern of the object pattern) The length of the straight line AA '. The area of a circle whose diameter is AA 'is set as the cross-sectional area of the spacer graph. The micro hardness tester uses "Shi Dynamic Super Micro Hardness Tester DUH-W201S" manufactured by Shimadzu Corporation. The test conditions are as follows: at a measuring temperature of 2 3 ° C, a diameter of 50 0 // m 326 \ Patent Specification (Supplementary Documents) ) \ 94-03 \ 93134393 79 Sometimes Zhongyi, Invention 7 (Medium-Operation Moderate Meter Manufacturing and Depicting Mazu ο Measured on the substrate interval to measure the case 200530279 surface pressure, at a certain speed (0.2 2 gf / sec) Apply a load to the spacer. When the load reaches 5 gf, hold it for 5 seconds, and then perform the load removal at this speed. According to the load-displacement curve obtained by this test (shown in Figure 3) (Schematic diagram), measure the maximum displacement Η [ma X], the final displacement Η [L ast], the displacement under load is 0.25 / zm, the excessive weight N (gf). Let the aforementioned maximum displacement Η [ma X] be the total deformation The total amount of deformation is preferably more than 1.4 // m, more preferably more than 1.5 // m, and more preferably 5 # m or less, and more preferably 3 // m or less. The displacement at the load is 0.2 5 // the load N at m is 0 4 5 gf or less Preferably, and more than 0.1 gf. If the total deformation amount is too large and / or the aforementioned load N is too small, the elastic recovery rate and / or recovery rate will deteriorate. On the other hand, if the total deformation amount is too small And / or the load N is too large, the hardened material cannot adapt to the uneven load of the panel during manufacture.

In addition, the elastic recovery rate and recovery rate are based on the values measured on the load-except load test using the micro hardness tester, and are calculated as follows: Recovery rate (%) = {Η [1 ast] Pattern height) 丨 X 1 0 0 Elastic recovery rate (%) = {(H [max] -H [last]) / H [max]} xlOO The recovery rate is preferably 85% or more, and more than 90% Even better. The elastic recovery rate is preferably 60% or more, and more preferably 80% or more. If the recovery rate and / or elastic recovery rate are too small, the hardened material cannot adapt to the uneven load of the panel during manufacture. If the hardenable composition of the present invention has the above-mentioned characteristics, its composition is not particularly limited, and in particular, it is possible to use the chemical formula 80 326 shown in (A-1) General Formula (I) (Patent Specification) \ 94-03 \ 93134393 200530279 compounds and / or (A-2) compounds with a p-phenol oxane structure. [1-1 6] The cross-sectional area of the bottom surface, the elastic recovery rate, and the recovery rate. Furthermore, the hardening composition of the present invention can form a cross-sectional area of the bottom surface of 24.5 // m2 or less, and an elastic recovery rate of 50% or more and / Or a hardened product with a recovery rate of 85% or more is characterized. For example, a spacer provided for a daytime panel of a mobile phone or the like is designed to have a small bottom area so as not to damage the daytime image because the pixels are small. On the other hand, products such as mobile phones are susceptible to shocks during use or other conditions, and are therefore easily loaded. The hardenable composition of the present invention exhibits a high elastic recovery rate and / or recovery rate of the hardened substance (spacer) even in this case, which is valuable in this regard. In addition, the bottom cross-sectional area refers to the contact area between the hardened object formed by the hardenable composition of the present invention and the substrate such as a spacer, and it can be measured by observing the spacer pattern using an optical microscope. The cross-sectional area of the bottom surface is preferably below 20 // m2, more preferably below 1 5 // m2, more preferably above 1 // m2, and even more preferably above 5 // m2. If the cross-sectional area of the bottom surface is too large, it is not suitable for a panel of a small-sized mobile phone or the like. If the bottom cross-sectional area is too small, a sufficient elastic recovery rate and / or recovery rate cannot be obtained. The elastic recovery rate and recovery rate are calculated in the same manner as described above based on the values measured on the load-except load test using the micro hardness tester. The recovery rate is preferably above 90%. The elastic recovery rate is preferably 60% or more, and more preferably 80% or more. If the recovery rate and / or elastic recovery rate are too small, the hardened material cannot adapt to the load of the panel 81 3 26 \ Patent Specification (Supplement) \ 94-03 \ 93134393 200530279. If the hardenable composition of the present invention has the above-mentioned characteristics, its composition is not particularly limited, and it is particularly possible to use a compound represented by (A-1) general formula (I) and / or (A-2) having a reference Phenol pinane structure to achieve this. [2] How to use hardenable composition The hardenable composition of the present invention can be used in various applications such as printed wiring boards, liquid crystal display elements, plasma display devices, large-scale integrated circuits, and thin transistors by conventional methods. , Semiconductor packages, color filters, organic electric field light emitting devices, etc., to form hardened products such as solder masks, cover films, and insulation coatings for various electronic parts, or to form liquid crystal panels such as liquid crystal display devices The pixels, black substrates, overcoat layers, ribs, and hardened materials such as spacers of the color filter in the following description will be described in particular regarding the case where it is used as a solder resist layer and the case where it is used as a spacer. [2-1] When used as a solder resist layer, a hardening composition dissolved or dispersed in a solvent is usually applied to the substrate to be provided with a solder resist layer in a film or pattern form by coating or the like. When the solvent is dried and supplied in a film form, the formation of a pattern is performed by a method such as a photo-etching method in which exposure-development is performed, if necessary. Alternatively, a hardening composition previously formed as a dry film photoresist material is supplied to a substrate according to a conventional method, and if necessary, a pattern is formed by a photo-etching method such as exposure-development. The film-like or pattern-like curable composition layer thus obtained is subjected to a heat curing treatment as necessary to form a solder resist layer on the substrate. [2-1-1] Substrate This substrate is used to expose the hardening composition formed thereon using laser 82 326 \ Patent Specification (Supplement) \ 94-03 \ 93] 34393 200530279 Those who carry out the development process and apply the image processing to the resulting image resistance, thereby forming patterns such as electrodes on the surface, are made of metals such as copper, aluminum, gold, silver, chromium, zinc, tin and nickel. The metal plate itself can also be used, but it is usually used for resins [such as thermosetting resins (such as epoxy resin, polyimide resin, butene diimide resin, unsaturated polyester resin, phenol resin, tertiary resin, etc. ), Thermoplastic resins (such as saturated polyester resins, polycarbonate polysulfone resins, acrylic resins, polyamide resins, polystyrene polyvinyl chloride resins, polyolefin resins, fluororesins, etc.), paper, inorganic substances ( Such as aluminum oxide, silicon dioxide, barium sulfate, calcium carbonate, etc.] materials (such as glass cloth substrate epoxy resin, glass nonwoven cloth substrate ring # paper substrate epoxy resin, paper substrate phenol resin, etc.) 0 . 0 2 ~ 10 mm insulation support On the surface, the aforementioned metal oxide (such as indium oxide, tin oxide, indium oxide-doped J oxide metal foil is heated and pressurized to be laminated on the surface, or the metal is deposited by evaporation, electroplating, etc. A conductive layer having a thickness of about 1 to about 1 is formed on the surface. The metal laminate thus obtained is used in the form of a substrate supplied in a state of being dissolved or dispersed in a solvent. [2-1-2] Utilizing methods known so far, such as spin coating, wire rod spray coating, dip coating, air knife coating, roll coating, blade coating, droop coating, etc. About the coating amount at the time of coating If the processing (formation of the day image, followed by welding processing, etc.) is considered, the dry film thickness is preferably 5 // m or more, and 1 0 // m is 326 \ Patent Specification ( (Supplements) \ 94-03 \ 93134393 83 As light path, electricity, lead, such as bismuth melamine resin, resin, glass, I or composite, resin, thickness, or metal, etc., etc., 1 0 0 // m 〇 Love on the coating It is better to go to the next step of 200530279. If sensitivity is taken into consideration, it is better to be less than 2 0 // m, and more preferably less than 100 V m. Press again, for this drying temperature, for example, you can It takes about 30 ~ 150 ° C, preferably about 40 ~ 110 ° C, and the drying time is, for example, about 5 seconds ~ 60 minutes, and about 10 seconds ~ The degree is preferably 30 minutes. In addition, in the case of directly coating and drying the hardening composition coating liquid to prepare a hardenable day image forming material, in order to suppress polymerization caused by oxygen of the hardenable composition For the prevention, etc., a solution of polyvinyl alcohol, polyvinylpyrrolidone, polyethylene oxide, fluorenyl cellulose, carboxyfluorenyl cellulose, hydroxymethyl cellulose, etc. is applied as described above to form the foregoing The above-mentioned hardening composition layer on the substrate to be processed is dried, and a protective layer is formed. "Oj * 〇" For the purpose of serving as a dry film photoresist material, it can be used on the substrate. Method to proceed. Specifically, each of the aforementioned components is dissolved or dispersed in a suitable solvent to be applied as a coating solution on a temporary support film and dried, and a coating film is applied to the formed hardening composition as necessary. On the surface of the material layer, as a so-called dry film photoresist material, etc., when the coating film is coated on the hardening composition layer side of the dry film photoresist material, the coating film is peeled off and laminated by heating. The method is laminated on the substrate to be processed, thereby supplying the substrate. When used as the dry film photoresist, etc., as the temporary support film required, for example, a polyethylene terephthalate film, a polyimide film, a polyimide film, polypropylene can be used. Films, polystyrene films, and the like that have heretofore been known. At this time, if these films have the solvent resistance required for the preparation of the dry film photoresist material 84 326 \ Patent Specification (Supplement) \ 94-03 \ 93134393 200530279, the hardening composition can be If the coating solution is directly coated on a temporary support film, such as drying, to make a dry film photoresist, and if these films have a low degree of solvent resistance or heat resistance, the dry film is also prepared as described below. Photoresist: For example, after forming a hardenable composition layer on a release film such as a polytetrafluoroethylene film, a temporary support film with low solvent resistance or heat resistance is laminated on the layer. Then, the above-mentioned film having release properties is peeled off to prepare a dry film photoresist. Furthermore, the solvent for the coating liquid mainly has a solubility for the components used and can provide good coating film properties. For this purpose, for example, a cellosolve solvent (such as 2-ethoxyethanol 氧 2-ethoxyethanol 乙 S, 2-ethylethoxyethanol ethyl, 2-ethylethoxyethyl) Etc.); propylene glycol solvents (such as propylene glycol monomethyl ether, propylene glycol monoethyl propylene glycol monobutyl ether, propylene glycol Glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monobutyl ether acetate, bis (propylene glycol) dimethyl ether, etc.); ester agents (such as butyl acetate, pentyl acetate, ethyl butyrate, butyl ether Succinic acid, ethylene glycol 8 purpose, ethyl pyruvate 6 purpose, ethyl 2-hydroxybutyrate, ethyl acetate ethyl acetate, ethyl δ purpose lactate, methyl 3-acetoxypropionate, etc.); alcohol Series solvents (alcohol, hexanol, diacetone alcohol, furfuryl alcohol, etc.); ketone series solvents (such as cyclohexanonepentyl ketone, etc.); highly polar solvents (such as dimethylfluorenylamine, difluorenylamine, N- Fluorenyl pyrrolidone, etc.), and these mixed solvents, and those containing aromatic hydrocarbons. The use ratio of the solvent is generally within the range of 1 to 20 times by weight based on the total amount of each component of the hardenable material. [2_1_3] Exposure method 326 \ Patent Specification (Supplement) \ 94-03 \ 93134393 85 Here, you can leave or remove the fixtures and materials. There are filling, ester, ethanol & I, acetic acid-soluble diacid, milk such as heptamine, acetone, etc. One step composition range 200530279 Second, regarding the hardenable day image forming material, there is a hardenable composition layer on the processed substrate Light exposure or heating (preferably scanning exposure under laser light as an exposure light source) is performed on the hardenable composition layer to expose the hardenable composition layer. In this case, when the protective layer is provided, exposure may be performed while the protective layer is provided, or exposure may be performed after peeling. When a hardening composition layer is formed from the dry film photoresist, the temporary supporting film may be maintained or the exposure may be performed after peeling. Examples of the exposure light source include a carbon arc lamp, a mercury lamp, a xenon lamp, a metal oxide lamp, a fluorescent lamp, a tungsten lamp, a halogen lamp, and a laser light source (such as a HeNe laser, an argon ion laser, and a YAG laser). Laser, HeCd laser, semiconductor laser, ruby laser, etc.), especially a light source that emits laser light in the blue-violet region with a wavelength range of 3 50 ~ 4 3 0 nm, and its center wavelength is about 4 0 5 nm Those are even better. Specific examples include an indium gallium nitride semiconductor laser oscillating at 405 nm. Furthermore, the scanning exposure method using a laser light source is not particularly limited, and for this purpose, for example, a planar scanning exposure method, an outer drum scanning exposure method, an inner drum scanning exposure method, etc., the scanning exposure conditions are the most It is possible to set the output light intensity of the laser to 1 ~ 100mW (more preferably 3 ~ 70mW), it is best to set the oscillation wavelength to 3 9 0 ~ 4 3 0 nm (with 4 0 0 ~ 4 2 0 nm Further preferred), it is best to set the spot diameter to 2 ~ 3 0 // in (4 to 2 0 μm is more preferred), and it is best to set the scanning speed to 50 to 50 0 m / Seconds (more preferably from 100 to 400 m / s), it is best to set the scan density to 2,000 dpi or more (more preferably 4,000 dpi or more) to perform scan exposure. In addition, the hardening composition of the present invention is not subjected to the aforementioned light hardening. 86 326 \ Patent Specification (Supplement) \ 94-03 \ 93134393 200530279 However, it can also be heated in the presence of a thermal polymerization initiator. A hardened layer is formed on the substrate. In this case, the heating conditions can be usually 80 ~ 250 ° C, preferably 100 ~ 200 ° C, usually 10 ~ 120 minutes, preferably 20 ~ 60 minutes. . [2-1-4] Development method Further, the aforementioned post-exposure development treatment is performed using an aqueous developing solution which preferably contains an alkali component and, if necessary, a surfactant. Examples of the test ingredient include inorganic test salts (such as sodium salt, potassium salt, lithium salt, ammonium silicate, sodium metasilicate, potassium metasilicate, sodium hydroxide, potassium hydroxide, and lithium hydroxide). , Sodium carbonate, sodium bicarbonate, potassium carbonate, sodium hydrogen phosphate, sodium phosphate, ammonium hydrogen phosphate, ammonium phosphate, sodium borate, potassium borate, ammonium borate, etc.), organic amine compounds (such as monoamine, diamine, triamine Amine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, monobutylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, etc.) It is used by the user at a concentration of about 0.1 to 5 wt%. Examples of the surfactant include the same surfactants as those exemplified in the aforementioned hardening composition. Among them, nonionic, anionic, or amphoteric surfactants are preferred, and amphoteric surfactants are preferred. Beet tincture type compounds are particularly suitable. According to the above, it is preferable that the aforementioned surfactant can be ◦ · 0 0 0 2 20 wt% (with 0. 0 0 5 ~ 1 0 wt ° / ◦ more preferably, and ◦ · 0 0 1 ~ 5 wt. % Is particularly suitable). In addition, the developing solution may contain organic solvents such as isopropyl alcohol, benzyl alcohol, 2-ethoxyethanol ethyl ester, 2-ethoxyethanol butyl ester, 2-ethoxyethanol phenyl ester, propylene glycol, diacetone alcohol, and the like, as necessary. . Furthermore, the pH of the developing solution is preferably set to 87 326 \ Patent Specification (Supplement) \ 94-03 \ 93134393 200530279 9 ~ 14, and 11 ~ 14 is more preferable. Further, the development process generally uses a conventional development method in which a day image forming material is immersed in the above-mentioned developing solution, or a day image forming material is sprayed with the above-mentioned developing solution, etc., preferably at a temperature of about 10 to 50 ° C. At a temperature of about 20 to 40 ° C, it is performed at a temperature of about 5 seconds to 10 minutes. Furthermore, after the development process, in order to improve the heat resistance or chemical resistance of a day image formed by a hardened material as a photoresist, it is preferably performed at a temperature of about 140 to 160 ° C, for example. Heat treatment. [2-2] When used as a spacer, a hardening composition dissolved or dispersed in a solvent is usually applied by a method such as coating to a film or a pattern on a substrate on which a spacer is to be provided, and the solvent is used. When it is supplied in a film form after drying, if necessary, the formation of a pattern is performed by a photo-etching method such as exposure-development. Then, if necessary, an additional exposure process or a thermal curing process is performed to form a spacer on the substrate. [2-2-1] Supply method to substrate The curable composition of the present invention is usually supplied to a substrate in a state of being dissolved or dispersed in a solvent. The supply method can be performed by a conventionally known method such as a spin coating method, a wire rod coating method, a flow coating method, a die coating method, a roll coating method, a spray coating method, or the like. In particular, according to the die coating method, the amount of coating liquid used can be greatly reduced, and it is completely unaffected by the moisture and the like that adhere to the spin coating method, and the generation of foreign matter can be suppressed. The coating amount varies depending on the application. For example, in the case of spacers, the dry film thickness is usually in the range of 0.5 to 10 // m, and in the range of 1 to 8 / zm. 88 326 \ Patent Specification (Supplement) \ 94-03 \ 93134393 200530279 is better, and it is particularly suitable in the range of 1 ~ 7 // m. In addition, in order to dry the film thickness or the height of the spacer formed at the end, it is important that it is uniform over the entire area of the substrate. When the variation is large, the LCD panel may have uneven defects. In addition, it may be supplied in a pattern by using an inkjet method, a printing method, or the like. [2-2-2] Drying method After the hardening composition is supplied onto the substrate, it is best to perform drying according to a drying method using a hot plate, an IR oven, or a convection oven. Furthermore, it may be combined with a reduced-pressure drying method (drying in a decompression box without increasing the temperature). The drying conditions can be appropriately selected according to the type of the solvent component and the performance of the dryer to be used. The drying time depends on the type of solvent composition and the performance of the dryer to be used. Usually, the temperature is selected within the range of 15 seconds to 5 minutes at a temperature of 40 ~ 130 ° C. Preferably, it is The temperature of ~ 110 ° C is selected from 30 seconds to 3 minutes. [2-2-3] Exposure method For exposure, a negative photoresist pattern is superimposed on a coating film of a curable composition, and the photoresist pattern is irradiated with a light source irradiated with ultraviolet rays or visible light to perform exposure. Furthermore, a scanning exposure method using laser light may be used. In this case, if necessary, in order to prevent the sensitivity of the photopolymerizable layer from being reduced by oxygen, exposure may be performed in a deoxidizing environment or after forming an oxygen blocking layer such as a polyvinyl alcohol layer on the photopolymerizable layer. . The light source used for the above exposure is not particularly limited. Examples of the light source include lamp light sources such as xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arc lamps, and fluorescent lamps; Argon ion laser, YAG laser, excimer laser, nitrogen laser, helium-based laser 89 326 \ Patent Specification (Supplement) \ 94-03 \ 93134393 200530279, blue-violet semiconductor laser, near infrared Laser light sources such as semiconductor lasers. In the case where light of a specific wavelength is irradiated for use, an optical filter may be used. [2-2-4] Development method After performing the above exposure, a day image pattern can be formed on a substrate by developing using an aqueous solution or an organic solvent containing a basic compound and, if necessary, a surfactant. This aqueous solution may further contain an organic solvent, a buffering agent, a complexing agent, a dye or a pigment. Examples of test compounds include sodium hydroxide, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, and phosphoric acid. Potassium, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide and other inorganic basic compounds; such as monoethanolamine, diethanolamine, triethanolamine, monomethylamine, dimethylamine, triamidine Amine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, n-butylamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, ethyleneimine, ethylenediamine Organic basic compounds such as ethylenediimide, tetraammonium hydroxide (TMA Η), gallbladder 4 etc. The test compound may be a mixture of two or more kinds. Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethyl alkyl aryl ethers, polyoxyethyl alkyl esters, sorbitan alkyl esters, and monoglycerides. Non-ionic surfactants such as esters; such as alkylbenzenenaphthenates, alkylnaphthalenesulfonates, alkylsulfates, alkylsulfonates, sulfosuccinates And other anionic surfactants; such as alkyl beets, amino acids and other amphoteric surfactants. Examples of the organic solvent include isopropanol, benzyl alcohol, 2-ethoxyethanol ethyl ester, 90 326 \ Patent Specification (Supplement) \ 94-03 \ 93134393 200530279 2-ethoxyethanol butyl ester, 2-ethoxyethanol Phenyl ester, propylene glycol, diacetone alcohol, etc. The organic solvent may be used alone or in combination with an aqueous solution. [2-2-5] Additional exposure and thermal curing treatment The substrate after development may be subjected to additional exposure in the same manner as the aforementioned exposure method as required, or thermal curing treatment may be performed. It is particularly preferable to perform a heat hardening treatment. For this heat curing treatment condition, the temperature is selected in the range of 100 to 28 ° C, preferably in the range of 150 to 250 ° C, and the time is selected to be 5 to 6. Within 0 minutes. < Examples > Hereinafter, the hardenable composition of the present invention will be described with reference to specific examples of solder mask use and spacer use. However, the present invention is not subject to the following implementations as long as the gist is not exceeded. Restrictions. [1] Examples 1 to 3 and Comparative Examples 1 to 2 of hardenable compositions for solder resist. Compounds represented by the aforementioned general formula (I) and other compounds and components ( B 1 ~ B 4) photopolymerization initiator, ethylenically unsaturated compound of component (C 1), epoxy compound of component (D 1), epoxy hardener of component (E 1), component (Η 1 ~ Η 2) Inorganic filler, component (J 1 ~ J 3), sensitizing pigment and other components of component (X 1) propylene glycol monomethyl ether acetate is added in a proportion of 1000 parts by weight , Stirring at room temperature to prepare a coating solution. In addition, for a copper-clad laminate substrate (thickness 1.5 mm, size 250 mm x 200 mm) with a polyimide resin with a copper foil thickness of 3 5 // m, a surface treatment material "Scotch-Bright SF "(manufactured by Sumitomo 3M Co., Ltd.) to polish the copper foil surface of the substrate and wash it with water. 326 \ Patent Specification (Supplement) \ 94-03 \ 93134393 91 200530279 Dry by air flow, the whole surface, and then in the oven After preheating to 60 ° C, the coating solution obtained above is coated on the copper foil of the copper-clad substrate in such a manner that the dry film thickness can be 2 5 // m. Dry at 30 ° C for 30 minutes to produce a photocurable image forming material. (A 1) 231 g of 9,9-bis (4′-hydroxybenzene) bisepoxide (epoxy 231) and 2-propenyloxyethyl succinic acid obtained from the compound obtained in the following production example (Acid value 260, product of Gong Rong Chemical Co., Ltd. "Η Ο A-MS") 2 16 g, triethylbenzyl ammonium chloride 0.45 g and p-oxybenzene O.lg into a 500 ml four-necked flask, While blowing in air at a rate of 25ml / min, heat and dissolve it at a temperature of 90 ~ 100 ° C, and then slowly raise the temperature to 120 ° C when the solution is cloudy, so that complete dissolution will follow. The transparent and viscous solution was continuously heated and stirred for 8 hours, and its acid value reached 0.8 K 0 Η · mg / g to obtain a colorless and transparent reaction product. Next, 4 4 7 g of the obtained reaction product was added. After 20 g of 2-ethylethoxyethanol S was dissolved, 1,2,3,6-tetrahydroacid anhydride 3 8 g of biphenyltetracarboxylic dianhydride 7 3.5 g, and bromine were added thereto. Tetraethylammonium (1 g) was reacted at a temperature of 110 to 115 ° C. for 2 hours to obtain a compound (A 1). The weight average molecular weight of the obtained compound was 3,500, and the double bond was 5,600. (A 2) From the compounds obtained in the following production examples, 200 parts by weight of succinic anhydride and 5 9 6 parts by weight of pentaerythritol tripropionate commercially available at 2.5 parts by weight of triethylamine and 0.2 of hydroquinone. In the presence of 5 parts by weight and at a temperature of 100 ° C for 5 hours, a multifunctional propylene with a carboxyl group and 2 or more acryl groups in the molecule is obtained. 326 \ Patent Specification (Supplement) \ 94-03 \ 93134393 92 A polyfunctional acrylate having an acid value of 9 4 consisting of 67 mol% of ethylenene and 30 mol of ethylene and 30 mol of pentaerythritol tetrapropionate, which will be divided into two parts: temperature and temperature. mixture. Except using 5 9 7 g of this polyfunctional acrylate mixture instead of 2 1 6 g of 2-propenyloxyethylsuccinic acid, production was performed in the same manner as in the production example of (A 1) to obtain the compound (A 2 ). The obtained compound had a weight-average molecular weight of 3,000 and a double bond equivalent of 211. (A 3) The compound obtained from the following production example In the production example of the aforementioned (A 1), in addition to using 80.5 g of diphenyl ketone tetracarboxylic dianhydride instead of 73.5 g of biphenyl tetracarboxylic dianhydride Except for this, production was carried out in the same manner as in the production example of (A1) above, and a compound (A 3) was obtained. The obtained compound had a weight average molecular weight of 3,500 and a double bond equivalent weight of 189. (A 4) Compounds obtained from the following production examples In the production examples of (A 1) above, except for the use of 9,9-bis (4′-hydroxy-3′-benzene) fluorene diepoxide 2 3 1 g was used instead of 9, 9-bis (4′-hydroxybenzene) buckwheat bis-epoxide 2 3 1 g, and the production was carried out in the same manner as in the production example of (A 1), to obtain compound (A 4 ). The obtained compound had a weight average molecular weight of 3,000 and a double bond equivalent weight of 187. (A 5; for comparative example) The compounds obtained in the following production examples were the same as those in the production example of (A1) except that 72 g of acrylic acid was used instead of 216 g of 2-propenyloxyethylsuccinic acid. Production was carried out in the same manner as in the production example of (A1) above to obtain compound (A 5). The obtained compound had a weight average molecular weight of 3,200 and a double bond equivalent weight of 416. (A 6; for comparative example) Compound (A6) having repeating units of the following constitution (acid value 100 mgKOH / g, weight average molecular weight 5,000, double bond equivalent 93 326 \ Patent Specification (Supplement) \ 94-03 \ 93134393 200530279 3 9 8, "PR-3 0 0 J" manufactured by Showa Polymer Co., Ltd.)

H〇CC OOC 〇CHiCHCHi〇〇CCH * CHi

(Bl) l- (4-fluoranthiobenzene) -2-morpholin-2-fluorenylpropan-1-one (B 2) 2,4-diethylthiosigmaxanone (B3) 2 -trans-4- N-octanoic acid diphenyl ketone (B 4) 2,2'-bis (o-chlorobenzene) -4,4 ', 5,5'-tetrabenzimidazole (C1) di (pentaerythritol) hexaacrylate (D 1 ) O-pyrene phenol-based phenolic resin epoxy resin (epoxy value 2 "EPICOAT180S70" manufactured by JAPAN EPOXY RESIN C0.) (E 1) cyanoguanidine (钡 1) barium sulfate (Η 2) talc (J 1) The sensitizing pigment described (J2) The sensitizing pigment described below (J3) The sensitizing pigment 3 described below 26 \ Patent Specification (Supplement) \ 94-03 \ 93134393 94 200530279 αΐ)

CHa (X 1) phthalocyanine green [1-1] exposure sensitivity of high pressure mercury lamp About the photocurable day image forming material obtained above, the exposure sensitivity was measured by the following method, and the results are shown in Table 1. The photocurable composition layer of the obtained day image forming material was irradiated with a 1 kW ultra-high pressure mercury lamp, and it was determined that it was developed at 30 ° C for 80 seconds using a 1 wt% aqueous sodium carbonate solution. The minimum exposure (m J / c m2) for the reproduction of the gradation day image is used as the sensitivity. [1-2] Adhesion to substrate Secondly, for the obtained photocurable day image forming material, the adhesion of the hardened layer to the substrate to be processed and its heat resistance were evaluated as shown below, and the results are shown in in FIG. 1.

For the light-curable composition layer of the obtained day image forming material, under the use of a 1 k W 95 326 \ Patent Specification (Supplement) \ 94-03 \ 93134393 200530279 ultrahigh-pressure mercury lamp, the minimum value obtained according to the foregoing is obtained. After the exposure amount is irradiated to form a comprehensive hardened layer, the obtained hardened layer is heat-treated at 150 ° C for 60 minutes, and then a cutting machine can be used at 1 mm intervals in accordance with JISD 0 2 02. 100 squares were applied to the hardened layer, and a cellophane tape made by Nichiban Co. was attached to the hardened layer to measure the peeling method of the hardened layer when the tape was peeled off. The number of divisions is evaluated on the basis of the following. A: In 100 squares, the number of peeled squares of the hardened layer is 0. B: In 100 squares, the number of peeled squares of the hardened layer is 1 or more and less than 5. C: In 100 squares, the number of peeling squares of the hardened layer is 5 or more, and less than 10. D: Among 100 squares, the number of peeled squares of the hardened layer is 10 or more. [1-3] Adhesive property and thermal properties are the same as above. After applying a cutting mark using a cutting machine so that it can be 1,000 squares, FLUX (manufactured by Tamurakaken Co.) is applied to the surface, followed by , Repeatedly perform an operation of immersing in a solder bath at 290 ° C for 30 seconds and then returning to room temperature 6 times. Then, the Saifan tape was affixed to the hardened layer, and the number of peeling squares of the hardened layer when the tape was peeled off was measured in the same manner as described above, and evaluated on the same basis. [1-4] Laser Exposure Sensitivity Example 4 (Curable composition for solder resist layer: Laser exposure) Regarding the photocurable image forming material prepared in the same manner as in Examples 1 to 3, the laser light was used as Under the exposure light source, the laser exposure was measured as follows: 96 326 \ Patent Specification (Supplement) \ 9'03 \ 93134393 200530279 degrees. Then, except that the exposure light source was changed to laser light, it was performed as before. The evaluation of the adhesion of the substrate and its heat resistance are shown in Table 1. The obtained photocurable composition layer of the daytime image forming material was fixed on an aluminum cylinder with a diameter of 7 cm, and the rotation speed was changed from 10 to 100 revolutions per minute using a center wavelength of 4 0 5 nm and a laser light source with a laser output of 5 m W ("NL Η V 5 0 0 C" manufactured by Ya Chemical Industry Co., Ltd.), according to the image plane illumination 2 m W and the spot diameter 2 0 // m and Scanning exposure was performed while changing the beam scanning interval and scanning speed. Secondly, it was sprayed under the condition of using 0.1 wt. , And spray development at 1.5 times the minimum development time to make the image appear. Regarding the obtained day image, an exposure amount required for reproduction with a line width of 20 μm was obtained as a sensitivity to a blue-violet laser. [2] Curable composition for solder mask layer: dry film photoresist Examples 5 to 7 The photocurable composition was applied with an applicator to a dry film thickness of 25 # m to serve as a temporary support film. On a polyethylene terephthalate film (thickness 19 // m), dried in an oven at 90 ° C for 5 minutes, and a photo-curable composition layer was formed as a coating film A polyethylene film (thickness: 25 μm) was left to stand for 1 day to make a dry film photoresist. Next, the obtained dry film photoresist material was peeled from the polyethylene film, and the peeling surface was under a manual roll laminator using a roll temperature of 100 ° C and a roll pressure of 0.3 MPa. At a lamination speed of 1.5 m / min, it was laminated on the copper foil of the same copper-clad substrate as used in Examples 1 to 3 to prepare a photocurable composition layer 97 326 \ Patent Specification (Supplementary Pieces) \ 94-03 \ 93134393 200530279 A photocurable image forming material formed on a copper-clad substrate. Regarding the photocurable composition layer of the obtained photocurable day image forming material, the laser exposure sensitivity was measured in the same manner as in Example 4, and then the adhesion of the substrate and its thermal properties were evaluated, and The results are shown in Table 1. 98 326 \ Patent Specification (Supplement) \ 94-03 \ 93134393 200530279 I < ^ ss-ss ^ ^ sf ^ ^ ^ ^ g

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/ ^ \ / ^ N 1—H CNI CO ^ CO CO CQ PQ (G) 荽 ^ JJT ^ r ^ K-si ^ oG) (le f ^ (13) § § Φ * ¥ S) (S (5 αχ ) X (X) $ s ^ e6e inch ei e6 \ s46 \ ff} s) _ ^ MVK-w \ 9ze 200530279 [3] Hardened composition for spacer Examples 8 ~ 1 4, Comparative Examples 3 ~ 4 The components (A2) and (A5) are compounds represented by the following general formula (I) and other compounds (A8) to (A12), polymerization initiators for the component (B1), components (C1), and (C 2) The ethylenically unsaturated compound, the amine compound of the component (F 1), the surfactant of the component (I 1), and the additive of the component (N 1) are added with propylene glycol monomethyl ether acetic acid according to the mixing ratio shown in Table 2. 100 parts by weight of the ester was stirred at room temperature to prepare a coating solution. The obtained coating liquid was evaluated for storage stability according to the following method, and the results are shown in Table 2. [3-1] Storage stability Regarding the case where the coating solution is sealed in a sample bottle and stored at a temperature of 35 ° C for 7 days, the changes in viscosity and minimum development time before and after storage are measured, and the following standards are used Be evaluated. 〇: The change in viscosity is within the range of ± 3 ° / 〇 and the change in the minimum development time is within the range of ± 3%. △: The viscosity change is outside the range of ± 3%, but the change of the minimum development time is within the range of ± 3%. X · · Viscosity change is within ± 3%, but the minimum development time change is outside ± 3%. (A 8) Compounds obtained from the following production examples except for the use of 137 g of 1,2,3,6-tetrahydrophthalic anhydride instead of 1,2,3,6-tetrahydro Si; 38 g of anhydride and biphenyltetracarboxylic acid di Except for 73.5 g of anhydride, production was performed in the same manner as in the production example of (A2) described above to obtain compound (A 8). The obtained compound had an acid value of 5 6, a weight average molecular weight of 2, 6 2 0 and a double bond equivalent of 2 1 6. 100 326 \ Patent Specification (Supplement) \ 94-03 \ 93134393 200530279 (A 9) The compound obtained from the following production example is a 9,9-bis (4'-hydroxybenzene) diglycidyl etherate (ring Oxygen equivalent 2 3 1) 100 parts, reaction mixture of succinic anhydride and pentaerythritol triacrylate (same as used in the above-mentioned production example (A 2), acid value 9 0 · 5) 2 7 3 · 2 parts, 0.19 parts of p-fluorenol, 7.4 parts of triphenylphosphine, and 3.8 parts of propylene glycol monofluorenyl acetate were charged into the reaction vessel, and stirred at 90 ° C until the acid value reached 5 mg- Up to K 0 H / g. In order to reach the goal of acid value, it takes 10 hours (acid value 1.0). Next, to 80 parts of the reaction solution obtained by the above reaction, 6 parts of propylene glycol monomethyl ether acetate was added, and 1.9 parts of hexamethylene diisocyanate and 0.01 part of dibutyltin dilaurate were added thereto. The reaction was carried out at 90 ° C for 3 hours, and then 3.8 parts of trimellitic anhydride was added. The reaction was carried out at 90 ° C for 3 hours, and a polybenzene having an acid value of 52 was measured by GPC. A compound (A 9) solution having an ethylene-equivalent weight average molecular weight of 3,100 and a double bond equivalent of 199. (A 1 0) Resin with p-phenol-pentane structure (product of Nippon Kayaku Co., Ltd. "TCR1286", its acid value is 10 bp, double bond equivalent is 315, bis (ethylene glycol) monoethyl ether acetate solution) (A 1 1 ) Compounds obtained from the following production examples (additional test of the acrylic resin described in Synthesis Example 3 in Japanese Patent Laid-Open No. Hei 13-600): 2, 2'-azobis 7 parts by weight of (2,4-dioxovaleronitrile) and 200 parts by weight of bis (ethylene glycol) dimethyl ether were charged into a flask equipped with a cooling tube and a stirrer. Next, 10 parts by weight of styrene, 20 parts by weight of methacrylic acid, 4 parts by weight of glycidyl methacrylate, and dicyclopentyl methacrylate 2 5 101 326 \ Patent Specification (Supplement) \ 94 · 03 \ 93134393 200530279 parts by weight, and after aeration with nitrogen, slowly start stirring. The temperature was raised to 70 ° C, and this temperature was maintained for 5 hours to obtain a polymer solution of (A 1 1). The solid solution of the obtained polymer solution was 33%, and the weight average molecular weight of the polymer was 18,000. (A 1 2) Compounds obtained from the following production examples except for the use of "RIKACIDBT-100 Physicochemical Product" which is a tetracarboxylic dianhydride 5 7. 5 g and 1,2,3,6-tetrahydrophthalic anhydride 4 3 1,2,3,6-tetrahydrophthalic anhydride 38 g and biphenyltetracarboxylic dianhydride 73. Both were produced in the same manner as in the production example of (A 2), and the compound had an acid value of 5 and the weight of the compound. The average molecular weight is 4 4 50, which is 2 0.: (C2) The (meth) acrylic acid S-containing moieties represented by the aforementioned general formula (VIIIc) (Nippon Kayakusho Co., Ltd. product "KAYARADP M 2 1"): ( F 1) Melamine resin and its modified resin (Sanwa Chemical r NIKALACK Ε-2151 ″) (, Π) Fluorine surfactant (Da Yueben Ink Chemical Industry r MEGAFAX F- 4 7 5 ″) (N1) stone Yuyao coupling agent (product of Toray Dow Corning Co. Γ) Then, a spin coater was used to coat the aforementioned coating solution on an ITO film on a glass substrate with ITO film, and heated and dried on a hot plate 3 Minutes to form a coating film. The obtained coating film has 9 circular openings each having a diameter of 5 to 2 0 // Hi and each of the square openings Under the pattern mask, the exposure gap 3 6 5 η η with ultraviolet light intensity of 3 2 m W / cm 2 is used to expose 326 \ Patent Specification (Supplement) \ 94-03 \ 93134393 102 to make the solution contain copolymer concentration For "(new Japan 8g instead of 5g, (A 1 2) ° of double bond equivalent of fluorinated oxygen group) company product company product SH 6 0 4 0") surface formation 8 0 ° C temperature on the side of use 5 mm at 1 5 0 // m, the amount of exposure can be 200530279 6 0 m J / cm 2. The ultraviolet irradiation at this time is performed in the air. Second, use 0.1% hydrogen at 2 3 ° C The oxidized bell aqueous solution is spray-developed at twice the minimum development time, and then washed with pure water for 1 minute. Here, the meaning of the minimum development time is the time under which the unexposed portion is completely dissolved under the same development conditions. The substrate with a spacer pattern formed by removing unnecessary parts by such operations is heated and hardened at 230 ° C for 30 minutes in an oven to obtain a plurality of spacer patterns with different bottom areas, and the film portion thereof. (Formed in a square of 5 mm or more on each side The height of the opening) is about 4 // m. The obtained spacer pattern was evaluated for adhesion and compression characteristics in accordance with the following method, and the results are shown in Table 2. [3-2] 密The tightness and tightness evaluation is performed on the subjects of Examples 8 to 11 and Comparative Examples 3 and 4. Regarding spacer patterns with different bottom areas obtained from patterned mask films with different aperture diameters, more than 8 patterns were formed in 9 spacer patterns of the same size having a pattern height of 3 // m or more The minimum pattern size (that is, less than one of the nine patterns to be formed) specifies the adhesion, and is shown in Table 2 as the bottom area. [3-3] Compression characteristics: Load-except load test using micro hardness tester For the spacer pattern obtained above, the ultra-deep color 3D shape measuring microscope manufactured by Keyence Corporation was used "VK-9 5 Below "0 0", a longitudinal cross-section through the middle axis of the spacer pattern is depicted. AA parallel to the substrate surface (substrate surface in the pattern of the spacer pattern) at 90% of the height (from the substrate surface shown in the schematic diagram of the figure 2 to the highest position Q) 'Is measured. Next, the area of this circle A A ′ is 103 326 \ Patent Specification (Supplement) \ 94-03 \ 93134393 200530279 diameter of the circle as the cross-sectional area above the spacer pattern. Among them, regarding a pattern having an upper cross-sectional area of 80 ± 10 // m2, Shi 4 Spear 1J used a load-removal load test of "Shimazu Dynamic Super Micro Hardness Tester DUH_W 2 0 1 S" to evaluate compression characteristic. The test conditions are set at a measurement temperature of 2 3 ° C, using a flat indenter with a diameter of 50 / m, and applying a load to the spacer at a certain speed (0.22 gf / sec). When the load reaches 5 gf, the load is maintained. After 5 seconds, the method of removing load is performed at this speed. Based on the load-displacement curve obtained from this test (the schematic is shown in Figure 3), the maximum displacement Η [ma X], the final displacement Η [L ast], and the recovery rate (%) = {Η [1 ast] Pattern height before M test) 丨 x 1 0 0, elastic recovery rate (%) = {(H [max] -H [last]) / H [max]} x100, the displacement under load is 0.25 // The excessive weight N (gf) at m is shown in Table 2. [3-4] Evaluation of Spacer Characteristics (Evaluation of Panel) A liquid crystal cell was prepared according to the following method to evaluate the characteristics of the spacer. An electrode substrate A was prepared, and an IT 0 film was formed on one side of a 2.5 cm square alkali-free glass substrate (Asahi Glass Products "AN-100") and an electrode substrate B. It is a 1 cm square ITO film formed on the central part of one side of the same glass substrate of 2.5 cm square, and an output electrode with a width of 2 mm is connected here. The hardening composition shown in each example was applied to the electrode substrate A by a spin coating method, and heated on a hot plate at 80 ° C for 3 minutes. A bottom area of 1 cm square at the center was used. The circular pattern of 80 // m2 can be designed as an exposure mask with 30 / cm X 3 // cm = 9 0 0 arranged on a grid at regular intervals, with an exposure gap of 1 5 0 // m performs exposure. The irradiation energy is 104 326 \ Patent Specification (Supplement) \ 94-03 \ 93134393 200530279 6 0 m J / c m 2. Next, a potassium hydroxide aqueous solution was used for development, followed by washing with pure water, and firing was performed at 230 ° C in a hot-air circulation furnace for 30 minutes. Adjust the coating conditions so that the height of the spacer after firing can be 4 // m. In this manner, an electrode substrate A having a test pattern in which a spacer was formed in the center was prepared. Next, an alignment film (Nissan Chemical Co., Ltd. product "Severever 7 4 9 2") was applied to the electrode substrates A and B by spin coating, and then applied on a hot plate at 110 ° C for 1 minute. It was dried and then heated at 200 ° C for 1 hour in a hot air circulation furnace to form a coating film with a film thickness of 70 nm. After applying an alignment treatment using a friction machine, an epoxy-based sealant containing silica beads of 4 # m in diameter was coated on the outer periphery of the surface of the electrode substrate B coated with the alignment film under a dispenser, It can be placed opposite to the outer edge of the surface on which the spacer test pattern is formed on the electrode substrate A so that it can be shifted by 3 mm, and it is heated at 180 ° C in a hot air circulation furnace while maintaining pressure. 2 hour. A liquid crystal cell (Melk Corporation product Z L I-4 7 9 2) was injected into the empty cell thus obtained, and the peripheral portion was sealed with a UV curing sealant to prepare a test liquid crystal cell. An AC voltage of 5 V, 60 Η z was applied to the liquid crystal cell thus obtained, and the in-plane unevenness of the electro-optical response of the electrode forming portion was observed with eyes and a microscope. In the case where no in-plane unevenness was found by visual inspection and the microscope, it was evaluated as 0. In the case where in-plane unevenness was not confirmed by visual inspection, but the in-plane unevenness was confirmed by the microscope, it was evaluated as △. The situation was evaluated as X, and the results are shown in Table 2. 3 26 \ Patent Specification (Supplement) \ 94-03 \ 93134393 105 200530279 Comparative Example 4 46.95 CO 46.95 rH CD CO X inch LO oo LO οα 1.26 o- CD CD CO oo 0.56 < Comparative Example 3 1 46.95 CO 46.95 CO r-H 〇 < CO inch CD 1 1 16.9 1.30 0. 75 OO (Nl inch 0.60 1 X Example 14 1 46.95 CO 46. 95 CO r-H ◦ < I 138.5 I 1 LO CJD 1—H 0.80 oo 0. 38 〇 Example 13 46.95 CO 46. 95 CO r—H cd 〇ymmmi i LO LO τ—Η 1 1.58 0. 74 ss times CO LO 1—H ◦ Example 12! 46.95 CO 46. 95 CO CD 〇1 136.6 1 1 1.40 0.59 times LO OO times oo LO ◦ CD ◦ 〇i Example 111 46.95 CO 46.95 t—H CD τ—H < rH CJ5 CO rH οά (ΝΙ 1.38 LO LO CD secondary CO oo g CO CO CO ◦ Example 10 46. 95 CO 46.95 ◦ 'CO 〇 [141.9 | 1 19.6 1 1.39 i_ 0.54 oo 2 CO (Nl CO ◦ 〇 Example 9 46.95 CO 46. 95 CO rH d 〇1 140.1 1 1 13.8 1 1.42 LO CD oo g CO ◦ CO CD 〇I Example 8 | 46.95 CO 46.95 CO r—H CD < 1 139.0 I 12.6 1 1.35 0. 55 1_ CO oo en > LO CO CO CD 〇 (A2) (A8) < (A10) (A12) (A5) (All) (Bl) (Cl)! (C2) (FI)! (ID (Nl) holds the double bond equivalent of the entire stable composition ε your vfi maximum displacement (total deformation) H [max] (/ zm) last displacement H [last] (// m) recovery rate 00 elastic recovery rate (° / o) e hh 5 U) LO ^ ^ Jmii 5 gas 5 ^ panel evaluation compound (B) polymerization initiator (C) ethylenically unsaturated compound (F) surfactant (I) amine compound (N) Additives ± i Jie compression special sex ¥ 趄 filings 荽 (side ♦! ^) 凛 嘀 荽 W attack taste

9〇i ^ ro6einchei e6 \ eb46 \ ff} r) _ ^^ fji * \ 9rsle 200530279 Although the present invention is described in detail using specific aspects, those skilled in the art should know that various modifications can be made without departing from the spirit and scope of the present invention. And change. In addition, this case is based on the Japanese patent application (Japanese Patent Application No. 2003- 3 8 0 6 6 6), which was filed on November 11, 2003, and the entirety thereof is cited and used. < Industrial availability > The curable composition of the present invention is used in printed wiring boards, liquid crystal display elements, plasma display devices, large scale integrated circuits, thin transistors, semiconductor packages, and color filters. The formation of solder masks, cover films, and insulation coatings for various electronic parts in fields such as wafers, organic electric field light emitting mechanisms, etc., is particularly suitable for direct drawing by laser light. Furthermore, the curable composition of the present invention is used in a liquid crystal panel such as a liquid crystal display device, and is useful as a curable composition for a color filter, a black substrate, an overcoat layer, a rib, and a spacer. [Brief description of the drawings] FIG. 1 is a schematic diagram showing a drawing position when a spacer pattern is viewed from above. FIG. 2 is a schematic view showing a profile of a longitudinal section of a spacer pattern. Figure 3 is a schematic diagram showing the load-displacement curve of the spacer load-removal load test. [Description of main component symbols] 1 Spacer pattern 2 Center axis 3 of the spacer pattern 4 Position of the spacer pattern 107 3 26 \ Patent Specification (Supplement) \ 94-03 \ 93134393 200530279 5 From the substrate surface to Height at highest position 6 Height from substrate surface to 90% of height at highest position 7 Diameter AA 'of upper section

326 \ Patent Specification (Supplement) \ 94-03 \ 93134393 108

Claims (1)

200530279 10. Scope of patent application: 1. A hardenable composition characterized by containing the following general formula (I) [In formula (I), R1 represents an alkylene group which may have a substituent, or an arylene group which may have a substituent; R2 represents an ethylenic unsaturated group which may have a substituent having 5 or more carbon atoms Carbonyloxy group; R3 and R4 each independently represent an optional substituent; η is an integer of 0 to 10; 4 benzene rings may further have a compound as shown in []. 2. The hardenable composition according to item 1 of the patent application, wherein R2 is the following general formula (I I) [In the formula (II), R7, R8, and R9 each independently represent a hydrogen atom or a fluorenyl group, Υ1 is an optional divalent group, where * represents -CH2- and R2 of the compound represented by the general formula (I) [Bonding] and a carbonyloxy group containing an ethylenically unsaturated group having 5 or more carbon atoms. 3. If the hardenable composition of the scope of application for item 1 or 2, wherein R3 is a hydrogen atom; the following formula (Ilia) 109 326 \ Patent Specification (Supplement) \ 94-03 \ 93134393 200530279 〇II (in a)-C — R51 [In the formula (Ilia), R51 represents an alkyl group which may have a substituent, an alkenyl group of 7-generation group, a cycloalkyl group which may have a substituent, may have a β-alkenyl group, or may have Substituent represented by aryl]; with stone (II lb) 〇 || H (rab) -C -N -R52 [In the formula (Illb), R52 represents an alkyl group which may have a substituent, ' Alkenyl, which may have a substituent, cycloalkyl which may have a substituent, may have a β-alkenyl group, or an aryl group which may have a substituent]. Among the substituents, 4 is selected. The curable composition is represented by the following general formula (IV) R2 — ch2 — ch — ch2 — (OR1) η— 氺 I 〇 (IV) I R3 [In formula (IV), R1, R2, R3, and n The definition is the same as the general definition, and * in the formula (IV) represents a substituent represented by the compound represented by the general formula (I) and the bond of R4]. 5. If the hardenable composition in the scope of application for item 1 or 2, 326 \ Patent Specification (Supplement) \ 94-03 \ 93134393 110 Rings with bases The following formula _ has bases and bases. Among them, R4 is represented by formula--0-where the compound represented by formula (I) is a compound obtained from a bis (hydroxybenzene) 苐 -type epoxy compound. 6. The hardenable composition according to item 1 or 2 of the scope of patent application, wherein the compound represented by the general formula (I) forms an ethylene-containing compound having a carbon number of 5 or more on a bis (hydroxybenzene) -type epoxy compound. The carbonyloxy group of an unsaturated group is obtained by further reacting one or more compounds selected from the group consisting of a polycarboxylic acid, its anhydride, and an isocyanate group-containing compound. 7. The hardenable composition according to item 1 or 2 of the patent application scope, which further contains the following (B) component: (B) Photopolymerization initiator and / or thermal polymerization initiator. 8. The hardenable composition according to item 1 or 2 of the patent application scope, which further contains the following (C) component: (C) Ethyl-unsaturated compound. 9. The hardenable composition according to item 1 or 2 of the scope of patent application, which further contains the following (J) ingredients: (J) Those who are sensitized with pigments. 1 0. A kind of hardening composition, characterized in that in the load-removal test using a micro hardness tester, a total deformation amount of 1.3 5 / m or more and / or a displacement under load can be formed. .25 // m Hardened product with load N of 0.50gf or less and elastic recovery rate of 50% or more and / or recovery rate of 80% or more 0 111 326 \ Patent Specification (Supplement) \ 94- 03 \ 93134393 200530279 1 1. A hardening composition characterized in that it can form a bottom cross-sectional area of 2 5 // Ι // 2 and an elastic recovery rate of 50% or more and / or a recovery rate of 85% or more Hardened person. 1 2. The hardenable composition according to item 10 or 11 of the scope of application for a patent, which further contains a compound having a p-phenol oxane structure. 1 3. The hardenable composition according to item 1 or 2 of the scope of patent application, wherein, in the load-except load test using a micro hardness tester, a total deformation amount of 1.35 // m or more and / or load can be formed. A hardened product having a load N at a displacement of 0.25 / zm of 0.5 gf or less and an elastic recovery rate of 50% or more and / or a recovery rate of 80% or more. 14. The hardenable composition according to any one of items 1, 2, and 10 of the scope of application for a patent, wherein the bottom surface cross-sectional area is 2 5 // m2 or less and the elastic recovery rate is 50% or more and / Or those with a recovery rate of more than 85%. 15. A hardened product, which is formed by using a hardenable composition according to any one of claims 1, 2, 10 and 11 in the scope of patent application. 16. A color filter, which is characterized by having a hardened product under the scope of patent application No. 15. 17. A liquid crystal display device, characterized in that it has a hardened product according to item 15 of the scope of patent application. 112 326 \ Patent Specification (Supplement) \ 94-03 \ 93134393