TWI297694B - Curable composition, cured product, color filter and liquid crystal display device - Google Patents

Description

1297694 IX. Description of the Invention: TECHNICAL FIELD The present invention relates to a curable composition using light or heat, and more particularly to a printed wiring board, a liquid crystal display element, an electric display device, and a large-scale product. Fields such as bulk circuits, thin transistors, semiconductor packages, color filters, and organic electric field illuminating mechanisms are useful in the formation of solder masks, overlay films, and insulating coatings for various electronic components, especially in the use of Directly depicting the sclerosing composition suitable for use. Furthermore, the present invention relates to a liquid crystal panel used in a liquid crystal display device or the like to serve as a hardening composition for a color filter, a black substrate, an overcoat layer, a rib, and a spacer, and to use the curable composition. A cured product formed of a substance, and a color filter or a liquid crystal display device having the cured product. [Prior Art] In the past, for example, when a printed wiring board is used to apply soldering to an electronic component, it is required to prevent the solder from adhering to the portion that does not need to be soldered, and to prevent the direct exposure of the circuit to the air. A method of providing a solder resist layer on a surface other than the soldered portion of the circuit conductor is applied. A photolithography method using a photosensitive image forming material (hereinafter sometimes referred to as an image forming material (A)) or the like is widely used for the formation of the solder resist layer. The image forming material (A) is a dry film resist material obtained by forming a photosensitive composition layer on a temporary supporting film and covering the surface of the photosensitive composition layer with a coating film. 6 326\Patent Specification (Refill)\94-03\93134393 1297694 Photolithography is performed in the following order. First, the coating film of the image forming material (A) is peeled off and laminated on the substrate to be processed to form a photosensitive image forming material (hereinafter sometimes referred to as an image forming material (B)). The image forming material (B) may be directly applied onto a substrate to be processed by a coating liquid of a photosensitive composition, dried to form a photosensitive composition layer, and covered with a protective layer as necessary. The method of constituting the surface of the layer is prepared. Next, the photosensitive composition layer of the image forming material (B) on the substrate to be processed is subjected to imagewise exposure by a photomask film having a circuit pattern. Then, the temporary supporting film or the protective layer is peeled off, and the difference in solubility between the exposed portion and the non-exposed portion to the developing solution is subjected to development processing to form a photoresist image corresponding to the circuit pattern. Then, under this photoresist image as a photoresist, a soldering process or the like is applied to the substrate to be processed, whereby the circuit pattern drawn on the photomask film is formed on the substrate. On the other hand, there has recently been a laser direct tracing method in which laser light is used as an exposure light source, thereby not using a photomask film, and a digital image is directly formed from a digital information such as a computer, since not only can the production be sought The improvement of sex can also be solved by improving the image and positional accuracy, and accordingly, photolithography technology is also actively studying the use of laser light. Secondly, as a laser light source, various light sources from the ultraviolet to the infrared field are known. However, regarding the laser light source usable for the exposure of the image, the argon ion is based on the viewpoints of output, stability, photosensitivity, and cost. Lasers, krypton lasers, YAG lasers, and semiconductor lasers, etc., which emit light visible to the infrared field, are the mainstays, such as ion lasers with a wavelength of 488 nm and wavelengths of 5 3 2 nm. The FD-YAG laser photolithography method has reached 326\patent specification (supplement)\94-03\93134393 1297694 into practical use. Furthermore, due to the significant advances in laser technology in recent years, semiconductor lasers that are stable in the blue-violet field have also become available. However, the conventional photosensitive composition in the case of using the direct drawing method of laser light does not necessarily mean that the sensitivity is sufficient, especially in the case of a blue-violet semiconductor laser, its output is lower than other visible fields, and therefore, the corresponding sensitivity. The sensitivity and the developability of the composition are not only in the direct tracing method, but also in the photolithography method, and the level of practicality has not yet reached the current reality. Therefore, there is a great need for materials for solder masks that are 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 as a liquid photoresist ink, for example, in view of high precision, high density, environmental considerations, and the like. A photocurable photoresist ink (a reaction product containing an epoxy resin, a reaction product of a /3 -unsaturated monocarboxylic acid adduct and a dicarboxylic acid anhydride, a photopolymerizable monomer, and a photopolymerization initiator) is known. . Further, a photosensitive composition is known which is improved in sensitivity and developability of a photocurable photosensitive composition which is used in a plating resist layer, a photoresist layer or a solder resist layer, and is formed of the composition. An alkali-soluble modified epoxy acrylate having an addition of a polyvalent carboxylic acid or an anhydride thereof to an epoxy resin α, a cold-unsaturated monocarboxylic acid addition product, for the purpose of improving the durability of the ruthenium or the like In the case of an ester resin, the composition is a dry film photoresist material, which is laminated on a substrate, or a coating liquid of the composition is applied onto a substrate to be dried, and a photosensitive composition is thus formed. The image forming method for forming a photoresist for a resist of a material layer by exposure to a high-pressure mercury lamp or a visible laser or an infrared laser to perform development processing (for example, refer to Patent Document 1, Patent Document 2, and Patent No. 8 326) (supplement) \94-03\93134393 1297694 Li document 3) and so on. In addition, a solder resist resin composition is also known, and a reaction product of a bis(hydroxyphenyl) fluorene type epoxy resin and a (fluorenyl) acrylic acid is further used together with a polycarboxylic acid for the purpose of improving solder heat resistance. The modified epoxy acrylate resin obtained by the reaction of the anhydride thereof (for example, refer to Patent Document 4). However, the photohardenable composition described in these documents has room for improvement in sensitivity, and is dense with the substrate to be processed, especially when it is in a high temperature state as a solder resist layer or the like. Inferiority. In the field of liquid crystal display devices and the like, when a color filter for a liquid crystal panel, a black substrate, an overcoat layer, ribs, and spacers are formed, a resin, a photopolymerizable monomer, and photopolymerization are always used. a resin composition composed of a reagent or the like. In the viewpoint of developability, pattern accuracy, adhesion, and the like, various compositions have been proposed, and one of them proposes to disclose a short period of formation and an increase in productivity in the formation step. Next, as the resin contained in the above resin composition, a technique of containing an unsaturated group-containing resin obtained by further reacting a reaction product of an epoxy resin and an unsaturated group-containing carboxylic acid or an anhydride thereof with a polyvalent carboxylic acid or an anhydride thereof is used ( Patent Document 5). On the other hand, the resin composition for a liquid crystal panel is sometimes required to have high hardenability or excellent mechanical properties. For example, in the present specification, the "spacer" is a resin composition which is formed of a resin composition and is a so-called "column spacer" or "photosensitive spacer". The user is separated by a certain interval. Because of the pressure step of the color filter and the substrate under high temperature and high pressure when manufacturing the liquid crystal panel, the spacer is required to be deformed before and after pressurization. 9 326\Patent Specification (Repair ) \94-03\93134393 1297694 Less, while maintaining the physical properties of the spacer function. That is, the resin composition for the spacer which is actually used has a mechanical property, and even if it is deformed by pressure, it can be restored to the original state when the external pressure is removed. In order to satisfy this mechanical property, a resin composition or the like which defines a polyfunctional acrylate content is proposed (Patent Document 6). However, such spacers are required to have pattern accuracy and adhesion in addition to being required to have the above mechanical properties. On the other hand, in the case of improving the accuracy of the pattern precision, if only the above-mentioned unsaturated fat is used, the resin composition having the mechanical properties suitable for the spacer cannot be formed, and the mechanical properties required are In the case of a pressurizing step, the shape is large, that is, the requirement of a soft spacer. However, when only the above-mentioned saturated base resin is used, although a simple soft spacer can be formed, the recovery after the partial pressure is insufficient, and the pressurization is insufficient. The deformation before and after is large, that is, it is not a wealthy thing. [Patent Document 1] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. 5 - 2 0 4 1 0 0 [Patent Document 2] Japanese Patent Laid-Open Publication No. Hei 2 0 0 _ 1 4 7 7 6 7 [Patent Document 3] Japanese Patent Publication No. 4 - 3 5 5 4 5 0 [Patent Document 5] Japanese Patent Laid-Open No. 2 0 0 1 - 1 7 4 6 2 Bulletin 326\Patent Specification (Replenishment)\94-03\93134393 10 Externally shaped esters outside the environment, and dense base trees. The present invention is based on the facts of the prior art described above, and therefore the invention is based on the facts of the prior art. An object of the present invention is to provide a curable composition which is excellent in adhesion to a substrate to be processed and heat resistance, and which is particularly suitable for use in a solder resist layer and is suitable for use. A curable composition that is used in direct scanning using laser light. Further, another object of the present invention is to provide a liquid crystal panel for use in a liquid crystal display device or the like which solves the above problems, and for use in color image forming of a color filter, use of a black substrate, and use of an overcoat layer. For the use of ribs and for the use of sclerosing compositions for use in spacers. As a result of intensive research on the above-mentioned problems, the inventors of the present invention have found that when the curable composition contains a compound containing an unsaturated group (particularly, a carbonyloxy group having an ethylenically unsaturated group having 5 or more carbon atoms), The fact that it is possible to achieve the above object is thus completed. That is, the gist of the present invention is as follows. A curable composition containing a compound represented by the following formula (I)

[In the formula (I), R1 represents an alkylene group which may have a substituent, or may have a substituted aryl group of the substituent 326\patent specification (supplement)\94-03\93134393 11 1297694, and η is 0 to 10 In addition, the four benzene rings may further have a substituent, and R2 represents a carbonyloxy group having an ethylenically unsaturated group having 5 or more carbon atoms which may have a substituent, and R3 and R4 each independently represent an optional substituent. 2. Regarding the load using a micro hardness tester - except for the load test, the load N which can form a total deformation amount of 1.35 / / m or more and / or the load when the displacement is 0.25 / / Π 1 is 0. 5 0 gf or less, A cured composition characterized by a cured product having an elastic recovery rate of 50% or more and/or a recovery rate of 80% or more. 3. A sclerosing composition characterized by a cured product having a bottom cross-sectional area of 2 5 // in 2 or less and an elastic recovery ratio of 50% or more and/or a recovery ratio of 85 % or more. 4. A cured product formed by using the curable composition described in the above 1 or 2. 5. A color filter having the cured product described in the above 4. 6. A liquid crystal display device comprising the cured product according to the above item 4. The present invention can provide a curable composition which has high sensitivity and excellent adhesion to a substrate and heat resistance thereof, and is particularly suitable for use in a solder resist application and is suitable for use in laser light. Directly trace the hardened composition used. Further, according to the present invention, it is possible to provide a liquid crystal panel for use in a liquid crystal display device or the like which has high hardenability and excellent mechanical properties to serve as a color filter, a black substrate, an overcoat layer, a rib, and a spacer. A hardening composition. [Embodiment] Hereinafter, the present invention will be described in detail. Further, the following description is an example of the embodiment of the present invention, and the present invention is not limited to the contents of the description as long as it does not exceed the gist of the present invention, and is not limited to 12 326\Patent Description Supplement)\94-03\93134393 1297694. [1] Curable composition The curable composition of the present invention is a compound containing (A - 1 ) a compound represented by the formula (I) and/or (A - 2 ) having a phenol decane structure. The time combination is called (A) component 丨 as a feature. Further, it is preferable to further contain (B) a photopolymerization initiator and/or a thermal polymerization initiator, and (C) an ethylenically unsaturated conjugate. Further, the curable composition of the present invention further contains (D) epoxy compound, (E) epoxy hardening in the case of the use of the solder resist layer, the use of the overcoat layer, the use of the rib, or the spacer. The agent, the (F) amine compound, and the (Η) inorganic filler may also be used. Further, in the case where the curable composition of the present invention is used for a color filter or a black matrix, it is preferred to further contain (L) a color material and (Μ) a dispersing agent and/or a dispersion aid. Agent. Further, in the case where the curable composition of the present invention is used in the direct laser scanning method, it is preferable to further contain (J) a sensitizing dye. Further, as other constituent elements, (G) a polymerization accelerator, (I) a surfactant, (other) other alkali-soluble resin, and other additives may be mentioned. Alternatively, the curable composition of the present invention is a load-to-load test using a microhardness tester described later so as to form a total deformation amount of 1. 3 5 // m or more and/or a displacement of 0.25// under load. The weight N at a time of m is 0.50 gf or less, and the cured product having an elastic recovery rate of 50% or more and/or a recovery rate of 80% or more is characterized. Alternatively, the curable composition of the present invention can be formed into a bottom surface 13 326 \ patent specification (supplement) \94-03\93134393 1297694 having a cross-sectional area of 2 5 // m 2 or less and an elastic recovery rate of 5 0. A cured product having a % or more and/or a recovery rate of 85% or more is characterized. Hereinafter, each constituent element of the curable composition of the present invention will be described. [1 - 1 ] (A-1) Compound represented by the formula (I) The curable composition of the present invention is characterized by containing the compound (A-1) represented by the formula (I):

[In the formula (I), R1 represents an alkylene group which may have a substituent, or an extended aryl group which may have a substituent, and R2 represents a carbonyloxy group having an ethylenically unsaturated group having 5 or more carbon atoms which may have a substituent. The group, R3 and R4 each independently represent an optional substituent, η is an integer of 0 to 10, and the four benzene rings may further have a substituent]. Here, the alkyl group of R 1 is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methylene group, an ethyl group, a propyl group or a butyl group. Further, The base is preferably a aryl group having 6 to 10 carbon atoms, and more preferably a phenyl group. In particular, in the present invention, a stretched base is preferred. In addition, examples of the substituent of the alkylene group and the aryl group include an alkyl group having 1 to 15 carbon atoms. Further, η is an integer of 0 to 10, preferably 0 to 5, and further preferably 0 to 3. When η is outside the above range, when the curable composition becomes a cured product, the film thickness of the image-forming portion is reduced during development or the heat resistance is lowered. 14 326\Patent specification (supplement)\94-03\93134393 1297694 is a "may have" substituent of R1, and examples thereof include a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, and a carbon atom I. The ethylenic unsaturated group which may have a substituent with respect to R2, the phenyl group, the carboxyl group, the sulfonyl group, the phosphino group, the aryl group, the nitro group, and the number of carbon atoms may be 5 or more, and the upper limit is not particularly However, it is preferably 50, and further preferably 30. In the case where the composition of the present invention is used for the use of a solder resist layer, the carbon atom is further preferably 20, and 15 is particularly suitable. Further, it is further preferred that the carbonyloxy group having an ethylenically unsaturated group of R2 is a group shown below.

R9 C (Π) R8 [In the formula (II), R7, R8 and R9 each independently represent a hydrogen atom or an optional divalent group, wherein * represents a bond of the formula (I), and a bond of R2] Preferably, Y1 represents a divalent group containing a aryl group and a carbonyloxy group which may have a substituent/and may have a substituent. Further preferably, Y1 represents a group which may have a substituent of 1 to 10 An alkyl group or/and a carbon atom group having a substituent and a valent group of a carbonyloxy group. R3 preferably represents a substituent represented by the following formula (Ilia), and 326\patent specification (supplement)\94-03\93134393 15 atom, alkene t 2~1 0 olefin, and the like. The carbonyl oxygen of the f-portion is restricted, and the upper limit of the hardening property is expressed by the general formula (II) sulfhydryl group, Y1 is ί _ _ C Η 2 - and the alkyl group or the number of broken atoms is 1 Substituent of 1297694 shown in aryl (III b ).

[In the formula (Ilia), R51 represents an alkyl group which may have a substituent, an alkenyl group which may have a substituent, a cycloalkyl group which may have a substituent, a cycloalkenyl group which may have a substituent or an aryl group which may have a substituent ]. Here, the alkyl group of R51 is preferably a carbon number of 1 to 20, the alkenyl group of R51 is preferably a carbon number of 2 to 20, and the cycloalkyl group of R51 has a carbon number of 3~. Preferably, the cycloalkenyl group of R51 is preferably a carbon atom having 3 to 20 carbon atoms, and the aryl group of R51 is preferably a carbon number of 6 to 2 0. • a substituent which may be a substituent of R51, and examples thereof include a hydrogen atom, a dentate atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and benzene. Base, carboxyl group, carbonyl group, sulfonyl group, phosphino group, amine group, nitro group and the like. Among them, those having a carboxyl group are preferred. 〇II H (fflb) - C - N - R52 [In the formula (Illb), R52 represents an alkyl group which may have a substituent, an alkenyl group which may have a substituent, a cycloalkyl group which may have a substituent, may have a substituent a cycloalkenyl group or an aryl group which may have a substituent]. Here, the alkyl group of R5 2 is preferably one having a carbon number of 1 to 2 0, the alkenyl group having R 5 2 is preferably a carbon number of 2 to 2 0, and the cycloalkyl group of R 5 2 is having The number of carbon atoms is preferably from 3 to 2, and the cycloalkenyl group of R52 is preferably one having a carbon number of 16 326\patent specification (supplement)\94-03\93134393 1297694 3 to 20, and an aryl group of R52. The substituent "may have a substituent" which is preferably a substituent having a carbon number of from 6 to 20, and examples thereof include a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, and a carbon atom. 2 to 10 alkenyl group, phenyl group, carboxyl group, carbonyl group, sulfonyl group, phosphino group, amine nitro group and the like. The substituent represented by R4 is not particularly limited, and examples thereof include a substituent represented by the following formula (IV). R2 —CH2 — CH—CH2—(OR1) η 一氺

I 〇αν) ι R3 [In the formula (IV), the definitions of R1, R2, R3 and η are the same as those of the formula (I), and * in the formula (IV) represents the compound of the formula (I) -0 - bonded thereto] As a substituent of the benzene ring in the formula (I), for example, an alkyl group of a carbon atom, an alkoxy group having 1 to 15 carbon atoms, and a carbon atom are mentioned. a phenyl group having 2 to 15 fluorenyl groups, an aryl group having 6 to 14 carbon atoms, a carboxyl group, a hydroxyl group, an alkoxycarbonyl group having 2 to 2 carbon atoms, a halogen atom, or the like, wherein the alkylphenyl group having 1 to 5 carbon atoms The halogen atom is further preferred. The compound represented by the formula (I) may have a structure, and is not particularly limited in the production method, and examples thereof include a bis(hydroxyphenyl) fluorene type represented by the following formula (V). The compound obtained by the epoxy compound, more specifically, a compound represented by the formula (V) is used as a raw material to form an ethylenically unsaturated carbonyloxy group having 5 or more carbon atoms, and then selected. Since the 326\ patent specification (supplement)\94-03\93134393 17 the original number of R4 is 16 Λ and the original 1297694 is more than one of the acid and the isocyanate-containing compound. A compound obtained by reacting a compound.

[In the formula (V), further substituents which may be possessed by R1, η, and 4 benzene rings have the same definitions as those defined in the formula (I), and R5 has the same definition as R1 of the formula (I)]. As the bis(hydroxybenzene) burial which forms the bis(hydroxyphenyl)fluorene type epoxy compound represented by the above formula (V), for example, 9,9-bis(4'-hydroxyphenyl)anthracene, 9 , 9-double (4, one-by-3, one benzene) 苐, 9,9 one pair (4,-wei-3, ,5, dioxin) burial, 9,9-double (4'-hydroxy -3' _Oxaphthalene), 9,9-bis(4'-hydroxy-3'-fluorobenzene) fluorene, 9,9-bis(4'-hydroxy-3'-chlorobenzene) fluorene, 9, 9-bis(4' _hydroxy-3',5'-dichlorobenzene) fluorene, 9,9-bis(4'-hydroxy-3'-bromobenzene) fluorene, 9,9-bis (4'-hydroxyl -3',5'-dibromophenyl)anthracene and the like. These bis(hydroxyphenyl)fluorene type epoxy compounds may be used alone or in combination of two or more. In addition, when the ethylenically unsaturated carbonyloxy group formed of the bis(hydroxyphenyl)fluorene type epoxy compound represented by the above formula (V) has a carbon number of 5 or more, the upper limit is not particularly It is limited, but it is preferably 50, and further preferably 20. In the case where the curable composition of the present invention is used for the use of the solder resist layer, the upper limit of the number of carbon atoms is further preferably 20, and particularly preferably 15 . When the number of carbon atoms is less than the above range, when the curable composition becomes a cured product, the flexibility is insufficient, so that the substrate is densely 326\patent specification (supplement)\94-03\93134393 18 1297694 The property is low in deterioration, and if the number of carbon atoms is too large, the heat resistance is lowered. The ethylenically unsaturated carbonyloxy group is preferably a group represented by the following formula (II).

R8 [In the formula (II), R7, R8, and R9 represent a hydrogen atom or a fluorenyl group, and Y1 is an optional valent group, wherein * represents an epoxy group for a bis(hydroxybenzene) fungic epoxy compound. The bond formed by the fluorene group formed by the ring opening] Here, the ethylenically unsaturated carbonyloxy group represented by the above formula (II) is mainly a compound represented by the above formula (V). If the result of the reaction is formed below, it is not limited in its formation method. Specific examples of the method for forming the compound represented by the above formula (V) include reacting an ethylenically unsaturated group-containing carboxylic acid, or firstly, a carboxylic acid having no ethylenically unsaturated group. After the reaction, a subsequent reaction is used to form a method. Examples of the ethylenically unsaturated carboxylic acid include (meth)acrylic acid. [In the present invention, "(meth)acrylic acid" means "acrylic acid" or/and "mercaptoacrylic acid". The reaction product with a lactone or a polylactone, from a saturated or unsaturated dicarboxylic anhydride (such as succinic anhydride, adipic anhydride, maleic anhydride, fumaric anhydride, itaconic anhydride, tetrahydrophthalic anhydride) , thiol tetrahydrophthalic anhydride, hexahydrophthalic anhydride, mercapto hexahydrophthalic anhydride, methyl and fluorenyltetrahydrophthalic anhydride, phthalic anhydride, etc.) and (meth)acrylic acid derivative reaction 19 326\patent Specification (supplement) \94-03\93134393 1297694 A semi-ester of the formula wherein the (fluorenyl) acrylate derivative is a (mercapto) acrylate [such as (hydroxy) hydroxy ethane s, ( Mercapto) hydroxypropyl acrylate, hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, glycerol di(meth) acrylate, trishydroxypropyl propane bis(indenyl) Acrylate, pentaerythritol bis(indenyl) acrylate, pentaerythritol tris(fluorenyl) propyl a compound having one or more hydroxyl groups in one molecule, such as an acid ester, bis(pentaerythritol) penta(indenyl) acrylate, etc., such as a saturated or unsaturated dicarboxylic anhydride as described above, such as phenyl glycidyl ether, (A) Glycidyl acrylate, 3,4-(meth)acrylic epoxycyclohexyl decyl ester, 8,9-(indenyl)acrylic acid epoxy [bicyclo[4 . 3 · 0 ] 壬-3 -yl] ester And a half ester obtained by reacting an unsaturated group-containing glycidyl compound such as 8,9-(fluorenyl)acrylic acid epoxy [bicyclo[4 · 3 · 0 ] 壬-3 -yl] oxonium ester. Among them, succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, etc., and hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, pentaerythritol The half esters obtained by reacting (mercapto) acrylate and bis(pentaerythritol) penta (meth) acrylate are particularly suitable. These compounds may be used alone or in combination of two or more. Further, examples of the carboxylic acid having no ethylenically unsaturated group include a hydroxycarboxylic acid such as lactic acid or dihydroxypropionic acid and an acid anhydride thereof such as succinic acid, maleic acid or tetrahydrofurfuric acid. A saturated or unsaturated dicarboxylic acid such as capric acid or tartaric acid and an anhydride thereof. Then, a compound having a functional group reactive with the generated hydroxyl group or carboxyl group is reacted to form an ethylenically unsaturated group-containing carbonyloxy group having 5 or more carbon atoms. Here, the compound having a functional group reactive with a hydroxyl group or a carboxyl group is preferably a compound having an epoxy group, a carboxyl group or an isocyanate group, and specifically, the above-mentioned ethylenic unsaturated 20 326\ patent may be mentioned. The specification (supplement) \94-03\93134393 1297694 and an ethylenically unsaturated group-containing compound such as a carboxylic acid or an unsaturated group-containing glycidyl compound are not limited by these compounds. Further, the bis(hydroxyphenyl)fluorene type epoxy compound represented by the above formula (v) further forms an ethylenically unsaturated carbonyloxy group having 5 or more carbon atoms after being used as a raw material. The reaction target is a polyvalent carboxylic acid or an anhydride thereof, and examples thereof include a saturated or unsaturated dicarboxylic acid (e.g., succinic acid, maleic acid, itaconic acid, tetrahydrofurfuric acid, mercaptotetrahydrofurfuric acid, Hexahydrophthalic acid, methyl hexahydrophthalic acid, mercapto and mercaptotetrahydrofurfuric acid, citric acid, etc.) and anhydrides thereof, trimellitic acid and its anhydrides, and substituted aliphatic or aromatic tetracarboxylic acids An acid (for example, 1,2,4,5-benzenetetracarboxylic acid, diphenylketonetetracarboxylic acid, biphenyltetracarboxylic acid, diphenylethertetracarboxylic acid, butanetetracarboxylic acid, etc.), an acid anhydride thereof, and the like. Among them, dicarboxylic acid, citric acid and the like dicarboxylic acid and its anhydride, trimellitic acid and its anhydride, 1,2,4,5-benzenetetradecanoic acid, biphenyltetracarboxylic acid, butane tetracarboxylic acid The tetracarboxylic acid such as tetrahydrofurfuric acid or citric acid is preferable because the obtained curable composition is excellent in the dissolving and removing property of the non-image portion during alkali development. Trivalent or lower carboxylic acids and anhydrides thereof, such as anhydrides thereof, trimellitic acid and anhydrides thereof, are particularly suitable. Further, examples of the isocyanate group-containing compound include, for example, butyl isocyanate, chlorophenyl 3-isocyanate, cyclohexyl isocyanate, 3-isocyanate-α, α-di An organic monoisocyanate such as p-benzyl ester, such as p-phenylene diisocyanate, 2,4-tolyl diisocyanate, 2,6-phenylphenyl diisocyanate, 4,4'-diphenylnonane diisocyanate, naphthalene- An aromatic diisocyanate such as 1,5-diisocyanate or behenilinoisocyanate, such as hexamethylene diisocyanate, 2,4,4-trisperylene diisocyanate, dimer fatty acid diisocyanate 21 326\patent Instructions (supplement)\94·03\93134393 1297694 Aliphatic diisocyanates such as isophorone diisocyanate, 4, dimethylene (cyclohexyl isocyanate), ω,ω '-diisocyanate An alicyclic diisocyanate such as dioxane or the like, such as a di-diphenylene diisocyanate α, α' , a 1 -tetradecyl quinone diisocyanate or the like having a cyclic aliphatic diisocyanate such as triisocyanate Acid lysate, hexamethylene monoisocyanate, 1,8-diisocyanate-4-isocyanate Tris-acids such as decane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, cyanate phenylmethane, cis (isocyanate phenyl) thiophosphate, and terpolymers thereof , a water adduct, and a polyol adduct thereof, wherein a dimer or a trimer of an organic diisocyanate is preferred, and a tris(hydroxymethyl)propane adduct of a bis-isocyanate is used. A tripolymer of cyanogen and isophorone diisocyanate is most suitable. The compounds may be used alone or in combination of two or more. Further, the compound of the formula (I) of the present invention may preferably have 30 to 150 mg·KOH/g, more preferably 40 to 100 mg·KOH/g. Further, the weight average molecular weight in terms of polystyrene according to the gel permeation chromatography may be 1,0 0 0 to 1 0 0,0 0 0, and further preferably 1,5 0 0 to 1 0,0 0 0. Further, the specific synthesis of the compound of the formula (I) of the present invention is exemplified by the conventional method described in the above-mentioned Patent Document 4 or the like, specifically, the above-mentioned bis(hydroxyphenyl) hydrazine. The epoxy compound is suspended and dissolved in an organic solvent such as methyl ethyl ketone, ethyl 2-ethoxyacetate or ethyl 2-ethoxyacetate, and is used in a tertiary amine such as triethylamine or decylamine. , tribenzylamine, etc.) or quaternary ammonium salts (such as tetramethylammonium chloride, triethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, triammonium chloride, etc.) 326\Patents (supplement)\94-03\93134393 22 4,-cyclohexyl, a, aromatic, 11-ylxin^ (isoisocyanide, etc.. phthalic acid esters, such acid value, the best method, the square or In the presence of a catalyst such as a butyl bromide or a phosphorus 1297694 compound (such as triphenylphosphine) or a terpenoid (such as triphenylsulfonium), and in hydroquinone, hydroquinone monoterpene ether, mercaptohydroquinone In the coexistence of the thermal polymerization inhibitor, the chemical equivalent of the epoxy group of the epoxy compound is usually 0.8 to 1.5 chemical equivalents (0 to 9 to 1 · 1 chemical equivalent). Preferably, the above-mentioned ethylenically unsaturated carboxylic acid is added, and an addition reaction is carried out at a temperature of usually 60 to 150 ° C (preferably 80 to 120 ° C), followed by the above reaction. The chemical equivalent of the obtained radical is added to the above-mentioned polyvalent carboxylic acid or its anhydride in an amount of usually 0.05 to 1.0 chemical equivalent, and the reaction can be carried out under the above conditions, etc. The method can be produced. [1 - 2 ]( A - 2 ) Resin of phenol phenol methane structure The curable composition of the present invention contains the components contained in [1 _ 1 ] if it satisfies the physical property conditions described in [1 - 15] and/or [1 _ 16 ] described later ( In addition to or in place of the component (A-1), a resin having a structure of (A-2) having a phenol decane may be contained. As a resin having a phenol decane structure of the present invention, if it is a resin thereof The structure having a phenol phenol methane structure in the structure is not particularly limited, and for example, an epoxy resin having a phenol decane structure and (anthracene) acrylic acid and an acid anhydride thereof or the above-mentioned ethylenic unsaturated group are mentioned. a product obtained by reacting a carboxylic acid to give the aforementioned polycarboxylic acid or The resin obtained by the reaction of the anhydride is a preferred resin. The resin having a phenol phenol methane structure, for example, "EPPN-501H", "EPPN-501HY", and "EPPN-" manufactured by Nippon Kayaku Co., Ltd. 502H, etc. Further, as the resin having a phenol decane structure, for example, 23 326\patent specification (supplement)\94-03\93134393 1297694 "TCR1025" manufactured by Nippon Kayaku Co., Ltd., TCR1064", "TCR1286" component (A-1) and/or component (A-2) serve as constituent elements of the hardenable composition of the present invention, and the double bond amount per unit weight can be double bond equivalent (ie, double bond equivalent) ) = (weight of compound (g)) / (number of moles of double bond of compound), that is, the more double bonds per unit weight, the smaller the equivalent value of double bonds. In the case where the curable composition of the present invention is used for a spacer, in order to increase the recovery rate and/or the elastic recovery rate, (A) the total double bond amount is preferably 550 or less, and is preferably less than 4,000. Further preferably, it is most suitable to be 305 or less. Further, the double bond amount of the entire curable composition of the present invention is preferably 200 or less, more preferably 1600 or less, and most preferably 1,500 or less. The double bond equivalent can be calculated according to the above formula according to the amount of the compound having an ethylenic double bond at the time of synthesis, or in a complex system such as a photoresist, by using a conventional method to measure the double bond equivalent of the solution. The solid content concentration of the photoresist is measured by a conventional method, and may be calculated according to (double bond equivalent) = (double bond equivalent of photoresist) X (solid 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 which generates a radical, an acid, or an active species when the curable composition is irradiated with active light to cause polymerization of the compound represented by the above formula (I). And, if necessary, a polymer which uses the ethylenically unsaturated compound of the component (C) mentioned later, for example, an acetophenone, a diphenyl ketone, a hydroxybenzene, a thioxanthone, an anthracene, and a shrinkage. Ketones, hexaarylbiimidazoles, bromo 24 326\patent specification (supplement)\94-03\93134393 1297694 Titanium, halogenated hydrocarbon derivatives, organoborates, rust salts, sulfone compounds, Aminic acid derivatives, sulfonamides, triaryl methanols, and the like. Examples of the acetophenones include 2,2-diethoxyethyl benzene, 2,2-dioxa-2-phenyl benzene, 1-hydroxy-cyclohexanone, and 1-hydroxy-1. (p-dodecylbenzene) ketone, 1-hydroxy-1-methylethyl-(p-isopropylbenzene) ketone, 1-trichloro-(p-butylphenyl) ketone, hydroxy-2-indene benzene Acetone, and α-amine acetonitrile, etc., which will be described later, and examples of the diphenyl ketone include diphenyl ketone, 2- fluorene diphenyl ketone, 3- fluorene diphenyl ketone, and 4- fluorene. Diphenyl ketone, 2-carboxydiphenyl ketone, 2- gas diphenyl ketone, 4-bromodiphenyl ketone, and benzyl ketone, and further, hydroxybenzenes, for example, 2-hydroxyl -4 - n-octyloxy diphenyl ketone, 2-hydroxy-4-benzyl diphenyl ketone, 2- (2-per 5-methyl-toluene) benzene tris-sine, 4-12 tert-butyl benzene-3, 5 - succinyl 4-hydroxybenzoate, etc. Further, sulfur sulphonones, for example, thioxanthone, 2-ethylthioxanthone, 2-isopropylthiouranone, 2 , 4 _ dimercaptothioxanthone, 2,4 _ diethyl thioxanthone, 2,4-diisopropyl thioxanthone, 2-chloro-thioxanthone, etc. For example, a 2-mercaptopurine or the like can be mentioned, and further, a ketal, for example, May include benzyl ketal two Yue. Further, the hexaarylbiimidazoles may, for example, be 2,2 '-bis(o-chlorophenyl)-4,4 ',5,5 '-tetrabenzimidazole, 2,2 '-double (neighbor) Chlorobenzene)-4,4 ' ,5,5 '-tetrakis (o-, p-dichlorobenzene)-biimidazole, 2,2 '-bis(o-, p-dichlorobenzene)-4,4 ',5, 5 '-tetra(o-, p-dichlorobenzene)-biimidazole, 2,2 '-bis(o-chlorobenzene)_ 4,4 ',5,5 ' _tetra(p-fluorophenyl)biimidazole, 2,2 '-Bis(o-chlorobenzene)-4,4 ',5,5 '-tetrakis (o-, p-dibromobenzene)-biimidazole, 2, 2 '-bis(o-bromophenyl)-4,4 ',5 , 5 '-tetra(o-, p-di-benzene) diimidazole, 2,2 '-bis(o-chlorophenyl)-4,4 ',5,5 '-tetra(p-chloronaphthalene)-linked 25 326\ Patent specification (supplement)\94-03\93134393 1297694 嗤, etc. Among them, a hexaphenyl 13 mw compound is preferred, and a benzene ring (bonded to the 2,2 '-position of the ornidazole ring) is further preferred, and the bond is further preferred. It is particularly suitable for those having a benzene ring at the -4,4',5,5' position of the imidazole ring which is not substituted or substituted with a halogen atom or an aerobic group. Further, examples of the titanocene include titanium dichloropentadiene, titanium biphenyl dicyclopentadiene, titanium bis(2,4-difluorophenyl)dicyclopentadiene, and bis ( Titanium di 2,6-difluorobenzene)dicyclopentadiene, titanium bis(2,4,6-trifluorobenzene)dicyclopentadiene, bis(2,3,5,6-tetrafluorobenzene) bicyclo Titanium pentadiene, bis(2,3,4,5,6-pentafluorobenzene) dicyclopentadienyl titanium, bis(2,6-difluorobenzene) bis(indenylcyclopentadiene) titanium, double (2,3,4,5,6-pentafluorobenzene) bis(indenylcyclopentadienyl)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 preferred, and a halogen atom at the ortho position of the biphenyl ring is particularly suitable. Further, examples of the hydrocarbon derivative include halomethylated symmetric tricotylation derivatives, and examples thereof include 2,4,6-parameter (monochloromethyl) symmetrical three tillage, 2, 4, 6 - The ginseng (two gas enthalpies) symmetrical three tillage, 2,4,6-para (trichloromethane) symmetry three. Well, 2-methyl-4,6-bis(trichloropurine) symmetric sakisaki, 2-n-propan-4,6-double (three gas enthalpy) symmetrical tristimulus well, 2-(α,α,/? _ Trichloroethylene)-4,6-bis(trichloropurine) symmetric three wells, 2-phenyl-4,6-bis(trichloromethane) symmetric sakisaki, 2-(p-methoxybenzene)-4, 6 - double (three gas enthalpy) symmetrical three tillage, 2-(3, 4-epoxybenzene)-4,6-bis (three gas) symmetrical tristimulus well, 2 _(p-chlorobenzene)-4,6 - bis(trichloropurine) symmetric three wells, 2-[1-(p-oxime) 2, 4-pentadienyl]-4,6-bis(trichloromethane) symmetrical three-pile, 2-styrene -4,6-bis(trichloropurine) symmetric three-ploughing, 2-(p-methoxystyrene)-4,6-bis(trichloropurine) symmetric three-ploughing, 2-(p-methoxy-inter- Hydroxybenzene B 26 326 \ patent specification (supplement) \94-03\93134393 1297694 olefin) _ 4,6-bis (trichloropurine) symmetrical three. Well, 2-(p-isopropoxystyrene)-4,6-bis(trichloropurine) symmetric three-plow, 2-(p-nonylbenzene)-4,6-bis(trichloromethane) symmetric three-plowing , 2 -(p-methoxynaphthalene)- 4,6-bis(trichloropurine) symmetrical three tillage, 2-(p-ethoxynaphthalene)-4,6-bis(trichloromethane) symmetrical three tillage, 2 _(p-ethoxycarbonylnaphthalene)-4,6-bis(trichloropurine) symmetry three. Well, 2-phenylsulfur-4,6-double (three gas) symmetrical tri-zero well, 2-benzylsulfide-4,6-bis(trichloromethane) symmetric three-ploughing, 2,4,6-parameter (two Bromomethyl) Symmetrical three-dimensional well, 2,4,6-parade (tribromo) symmetry three. Halogenated methylated symmetrical tristimulus wells derived from wells, 2 -mercapto-4,6-bis(tribromomethyl)-symmetric tri-farming, 2-methoxy-3,6-bis(tribromomethyl)-symmetric tri-farming The species, in which the bis (trihalo) symmetrical three-well well is preferred. Further, examples of the organoborate include an organoboron ammonium complex, an organic boron lanthanum complex, an organoboron compound, an organoboron oxime complex, an organic boron lanthanum complex, and an organic compound. Boron transition metal coordination complex, etc., its organic boron anion, for example, n-butyl-triphenylboron anion, n-butyl-parade (2,4,6-triphenylene) boron anion, n-butyl-para (pair a borophthalide anion, a n-butyl-parade (p-fluorophenyl) boron anion, a n-butyl-parade (m-fluorophenyl) boron anion, a n-butyl-parade (3-fluoro-4-indolyl) boron anion, n-D-Shen (2,6-difluorobenzene) boron anion, n-butyl-parade (2,4,6-trifluorobenzene) boron anion, n-butyl-para (2,3, 4, 5, 6 -5 Fluorobenzene) boron anion, n-butyl-parade (p-chlorophenyl) boron anion, n-butyl-parade (2,6-difluoro-3-indole benzene) anthracene anion, etc. Preferably, the cation is preferably a rust compound such as an ammonium cation, a scaly cation, a phosphonium cation or a phosphonium cation, and particularly an organic ammonium cation such as a tetraalkylammonium. Further, the wrong salt may, for example, be an ammonium salt such as tetraammonium bromide or brominated tetra 27 326\patent specification (supplement)\94-03\93134393 1297694 ethylammonium or the like, such as hexafluoroarsenic. Acid diphenyl hydrazine, diphenyl sulfonium tetrafluoroborate, diphenyl benzene p-toluene sulfonate, diphenyl hydrazine sulfonate, dicyclohexyl hexafluoroarsenate, dicyclohexyltetrafluoroborate, p-toluene sulfonic acid Bismuth salts such as dicyclohexyl, camphorsulfonic acid dicyclohexanone, such as triphenylsulfonium hexafluoroarsenate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium p-nonylbenzenesulfonate, triphenylsulfonium camphorsulfonate, Strontium salt such as tricyclohexyl hexafluoroarsenate, tricyclohexyltetrafluoroborate, tricyclohexyl p-toluenesulfonate, and tricyclohexyl shovel of camphorsulfonic acid. Further, examples of the sulfone compound include, for example, bis(phenylsulfonyl)decane, bis(p-hydroxyphenylsulfonyl)decane, bis(p-methoxyphenylsulfonyl)methane, and di(α). -naphthalene sulfonate) methane, bis(yS-naphthalene sulfonate) decane, bis(cyclohexylsulfonyl)methane, bis(t-butylsulfonate) decane, benzenesulfonate (cyclohexylsulfonyl)methane, etc. Bis(sulfonate) decane compounds such as phenylcarbonyl (phenylsulfonyl) decane, naphthalene carbonyl (phenylsulfonium) methane, phenylcarbonyl (naphthalenesulfonyl) decane, cyclohexylcarbonyl (phenylsulfonyl) decane, a carbonyl (sulfonate) decane compound such as a third butanone (phenylsulfonyl) decane, a benzene carbonyl (cyclohexylsulfonyl) methane, a benzene carbonyl (t-butane carbonyl) methane, or the like, such as bis(phenylsulfonate) Nitrogen methane, bis(p-hydroxyphenylsulfonium)diazomethane, bis(p-methoxyphenylsulfonium)diazomethane, bis(α-naphthalenesulfonium)diazononane, bis(d-naphthosulfonate) Bis (sulfonate) diazonium such as diazomethane, bis(cyclohexylsulfonium)diazomethane, bis(t-butylsulfonate)diazomethane, benzenesulfonate (cyclohexylsulfonium) diazonium Methane compounds, such as phenylcarbonyl (phenylsulfonate) Methane, naphthalene carbonyl (benzene sulfonium) diazonium hydride, benzene carbonyl (naphthalene sulfonate) diazomethane, cyclohexyl carbonyl (benzene sulfonate) diazomethane, third butane carbonyl (benzene sulfonate) diazomethane, a carbonyl (sulfonate) diazonium compound such as benzenecarbonyl (cyclohexylsulfonium) diazonium alkane or phenylcarbonyl (t-butanecarbonyl)diazomethane. Further, examples of the amide derivative include, for example, phenylhydrazine phthalate 28 326\patent specification (supplement)\94-03\93] 34393 1297694 cyclohexyl ester, 2-n-benzylcarbamate ring Hexyl ester, 3,5-dioxabenzylamine decanoic acid cyclohexyl ester, 3-nitroanilinic acid cyclohexyl ester, etc. Further, the sulfonamide may, for example, be N-cyclohex-4-toluene. Examples of the triarylmethanol include trityl alcohol and tris(4-chlorobenzene) decyl alcohol. Further, the thermal polymerization initiator constituting the component (B) of the curable composition of the present invention is an active compound, and when the curable composition is heated, an active species such as a radical is generated, resulting in the above formula (I). The polymerization of the compound and the polymerization of the ethylenically unsaturated compound of the component (C) described later are used, and examples of the thermal polymerization initiator include organic peroxides and azo-based tetramines. Examples of the organic peroxides include, for example, decyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, acetoxyacetone peroxide, cyclohexanone peroxide, and decyl cyclohexanone peroxide. , 3,3, 5 - peroxy ketones such as trioxane cyclohexanone, such as isobutyl peroxide, 3,3,5-trioxane cyclohexane, benzoquinone peroxide, peroxidation O-benzonitrile, peroxy-p-benzoquinone, 2,4-dichlorobenzoquinone, peroxy-p-benzoquinone, etc., such as hydroperoxide Tributyl, cumene hydroperoxide, dicumyl hydroperoxide, hydroperoxide p-cap, 2,5-dihydroperoxide 2,5-dimercaptohexane, 1,1,3, a hydroperoxide such as tetramethylbutyl hydroperoxide or 2,4, 4-trimethylpentyl hydroperoxide, such as dibutyl butyl peroxide or third butyl peroxide Propylene, dicumyl peroxide, 1,3 (or 1,4)-bis(t-butylperoxyisopropyl)benzene, 2,5-dioxin-2, 5-di(third-butoxy Peroxidation of hexane, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, etc. 29 326\patent Instructions (supplements)\94-03\93134393 1297694 Dialkyls such as 1,1-bis(t-butylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)-3, 3 , peroxy ketals such as 5-trimethylcyclohexane, 2,2-bis(t-butylperoxy)butane, 4,4-bis(t-butylperoxy)pentanoic acid, etc. Third butyl oxyacetate, tert-butyl peroxyoctanoate, tert-butyl peroxytrimethylacetate, tert-butyl peroxy neodecanoate, peroxy-3, 5,5-tridecylhexanoic acid Third butyl ester, third butyl laurate, ditributyl peroxytridecyl adipate, tert-butyl peroxybenzoate, α-cumyl peroxy neodecanoate, Alkyl peroxyesters such as oxyphenoxyacetic acid 2,4,4-trimethylpentyl ester, such as di-2-ethylhexyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate , diisopropyl peroxydicarbonate, di-n-isopropyl isopropyl dicarbonate, di- 3 - butyl oxyperoxy peroxydicarbonate, bis (3-methyl-3- oxiranidine peroxydicarbonate) Ester), tert-butyl peroxyisopropoxide, tert-butyl peroxypropylene carbonate, bis(4-tricyclohexyl)peroxydicarbonate, sulfonium sulfonate Di-oxo-cyclohexyl acrylate, etc. acetyl peroxy carbonates and the like. Further, examples of the azo compound include 1, Γ-azobiscyclohexane-1-nitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), and 2, 2'-azobis(4-oxo-2,4-didecyl valeronitrile), 2, 2'-azobis(mercaptoisobutyric acid), α,α'-azobis(isobutyl) Nitrile), 4,4'-azobis(4-cyanovaleric acid), and the like. In the photopolymerization initiator or/and the thermal polymerization initiator of the above component (Β), the α-aminoacetamidine derivative of the phthalic acid benzene which is preferably a photopolymerization initiator of the present invention, in particular, The formula (VII) is particularly suitable. 30 326\Patent specification (supplement)\94-03\93134393 1297694

[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 represents an alkyl group which may have a substituent or an alkyl group which may have a substituent The propyl group, 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, R37 and R38 are linked to each other, or R37 or R38 and R35 or R36 are linked to each other. The ring structure may be formed, and the benzene ring may have a substituent. Here, the alkyl group of R35, R36, R37 and R38 in the above formula (VII) is preferably a carbon number of 1 to 15 (especially 1 to 10). Further, examples of the alkyl group, the allyl group, and the substituent on the phenyl group include an alkyl group, an alkoxy group, an alkyl group, a hydroxyalkoxy group, an ethoxylated alkoxy group, and an alkoxylated alkoxy group. An alkylcarbonylalkyl group, an alkylthio group, a haloalkyl group, a phenyl group, a halogen atom or the like. Further, examples of the ring structure in which R3 7 and R38 are bonded to each other or R37 or R38 and R35 or R36 are bonded to each other include pyrrolidine, hexahydropyridine, hexahydropyridyl, morpholine, and σ咢. Sit σ, ϋ σ σ and so on. Further, examples of the substituent on the benzene ring include an alkyl group, a hydroxyl group, an alkoxy group, a dipropyloxy group, a phenoxy group, a benzoinyl group, a sulphur group, a thiol group, a sulfur group, and a sulfur group. Allylthio, cycloalkylthio, benzylthio, phenylthio, alkanesulfonyl, fluorenyl, sulfonyl, acryl, alanine, anthracene, hexahydro . Ratio σ base, hexahydro 吼 σ well base, σ σ lin base, ii atom, etc. Further, 31 326 \ patent specification (supplement) \94-03\93134393 1297694 benzene ring can also form a condensed ring, as this Examples of the condensed ring include anthrone, dibenzocycloheptanone, dihydrogen 丨 σ, 啥$ °林, 吟σ sitting, phenazine, acridine η ο ne , benzodiazepine Mau, benzofuran, xanthene, ketone, benzophenone, benzo D-serazole, phenoxypyrazine, and the like. The α-aminoacetamidine derivative represented by the above formula (VII) is classified according to the basic skeleton of the compound, and when exemplified by the number of carbon atoms, the following compounds are mentioned, and particularly preferred R35 and R36 each independently represent a methyl group, an ethyl group or a benzyl group, and each of R37 and R38 represents a fluorenyl group, or a morpholino group which is bonded to each other in a cyclic structure, and has no substituent or a sulfonium sulfide in the benzene ring. The compound of the group, the diammonium group or the morpholinyl group is particularly preferably a compound having a morpholinyl group only in the para position. Regarding the propane-1 -one having 3 carbon atoms classified as a basic skeleton, 1-phenyl-2-didecylamine-2-mercapto-3-(4-indolyl)propan-1-one is exemplified. , 1-phenyl-2-dimethylamine-2-mercapto-3-(4-indolyl)propan-1-one, 1-phenyl-2-diguanamine-2-mercapto-3 (3,4-dioxabenzene)propan-1-one, 1-phenyl-2-diguanamine-2-mercapto-3-(4-indolesulfonyl)propan-1-one, 1- Phenyl-2-diguanamine-2-mercapto-3-(4-fluorophenyl)propanone-1-one, 1-phenyl-2-didecylamine-2_indolyl-3-(2-gas Benzene)propan-1-one, 1-phenyl-2-dimethylamine-2-methyl-3-(4-gasbenzene)propan-1-e, 1-phenyl-2-dimethylamine- 2-mercapto-3-(4-bromophenyl)propane-1-ketone, 1-phenyl-2-diguanamine-2-methyl-3-(4-benzylidenephenyl)propan-1-one , 1-phenyl-2-dimethylamine-2-benzyl-propan-1-one, 1,3-diphenyl-2-diozide-2-phenyl-propan-1-one, 1-( 4-oxobenzene)-2-didecylamine-2-benzyl-propan-1-one, 1-(4-fluorophenyl)-2-didecylamine-2-benzyl-3-phenyl-propane_1 -keto, 1-(4-benzoquinone)-2-diguanamine-2-benzyl-propane-1- 32 326\patent specification (supplement)\94-03\93134393 1297694 ketone, 1 - ( 4 - Bismuth thiophenyl)-2-morpholine-2-methylpropane-1 ketone, 1 -( 4 -indole thiophenyl)-2-didecylamine-2-mercapto-3 -(4-indolyl)propane 1-ketone, 1-(4-indenethiobenzene)_2-diguanamine-2-mercapto-3-(4-methoxyphenyl)propan-1-one, 1-(4-indolethiobenzene)- 2-dimethylamine-2-methyl-3-(3,4-dimethoxyphenyl)propane-1-one, 1-(4-indolethiobenzene)-2-diguanamine-2-methyl- 3-(4_Gaphene)propan-1-one, 1-(4-indenethiobenzene)-2-didecylamine-2-mercapto-3-(2-acetophenone)propan-1-one , 1 -(4-oxothiobenzene)-2-diamine 0.2-mercapto-3-(4-chlorophenyl)propan-1-one, 1-(4-indenethiobenzene)-2-di Methylamine 2 - methyl-3-(4_ desert benzene) propane- 1 -ketone, 1 -(4-indolylthio)-2-dimethylamine-2-indenyl-3-(4-benzene Toluene)propane-1-ketone, 1,3-bis(4-monothiobenzene)-2-diamine- 2-methylpropan-1-one, 1-(4-butylthiobenzene)-2 -dimethylamine-2-member-3-phenyl-propanone-1-8, 1-(4-cyclohexylthiophenyl)-2-didecylamine-2-phenyl-3-phenyl-propyl 1-ketone, 1-(4-sulfophenyl)-2-dimethylamine-2-benzyl-propan-1-one, 1-(4-diamidinobenzene)-2-dimethylamine-2 - benzyl-propan-1-one, 1-(4- Dimethylamine benzene)-2-didecylamine-2-phenyl-3-phenyl-propan-1-one, 1-(4-indolyl)-2-dimethylamine-2-(2-chloro Ethylene)-propanone- 1-ketone, 1-(4-morphinyl)-2-dimethylamine-2-succinyl-propan-1-one, 1-(4-oxo-phenylene)-2- Dimethylamine-2 -cathe-3-phenyl-propanone-1 -3, 1-(N-methylindoline-5-yl)-2-diamine- 2-benzyl-propane- 1-ketone, 1-(N-butylphenazine-2-yl-2-morpholine-2-benzyl-propane-1-one, and the like. With respect to the butane-1-one having a carbon number of 4 classified as a basic skeleton, 1-phenyl-2-diguanamine-2-benzyl-butane-1-one, 1-(4- Toluene-2-diguanamine-2-benzyl-butan-1-one, 1-(4-oxophenyl)-2-dimethylamine-2-benzyl-butan-1-one, 1- (3,5-dioxa-4-methoxybenzene)-2-dimethylamine-2-pyrrol-butan-1-se, 1-(3,4-dioxabenzene)-2-di Methylamine-2-pyryl-33 326\patent specification (supplement)\94-03\9313β93 1297694 Butane-1-one, 1-(3,4,5-trimethoxybenzene)-2-dimethylamine -2-gangyl-butane-1-anthracene, 1-(4-phenylene)-2-dimethylamine-2-pyrrolidine-butane _1-_, 1 - [4 -(2- Ethoxy)benzene]-2-diamine 0.2-pyranyl-butyrol-1-one, 1-(4-silopropoxybenzene)-2-diguanamine-2-pyrrolidine-butane-1 -嗣, 1-(4-ethoxyxaoxybenzene)-2-diguanamine-2-pyrylbutan-1-one, 1-[4-(1,1,2-tridecyl) Propyl dimethyl decyloxy) phenyl]-2-dimethylamine-2-benzyl-butan-1-one, 1-(4-fluorophenyl)-2-didecylamine-2-cobalt-butyl 1-ketone, 1-(4-chlorophenyl)-2-diguanamine-2-benzyl-butan-1-one, 1-(2,4-dichlorophenyl)-2-didecylamine-2 -benzyl-butan-1-one, 1-(3,4 - Chlorobenzene)-2 -dioxin.Amine-2_gangyl-butan-1-one, 1-(3,5-dichlorophenyl)-2-didecylamine-2 -pyringyl-butanze-1- 8 with, 1_(4-indolyl)-2-didecylamine-2-mercapto-butyr-1-ate, 1-(4-weiphenyl)-2-diguanamine-2-benzyl- Butan-1-one, 1-(4-indenethiobenzene)-2-diguanamine-2-benzyl-butan-1-one, 1-(4-methylthiobenzene)-2-diamine -2-benzyl-butan-1-one, 1-(4-methylthiobenzene)-2-bis(2-oxoethoxy)amine-2-benzyl-butan-1-one, 1-[ 4-(2-methoxyethylthio)benzene]_2-diguanamine-2-benzyl-butan-1-one, 1-[4-(2-hydroxyethylthio)benzene]-2-dimethylamine -2-benzyl-butan-1-one, 1-(4-octylthio)-2-diguanamine-2-benzyl-butan-1-one, 1-(4-oxasulfonylbenzene )- 2-dimethylamine-2-benzyl-butan-1-one, 1-[4-(4-indolylsulfonyl)benzene]-2-dimethylamine-2-benzyl-butane-1 -ketone, 1-(4-phenylsulfonylbenzene)-2-dimethylamine-2-benzyl-butan-1-one, 1-(4-sulfinylbenzene)-2-dimethylamine- 2-benzyl-butan-1-one, 1-(4-aminophenyl)-2-diguanamine-2-benzyl-butane-butanone, 1-(4-guanamine benzene)-2- Diamine-2-benzyl-butan-1-one, 1-(4-dimethylaminobenzene)-2-dimethylamine-2- -butane-1-one, 1-(4-dimethylaminophenyl)-2-diguanamine-2 -(4-anthracene)butane-1_嗣, 1-(4-diguanamine benzene )- 2 - 34 326\Patent specification (supplement)\94-03\93134393 1297694 Diamine-2_(4-isopropylf)butane-one, 1-(4-diguanamine)-2 - Diamine-2-(4-H-diyl) butyl--1-S, 1-(4-diaminophen)-2-didecylamine-2-(1-chlorohexene) Alkan-1-one, 1-(4-diguanamine benzene)-2-diguanamine-2-(2-pinaze-10-yl)butan-1-one, 1-(4-dioxylamine -2- phenylene)- 2 -dimethylamine-2-pyrrolyl-butyrrol-1 - hydrazine, 1-(4-dioxamethylene-3-ethylbenzene)-2-dimethylamine-2-benzyl -butan-1-one, 1-(4-diethylamine)-2-diguanamine-2-benzyl-butan-1-one, 1-(4-isopropylamine benzene)-2 Dimethylamine-2-butyl-butanol-1-one, 1-[4-(2-oxoethylamine)benzene]-2-diamine-nodal-butyr-1-one, 1-[ 4-(3-oxopropylamine) phenyl]-2-dimethylamine-2 -pyringyl-butyring-1-one, 1-(4-ethylaminophen)-2-diamine-2 - Dingxuan-1- 3 with, 1 - [4-(N-ethylidenemethylamine) benzene]-2-didecylamine-2-pyryl-butane _1 - S, 1-[4 - (N-acetyl-3-methoxypropylamine) ]-2-diamine 0.2-benzyl-butan-1-one, 1-(4-hexahydrogen ratio benzene) 2- 2 -dimethylamine-2 - aryl-butane-1 Ketone, 1 _ (4 -?). Benzene)- 2 -dioxamethylene-2 -pyringyl-butylene- 1 -ketone, 1 -( 4 -?.lin phenyl)-2-dimethylamine-2 -(3,4-dimethylf) Butane-:!-ketone, 1-(4-morpholinium)-2-diguanamine-2-(4-oxo)butan-1-one, 1-(4-norloline)-2 -diamine--2-(4-isopropylbenzyl)butan-1-one, 1-(4-morpholinium)-2-diamine- 2-(4-butyl)butane-1_S , 1-(4-morphin phenyl)-2-diguanamine-2 -(4-isobutyl)butan-1-one, 1-(4-morpholinyl)-2-didecylamine-2 -(4 - Twelve bases) Dingxiao-1~8 with, 1_(4-morphin benzene)-2_dimethylamine-(4_ via A) butane-1-one, 1-(4 -morpholinium)-2 -diguanamine-2-(4-ethylbenzylidene)butane-1 -one, 1 -( 4 -morphine phenylbenzene)-2-dimethylamine-2 -(4 - oxime) butyl ketone-1 ketone, 1-(4-morpholine)-2-diamine-2-(4-butoxybenzyl)butan-1-one, 1-(4-morpholine Benzene)-2-diamine-2 - [4-(2-hydroxyethoxy)benzyl]butane-b 35 326\patent specification (supplement)\94·03\93134393 1297694 ketone, 1 - ( 4 - Morpholine benzene)-2-diamine _ 2 - [ 4 - ( 2 - oxoethoxy) benzyl] butan-1-one, bu (4 - morpholin benzene) - 2 Amine-2 - [4 -(2 -(2-oxime oxyethoxy) ethoxy)] butyl sulphate, 1-(4- π phenyl phenyl)-2-didecylamine-2-[4 - ( 2-(2-oxoethoxy)ethoxycarbonyl)benzyl]butan-1-one, 1-(4-morpholinyl)-2-diamine-2 - [4-(2-(2- (2-oxoethoxyethoxy)ethoxycarbonyl)ethyl)benzyl]butan-1-one, 1-(4-?.lin phenyl)-2-diguanamine-2-[4-(2-Mo )] butyl ketone-1-ketone, 1_(4_morphin benzene)-2-dimethylamine-2 - [4- (2-diethylamine) benzyl] butane-1-one, 1-( 4_morpholinium)-2-dimethylamine-2-benzyl-butane-: 1-keto-trifluoroacetate, 1-(4-morpholinium)-2-dimethylamine-2 Benzyl-butane-1 -g with -h diphenyl phthalate, 1-(4-norlophenylene)-2 -didecylamine-2-pyrrolidine-butan-1-one-p-toluene Acid ester, 1-(4-morpholinium)-2-dimethylamine-2-benzyl-butane-1-one-camphorsulfonate, 1-(4-morpholinium)-2-diethyl Amine-2-benzyl-butan-1-one, 1-(4-morpholinium)-2-bis(2-oxoethoxy)amine-2-benzyl-butane-1-one, 1- (4-morpholinobenzene)-2-butylammonium-2-benzyl-butane-1-one, 1-(4-morpholinium)-2-butylguanamine-2-(4-iso Propane f) butane-1-one, 1 - (4-morpholinium)-2-dibutylamine-2-yl-butan-1-one, 1-(4-morpholinium)-2-mercapto-2-phenyl-butan- 1- Ming, 1-(3-chloro-4-?σ-lin phenyl)-2-diguanamine-2-benzyl-butan-1-one, 1-[4-(2,6-dioxin? Porphyrin-4-yl) phenyl]-2 - dimethylamine-2-pyristyl-butan-1-one, 1-(1,4-dimethyl-1,2,3,4-tetrahydroquinoline Phenyl-6-yl)-2-diamine-2-n-butan-1-one, 1-(indolyl-butyrazole-3-yl)-2-didecylamine-2-benzyl- Butan-1-one, 1-(1,3-benzodiazepine-5-yl)-2-diamine 0.2-butanbutan-1-one, 1-(2,3-di Hydrogen benzofuran-5-yl)- 2-diamine 0.2-benzyl-butan-1-one, hydrazine-(a) ton-2-yl)-2-didecylamine-2-benzyl -butane-1-one, 1-(2,3-dihydro-2,3-dioxin 36 326\patent specification (supplement)\94-03\93134393 1297694 benzothiazole-5-yl)- 2-diamine 0.2-benzyl-butan-1-one, 2-(2-amino-2-pyrene) fluorenone, 2-(2-dioxam-2-pyrene) II Benzoindene, 3,6~bis(2-dioxam-2-pyrene)-9-butyl-indole. Wait and wait. Regarding pentane-1-one having a carbon number of 5 classified as a basic skeleton, 1-(4-morpholinyl)-2-didecylamine-2-allyl-pentan-1-one, 1 Σσ林苯)- 2 -Diamine- 2 -pyringyl-pentan- 1 -one, 1-(4-oxophthalamide-2 -(2-isopropylbenzyl)pentan-1- Ketone, Bu (4-morpholinyl)-2-butylamine-2-(4-isobutylbenzyl)pentan-1-one, 1-(4-morpholinium)-2-butyl-2-- 4-butoxy nodal) pentan-1-one, etc. Further, as the penten-1-one, 1-phenyl-2-dimethylamine-yl-4-penten-1-one, 1 -Phenyl-2-dimethylamine-2-ethyl-4-pentanone, 1-phenyl-2-dimethylamine-2-mer-4-pentan-1-ene, 1-phenyl- 2 - Methyl-4-penta-1-one, 1-phenyl-2-morphine- 2-pyrimidine-4-pentyl ketone, 1,2-diphenyl-2-morphine- 4- Butan-1-one, 1-(4-toluene)-2--2-methyl-4-penten-1-one, 1-(4-didodecyl)-2-morpholine-2- -4-penta-1-one, 1-(4-methoxyphenyl)-2-diamine, 2-ethyl-4--1-indole, 1-(4-indolylbenzene)-2 -dibutylammonium-4-pentazol-1 -1-(4-indolylbenzene)-2-hexahydropyridine-2-ethyl-4-penten-1-one, 1-oxime phenyl)- 2-°号°坐定定-2 -曱基-4 -penta-1-inden, 1-(4-phenyl)-2-morpholin-2-ethyl-4-penten-1-one, 1-(4-oxobenzoquinone)-2--2 -Phenyl- 4-pentan-1-one, 1-(3,4-dioxabenzene)-2-?~林_2--4-penten-1-one, Bu [4-(2 -methoxyethoxy)benzene]-2-morpholin-2-indolyl-1-one, 1-[4-(2-(2-oxoethoxy)benzene]-2-morphin-2-ethyl- En-1-one, 1-[4-(2-hydroxyethoxy)benzene]-2-morpholin-2-ethyl-4-pentanyldifluorene, heptyl-(4-)-2-yl Methylamine 2-曱3 _ 1 ~ 淋 3 3 ~ 1 _ 淋 乙基 ethyl pentenone, one (4-曱 吗 吗 乙基 ethyl s - 4 ~ 4- pentene -1- 326 \ patent specification ( Supplement)\94-03\93134393 37 1297694 S, 1-(4-isopropoxybenzene)-2-dimethylamine-2-mer-4-indol-1-one, butoxybenzene-2 -morpholin-2-ethyl_4-penten-1-one, 1-[4-(2-(beta)oxy)benzene]-2-morpholin-2-methyl-4-penten-1-one , 1_[4-(2-enoxy)benzene]_2-Merlin-2-ethyl_4-penta-1-ene, 1-(4-trimute j benzene)- 2-Merlin-2 - mercapto-4-pentan-1-one, 1-(4_|L phenyl)-2-didecyl _4-penta-1-se, 1-(4-phenylene)-2- 2- Methylamine 2-ethylpenten-1-one, 1-(4-fluorophenyl)-2-didecylamine-2-benzyl-4-pentene-1 1 -(4 - gas benzene)-2 -? lin-2-methyl_4-pentazol-1-S, 1-(4-fluoro]-. Lin-2-ethyl-4-pentane--1-S, 1-(4-gasbenzene )-2 -??-2 - 4 -Methyl-4-penten-1-one, 1-(4-fluorophenyl)-2-morpholin-2-ethyl-4-pentene-1- Ketone, 1-(4-fluorophenyl)-2_morpholin-2-benzyl-4-pentanone, 1-(3,4-dichlorobenzene)-2-dimethylamine-2-ethyl-4 Pentene-1 Bu (3,5-Dichloro-4-indolyl) 2- morpholin-2-methyl-4-pentene-1 1 -(4-indiylbenzene)-2 -? -2 -mercapto-4-pentan-1-one, 1-(4-in% morpholine-2-ethyl-4- pentene-1 -one, 1-(4-bromophenyl)_ 2 _ Morpholine-2 - | -4-pentofyl-1-one, 1-(4-methylthiobenzene)-2-dimethylamine-2-mercapto-4-1-one, 1-(4-anthracene sulfur Benzene)-2-didecylamine-2-ethyl-4-pentane-1 - 1-(4-indenethiobenzene)-2-dimethylamine-2-phenyl-4-pentene-1-S , 1 -(4 phenyl)-2-dimethylamine-2-benzyl-4-penten-1-one, 1-(4-indenethiobenzene)-2pyridine-2-etht-4-pentene- 1-ketone, 1-(4-oxathiobenzene)-2-morpholine-2-4-pentene-1-one, 1-(4-indolylthio)-2-morpholin-2-ethyl- 4-pentanone, 1-(4-methylthiobenzene)-2-morpholin-2-ethyl-4-methyl-4-pentene-] 1-(4-oxathiobenzene)-2-morpholine -2-phenyl-4-penten-1-one , 1 -(4 phenyl)-2 -morpholine-2 -4 pentene-butanone, 1 - (4-ethylthiobenzene)-2 -? 1-(4-b oxyethyl i oxyethane 7 Alkoxy dimethylamino-4-ketone, L)-2-ethyl-5-nonene Μ-ketone, -ketone, L)-2- tributyl-pentene-酉, - A Sulfur-hexahydro-methyl olefin-bu-ketone, -methionine-2 - 326\patent specification (supplement)\94-03\93134393 38 1297694 ethyl-4-penten-1-one, 1 -(4-isopropylthiobenzene)-2-morpholine-2-mercapto-4-penten-1-one, 1-(4-isopropenylthio)_2_morpholin-2-ethyl-4 -pentene-buxoton, 1-[4-(2-hydroxyethylthio)benzene]-2-morpholin-2-indolyl-4-penten-1-one, 1-[4-(2- Ethylthio)benzene]-2 -?-Linethyl-4-pentenone, 1-[4-(2-hydroxyethylthio)benzene]-2-morpholine-2-propyl-4-pentene-1 Ketone, 1-[4-(2-hydroxyethylthio)benzene]-2_morpholin-2-tribut-4-penten-1-one, Bu [4_(2-methoxycarbonylethylthio)benzene ]-2-morpholin-2-indolyl-4-penten-1-one, 1-(4_valetite yellow benzene)-2-dimethylamine-2-ethyl-4-pentyl-1 -嗣, 1-(4-butylsulfenylbenzene)-2-didecylamine-2-ethyl-4-penten-1-one, 1-[4-(4-toluenesulfonyl)benzene-2 -morpholin-2-ethyl-4-penten-1-one , 1-[4-(4-toxite yellow) benzene]_2~~?-lin-2-ethyl-4-indolyl-4-pentan-1-one,-chlorophenylthiobenzene-2- Diammonium-2-benzyl-4-penten-1-one, 1-(4-dimethylaminophenyl)-2-diguanamine-2-methyl-4-penten-1-one, 1- (4-dimethylaminobenzene)-2-didecylamine-2-ethyl-4-penten-1-one, 1-(4-diguanamine benzene)-2-diguanamine-2-benzyl- 4-pentene-: 1-ketone, 1-(4-dimethylaminophenyl)-2-indolani-2-ethyl-4-penten-1-one, 1-(4-dimethylaminobenzene) -2 -(pyrrolidin-1-yl)-2-nonyl-4-penten-1-one, 1-(4-diguanamine benzene)-2-morpholin-2-indolyl-4-pentyl En-1-one, 1-(4-dimethylaminophenyl)-2-morpholin-2-ethyl-4-mercapto-4-penten-1-one, 1-(4-diguanamine benzene )-2 - ̄°林- 2 -节-4-戊稀-1-®^, 1-(4-diguanamine benzene)-2 -(2,6-dimethylmorphine_4-yl)- 2-ethyl-4-penta-1-one, 1-(4-diethylamine benzene)-2-dimethylamine-2-benzyl-4-penten-1-one, 1-[4-di (2-oxoethoxy)amine benzene]- 2-morpholine-2-indenyl-4-penten-1-one, 1-(4-butylamine benzene)_2-dibutylamine-2-indenyl- 4-penten-1-one, 1-(4-butylaminophenyl)-2-morpholin-2-indolyl-4-penten-1-one, 1- (4- Butylamine -2-) 39 326\patent specification (supplement)\94-03\93134393 1297694 σ林-2 -mercapto-4-pentan-1-one, 1_(4-di-propyl propyl benzene) -2 -? Lin-2-mercapto-4-pentene-1 ketone, 1-[4-(pyrrolidin-1-yl)benzene]-2-morpholin-2-indole-4-pentyl En-1-one, 1-(4-hexahydropyridinium)-2-hexahydropyridin-2-mercapto-4-penten-1-one, 1-[4-(hexahydropyrazole-1- Phenyl]-2-didecylamine-2-ethyl-4-penten-1-one, :!-[4-(4-methylhexahydropyrylene-1-yl)benzene]-2- Morpholine-2-mercapto-4-penten-1-one, 1-[4-(indolyl-nonylhexahydropyrrol-1-yl)benzene]-2-(N-methylhexahydropyrazole -1-yl)-2-mercapto-4-penten-1-one, 1-(4-morpholinium)-2-dimethylamine-2-methyl-4-penten-1-one, 1-(4-morpholinium)-2-diguanamine-2-ethyl-4-penten-1-one, 1-(4-morpholinium)-2-didecylamine-2-isopropyl -4 -penten-1-one, 1-(4-morpholinyl)-2-didecylamine-2-benzyl-4-penten-1-one, 1-(4-morpholinene)-2 -diethylamine 2-ethyl-4-penten-1-one, 1-(4-morpholinium)-2-bis(2-methoxyethyl)amine-2-ethyl-4-pentene - 1-ketone, 1-(4-morpholinium)-2-butylmethylamine-2-methyl-4-penten-1-one, 1 -(4-morpholinium)_2-allylamide-2-ethyl-4-penten-1-one, 1-(4-norphinphenyl)-2-diisopropylamine-2-ethyl- 4-penta-1-one, 1-(4-mercaptophenyl)-2-benzylmethylamine-2-ethyl-4-penten-1-one, 1-(4-morpholinoline)-2 -(hexahydropyridinium-;!-yl)-2 -ethyl-4-pentane-butanone, 1 - (4-morpholinoline)-2 -?~林-2 -mercapto-4 -penta-1-one, 1-(4-morphin benzene)-2-oxalate-2-ethyl-4-pentan-1-one, 1-(4-morphin benzene)-2 - 2-ethyl-4-penta-1-one-h-diphenylphosphinic acid S, 1-(4-morphin phenyl)-2-morphin-2-ethyl-4-methyl- 4-penten-1-one, 1-(4-norloline)_2•?σ林-2-section-4-penta-1-one, 1-[4- (2,6-dimethyl) Physo-4-yl)benzene]-2-morpholin-2-indenyl-4-penten-1-one, 1-[4-(2,6-dioxamorpho-4-yl)benzene]- 2-(2,6-dioxinolin-4-yl)_2_ethyl-4-pentan-1 - S, 1_(Ν - 丁°引°五-基)- 2- 40 326 \Patent specification (supplement)\94-03\93134393 1297694 Morpholine-2-ethyl-4-penten-1-one, 1-(1,4-dibutyl-1,2,3,4-tetra Hydroquine. No. ° Lin - 6-base) - 2 -? -2-ethyl-4-pentan-1-one, 1-(N-butyl-carbazol-3-yl)-2_morpholin-2-ethyl_4-penten-1-one , 1-(5,10-dibutyl-5,10-dihydrophenazine-6-yl)-2-dimethylamine-2-mercapto-4-penten-1-one, 1-(1, 3-Benzene sigma quaternary _5-yl)- 2- phenan-2-methyl-4-pentan-1-one, benzofurazol-3-yl)_2-morpholin-2-yl 4-penten-1-one, 1-(benzofuran-6-yl)-2-morpholine-2-ethyl-4-pentene-1-one, 1-(2,3-di Hydrobenzo benzofuran-5-yl)-2-morphin-2-mercapto-4-pentan-1-one, 1-(anthracene-methylphene thiophene-2-yl)-2 Diammonium-2-female-4-pentan-1-one, 3,6-bis(2-morpholin-2-methyl-4-pentenyl) carbazole, 2-(2-diindole Amine-2-allyl-4-pentenyl)acridone, 2-(2-morpholine-2-ylindolyl-4-pentenyl)-pyrrolidone, 2-(4-morpholinebenzamide醯)-2-Ethyl-hydrazine-mercapto-1,2,3,6-tetrahydropyridine and the like. With respect to the hexane-1-ketone having 6 carbon atoms classified as a basic skeleton, 1-(4-indenethiobenzene)-2-morphin-2-dipropyl-hexan-1-lan, 1 -(4-morphin benzene)-2-dimethylamine-2-pyrene-1-one, 1-(4-morphin phenyl)-2-dimethylamine-2-benzyl-4, 5, 5-tridecylhexan-1-one, 1-(4-morpholinium)-2-butylmethylamine_2_(4_butyl)hexan-1-S, 1-(4-oxonium benzene) -2_Dioctylamine-2-(4-benzylbenzyl)hexane-1-one. Further, as the hexene-1-one, 1-( 4 曱 thiophenyl)-2- morpholin-2 -ethyl-4-methyl-4-hexen-1-one, 1-( 4-dimethylamine benzene)-2-dimethylamine-2, 4,5-tris--4-hexen-1-one, 1-(4-dimethylaminobenzene)-2-morpholin-2- Ethyl-4_hexose-1_S, 1 -(4_morphine benzene)-2-?4 wood- 2-ethyl_4-hexa-1-one, and the like. Regarding heptane-1 -one having 7 carbon atoms classified as a basic skeleton, 41 326\patent specification (supplement)\94-03\93134393 1297694 1 -(4-dimethylamine benzene)-2 - Dimethylamine-2-[4-(2-oxo)benzyl]heptanone-one, 1-(4-morpholine)-2-diguanamine-2-benzyl-heptane-1-one Wait. Further, it is a heptane-1,6-diene, which may be exemplified by 4-phenylene-4-diamine-heptane-1,6-diene, 4-(4-oxobenzoquinone)-4- Diamine-heptane-1,6-diene, 4-(4-methoxybenzothymidine)-4-yolin-glycine-1,6-dipyridyl, 4-(3,4-dioxabenzene曱醯)-4-diamine-heptane-1,6-diene, 4-(4-phenoxybenzidine)-4-diguanamine-heptane-1,6-diene, 4-(4 -fluorobenzoquinone)-4 -diamine-heptane-1,6-diene, 4-(4-fluorophenylhydrazine)-4-morpholine-heptan-1,6-diene, 4-( 4-nonylthiobenzoquinone)-4-diamine-heptane-1,6-diene, 4-(4-methylthiobenzoquinone)-4-morpholine-heptane-1,6-diene, 4-(4-dimethylaminophenylhydrazine)-4_dimethylamine-heptane-1,6-diene, 4-(4-dimethylaminophenylhydrazine)-4-morpholine-heptane-1, 6-diene, 4-(4-morpholinanilide)-4-diamine-heptane-1,6-diene, 4-(4-morpholinylbenzhydrazide)-4 -? Geng - 1,6 - dilute, etc. Examples of the octane-1-one having 8 carbon atoms classified as a basic skeleton include 1-(4-morpholinium)-2-dimethylamine-2-benzyl-octane-1-one. 1-(4-norlophenyl)-2-diamine-2 -(4-^2)-octane-1-one. In the case where the curable composition of the present invention contains the compound represented by the above formula (I) and the photopolymerization initiator or/and the thermal polymerization initiator of the component (B), the content ratio of each component is relative The component (A) is preferably 20 to 95% by weight, more preferably 30 to 90% by weight, based on the total amount of the curable composition. Further, the component (B) is preferably from 0.1 to 40% by weight, more preferably from 0.2 to 20% by weight. When the component (A) is too little or too little, the cum component (B) is too small, which tends to cause insufficient hardenability of the curable composition, and if the component (B) is too much, it is 42.

326\Patent specification (supplement)\94-03\93134393 1297694 The substrate is prone to fouling. [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 curable composition of the present invention. The ethylenically unsaturated compound has at least one radically polymerizable ethylenically unsaturated bond in the molecule so as to photopolymerize the component (B) when the curable composition is irradiated with active light or when heated. The initiator or the polymerization initiator of the thermal polymerization initiator initiates addition polymerization, even 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, (meth)acrylic acid, crotonic acid, isocrotonic acid, and maleic acid An unsaturated carboxylic acid such as diacid, itaconic acid or citraconic acid or an alkyl ester thereof, (meth)acrylonitrile, (fluorenyl) acrylamide, styrene or the like may be used, but depending on the polymerizability and crosslinking And a compound having two or more ethylenically unsaturated bonds in the molecule, and further having a (fluorenyl)-propyl group, in view of the difference between the solubility of the developer in the exposed portion and the non-exposed portion, and the like. An acrylate compound having a dilute oxy group derived from an unsaturated bond is particularly suitable. Examples of the compound having two or more ethylenically unsaturated bonds in the molecule include an ester formed of an unsaturated carboxylic acid and a polyhydroxy compound (hereinafter, also referred to as an ester-based group). ) acrylates, phosphates containing (meth) propylene decyloxy groups, amino phthalate acrylates formed from hydroxy(fluorenyl) acrylate compounds and polyisocyanate compounds Epoxy (mercapto) acrylate formed from 43 326\patent specification (supplement)\94-03\93134393 1297694 and (meth)acrylic acid or hydroxy(fluorenyl) acrylate compound and polyepoxide Wait. Examples of the ester formed of the unsaturated carboxylic acid and the polyhydroxy compound include, for example, the aforementioned unsaturated carboxylic acid and an aliphatic polyhydroxy compound [polyol (e.g., ethylene glycol, polyethylene glycol ( Addition number 2~1 4 ), propylene glycol, polypropylene glycol (addition number 2 to 14), trimethylene glycol, tetrapropylene glycol, hexamethylene glycol, tris(hydroxyindole) propane, glycerol, pentaerythritol, The reactant of dipentaerythritol and its ethylene oxide adduct, propylene oxide adduct, diethanolamine, triethanolamine, etc., specifically, for example, ethylene glycol di(meth)acrylate, di(b) Glycol) bis(indenyl) acrylate, propylene glycol bis(indenyl) acrylate, tris(hydroxyindole) propane bis(indenyl) acrylate, tris(hydroxyindole) propane tris(indenyl)propionate, Addition of tris(sulfonate) acetoacetate, glycerol di(meth) acrylate, glycerol tri(meth) acrylate, glycerol epoxide Propane addition tris(indenyl) acrylate, pentaerythritol di(decyl) acrylate, pentaerythritol three Methyl) acrylate, pentaerythritol tetrakis(yl) acrylate, bis(pentaerythritol) penta (meth) acrylate, bis(pentaerythritol) hexa(indenyl) acrylate, and the like, and the same crotonate, isocrotonic acid Ester, maleate, itaconate, citraconate, and the like. Further, examples of the ester formed from the unsaturated carboxylic acid and the polyhydroxy compound include unsaturated carboxylic acids and aromatic polyhydroxy compounds (such as hydroquinone, resorcin, gallic phenol, bisphenol). Specific examples of the reactant formed by F, bisphenol A or the like or an ethylene oxide adduct thereof include bisphenol A bis(indenyl) acrylate and bisphenol A bis [oxygen extension (methyl)). Acrylate], bisphenol A bis [glycidyl ether (meth) acrylate], etc., as further as the above unsaturated 44 326 \ patent specification (supplement) \94-03\93134393 1297694 carboxylic acid and miscellaneous A reactant formed of a cyclic polyhydroxy compound (for example, bis(2-hydroxyethyl) isocyanide J, for example, bis(indenyl) acrylate of bis(2-hydroxyethyl) isoester, and tris (A) The acrylate or the like is formed of an unsaturated carboxylic acid and a polyvalent carboxylic acid and a polyhydroxy compound, and specific examples thereof include a (meth)acrylic acid, a condensate of (meth)acrylic acid, decanoic acid, and ethylene. a condensate of maleic acid and two, formed by (meth)acrylic acid, glutamic acid, and quaternary formation a condensate formed of (fluorenyl)acrylic acid, adipic acid or butyl glycerin, etc. Further, as the present (fluorenyl) propylene oxy oxyphosphate, it contains (mercapto) propylene. The phosphonium phosphate compound is limited, but it is preferably represented by the following general formulae (VIII a ) and ( VI (VIII c ). - an acid ester or the like), and isocyanuric acid, as a reactant, Alcohol formed by ethylene glycol pentaerythritol, and the main genera is not particularly [Ib), or, 10 H2C=C-C-0-(CH2)15-0

0 II , N -p—(〇H)3-Q (Via) H2C=C—C—0—(CH2CH2O)] One (10))3_q (Mb)

QH pl0s 0 II ... P——(OH) 3-q }^2〇==〇一C—0—(CH2CH2O) p—~[〇C (=0) CH2CH2CH2CH2CH23 p* 一〇[Villa (Villa), In (Vlllb) and (VIIIc), R1Q represents a hydrogen atom p and p' is an integer of 1 to 25, and q is 1, 2, or 3]. Here, p and p ' are preferably 1 to 10, and specific examples of the compound having 1 to 4 are, for example, phosphoric acid (methyl) propylene 326\patent specification (supplement)\94· 03\93134393 45 (Vic) or sulfhydryl, suitable as oxime B 1297694 ester, bis((meth) propylene oxirane phosphate), phosphoric acid (fluorenyl) propylene oxyethylene glycol ester, etc. These compounds may be used singly or as a mixture. Further, examples of the amino phthalate acrylates include hydroxy(indenyl) acrylate compounds [such as hydroxymethyl (meth) acrylate and hydroxyethyl (meth) acrylate. Ester, tetrahydroxydecylethane tri(meth)acrylate, etc. with polyisocyanate compounds [eg aliphatic polyisocyanates (eg hexamethylene diisocyanate, 1,8-diisocyanate-4 -isocyanate methyloctane, etc.) ), alicyclic polyisocyanate (such as cyclohexane diisocyanate, dimethylcyclohexane diisocyanate, 4,4 '-arylene bis(cyclohexyl isocyanate), isophorone diisocyanate, bicycloheptane triisocyanate, etc.) ), the reaction of aromatic polyisocyanates (such as 4,4 '-diphenylnonane diisocyanate, thiophosphoric acid (isocyanate phenyl ester), etc.), heterocyclic polyisocyanate (such as isocyanuric acid ester, etc.) product. In particular, the urethane (mercapto) acrylate has four or more amino phthalate linkages [-NH - C0-0-] and four or more (fluorenyl) propylene oximes in one molecule. The compound of an oxy group is preferably a compound (i-1) which is a compound having 4 or more hydroxyl groups in one molecule (e.g., pentaerythritol, polyglycerol, etc.) and a diisocyanate compound (e.g., hexamethylene diisocyanate). , a reaction product obtained by reacting, a trimethylhexamethylene diisocyanate, an isophorone diisocyanate, a phenylene diisocyanate, or the like; or a compound (i - 2 ) having a compound having two or more hydroxyl groups in one molecule (such as ethylene-2) (Alcohol, etc.) and a compound having three or more isocyanate groups in one molecule (such as Asahi Kasei Industrial Co., Ltd. "DURANATE24A-100", "DURANATE22 A - 75PX",

Diuret type such as "DURANATE21S_75E" or "DURANATE18H-70B", such as Asahi Kasei Industrial Co., Ltd. "DURANATEP-301-75E", "DURANATE 46 326\patent specification (supplement)\94-03\93134393 1297694 E-402 Addition of -90T", "DURANATE E-405-80T", etc., or a compound (i _ 3 ) obtained by polymerization or copolymerization of (meth)acrylic acid isocyanic acid There are four or more (6 is preferable) isocyanate-based compounds in one molecule, and for example, the product "DURANATEME20-100" (i) of Asahi Kasei Co., Ltd. and one or more hydroxyl groups and one molecule in one molecule are used. The above (more preferably 3 or more) compounds of the (fluorenyl) decyloxy group (ii) (eg pentaerythritol bis(indenyl) acrylate (pentaerythritol) tri(indenyl) acrylate, di(pentaerythritol) tetra (曱) 3 The enoate, bis(pentaerythritol) penta (meth) acrylate, etc. are reacted to obtain the compound. Here, the molecular weight of the above compound (i) is 500 to 200,000 and 1,000 to 150. 00 is particularly suitable. Furthermore, such as the aforementioned amino esters ( The acrylates have a molecular weight of from 6,000 to 1,500, and more preferably have 6 or more urethane linkages, and 8 are particularly suitable. The propylene oxy group is preferably 6 or more, and the above is particularly suitable. Further, regarding such urethane oxime acrylates, for example, the aforementioned compound (i) and the aforementioned compound ( Ii) in the organic solution of phenylene or ethyl acetate, etc., according to the ratio of the former isocyanate group to the latter molar ratio of 1 / 1 0 ~ 1 0 / 1, according to the needs of the use of tin dilaurate The medium can be produced by a reaction at a temperature of 10 to 150 ° C for 5 minutes to 3 hours. In the present invention, the urethane (mercapto) acrylate is particularly suitable as shown by the following formula (I X ). 326\Patent specification (supplement)\94-03\93134393 47 ^) Into the ethyl ester, it is better to have 1 propylene, 2, and C, and the tannic acid is good. The upper one and 8 use a ^ (such as hydroxy-n-butyl, 1297694

Ra-|~fRb—〇)yC—N—(—Rc—)yN—C—Ο—Rd (ix) [In the formula (IX), Ra represents a reversible structure having an alkoxy group or an extended aryloxy group and There are 4 to 20 groups which can be bonded to Rb to obtain an oxy group, and Rb and Rc each independently represent an alkylene group having 1 to 10 carbon atoms, and R d represents 1 to 10 (fluorenyl) propylene oxide. The organic residue of the group, Ra, Rb, Rc, and Rd each may have a substituent, x is an integer of 4 to 20, y is an integer of 0 to 15, and z is an integer of 1 to 15. Here, the structure of the overhanging oxy group of R a in the formula (IX) may, for example, be a structure derived from glycerin, glycerin or pentaerythritol, and may be, for example, a reversible structure of an extended aryloxy group. For example, the structure is derived from gallnut, 1,3,5-benzenetriol and the like. Further, it is preferred that the number of carbon atoms of the alkylene group of Rb and Rc is independently from 1 to 5, and the number of the (fluorenyl) propyleneoxy group of Rd is preferably from 1 to 7. Further, X is preferably 4 to 15, y is preferably 1 to 10, and z is preferably 1 to 10. Further, R a is particularly preferably represented by the following formula [also, wherein k is an integer of 2 to 10], and Rb and Rc each independently become a diindolyl group, a monomethylidene group, or a trimethylene group. The base is particularly suitable, and further, R d is particularly suitable as shown in the following formula. 48 326\Patent specification (supplement)\94-03\93134393 1297694

Ra ; -f-0—CH2一(|H-CH2—0士0

Q Q I Q 1 1 0 1 0 0 1 CH〇 | ch2 CH

Rd ; —0-CH2-C—CH2-0-CH2-〒一CH2一〇—Q —0-CH2-(j;-CH2 一〇一Q CH2 ch2 ?h2 ? ? ? QQ 〇0 —o-ch2 -ch~{ch2-oq)2 (however, q is -c-ch=ch2) Further, as the epoxy (fluorenyl) acrylate, specifically, (meth) Acrylic acid or a hydroxy(indenyl) acrylate compound as described above and a polyepoxy compound [such as an aliphatic polyepoxide (such as (poly)ethylene glycol polyglycidyl ether, (poly) propylene glycol polyglycidyl ether, (poly ) tetramethylene glycol polyglycidyl _, (poly) pentaethylene glycol polyglycidol, (poly) neopentyl glycol polyglycidyl ether, (poly) hexamethylene glycol polyglycidyl ether, ( Poly) glycerin, polyglycidol, poly(glycidyl polyglycidyl ether, (poly)glucitol polyglycidyl ether, etc.); aromatic polyepoxide (such as phenolic phenolic resin) Compound, brominated phenolic phenolic resin polyepoxide, (o-, m-, p-) phenol phenolic resin polyepoxide, bisphenol A polyepoxide, bisphenol F polyepoxidation Compounds, etc.; heterocyclic polyepoxides (such as sorbitol polyglycidyl ether, triglycidyl isocyanurate, triglycidyl (2-hydroxyethyl) isocyanurate, etc.) Etc.] formed reaction product and the like. 49 326\Patent specification (supplement)\94-03\93134393 1297694 Further, as the other ethylenically unsaturated compound, in addition to the above, for example, (meth) acrylamide (for example, Bis(fluorenyl) acrylamide, etc.), allyl esters (such as diallyl phthalate), vinyl-containing compounds (such as divinyl citrate), and thioether-containing compounds (including The ether bond of the ether-bonded ethylenically unsaturated compound is vulcanized by phosphorus pentasulfide or the like to become a thioether bond to increase the crosslinking speed, and, for example, the Japanese Patent No. 3 1 4 4 4 7 7 and the special Kaiping 9 - 1 0 0 1 1 (1), such as a polyfunctional (fluorenyl) acetoacetate compound and a particle size of 5 to 30 nm of a cerium oxide sol [for example, isopropanol dispersed organic two Cerium oxide sol (product "IPA-ST" from 曰Product Chemical Co., Ltd.), thioglycol ketone dispersed organic cerium oxide sol (product of "MEK-ST" by Nissan Chemical Co., Ltd.), fluorenyl isobutyl ketone dispersed organic cerium oxide Sol (Nissan Chemical Co., Ltd. product "MIBK-ST"), etc., using an isocyanate-containing group Silane coupling agents and other compounds sulfonamide group of the bonded, to one ethylenically unsaturated compound Silane coupling agent by making react silicon dioxide sol and binding, thereby increasing the strength of a cured heat resistance or the like of the compounds. 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), an ester-(mercapto) acrylate, a (fluorenyl) propylene oxy oxyphosphate, or an amino phthalate ( Mercapto acrylates are preferred, with ester-(fluorenyl) acrylates being particularly suitable, and ester-(mercapto) acrylates containing, for example, polyethylene glycol, polypropylene glycol, or bisphenol A. Further, a polyoxyalkylene group such as a polyethylene oxide adduct and a (meth) acrylate containing two or more (fluorenyl) acryloxy groups are further preferred. In the curable composition of the present invention, the ethylenic unsaturated 50 326 \patent specification (supplement) \94-03\93134393 1297694 and the compound content of the component (C) are relative to the total amount of the hardenable composition. It is preferably from 1 to 70% by weight, more preferably from 5 to 60% by weight. When the content of the component (C) is less than the above range, the curability of the curable composition tends to be insufficient, and if it is larger than 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 to improve the heat resistance or chemical resistance of the cured product when the curable composition of the present invention is used for a solder resist layer application, an overcoat layer application, a rib application, or a spacer application. Or other purposes may be included. The epoxy compound may be a polyglycidyl ether compound obtained by a reaction of a polyhydroxy compound constituting a repeating unit of a so-called epoxy resin with epichlorohydrin, or a polyglycidol obtained by reacting a polyvalent carboxylic acid compound with a surface alcohol. The ester compound and the polyglycidylamine compound obtained by the reaction of the polyamine compound and epichlorohydrin are compounds from a low molecular weight substance to a high molecular weight substance. Examples of the polyglycidyl ether compound include a diglycidyl ether type epoxy compound of polyethylene glycol, a diglycidyl ether type epoxy compound of bis(4-hydroxybenzene), and bis(3,5- Di-glycidyl ether type epoxy compound of dioxon-4-hydroxybenzene), bis-glycidyl ether type epoxy compound of double age F, diglycidyl epoxy compound of double expectant A, and bismuth A a diglycidyl ether type epoxy compound, an ethylene epoxidation addition double aging A diglycidyl ether type epoxy compound, a phenol type phenol resin type epoxy compound, a phenol phenol type phenol resin type epoxy compound, etc. The polyglycidyl ether compound may be a compound obtained by reacting a residual hydroxyl group with an acid anhydride or a divalent acid compound, etc. 51 326\patent specification (supplement)\94-03\93134393 1297694. In addition, examples of the polyglycidyl ester compound include a diglycidyl ester type epoxy compound of hexahydrophthalic acid, a diglycidyl ester type epoxy compound of citric acid, and the like. Examples of the glycerolamine compound include a diglycidylamine compound of bis(4-aminophenyl)nonane, a triglycidylamine compound of isocyanuric acid, and the like. In the curable composition of the present invention, the epoxy compound content of the component (D) is preferably from 1 to 70% by weight, more preferably from 5 to 50% by weight, based on the total amount of the curable composition. Preferably. When the content of the component (D) is less than the above range, the curability of the curable composition tends to be insufficient, and if it is larger than the above range, problems such as poor whitening of the image-forming portion during development tend to occur. [1 - 5 ] (E) Epoxy curing agent The curable composition of the present invention may further contain (E) an epoxy curing agent. 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 hardening property of the curable composition or the like. Examples of the epoxy curing agent of the component (E) include polycarboxylic acid anhydrides (e.g., succinic anhydride, maleic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, and 3-mercapto-4). Hydrophthalic anhydride, 4-mercaptotetrahydrophthalic anhydride, 3-ethyltetrahydrophthalic anhydride, 4-ethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3-mercaptohexahydrophthalic anhydride, 4-mercapto-6 Hydrophthalic anhydride, 3-ethylhexahydrophthalic anhydride, 4-ethylhexahydrophthalic anhydride, trimellitic anhydride, biphenyltetracarboxylic anhydride, etc.; organic phosphines (such as tributylphosphine, triphenylphosphine, ginseng -2 - cyanoethyl phosphine, etc.); imidazoles (such as imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-mercaptoimidazole, 2-phenylimidazole, 4-phenylimidazole, 1 _( 2 -Cyanoethyl)-2-phenylimidazole, 1 - ( 2 - 52 326 \ patent specification (supplement) \94-03\93134393 1297694 cyanoethyl)-2-ethyl-4-methylimidazole And other amine compounds (such as cyanogen, benzylamine, 4-methylbenzyl-N,N-dimethylamine, 4-oxime-benzyl-N,N-diamine, 4-diguanamine-benzyl-N , N-dimethylamine, etc.; amine symmetrical three wells (such as 2,4,6-triamine symmetrical three wells, 2 - Women-4,6_diamine symmetric three-sigma well, 2-ethylene-4,6-diamine symmetric three-pile • isocyanuric acid adduct, 2,4-diamine-6-methylpropene oxime Symmetrical three-ploughing, 2,4-diamine-6-methylpropene oxyethylene symmetrical three-tillage, isocyanuric acid addition, etc.); quaternary ammonium salts (such as gasified benzalkonium chloride, chlorinated butyl chloride) Ammonium, etc.; strontium salts (such as tri-n-butyl bromide - 2,5-dihydroxybenzene scale, hexadecyltrimethane chloride, etc.), etc., wherein the group has a -ΝΗ- group, and an amine Compounds and amines are preferably symmetrical, especially in the case of cyanogenic and 2,4,6-triamine symmetrical triterpenes. In the curable composition of the present invention, the content of the epoxy hardener of the above component (Ε) is based on the stability of the curable composition with respect to the stability of the composition, and is 1 wt% based on the total amount of the curable composition. % is preferably lower, and further preferably 0.7% by weight or less. [1 - 6 ] (F) Amine compound The curable composition of the present invention may further contain (F) an amine compound. The amine compound of the component (F) is preferably contained in the composition for improving the heat resistance or chemical resistance of the cured product or the like. The amine compound of the component (F) may, for example, be an amine compound having at least two alkoxymethyl groups modified by condensation of a hydroxy group serving as a functional group with an alcohol having 1 to 8 carbon atoms, for example, a melamine resin obtained by polycondensation of melamine and furfural, a benzoguanamine resin obtained by polycondensation of Benzoguanamine with formic acid, an acetylene urea resin obtained by polycondensation of acetylene urea with formaldehyde, 53 326 \Patent specification (supplement) \94-03\93134393 1297694 Urea resin obtained by polycondensation of urea and formaldehyde, obtained by copolymer condensation of two or more kinds selected from melamine, benzoguanamine, acetylene urea, urea, etc. with formaldehyde The resin and the modified resin obtained by reforming the hydroxy thiol group of the resin by alcohol condensation. In the present invention, the melamine resin and the modified resin thereof are preferred, and the modified resin having a hydroxyhydrazine group modification ratio of 70% or more is further preferably more preferably 80% or more. The resin is particularly suitable. Specific examples of the amine compound of the component (F) include a "THYMEL" (registered trademark) 3 Ο Ο '301 > 3 0 3 > 3 of the melamine resin and its modified resin. 5 0 ' 7 3 6 > 7 3 8 , 3 7 0 ' 771 > 3 2 5 ' 327, 703 > 701 > 266 > 267' 285, 232' 235' 238, 1141, 272, 254, 202, 1156, 1158, and "NIKALACK" (registered trademark) E-2151, MW-100LM, MX-750LM of Sanwa Chemical Co., Ltd. Further, benzoguanamine resin and its modified resin can be cited as "Τ Η Υ Μ EL" (registered trademark) 1 1 2 3, 1 1 2 5, 1 1 2 8 . Further, acetylene urea resin and its modified resin include "THYMEL" (registered trademark) 1170, 1171, 1174, 1172. And "NIKALACK" (registered trademark) MX-277. Further, urea resin and its modified resin include "UFR" (registered trademark) 65, 300, and "NIKALACK" (registered trademark) of Mitsui Thytec Co., Ltd. MX-290 and so on. In the curable composition of the present invention, the content of the amine compound of the component (F) is preferably 20% by weight or less, more preferably 10% by weight or less, based on the total amount of the curable composition. . [1 - 7 ] (G) Polymerization Accelerator The curable composition of the present invention may further contain (G) a polymerization accelerator. The polymerization accelerator of the component (G) may be contained in the polymerization initiation of the curable composition, 54 326\patent specification (supplement)\94_〇3\93134393 1297694 for performance or other purposes. The polymerization accelerator of the component (G) is preferably an amino acid ester or a bipolar ion compound, and the amino acid ester or bipolar ion compound is represented by the following formula (X a ) or (X b ). The display is preferred. R39 r41 ο Ν——C—(CH2)s—C—〇—R43 (X a ) R40 R42 r39 r41 〇R44—N1—0—(CH2) S—C—〇—(X b ) R40 R42 [ In the formulae (Xa) and (Xb), R39 and R4Q each independently represent an alkyl group which may have a substituent, an aryl group which may have a substituent, a heterocyclic group which may have a substituent or a hydrogen atom, and R41 and R42 each independently represent 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 have a substitution The aryl group or a heterocyclic group which may have a substituent, s is an integer of 0 to 10]. Here, the alkyl groups of R39, R4°, R41, R42, R43, and R4 4 in the formulae (Xa) and (Xb) are preferably those having 1 to 8 carbon atoms, and further preferably 1 to 4; Preferably. Further, examples of the alkenyl group of R4 3 include an ethyl group, an allyl group, an isopropenyl group and the like. Further, examples of the aryl group of R39, R4G, R41 and R44 include a phenyl group and a naphthyl group. Further, examples of the heterocyclic group of R39, R4Q and R44 include furyl (fury 1 ), furanyl (furany 1 ), ° specific group, and ϋ ϋ 。. Further, examples of the substituent on the alkyl group and the alkenyl group include alkane 55 326\patent specification (supplement)\94-03\93134393 1297694 oxy group, alkoxycarbonyl group, alkenyloxy group, olefinoxy group Further, examples of the substituent on the aryl group and the heterocyclic group include a carbonyl group, a phenyl group, a halogen atom, and the like, and an alkyl group or an alkoxy group which may have a substituent such as an alkoxy group or a phenyl group. Alkenyl, alkenyloxy, decyl, decyloxy, olefinoxycarbonyl, phenoxy, alkylthio, alkanesulfonyl and aldehyde groups, carboxyl group, hydroxyl group, sulfonic acid group, nitro group, cyano group, i element Atoms, etc. In the present invention, in the above-mentioned ester of an amino acid represented by the above formula (Xa) or (Xb) or a bipolar ion compound, one of R39 and R4 in the formula (Xa) is a hydrogen atom and the other is The phenyl group which may have a substituent, R41 and R42 are each a hydrogen atom, R43 is an alkyl group which may have a substituent or a phenyl group which may have a substituent, and an amino acid ester of s of 0, 1, or 2 is preferably. Or R3S and R4° in the formula (Xb) are each a hydrogen atom or one of them may be an alkyl group which may have a substituent, R41 and R42 are each a hydrogen atom, and R44 is an alkyl group which may have a substituent or may have a substitution. The phenyl group of the group is preferably an amine bipolar ion compound having s of 0, 1, or 2; wherein, in the above formula (Xa), s is 0, and one of R39 and R4° is a hydrogen atom and the other side An ester of N-anilineacetic acid in the case of a phenyl group, wherein R41 and R42 are each a hydrogen atom (especially N-aniline acetate in the case where R4 3 is a benzyl group) is particularly suitable, or s in the formula (Xb) is 0. A bipolar ionic compound of N-phenylaminoacetic acid wherein R39, R4°, R41 and R42 are each a hydrogen atom and R44 is a phenyl group is particularly suitable. Further, in the present invention, a polymerization accelerator other than the ester of an amino acid or a bipolar ion compound may be further contained as a polymerization accelerator of the component (G). Examples of the polymerization accelerator include a sulfonamide. Base compounds (such as 2-indolyl benzopyrene. Sit, 2-wei-benzo benzoquinone, 2-weibenzo-4 sigma, 3-wei-1,2,4-triazole, 2-indole- 4 ( 3 Η )-quinazoline, /3 _ 酼 naphthalene, ethylene glycol disulfide 56 326 \ patent specification (supplement) \94-03\93〗 34393 1297694 propionate, trihydroxy decyl propane ginseng ( Thiopropionate, # brewing, etc.; polyfunctional thiol compounds (such as hexadiene ginseng (indole acetate), pentaerythritol bismuth (the amino acid of thiopropionate or its derivatives (such as N,N-dialkylamine acetic acid or a derivative thereof such as an ammonium salt or a sodium salt, a derivative such as a phenyl salt or an ester, etc.). In the curable composition of the present invention, the content ratio of the above 4 is It is more preferably 10 wt% or less with respect to the total amount of the curable composition. [1 _ 8 ] ( Η ) Inorganic filler Further, the component used in the curable composition of the present invention is improved. Examples of the inorganic filler of the strength of the compound or the other component (Η) for the purpose of the composition include, for example, aluminum slip, barium sulfate, magnesium oxide, etc. In the curable composition of the present invention, the content of the component is relatively The total amount of the curable composition is good, and more preferably 50% by weight or less. [;! - 9 ] (I) Surfactant Further, the sputum system used in the curable composition of the present invention improves the hardenability. The composition may be contained as a coating liquid or for other purposes. Specifically, specific anionic, cationic, amphoteric, fluorine-based, etc., for example, the nonionic surfactant-based alkyl ethers, Polyoxyethylene ethyl polyoxyalkylene 326\patent specification (supplement)\94-03\93134393 57 ipentaerythritol (thiol thiol, trishydroxypropyl propyl), etc.; with aromatic ring A benzoyl phthalate, a polymerization accelerator of N-phenylalanine or its ammonium or sodium w (G), may be contained under an inorganic filler of 20% by weight or less, and may be contained as a stone or a dioxide.无机, oxygen, (Η) inorganic filler, with an interface of 70% or less and w (I) The coating property and the developability include a nonionic surfactant, and examples thereof include polyoxyethylene ether, polyoxyethylene 1297694 alkyl phenyl ether, and polyoxyethyl ether. Alkyl esters, polyoxyethylidene esters, glycerol fatty acid esters, polyoxyethylene ethyl glycerol fatty acid esters, pentaerythritol fatty acid esters, polyoxyethylene pentaerythritol fatty acid esters, sorbitol a fatty acid ester, a polyoxyethylene sorbitan fatty acid ester, a glucose alcohol fatty acid ester, or a polyoxyethylene glycol alcohol fatty acid ester. Further, the anionic surfactant may be an alkyl sulfonic acid. Salts, alkylbenzenesulfonates, alkylnaphthalenesulfonates, polyoxyethylene ethyl ether sulfonates, alkyl sulfates, alkyl sulfates, higher alcohol sulfates Classes, aliphatic alcohol sulfates, polyoxyethylene ethyl ether sulfates, polyoxyethylene ethyl phenyl ether sulfates, alkyl phosphate salts, polyoxyethylene ethyl ethers Phosphate, polyoxyethylene ethyl phenyl ether phosphate, etc. Further, the cation Examples of the surfactant include a grade 4 ammonium salt, an imidazole sigma derivative, an amine salt, and the like. Further, the amphoteric surfactant may be a beet type compound or an imida ζ ο. 1 ium ) salts, taste σ sitting, amino acids, etc. In the curable composition of the present invention, the content of the surfactant of the component (I) is preferably 1% by weight or less based on the total amount of the curable composition, and more preferably 5% by weight or less. . [1 - 1 0 ] (J) sensitizing dye, the sensitizing dye of the component (J) used in the curable composition of the present invention is preferably contained in the photosensitive or other purpose of improving the curable composition. Within the composition. The sensitizing dye is a light absorbing dye having a maximum absorption (value) in the blue-violet region of a wavelength of 550 to 43 Onm, and examples thereof include a dialkylamine benzene compound, a pyrrole amide compound, and a trihydroxyl group. Pyrimidine derivatives and the like, 58 326\patent specification (supplement) \94-03\93134393 1297694 Among them, a dialkylamine benzene compound is preferred. In the preferred dialkylamine benzene compound, especially a dialkylamine phenyl ketone compound having a heterocyclic group as a substituent in the para position (based on the amine group on the benzene ring) a dialkylamine benzene-based compound, a dialkylamine benzene compound having a sulfonium imide group-containing substituent at a carbon atom in the para position (based on an amine group on the benzene ring), and formed with 2 - The dialkylamine benzene compound of the hydroxyquinoline skeleton is preferred. The dialkylamine diphenylketone compound is preferably represented by the following 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 each of R16 and R18 independently form a nitrogen-containing heterocyclic ring. Here, the number of carbon atoms of the alkyl group of R11, R12, R15, and R16 in the formula (XI) and the number of carbon atoms in the case where R 13 , R 14 , R 17 , and R 18 are alkyl groups are 1 to 6 Preferably. Further, in the case of forming a nitrogen-containing heterocyclic ring, it is preferred to form a 5- or 6-ring chain, and a tetrahydroquinoline ring which forms a 6-ring chain with R11 and R13, R12 and R14, R15 and R17 or R16 and R18. Preferably, especially R11, R12, R13, and R14 form a dur ο 1 idine ring or/and R 15 , R 16 , 59 326\patent specification (supplement)\94- 03\93134393 1297694 R17, and R18 are preferred to form a broachidine ring. Further, a tetrahydroquinoline ring having an alkyl group as a substituent at the 2-position or a p-pyridine ring containing the tetrahydroquine ring is particularly suitable. Specific examples of the compound represented by the above formula (XI) include 4,4'-bis(dimethylamine)diphenyl ketone and 4,4' bis(diethylamine)diphenyl ketone. And a compound of the following structure.

Further, the heterocyclic group in the dialkylamine benzene compound having a heterocyclic group as a substituent in the carbon atom of the (amino group on the phenyl ring) is a nitrogen atom, an oxygen atom, or The 5 or 6-ring chain of the sulfur atom is preferred, and the 5-ring chain having a condensed benzene ring is particularly suitable, and it is preferably one represented by the following formula (XII). 0 60 326\patent specification (supplement)\94- 03\93134393 1297694

[In the formula (XII), R19 and R2G each independently represent an alkyl group which may have a substituent, and R21 and R22 each independently represent an alkyl group or a hydrogen atom which may have a substituent, and R19 and R2Q, R19 and R21 and R2° and Each group of R22 may independently form a nitrogen-containing heterocyclic ring, and X represents an oxygen atom, a sulfur atom, a dialkyl fluorenylene group, an imido group, or an alkylimine group, and the benzene ring condensed in the hetero ring has a substitution. Base can 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 in the case where R2] and R22 are an alkyl group are preferably from 1 to 6. Further, in the case of forming a nitrogen-containing heterocyclic ring, it is preferred to form a 5- or 6-ring chain, and it is preferred to form a 6-ring chain tetrahydroquinoline ring with R19 and R2] or R^ and R2 2 , especially It is preferred that R19, R2, R21, and R2 2 form a azole ring. Further, it is particularly preferable to use a tetrahydroquinoline ring having a substituent at the 2-position of the alkyl group or a pyridine ring having a mouthpiece containing the tetrahydroquinone ring. Further, in the case where X is a dialkylmethylene group, the number of carbon atoms of the alkyl group is preferably from 1 to 6, and the number of carbon atoms of the alkyl group in the case of the alkylimine group is preferably from 1 to 6. Specific examples of the compound represented by the above formula (XII) include 2-(p-diamine benzene) benzoxazole, 2-(p-diethylamine benzene) benzoxazole, and 2- (p-dimethylaminobenzene) benzene [4,5 ]benzoxazole, 2-(p-dimethylaminobenzene)benzene [6,·7 ]benzoxazole, 2-(p-diamine benzene) Benzothiazole, 2-(p-diethylamine benzene)benzothiazole, 2 _(p-dimethylaminobenzene) benzimidazole, 2 -(p-diethyl 61 326\patent specification (supplement)\ 94-03\93134393 1297694 Amin benzene) benzimidazole, 2-(p-dimethylaminobenzene)-3,3 _dioxane-3 Η-吲哚, 2-(p-diethylamine benzene)~3, 3-dioxin-3Η - σ 引# and a compound of the following structure.

Further, the dialkylamine benzene compound having a heterocyclic group as a substituent on a carbon atom which is para-position to the (amino group on the phenyl ring) may be, for example, a compound represented by the above formula (XII). 2 _(p-dimethylaminobenzene)pyridine, 2-(p-diethylamine benzene)pyridine, 2-(p-diguanamine benzene)quinoline, 2-(p-diethylamine benzene)quinoline , 2 _(p-dimethylaminobenzene)pyrimidine, 2-(p-"diethylamine benzene)pyrimidine, 2,5-bis(p-diethylamine benzene)-1,3,4-oxadiazole , 2,5-bis(p-diethylamine benzene)-1,3,4-thiadiazole, and the like. Further, the dialkylamine benzene compound having a sulfonium imide group-containing substituent in the carbon atom (position of the amine group on the phenyl ring) is preferably represented by the following formula (XIII). .

326\Patent Specification (Repair)\94-03\93134393 62 1297694 [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 each of 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 the formula (XI II) and the number of carbon atoms in the case where R25 and R2 6 are an alkyl group are preferably from 1 to 6, more preferably, in the formation of a nitrogen-containing impurity In the case of a ring, it is preferred to form a 5 or 6 cyclic chain, but R25 and R26 are preferably a hydrogen atom. Further, examples of the monovalent group of R2 7 and R2 8 include an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkoxy group, an alkenyloxy group, a decyl group, a decyloxy group, an aryl group, and the like. Aryloxy, aralkyl, aralkenyl, hydroxy, methionyl, carboxy, carboxylate, amine sulfhydryl, amine, decylamino, amino decanoate, sulfonamide, sulfonate An acid group, a sulfonate group, an aminesulfonyl group, an alkylthio group, an imido group, a heterocyclic group or the like. Among them, R27 is preferably a hydrogen atom, and R28 is preferably an aryl group. Further, as the dialkylamine benzene compound having a 2-hydroxyquinoline skeleton formed, it is preferably represented by the following formula (X I V ).

[In the formula (XIV), R29, R3G, and R33 each independently represent an alkyl group which may have a substituent of 63 326\patent specification (supplement)\94·03\93134393 1297694, and R31 and R32 each independently represent a substituent. An alkyl group or a hydrogen atom, and R29 and R3°, R29 and R31, and each of R3G and R32 each independently form a nitrogen-containing heterocyclic ring, and R34 represents an alkyl group which may have a substituent, and an aryl group which may have a substituent. Or a hydrogen atom. Here, the number of carbon atoms of the alkyl group of R29, R3G, and R33 in the formula (XIV) and the number of carbon atoms in the case where R31, R3 2, and R3 5 are alkyl groups are preferably from 1 to 6, more preferably In the case of forming a nitrogen-containing heterocyclic ring, it is preferred to form a 5 or 6 cyclic chain, but R31 and R3 2 are preferably a hydrogen atom. Further, R3 4 is preferably a phenyl group. In the sensitizing dye of the above component (J), in the present invention, the dialkylamine diphenyl ketone compound represented by the above formula (XI) and the formula (XIII) are a dialkylamine benzene compound having a sulfonium imide group-containing substituent at a carbon atom of a para-phenyl group, or a 2-hydroxyquinoline formed by the above formula (XIV) The dialkylamine benzene compound of the skeleton is particularly suitable. In the curable composition of the present invention, the content of the sensitizing dye of the component (J) is preferably 〇1 to 2 0 wt%, and 0.1 to 10 wt%, based on the total amount of the curable composition. % is further preferred. When the content of the component (J) is less than the above range, the photocurability of the curable composition tends to be insufficient, and if it is larger than the above range, the base tends to be stained during development. Further, the curable composition of the present invention preferably has a sharp peak value of the 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 value of the spectral sensitivity is less than the above wavelength range, the photocurable composition tends to be inferior to the wavelength of the 3,500 to 4,300 nm laser light, and the spectroscopic sensitivity 326\patent specification ( Supplement) \94-03\93134393 64 1297694 The maximum peak value exists in the above wavelength range, which causes a tendency to be inferior in safety under yellow light. When the respective components constituting the curable composition are appropriately selected in the wavelength range of the maximum peak of the spectral sensitivity, the wavelength range may be adjusted by this, and in particular, the photopolymerization initiator and/or heat of the component (B) may be used. The polymerization initiator and the type and content of the sensitizing dye of the component (J) are adjusted to be selected. Further, in the present invention, the maximum peak value of the spectral sensitivity refers to the following maximum peak value, that is, ^ (Lishiokou "photo polymer · technology" (Shanoka Yafu, 1988, Industrial News) According to the company's publication, page 2 6 2, etc., under the use of a spectrophotometric measuring device, light split from a light source such as a xenon lamp or a tungsten lamp can be linearly changed in the horizontal axis direction with an exposure intensity. It is possible to set a logarithmic change in the direction of the longitudinal axis so as to be irradiated to the photocurable photographic image forming material sample (the photocurable composition layer is formed on the surface of the substrate), and after exposure, a development process is performed, thereby obtaining each The image of the sensitivity of the exposure wavelength, thereby calculating the exposure energy of the image, and plotting the wavelength on the horizontal axis and the inverse of the exposure energy on the vertical axis, thereby obtaining the spectral sensitivity curve The maximum peak value is the above-mentioned maximum peak value. Further, regarding the curable composition of the present invention, in the case where a blue-violet semiconductor laser is used as an exposure light source, it is possible to form a minimum image at 41 nm wavelength. The amount of light [S410] is preferably 50 mJ/cm2 or less, more preferably 30 mJ/cm2 or less, and particularly preferably 20 mJ/cm2 or less. When the minimum exposure amount [S 4 1 0 ] is larger than the foregoing range Although depending on the exposure intensity of the laser source, there is a tendency to cause the exposure time to become longer and the practicality is lowered. 65 3 26\patent specification (supplement)\94-03\93134393 1297694 direction. The lower the lower limit of the exposure amount [S 4 1 Ο ], the better, usually 1 m J / c m2 or more. Furthermore, the above [S410] and the wavelength of 450 nm may form the minimum exposure amount of the image [S4 5 0 ( The ratio [S410/S 4 5 0 ] of mJ/cin2)] is preferably 0.1 or less, and more preferably 0.05 or less. If the ratio [S410/S450] is higher than the above range, blue-violet thunder is caused. It is difficult to combine the photosensitivity with the safety light under the yellow lamp. Further, it is preferable that the minimum exposure amount of the image is formed at each wavelength of more than 450 nm and below 650 nm [S450-650 (mJ/). Cm2)] is the ratio of the minimum exposure amount [S450-650/S450] which is likely to form an image with the wavelength of 450 nm [S450-650/S450] is greater than 1, if this When the ratio [S450-650/S450] is less than the above range, it is difficult to achieve both the blue-violet laser sensitivity and the safety light under the yellow lamp. Further, the above-mentioned minimum of possible formation of the image at a wavelength of 410 nm is possible. The exposure amount [S410], the minimum exposure amount that is likely to form an artifact at a wavelength of 450 nm [S450], and the minimum exposure amount at which an image is formed at wavelengths greater than 450 nm and below 650 nm [34 5 0 _ 6 5 0 (111 *1 /^2)] In the measurement of the maximum peak value of the spectral sensitivity measured by the spectroscopic sensitivity measuring device, the exposure energy of the image which is calculated from the obtained imaging height can be obtained, and the meaning is The optimum development condition determined by the change of the development conditions such as the type of developer, the development temperature, and the development time at that time can form the minimum exposure energy of the image, and for the optimum development condition, it is usually taken at Ρ Η 1 1~ 1 4 alkali developer was immersed at a temperature of 2 5 ° C for 0 · 5 to 3 minutes. [1 - 1 1 ] (K) Other alkali-soluble resin 66 326\Patent specification (supplement)\94-03\93134393 1297694 The component (κ) alkali-soluble resin used in the curable composition of the present invention is used as The binder of the curable composition may be contained. Examples of the alkali-soluble resin include (mercapto)acrylic acid, (meth)acrylic acid ester, (fluorenyl)acrylonitrile, (fluorenyl)acrylamide, maleic acid, styrene, and vinyl acetate. , homopolymer or copolymer of dichloroethylene, maleimide, etc.; acid-modified epoxy acrylate, polyamine, polyester, polyether, polyamino phthalate, poly Among them, vinyl butyral, polyvinyl alcohol, polyvinylpyrrolidone, and ethyl phthalocyanine are preferable, and a carboxyl group-containing vinyl resin or an acid-modified epoxy acrylate is preferable from the viewpoint of alkali developability and the like. Specific examples of the carboxyl group-containing vinyl resin include unsaturated carboxylic acids (e.g., (mercapto) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, maleic anhydride, and itaconic acid. Acid, citraconic acid, etc.) and vinyl compounds (such as styrene, α-mercaptostyrene, hydroxystyrene, decyl methacrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (fluorenyl) butyl acrylate, amyl (meth) acrylate, hexyl (meth) acrylate, dodecyl (decyl) acrylate, 2-ethylhexyl (meth) acrylate, (fluorenyl) acrylate Dicyclopentyl ester, adamantyl (meth) acrylate, isobutyl (meth) acrylate, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl (mercapto) acrylate, Benzyl (meth) acrylate, hydrazine (mercapto) acrylate, hydrazine - dimethylamine ethyl ester, hydrazine - (hydrazino) propylene morpholine, (mercapto) acrylonitrile, (fluorenyl) acrylamide, hydrazine - Hydroxyl hydrazine (meth) acrylamide, hydrazine, hydrazine - dimethyl (meth) acrylamide, hydrazine, hydrazine - two a copolymer of methylamine (mercapto) acrylamide, vinyl acetate, etc.). Among them, styrene-(meth)acrylate-(meth)acrylic acid copolymer is better than 326\patent specification (supplement)\94-03\93134393 67 1297694 to styrene 3~3 0 m ο 1 % Further, a copolymer of (meth) acrylate 10 0 to 70 m ο 1 %, and (mercapto) acrylic acid 10 to 60 mol% is further preferably used, and styrene is 5 to 2 5 m 〇1. A copolymer composed of %, (fluorenyl) acrylate 2 0 to 6 0 m ο Γ / 〇, and (methyl) acrylic acid 15 to 55 mol% is particularly suitable. Further, these carboxyl group-containing vinyl resins preferably have an acid value of from 3 to 250,000 g·KOH/g, and a weight average molecular weight of from 1,000 to 300,000 in terms of polystyrene. Further, as the carboxyl group-containing vinyl resin, it is preferred to have an ethylenically unsaturated bond in a side chain, and specific examples thereof include, for example, a carboxyl group-containing polymer and an aliphatic epoxy group-containing unsaturated compound ( Such as propyl glyceryl ether, glycidyl (mercapto) acrylate, α-ethyl glycidyl (meth) acrylate, glycidyl crotonate, glycidyl isocyanate, crotonyl glycidyl , itaconic acid mono-monoglycidyl S, succinic acid monoalkyl monoglycidyl ester, maleic acid monoalkyl monoglycidyl ester, etc.) or alicyclic epoxy Unsaturated compounds (such as 3,4-epoxycyclohexylmethyl (meth)acrylate, 2,3-epoxycyclopentylmethyl (meth)acrylate, 7,8-epoxy (meth)acrylate [Tricyclo[5 · 2 . 1 . 0 ] 癸-2-yl] oxonium ester, etc.), according to the ruthenium-containing polymer, 5 to 90 mol% of the thiol group (to 3 0 to 7 0 m ο 1 %) a preferred reaction product obtained by reacting, and a compound having two or more kinds of unsaturated groups (such as (meth)acrylic acid Allyl ester, 3-allopropoxy-2-hydroxypropyl (meth)acrylic acid, cinnamate (mercapto)acrylate, crotonyl (meth) acrylate, methyl allyl (meth) acrylate, hydrazine, Ν-diallyl (fluorenyl) acrylamide, etc. or other compounds having two or more kinds of unsaturated groups (such as (mercapto) vinyl acrylate, 1-methyl vinyl (meth) acrylate, (曱2-acrylic acid 2-styrene ester, (mercapto)acrylic acid 1- 68 326\patent specification (supplement)\94·03\93134393 1297694 propylene ester, vinyl crotonate, ethylene (meth) acrylamide, etc.) With an unsaturated carboxylic acid (such as (meth)acrylic acid, etc.) or further with an unsaturated carboxylic acid ester, the ratio of the former unsaturated group-containing compound may be 10 to 90 m ο 1 % (in terms of 3 0 to 8 0 m ο 1 % preferably) The reaction product obtained by copolymerization in the same manner. Further, a reaction product of an epoxy group-containing polymer and an ethylenically unsaturated compound having a functional group reactive with an epoxy group (e.g., a carboxyl group, a hydroxyl group, etc.) may be mentioned. Further, the acid-modified epoxy acrylate is a compound obtained by further reacting a reaction product containing an epoxy group-containing compound and an unsaturated group-containing carboxylic acid or an anhydride thereof with a polyvalent carboxylic acid or an anhydride (c) thereof. Further, a resin obtained by adding an epoxy group-containing compound to a part of a carboxyl group of the compound may be used. Its manufacture can be carried out by conventional methods. Examples of the epoxy group-containing compound include an epoxy compound described in Japanese Patent Laid-Open Publication No. Hei 2 0 0 1 - 1 7 4 6 2 1 [In this publication, there are two or more molecules in one molecule. Specific examples of the epoxy group-containing compound (a) and the like include a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a bisphenol S type epoxy compound, a biphenyl glycidyl ether, and a phenol type phenol resin type. An epoxy compound, a cresol type phenol resin type epoxy compound, a triglycidyl isocyanurate, an alicyclic epoxy compound, and a cyclic hydrocarbon compound having two or more unsaturated groups per molecule and a phenol An epoxy compound or a copolymerized epoxy compound having an addition polymer structure formed by the like. In the curable composition of the present invention, the content of the soluble resin of the component (K) is preferably 70% by weight or less, and more preferably 40% by weight or less, based on the total amount of the curable composition. good. 326\Patent Specification (Supplement)\94-03\93134393 69 1297694 [1 - 1 2 ] (L) Color material In the case where the curable composition of the present invention is used for color filter use or black matrix use, It is best to use it under the inclusion of color materials. In the case where the coloring material is used to color the curable composition according to the present invention, a dye or a pigment can be used as the coloring material, and a pigment is preferable from the viewpoint of heat resistance, light resistance and the like. The 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. Furthermore, its structure may utilize azo, S, and quinacrid ο ne, benzoxanone, isoindrone, and ° ϋ In addition to organic pigments such as indanthrene and a 1,b 1 -dibenzopyrene (P ery 1 ene ), it is also possible to use various inorganic pigments. Hereinafter, specific examples of the pigments that can be used are indicated by pigment numbers. In the terms "C · I. Pigment Red 2" and the like, the meaning of C · I · is the color index. The red pigment may be C · I · Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37 , 38, 41, 47, 48, 48:1, 48:2: 48:3, 48:4, 49, 49:1, 49:2, 50:1' 52:1^ 52:2 > 53' 53:1 ^ 53:2, 53:3' 57' 57:1' 57:2, 58:4' 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 8 81: Bu 81:2, 81:3, 81:4, 83, 88, 90], 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 1297694 210, 214, 216, 220, 221' 224, 230' 231, 232, 233 > 235, 236 , 237, 238' 239, 242, 243' 245, 247, 249, 250, 25 253 > 254, 255' 256 > 257' 258' 259' 260' 262 , 263 ' 264 , 265 ' 266 ' 267 > 268 , 269 ' 270 , 271 , 272 , 273 , 274 275, 276. Among them, preferred are CI pigment red 48:1' 122, 168, 177, 2 0 2, 2 0 6 , 2 0 7 , 2 0 9 , 2 2 4 , 2 4 2, 2 5 4, and further preferred are C. I. Pigment Red 177, 209, 224, 254 Indigo pigments can be cited as CI Pigment Blue 1, 1: 2, 9, and 14. 1 5, 1 5 : 1, 15:2' 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1 60, 61, 61: 1, 62' 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78., 79. Among them, preferred examples are C · I. Pigment Blue 1 5, 1 5 : 1, 1 5 : 2, 1 5 : 3, 1 5 : 4, 1 5 : 6, and further preferred C. I · Pigment Blue 1 5 : 6 can be mentioned. The green pigment may be CI pigment green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55°. Preferred examples are C.I. Pigment Green 7, 3 6 . The yellow pigments may be CI 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], 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1 > 63, 65, 73, 74, 75, 8 83 87, 93, 94, 95, 97, 100, 1 0 1 , 1 04, 1 0 5, 108, 10 9, 110, 1 1 1 , 1 1 6 , 117, 119, 120, 126, 127, 127: 1 > 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 71 326\patent specification (supplement)\94-03\93134393 1297694 155^ 157 '158' 159' 160, 16 Bu 162, 163' 164, 166, 167, 168, 169, 170, 172, 173, 174, 175, 180, 181, 182, 183, 184, 185, 188, 189, 190 '191:1, 192, 193, 194, 195, 196, 197, 198, 199, 202, 203, 204, 205, 206, 207, 208. Among them, C·I. Pigment Yellow 83, 117, 129, 138, 139, 150, 1 5 5, 1 8 0, and 1 8 5 may be mentioned, and C · I is further preferable. · Pigments, 138, 139, 150, 180 ° Orange pigments can be given C. I · Pigment Orange 1, 2, 5, 1 3, 16 6 , 1 7 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 7 4 7 7 , 7 8 , 7 9 . In the above, C. I. Pigment Orange 3 8 purple pigment is exemplified by C. I. Pigment Violet 1, 1 ··1, 2, 2: 2, 3, 3:3' 5 5 : 1 > 14' 15' 16, 19, 23' 25' 27, 29 > 31 37, 39, 42, 44, 47, 49, 50. Among them, preferred are 3 C. I. Pigment Violet 9 9 and 2 3, and further preferred are C. I. Yan j 2 3 〇 In addition, the curable composition of the present invention is used. In the case of black enamel, a black color material can be used. The black color material can be used alone or in a mixture of red, green, and blue. Further, as the ill material, it can be appropriately selected from inorganic or organic pigments and dyes. In the case of 彳 organic pigment, it is preferred to use it in a state in which the average particle diameter of 1 #, m is preferably 0.5 Å or less. As a color material which is possible to be mixed and used in the preparation of a black color material, 165 ^ 176 ' 191 > 2 0 0 > t good 154 > t 83, , : I 9 , , 49 , > 75 ' , 71° 3 : 1 > ' 32, 「 I ic i purple base I color 3 equal color machine, lower (to 326 \ patent specification (supplement) \94-03\93134393 72 1297694 out of Victoria Pure Blue ( 42595) , Auramine 0 (41000), Catilon Brilliant Flavin (basic 13), Rhodam i ne

6GCP (45160), Rhodamine B (45170), safranine OK 70: 100 (50240), Erioglaucine X (42080), No. 120/Lionol Yellow (21090), Lionol Yellow GRO (21090), Simular 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), and the like. In addition, the number in the above brackets is the color index (C · I ·). Further, as for other pigments which may be used in combination, when expressed by C·I., for example, C·I. Yellow pigments 2 0, 2 4, 8 6 , 9 3, 1 〇 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, 2 2 0, 2 2 3, 2 24, 2 2 6 , 2 2 7 , 2 2 8 , 2 4 0, C I. Purple Pigment 19, 2 3, 2 9 , 3 0, 3 7 , 4 0, 5 0, C · I · Blue Pigment 15, 15: 1, 15: 4, 2 2, 60, 64, C I. Green pigment 7, C. I · Brown pigment 2 3, 2 5, 2 6 and the like. Further, 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, carbon black is preferred from the viewpoint of light blocking ratio and image characteristics, 326\patent specification (supplement)\94-03\93134393 73 1297694. Examples of the carbon black include carbon black as described below. MA7, MA8, ΜΑΗ, MA100, MA100R, MA220, MA230, MA600, #5, #10, #20, #25, #30, #32, #33, #40, #44 > manufactured by Mitsubishi Chemical Corporation #45,#47,#50,#52,#55,#650,#7 5 0, #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, iron bone sand, made by the company Printex3, Printex30P, Printex30, Printex300P, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, Printex L, Printex G, Printex P, Printex U 'Printex V 'PrintexG, Specia 1 B1 ack 5 5 0, SpecialBlack350, 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 S170 Monarch 1 2 0, Monarch280, Monarch 4 6 0, Monarch 800, Monarch880 'Monarch900, MonarchlOOO, MonarchllOO, Monarchl 30 0, Monarchl 400, Monarch 4630, REGAL 9 9, REGAL99R, REGAL415, REGAL415R, made by the company REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK PEARL S480, PEARLS130, VULCANXC72R, ELFTEX-8, RAVEN11, RAVEN14, RAVEN15, RAVEN16, 326V patent specification (supplement)\94-03\ by Columbia Carbon 93134393 74 1297694 RAVEN22, RAVEN30, RAVEN35, RAVEN40, RAVEN41 Ο, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN890H, RAVEN1000, RAVEN1020, RAVEN1040, RAVEN 1 0 6 0 U, RAVEN 1 0 8 0 U, RAVEN1 170, RAVE N119 0 U, 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 〇 For other examples of black pigments, titanium black , aniline black, iron oxide black pigment, and red, green Blue three color organic pigment used as a black pigment mixed. Further, as the pigment, barium sulfate, lead sulfate, titanium oxide, yellow lead, iron red, chromium oxide or the like may be used. These various pigments may be used in combination of two or more kinds. For example, for the purpose of adjusting the chromaticity, the pigment may be combined with a green pigment and a yellow pigment, or a combination of a blue pigment and a violet pigment. Further, the average particle diameter of these pigments is usually 1 // m or less, preferably 0.5 Å or less, and more preferably 〇 2 5 // m or less. In addition, examples of the dye that can be used as the color material include an azo dye, an anthraquinone dye, a phthalocyanine dye, a quinone dye, a quinoline dye, a nitro dye, and a carbonyl dye. Sub-systemic dyes, etc. Examples of the azo dye include C. I. Acid Yellow 1 1 , C. I. Acid Orange 7, C · I · Acid Red 3 7 , C · I · Acid Red 180, CI 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. Reactive Yellow 2, C · I. Activity 75 326\Patent Specification (Supplement)\94-03\93134393 1297694 Red 1 7、C. I. Reactive Red 1 2 Ο, 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. Confirmatory blue 4 1 , C. I. Verify red 1 8, C. I. mordant red 7, C. I. mordant yellow 5, C. I. mordant black 7 and so on. Examples of the lanthanoid dyes include C. I. Indigo 4 > C. I. Acid Blue 4 Ο, C. I · Acid Green 2 5, C. I. Reactive Blue IX, 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 the phthalocyanine-based dye include C.I. Indigo-5, and the quinoneimine-based dyes include, for example, C.I. Basic Blue 3, C.I. Basic Blue 9, and the like. Examples of the quinoline-based dye include C. I. Solvent Yellow 3 3, C. I. Acid Yellow 3, C. I. Disperse Yellow 6 4, and the like, and the nitro-based dye may, for example, C. I. Acid Yellow 1. C. I. Acidic orange 3, C. I. Disperse yellow 4 2 and the like. The ratio of the color material of the component (L) to the total solid component of the curable composition is usually selected within the range of 70% by weight relative to the total solid component of the curable composition. Within this range, it is further preferable to use 1 0 to 7 0 w t %, particularly 2 0 to 6 0 w t %. If the ratio of the color material is too low, the film thickness of the color density becomes too large, and the gap control of the liquid crystal unit is adversely affected. On the other hand, if the ratio of the color material is too high, sufficient image formability may not be obtained. Further, the solid content in the curable composition of the present invention is usually 10 w t % or more and 80 w % or less. Further, in order to improve the dispersibility of the pigment and the stability of dispersion, a pigment derivative or the like may be added. Examples of the pigment derivative include an azo system, a phthalocyanine system, a quinacridone system, a benzimidazolone system, a quinacridone system, an isoindolinone system, a diterpenoid system, an anthraquinone system, and an indanthrene group. A, b 1 -dibenzofluorenene, perryn η ο ne system, diketone.比 各 并 ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° Preferably. Examples of the substituent of the pigment derivative include a sulfonic acid group, a sulfonamide group, a quaternary salt thereof, a quinone iminium group, a dialkylamine alkyl group, a hydroxyl group, a carboxyl group, a decylamino group, and the like. The skeleton is bonded directly or by an alkyl group, an aryl group, a heterocyclic group or the like, and a sulfonic acid group is preferred. Further, these substituents may be substituted with a plural number in a pigment skeleton. Specific examples of the pigment derivative include a sulfonic acid derivative of phthalocyanine, a ruthenium acid derivative of 喧g, a brewed acid derivative, a sulfonic acid derivative of salivary sigma ketone, and a diketopyrrole. And a sulfonic acid derivative of pyrrole, a sulfonic acid derivative of Erqi Well, and the like. The amount of the pigment derivative added is usually from 0 to 1 to 30% by weight, preferably from 0 to 1 to 2 0 wt%, and further preferably from 0 to 1 to 10 wt%. Further, it is more preferably 0.1 to 5 wt%. [1 - 1 3 ] ( Μ ) dispersant and/or dispersing aid When the curable composition of the present invention is used for color filter use or black matrix use, especially when the pigment is used as the aforementioned component (L) In the case of the color material, it is preferable to use a dispersing agent and/or a dispersing aid as a component (Μ) in order to improve the dispersibility of the pigment and the stability of dispersion. In particular, if a high molecular dispersant is used to act as a pigment dispersant, it exhibits excellent stability over time and is therefore preferred. Examples of the polymer dispersant include an amine sulfonate dispersant, a polyethylenimine dispersant, a polyoxyethylene ethyl ether dispersant, and a polyoxyethylene glycol diester dispersant. A sorbitol aliphatic ester dispersant, an aliphatic modified polyester dispersant, or the like. Specific examples of such a dispersant include "EFKA" (manufactured by FKA CHEMICAL BV), r Disperbik (manufactured by BigChemir Co.), and r DISPARLON (manufactured by Nanben Chemical Co., Ltd.). "SOLSPERSE" (made by Zeneka Co., 77 326\patent specification (supplement)\94-03\93134393 1297694), "KP" manufactured by Shin-Etsu Chemical Co., Ltd.), "Polyflow" (Kyoeisha Chemical Co., Ltd.) ))). These dispersing agents may be used singly or in combination of two or more kinds. The content of the pigment dispersant in the solid content of the photosensitive coloring composition is usually 50 w t % or less, preferably 3 0 w t % or less. Further, as the dispersing aid, the compound represented by the formula (I), the ethylenically unsaturated compound of the component (C), the epoxy compound of the component (D), and other alkali-soluble resin of the component (K), etc. After optional, it can be used at the time of dispersion processing. [1 - 1 4 ] (N) Other additives Further, the curable composition of the present invention may further contain various additives, for example, a thermal polymerization preventing agent in a ratio of 2 wt% or less with respect to the curable composition ( For example, hydroquinone, p-nonoxyphenol, 2,6-di-t-butyl-p-non-phenol, etc., containing a coloring agent composed of an organic or inorganic dye or pigment in a ratio of 20% by weight or less, according to The ratio of 40% or less contains a plasticizer (such as dioctyl phthalate, dilauryl citrate, cresyl phosphate, etc.), and contains a sensitivity improving agent (for example, a tertiary amine or a ratio of 10% by weight or less) A mercaptan or the like contains a pigment precursor in a ratio of 30% by weight or less, and a decane coupling agent in a ratio of 10% by weight or less. [1 - 1 5 ] Total deformation amount, displacement at load and elastic recovery rate, recovery rate The hardenable composition of the present invention relates to a load-de-load test using a micro hardness tester, which can form a total deformation amount of 1 3 5 / / m or more and / or load when the displacement is 〇.25 #m, the load N is less than 0.50gf, and the elastic recovery rate is more than 50% and / or the recovery rate is more than 80% The object is a feature. 78 326\Patent specification (supplement)\94-03\93134393 1297694 For example, the spacer for the supply of liquid crystal display devices (hereinafter referred to as "panels") for large-size LCD TVs is used in the manufacturing process of the panel. The load is heavy, and there is a tendency to increase the total deformation amount of the spacer. In particular, in the large face panel, the unevenness of the load of each part is apt to occur. The elastic resilience rate and/or recovery rate of the hardened composition of this hardening composition even in this case, that is, the value at this point, and the load-de-loading test using a micro hardness tester It is as follows. Regarding the pattern of the spacer pattern formed by the [2 - 2 ] or the conventional method described later, which has an upper sectional area of 80 ± 10 0 / m 2 , a small hard is used for measurement. The cross-sectional area above the spacer pattern refers to the area described below. First, with respect to one spacer pattern, a longitudinal section of the axis passing through the spacer pattern is used under the ultra-depth color 3D shape measuring microscope "V K - 950" which is based on the base. The location depicted is in Figure 1. Next, a line parallel to the substrate surface (substrate surface in the pattern of the object pattern) from the surface of the drawn pattern (the schematic diagram is shown in FIG. 2) to the height of 90% of the height of the highest position point Q The length of AA ' is a quantity. The area of the circle on which the straight line AA' is the diameter is set as the cross-sectional area on the spacer map. For the micro hardness tester, the "Sh i Dynamic Super Micro Hardness Tester DUH-W201S" manufactured by Shimadzu Corporation is tested at a temperature of 23 °C using a diameter of 50 // m 326\ patent specification (supplement) ) \94-03\93134393 79 Sometimes the middle of the easy, invention 7 (the implementation of the interim measure is shown on the substrate spacing to measure the ma ζ ο ο flat 1297694 surface pressure, at a certain speed (0.22 Gf/sec) applies a load to the spacer. When the load reaches 5 gf, it is held for 5 seconds, and then the load is applied according to the speed. According to the load-displacement curve obtained by this test (shown in Figure 3 Schematic), measure the maximum displacement Η [ ma X ], the final displacement Η [ L ast ], the displacement at load is 0.25, and the excess weight N(gf) at zm. The maximum displacement Η [ ma X ] is taken as the total deformation The total deformation amount is preferably 1. 4 // m or more, more preferably 1.5 / m or more, and more preferably 5 # m or less, and further preferably 3 / 4 m or less. The displacement of time is 0. 2 5 // The load of N is better than 0 · 4 5 gf. Preferably, the total deformation amount is too large and/or the load N is too small, the elastic recovery rate and/or the recovery rate are deteriorated. On the other hand, if the total deformation amount is too small and/or The aforementioned load N is too large, and the hardened material cannot be adapted to the unevenness of the load when the panel is manufactured.

Furthermore, the elastic recovery rate and recovery rate are calculated according to the above-mentioned load-de-load test values using a micro hardness tester, and are calculated as follows: Recovery rate (%) = { Η [ U st ] Eight before the test Pattern height) 丨X 1 0 0 Elastic recovery rate (%) = {(H[max]-H[last])/H[max]}xlOO Recovery rate is preferably 85% or more, and more than 9%% Further preferred. The elastic recovery rate is preferably 60% or more, and more preferably 80% or more. If the recovery rate and/or the elastic recovery rate are too small, the hardened material cannot be adapted to the unevenness of the load when the panel is manufactured. When the curable composition of the present invention has the above characteristics, its composition is not particularly limited, and in particular, (A-1) the compound represented by the formula (I) 80 3 26\patent specification (supplement) ) \94-03\93134393 1297694 The compound and/or (A-2) is obtained by a compound having a phenol methane structure. [1 - 1 6 ] The cross-sectional area of the bottom surface, the elastic recovery rate, and the recovery rate. Further, the curable composition of the present invention can form a cross-sectional area of the bottom surface of 2 4 . 5 // m 2 or less, and the elastic recovery rate is 5 0. A cured product having a % or more and/or a recovery rate of 85% or more is characteristic. For example, a spacer for supplying a face panel for a portable telephone or the like is small in size, and a small bottom area is designed so as not to damage the image. On the other hand, a product such as a portable telephone or the like is easily impacted at the time of use or other conditions, and thus is easily loaded. The curable composition of the present invention exhibits an elastic recovery rate and/or a recovery rate of a cured product (spacer) of a high degree even in such a case, i.e., has a value at this point. Further, the cross-sectional area of the bottom surface refers to the contact area between the cured product formed of the curable composition of the present invention such as a spacer and the substrate, and the spacer pattern can be observed by an optical microscope. The cross-sectional area of the bottom surface is preferably 2 0 #m2 or less, more preferably 1 5 " m2 or less, and more preferably 1 # m2 or more, and further preferably 5 // m2 or more. If the cross-sectional area of the bottom surface is too large, it is not suitable for a panel such as a cellular phone having a small pixel. In addition, if the cross-sectional area of the bottom surface is too small, a sufficient elastic recovery rate and/or recovery rate cannot be obtained. Further, the elastic recovery rate and the recovery rate are the same as those described above based on the values measured on the load-de-load test using the micro hardness meter described above. The recovery rate is preferably more than 90%. The elastic recovery rate is preferably 60% or more, and more preferably 80% or more. If the recovery rate and/or the elastic recovery rate are too small, the hardened material cannot be adapted to the load such as the impact of the panel 81 326\patent specification (supplement)\94-03\93134393 1297694. When the curable composition of the present invention has the above characteristics, its composition is not particularly limited, and in particular, (A-1) a compound represented by the formula (I) and/or (A-2) having a ginseng can be used. A compound of phenol methane structure is achieved. [2] Method of using the curable composition The curable composition of the present invention can be used in various applications such as a printed wiring board, a liquid crystal display element, a plasma display device, a large-scale integrated circuit, a thin transistor by a conventional method. In the use of a semiconductor package, a color filter, an organic electric field illuminating mechanism, etc., a cured film such as a solder resist film, a cover film, and an insulating coating of various electronic components, or a liquid crystal panel such as a liquid crystal display device is formed. The pixels of the color filter, the black matrix, the overcoat layer, the ribs, and the cured material of the spacer or the like are described below, particularly in the case of being used as a solder resist layer and in the case of being used as a spacer. [2 - 1 ] When used as a solder resist layer, a curable composition dissolved or dispersed in a solvent is usually supplied to a substrate on which a solder resist layer is to be provided in a film form or a pattern by a coating method or the like. When the solvent is dried and supplied in the form of a film, if necessary, the formation of a pattern is performed by a method such as photolithography using an exposure-developing method. Alternatively, the curable composition which has been previously formed as a dry film resist material is supplied onto the substrate in accordance with a usual method, and if necessary, a pattern is formed by a method such as photolithography using an exposure-developing method. The film-like or patterned curable composition layer thus obtained is subjected to a heat hardening treatment as needed to form a solder resist layer on the substrate. [2 - 1 - 1 ] Substrate This substrate is used to develop a hardenable composition formed thereon by exposing it to a laser 82 326\patent specification (supplement)\94-03\93134393 1297694 light or the like. Processing, the resulting image is used as a photoresist, and a welding process or the like is applied thereto, thereby forming a pattern of a circuit, an electrode, or the like on the surface thereof, which is copper, inscription, gold, silver, chromium, zinc, tin, A metal plate made of a metal such as a ship or a nickel may be used as it is, but usually it is, for example, made of a resin [such as a thermosetting resin (such as an epoxy resin, a polyimide resin, a bis-methylene iodide resin, or not). Saturated polyester resin, phenol resin, melamine resin, etc.), thermoplastic resin (such as saturated polyester resin, polycarbonate resin, polysulfone resin, acrylic resin, polyamide resin, polystyrene resin, polyvinyl chloride resin, Polyolefin resin, fluororesin, etc.], paper, glass, inorganic materials (such as alumina, ceria, barium sulfate, calcium carbonate, etc.) or composite materials (such as glass cloth substrate epoxy resin, glass non-woven substrate ring) Oxygen resin, paper base a surface of an insulating support having a thickness of about 0.02 to 10 mm, such as an epoxy resin or a paper base material phenol resin, and the like, or a metal or metal oxide (such as indium oxide, tin oxide, tin oxide doped with indium oxide) Etching or the like, the metal foil is heated and pressurized to be laminated on the surface, or the metal is subtracted: plating, vapor deposition, electroplating, etc., forming a conductive layer having a thickness of about 1 to 1 〇〇//m on the surface. The layer, the metal laminate thus obtained is used hobbies. [2 - 1 - 2 ] When the method of supplying the substrate is supplied to the substrate in a state of being dissolved or dispersed in a solvent, a conventional method such as spin coating, wire coating, spray coating, or the like can be used. , dipping coating, air knife coating, roll coating, blade coating, screen coating, droop coating, and the like. The coating amount at the time of coating is preferably 5 / 5 m or more in consideration of the workability in the treatment (the formation of an image, the subsequent welding, etc.), which will be described later. 1 0 // m or more into 83 326\patent specification (supplement)\94-03\93134393 1297694 The step is better, and if the sensitivity is taken into consideration, it is better to use 2 Ο Ο // m or less, and 1 0 0 / m or less is further preferred. Further, the drying temperature for this purpose can be, for example, about 30 to 150 ° C, preferably 40 to 110 ° C, and for drying time, for example, 5 seconds can be taken. The degree of 60 minutes is preferably from 10 seconds to 30 minutes. In addition, in the case where the curable composition forming material is directly applied and dried by the coating liquid of the curable composition, the polyvinyl alcohol is used for the prevention of polymerization inhibition by oxygen of the curable composition. a solution of polyvinylpyrrolidone, polyethylene oxide, decyl cellulose, carboxymethyl cellulose, hydroxydecyl cellulose or the like applied to the aforementioned hardenability formed on the substrate to be processed as described above The composition layer may be dried and formed into a protective layer. The supply to the substrate can be carried out by a conventional method for the purpose of serving as a dry film photoresist. Specifically, each of the above components is dissolved or dispersed in a suitable solvent, applied as a coating liquid onto a temporary supporting film, and dried, and if necessary, a coating film is applied to apply the formed curable composition. On the surface of the layer, as a so-called dry film photoresist or the like, the coating film is coated on the side of the curable composition layer of the dry film resist, and the coating is peeled off and laminated by heating. The method is laminated on the substrate to be processed, thereby being supplied onto the substrate. In the case of acting as the dry film resist material or the like, as the temporary supporting film required, for example, a polyethylene terephthalate film, a polyimide film, a polyamide film, a polypropylene, or a polypropylene can be used. Films, polystyrene films, and the like which have hitherto been known. In this case, if the film has the solvent resistance 84 326\patent specification (supplement)\94·03\93134393 1297694 or heat resistance required for the preparation of the dry film photoresist material, the hardenable composition may be used. The coating liquid is directly supported on the film, and dried to form a dry film resist material, and the film is made to have low solvent resistance or heat resistance, etc., and a dry film resist material is prepared as follows: for example, First, a temporary supporting film having a low solvent resistance or heat resistance such as a curable composition layer is formed on a film having a release property such as a polytetrafluoroethylene film, and then the film having the release property is peeled off. Further, by preparing a dry film, the solvent for the coating liquid can provide good film coating properties mainly for the solubility of the components to be used, and is not particularly affected, and for example, a cellosolve solvent (for example) Such as 2-ethoxyethyl 2-ethoxyethanol ethyl ester, 2-mercaptoethoxyethyl alcohol ethyl ester, 2-ethyl ethyl ethoxide, etc.); propylene glycol solvent (such as propylene glycol monoterpene ether, propylene glycol propylene glycol monobutyl ether, propylene glycol) Monoterpene ether acetate, propylene glycol monoester, propylene glycol monobutyl ether acetate, Di(propylene glycol) dioxime ether, etc. (such as butyl acetate, amyl acetate, ethyl butyrate, butyl butyrate, diethyl acetate, ethyl pyruvate, ethyl 2-hydroxybutyrate, acetonitrile acetic acid曱 vinegar, lactic acid B, 3 - methoxypropionate, etc.; alcoholic alcohol, hexanol, diacetone alcohol, decyl alcohol, etc.); ketone solvent (such as cyclopentyl ketone, etc.); high polarity A solvent (such as dimethyl decylamine, diamine, N-methylpyrrolidone, etc.), and a mixed solvent of these, added with an aromatic hydrocarbon. The solvent usage ratio is usually from 1 to 20 times by weight in terms of the total amount of the components of the hard material. [2-1-3]exposure method 326\patent specification (supplement)\94-03\93134393 85 coated on the other, that is, the olefin film or the detachment layer can be used to make the layer . The content has a charge limit, alcohol oxime ester, ethoxyethanol monoethyl ether, diethyl ether acetic acid; S is a solution, ethyl oxalate, milk L agent (such as heptyl ketone, methyl ethyl hydrazine and further chemical composition right Scope 1297694 Next, regarding the curable smear forming material, if the curable composition layer is provided on the substrate to be processed, the curable composition layer is irradiated with light or heated (preferably, the laser light is under the exposure light source). In the case where the protective layer or the like is provided, the exposure may be performed while the protective layer or the like is held, or the exposure may be performed after peeling off. When the curable composition layer is formed of the dry film resist material, the temporary support film may be retained or exposed after peeling. The exposure light source may, for example, be a carbon arc lamp, a mercury lamp, a xenon lamp, or a metal compound. Lamps, fluorescent lamps, tungsten lamps, halogen lamps, and laser sources (such as Hee e e lasers, argon ion lasers, YAG lasers, HeCd lasers, semiconductor lasers, ruby lasers, etc.), especially Wavelength domain 3 5 0~4 The light source of the laser light in the blue-violet field of 30 nm is preferable, and the center wavelength of the light source is about 405 nm. More specifically, a 405 nm oscillation indium gallium nitride semiconductor laser is used. The scanning exposure method of the laser light source is not particularly limited, and for this purpose, for example, a plane scanning exposure method, an outer drum scanning exposure method, an inner drum scanning exposure method, etc., and a scanning exposure condition preferably can be used for laser irradiation. The output light intensity is set to 1 to 100 mW (more preferably 3 to 70 mW), and it is preferable to set the oscillation wavelength to 3 9 0 to 4 3 0 ηπι (a further preferred is α 4 0 0 to 4 2 nm). It is better to set the spot diameter to 2~3 0 // m (more preferably 4~2 0 // m), and it is better to set the scan speed to 5 0~5 0 m / sec (in 1 0 0 to 4 0 0 m / sec is further preferable), and it is preferable to set the scanning density to 2,0 0 dpi or more (more preferably 4,0 0 dpi or more) to perform scanning exposure. Furthermore, the photohardening of the hardening composition of the present invention is not performed, 86 326\Patent Specification (Supplementary [94]\93134393 1297694 However, it is heated in the presence of a thermal polymerization initiator, whereby a hardened layer can be formed on the substrate. The heating condition can be usually 80 to 250 ° C. 1 0 0~2 0 0 °C The preferred temperature is usually 1 0~1 2 0 minutes, preferably 2 0~60 0 minutes. [2 _ 1 - 4 ] Development method, the development after the aforementioned exposure The treatment is carried out using an aqueous developer which preferably contains an alkali component and, if necessary, a surfactant. The test component can be exemplified by inorganic salt (such as sodium citrate, succinate, lithium citrate, ammonium citrate, sodium metasilicate, potassium metasilicate, sodium hydroxide, potassium hydroxide, lithium hydroxide). , sodium carbonate, sodium hydrogencarbonate, potassium carbonate, sodium hydrogen phosphate, sodium phosphate, ammonium hydrogen phosphate, ammonium phosphate, sodium borate, potassium borate, ammonium borate, etc.), organic amine compounds (such as monomethylamine, diamine, three Indamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, monobutylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, etc.) , according to the concentration of 0.1 to 5 wt% by the user. The surfactant may be the same surfactant as mentioned in the above-mentioned curable composition, wherein a nonionic, anionic or amphoteric surfactant is preferred, and especially an amphoteric surfactant is preferred. Beet 4 gold type compounds are particularly suitable. Further, it is preferable that the above surfactant is used in a concentration of 0.0001 to 20% by weight (more preferably 0.0005 to 10% by weight, and particularly preferably 0. 0.001 to 5%). Further, the developer may contain, if necessary, an organic solvent such as isopropyl alcohol, benzyl alcohol, 2-ethoxyethoxyethyl ester, 2-ethoxyethanol butyl ester, 2-ethoxyethanol phenyl ester, propylene glycol, diacetone alcohol or the like. . Further, the pH of the developer can be preferably set to 87 326\patent specification (supplement)\94-03\93134393 1297694 9 to 14, further preferably 11 to 14. Further, the development processing is usually carried out by a conventional developing method in which the image forming material is immersed in the developing solution or the developer is sprayed onto the image forming material, and preferably at about 10 to 50 ° C. At a further preferred temperature of about 2 0 to 4 ° C, it is carried out for about 5 seconds to 10 minutes. Further, after the development treatment, in order to improve heat resistance or chemical resistance when the image formed by the cured product acts as a photoresist, it is preferably carried out, for example, at a temperature of about 140 to 160 °C. Heat treatment. [2 - 2 ] When the spacer is used, the curable composition dissolved or dispersed in the solvent is usually supplied to the substrate on which the spacer is to be provided in a film form or a pattern by a coating method or the like, so that the solvent In the case of being supplied as a film after drying, if necessary, the formation of a pattern is carried out by a method such as photo-etching by exposure-development. Then, an additional exposure treatment or a heat hardening treatment is performed as needed to form spacers on the substrate. [2 - 2 - 1 ] Method of supplying the 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 carried out by a conventional method such as a spin coating method, a wire coating method, a flow coating method, a die coating method, a roll coating method, a spray coating method or the like. In particular, in the case of the die-coating method, the amount of the coating liquid to be used can be greatly reduced, and it is not affected by moisture or the like which adheres to the spin coating method, and the generation of foreign matter can be suppressed, which is preferable from the viewpoint of comprehensiveness. The coating amount varies depending on the application. For example, in the case of a spacer, the dry film thickness is usually in the range of 0.5 to 10/m, and is in the range of 1 to 8//m. It is preferred to use \94-03\93134393 1297694, and it is particularly suitable in the range of 1~7 #m. Further, in order to dry the film thickness or the height of the spacer formed last, it is important that the substrate is uniform throughout the entire substrate. In the case of large variations, the liquid crystal panel will produce uneven defects. Further, it may be supplied in a pattern by an inkjet method, a printing method, or the like. [2 _ 2 _ 2 ] Drying method Drying after the hardening composition is supplied onto the substrate is preferably carried out in accordance with a drying method using a hot plate, an I R oven, or a convection oven. Further, it may be combined with a vacuum drying method (drying in a pressure-reducing box without increasing the temperature). The drying conditions can be appropriately selected depending on the kind of the solvent component, the performance of the dryer to be used, and the like. The drying time is usually selected according to the type of the solvent component, the performance of the dryer to be used, etc., at a temperature of from 40 to 130 ° C in the range of from 15 seconds to 5 minutes, preferably, by 50. The temperature of ~1 1 0 °C is selected within the range of 30 seconds to 3 minutes. [2 - 2-3] Exposure method Regarding the exposure, a negative resist pattern is superposed on the coating film of the curable composition, and the light source is irradiated with a light source of ultraviolet light or visible light to perform exposure. Furthermore, it is also possible to use a scanning exposure method using laser light. In this case, if necessary, in order to prevent the sensitivity of the photopolymerizable layer caused by oxygen from being lowered, an oxygen barrier layer such as a polyvinyl alcohol layer may be formed in a deoxidizing environment or on the photopolymerizable layer, and exposure may be performed. . The light source used for the above exposure is not particularly limited. The light source may, for example, be a lamp source such as a xenon lamp, a tooth lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal i hydride lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a fluorescent lamp or the like; Argon ion laser, YAG laser, excimer laser, excimer laser, nitrogen laser, 氦编雷89 326\patent specification (supplement)\94-03\93134393 1297694 shot, 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, an image of an image can be formed on a substrate by using an aqueous solution or an organic solvent containing an organic compound containing an organic compound and, if necessary, a surfactant. . The aqueous solution may further contain an organic solvent, a buffer, a dismutating agent, a dye or a pigment. The test compound may, for example, be sodium hydroxide, potassium hydroxide, hydrogen peroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium citrate, potassium citrate, sodium metasilicate, sodium phosphate, phosphoric acid. Inorganic compounds such as potassium, sodium hydrogen phosphate, potassium hydrogen phosphate, dihydrogen phosphate, dihydrogen hydride, and hydrazine; such as monoethanolamine, diethanolamine, triethanolamine, monomethylamine, diamine, three Indoleamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, n-butylamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, ethyleneimine, An organic basic compound such as ethylenediamine, tetraammonium hydroxide (TMAH), or cholestyramine. This test compound may also be a mixture of two or more. Examples of the surfactant include, for example, polyoxyethylene ethyl ethers, polyoxyethylene ethyl aryl ethers, polyoxyalkylene esters, sorbitol alkyl esters, and monoglycerides. Nonionic surfactants such as esters; such as alkyl benzoate, alkylnaphthalene sulfonate, alkyl sulfate, alkyl sulfonate, sulfonate succinate Or anionic surfactant; such as alkyl beet 4, amphoteric acid 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 1297694 2 - ethoxyethanol butyl ester, 2-ethoxyethanol Stable ester, propylene glycol, diacetone alcohol, and the like. The organic solvent may be used alone or in combination with an aqueous solution. [2 - 2 _ 5 ] Additional exposure and thermal hardening treatment The substrate after development may be subjected to additional exposure in the same manner as the above-described exposure method, or may be subjected to thermal hardening treatment. It is especially preferred to carry out a heat hardening treatment. For the thermal hardening treatment conditions, the temperature is selected in the range of 100 to 280 ° C, preferably in the range of 150 to 250 ° C, and the time is selected in the 5 to 6 Within 0 minutes. <Examples> Hereinafter, specific examples of the use of the solder resist layer and the use of the spacers will be described with respect to the curable composition of the present invention. However, the present invention is not subjected to the following embodiments as long as the gist of the present invention is not exceeded. Example limits. [1] Curable composition for solder resist layer Examples 1 to 3, Comparative Examples 1 to 2 The compounds of the above formula (I) and other compounds of the following components (A 1 ) to (A 6 ), a photopolymerization initiator of the component (B 1 to B 4 ), an ethylenically unsaturated compound of the component (C 1 ), an epoxy compound of the component (D 1 ), an epoxy hardener of the component (E 1 ), and a component (Η) 1 to Η 2) inorganic filler, sensitizing dye of component (J 1 to J 3 ), and other components of component (X 1 ), 100 parts by weight of propylene glycol monoterpene ether acetate was added according to the mixing ratio shown in Table 1. A coating liquid was prepared by stirring at room temperature. In addition, for a copper-clad laminate substrate (thickness 1.5 mm, size 2 5 0 mm x 200 mm) of a polyimide foil having a thickness of 3 5 // m thick, a surface treatment material "Scotch-Bright" was used. SF" (manufactured by Sumitomo 3) to polish the surface of the copper joint of the substrate and wash it with water, 91 326\patent specification (supplement)\94-03\93134393 1297694 by air flow drying, the whole surface, and secondly, in the oven After preheating to 6 (TC), the coating liquid obtained as described above is applied to the copper foil of the copper clad layer substrate so that the dry film thickness can be 2 5 // m, and the hot air circulating drying oven is 8 The photocurable ruthenium-forming material was formed by drying at 0 ° C for 30 minutes. (A 1 ) The compound obtained by the following production example was 9,9-bis(4'-hydroxyphenyl)anthracene. Epoxide (epoxy equivalent 231) 231 g, 2-propenyloxyethyl succinic acid (acid value 260, product of "Kongrong Chemical Co., Ltd. "Η Ο A - MS") 2 16 g, triethylbenzylammonium chloride 0 · 4 5 g and p-oxobenzene O.lg were placed in a 500 ml four-necked flask while blowing air at a rate of 25 ml / minute while at 90 ° 1 The solution was heated and dissolved at 0 ° C, and then slowly heated to 120 ° C in a state where the solution was cloudy, so that it was completely dissolved, and then the solution became a transparent viscous solution, and the mixture was further heated and stirred for 8 hours to make it acid. The value reached 0. 8 K 0 Η · mg / g, and a colorless and transparent reaction product was obtained. Then, to the obtained reaction product 4 4 7 g, 2 - ethyl ethoxyethanol ethyl ester 20 g was added to dissolve Thereafter, 3,8 g of 1,2,3,6-tetrahydro-S-acid anhydride, 7 3 g of biphenyltetracarboxylic dianhydride, and 1 g of tetraethylammonium bromide were added thereto, and the temperature was gradually raised in 1 The reaction was carried out at a temperature of 1 0 to 1 1 5 ° C for 2 hours, thereby obtaining a compound (A 1 ). The obtained compound had a weight average molecular weight of 3,500 and a double bond equivalent of 5 60 Å (A 2 ). The compound obtained in the following production example, 200 parts by weight of succinic anhydride and 596 parts by weight of commercially available pentaerythritol triacrylate in the presence of 2.5 parts by weight of triethylamine and 0.25 parts by weight of hydrogen and at 1 0 0 The reaction was carried out at a temperature of ° C for 5 hours to obtain a polyfunctional C having one carboxyl group and two or more acryl groups in one molecule. 92326 \ patent specification (complement member) \ 94-03 \ 931,343,931,297,694 ester 6 7 m ο 1% of pentaerythritol tetraacrylate and 3 3 m ο 9 4 many functional acrylic ester mixtures constituted 1% of the acid value. (A 2 ) was obtained in the same manner as in the production example of the above (A 1 ) except that the polyorganic acid ester mixture was used in place of 2 - propylene oxide ethyl succinic acid. The weight average molecular weight of the obtained compound was 3,0 0 0 and the double was 2 1 0. (A3) A compound obtained by the following production example, in the production example of the above (A1), except that diphenyl ketone tetracarboxylate 80.5 g is used instead of biphenyltetracarboxylic dianhydride 7 3 · 5 Except for g, the same procedure as in the previous production example was carried out to obtain a compound (A 3 ). The weight average molecular weight obtained was 3,500 and the double bond equivalent was 189.

(A4) A compound obtained by the following production example, in the production example of the above (A1), except that 9,3 -bis(4' fluorene benzene) quinone diepoxide 2 3 1 g is used instead of 9, The compound (A 4 ) was obtained in the same manner as in the production example of the above (A 1 ) except that 9 -bis (4 '-hydroxy J diepoxide 2 3 1 g). The obtained compound had an average weight of 3,000. The double bond equivalent was 187. (A5; used in Comparative Example) The compound obtained by the following Production Example was used in the production example of the above (A1) except that 72 g of acrylic acid was used to give propylene oxide succinic acid 216 g. All of them were produced by the preparation of the above (A1) to give the compound (A 5 ). The obtained compound had a molecular weight of 3,200 and a double bond equivalent of 416. (A 6 ; for comparative examples) (A6) (acid value 100 mgKOH/g, weight average molecular weight 5,000, double 326\patent specification (supplement)\94-03\93134393 93 with a compound repeating acid having a propylene oxide of 16 g The dianhydride (A1) compound 3,-t) oxime is used as a substitute for 2 - the first amount of the average compound bond equivalent 129769 4 3 9 8, "P R - 3 Ο 0 J" manufactured by Showa Polymer Co., Ltd.)

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(Bl) l-(4_曱thiobenzene)-2-Mallin-2-mercaptopropan-1-yin (B2) 2,4-diethylsulfanthone (Β3)2-hydroxy-4 - n-octyl diphenyl ketone (Β4) 2, 2'-bis(o-chlorophenyl)_4, 4', 5, 5'-tetrabenzimidazole (C1) bis(pentaerythritol) hexaacrylate (D 1 O-p-phenol phenolic resin type epoxy resin (epoxy value 2 1 JAPAN EPOXY RESIN C0·"EPICOAT180S70") (E 1 )Cyanide (Η 1 ) barium sulfate (Η 2 ) talc (J1) Sensitizing dye (J2) The following sensitizing dye (J3) The following sensitizing dye 326\Patent specification (supplement)\94-03\93134393 94 1297694 αΐ)

Ch3 (X 1 ) phthalocyanine green [1 - 1 ] High-pressure mercury lamp exposure sensitivity The photocurable photographic image-forming material obtained as described above was measured for exposure sensitivity as shown below, and the results were not shown in Table 1. The photocurable composition layer of the obtained image forming material was irradiated with a 1 kW ultrahigh pressure mercury lamp, and it was found to be under the use of a 1 wt% aqueous sodium carbonate solution and developed at a temperature of 30 ° C for 80 seconds. The minimum exposure (m J / c m2 ) of the tone image is reproduced as the sensitivity. [1 - 2 ] Adhesiveness to the substrate Next, the obtained photocurable image forming material was evaluated for the adhesion of the cured layer to the substrate to be processed and the heat resistance thereof as shown below, and the results were shown in in FIG. 1.

The photohardenable composition layer of the obtained ruthenium-forming material is obtained by using the 1 k W 95 326\patent specification (supplement)\94-03\93134393 1297694 ultra-high pressure mercury lamp as described above. After the exposure amount is irradiated so that the entire hardened layer is formed, the obtained hardened layer is subjected to heat treatment at a temperature of 150 ° C for 60 minutes, and then, according to JIS D 0 2 0 2, a cutting machine can be used at intervals of 1 mm. A cut pattern was applied to the hardened layer by a method of 100 squares, and a cellophane tape manufactured by Nichiban Co. was attached to the hardened layer to measure the peeling of the hardened layer when the tape was peeled off. The number of cells is evaluated on the basis of the following criteria. A: In 100 squares, the number of peeled squares of the hardened layer is zero. B: In 100 squares, the number of peeling squares of the hardened layer is one or more and less than five. C: In 100 squares, the number of peeling squares of the hardened layer is 5 or more and less than 10 pieces. D: In 100 squares, the number of peeled squares of the hardened layer is more than 10 pieces. [1 _ 3 ] The heat of adhesion is the same as described above, and after applying a cut by a cutting tool so that it can become 100 squares, FLUX (TAMURΑ ΚΑΚΕN C0.) is applied to the surface, Next, the operation of returning to room temperature after immersing in a solder bath at 290 ° C for 30 seconds was repeated six times. Then, the cellophane tape was attached to the hardened layer, and as described above, the number of peeled squares of the hardened layer at the time of peeling of the tape was measured, and evaluated on the same basis. [1 - 4] Laser exposure sensitivity Example 4 (curable composition for solder resist layer: laser exposure) With respect to the photocurable image forming material produced in the same manner as in Examples 1 to 3, laser light was used. Under the exposure light source, measure the laser exposure 326\patent specification (supplement)\94-03\93134393 96 1297694 degrees as follows, and then, except for changing the exposure source to laser light, The evaluation of the adhesion of the substrate and the heat resistance thereof was carried out, and the results are shown in Table 1. The photocurable composition layer of the obtained ruthenium-forming material is fixed on a cylinder of a diameter of 7 cm, at a frequency of 10 to 100 rpm, and a wavelength of 0.45 nm is used under a change of the number of revolutions. Laser output 5 m W laser source ("NLHV 5 0 0 C" manufactured by Yuya Chemical Industry Co., Ltd.), with image area illumination of 2 mW and spot diameter of 2 0 // m and changing beam scanning interval and scanning speed Scanning exposure was carried out underneath, and then, under the use of a 10 wt% aqueous solution of sodium carbonate at 30 ° C as a developing solution, it was sprayed in a manner of 0.15 Μ P a , and the minimum development time was 1 . The spray development was performed 5 times, thereby causing the image to appear. Regarding the obtained artifact, the exposure amount required for reproduction of the line width of 2 0 // m was obtained as the sensitivity to the blue-violet laser. [2] Hardenable composition for solder resist layer: dry film resist Examples 5 to 7 The photocurable composition was applied as an auxiliary support using an applicator in a dry film thickness of 25 // m. The film of polyethylene terephthalate film (thickness 1 9 // m) was dried in an oven at 90 ° C for 5 minutes, and a layer of the photocurable composition layer was formed as a coating film. The polyethylene film (thickness 2 5 // m) was placed for 1 day to form a dry film photoresist. Next, the obtained dry film resist material was peeled off from the polyethylene film, and the peeled surface was rolled under a manual roll laminator at a roll temperature of 100 ° C, and rolled by 0.3 Μ P a The lamination speed was 1.5 m/min and laminated on the copper foil of the copper clad layer substrate which was the same as those used in Examples 1 to 3, and a photocurable composition layer 97 326\patent specification (supplement) was prepared. </ RTI> <RTIgt; The adhesion and its heat resistance were evaluated, and the result 98 was formed. The composition layer, and then the implementation is shown in Table 1. 326\Patent specification (supplement)\94·03\93134393 1297694

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r~\ /^N /^-N /-\ 1-H CN] CO 〇Q PQ CQ 〇Q 1-ϊ^§ £ Μ 2i JJl· (la) in^s^Ae (13) s § (5 (S (5 SFSf) * ¥ (IX) ss $s^ e6e々el e6\e046\ff}s)_ra^rji#\9le 1297694 [3] Hardened composition for spacers Example 8~1 4, comparison Examples 3 to 4 The components (A2) and (A5) are a compound represented by the formula (I) of the following components (A8) to (A12), and a polymerization initiator and a component (C) of the other compound and the component (B1). 1) and (C 2 ) of 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 to the propylene glycol in the mixing ratio shown in Table 2. 100 parts by weight of monoterpene ether acetate, and a coating liquid was prepared by stirring at room temperature. Regarding the obtained coating liquid, the evaluation of storage stability was carried out according to the following method, and the results are shown in Table 2. [3 - 1 ] Preservation stability When the coating solution is sealed in a sample bottle and stored at a temperature of 35 ° C for 7 ,, the change in viscosity and minimum development time before and after storage is measured, and the following is as follows. The basis is evaluated. 〇: Viscosity change is ± Within 3 % and the minimum development time varies within ± 3 %. △: Viscosity change is outside the range of ± 3 %, but the minimum development time varies within ± 3 %. X : Viscosity change is within ± 3 % However, the change of the minimum development time is outside the range of ± 3 %. (A 8 ) The compound obtained by the following production example is used instead of 1, 2, 3, using 137 g of 1,2,3,6-tetrahydrophthalic anhydride. Each of 38-g of tetrahydrophthalic anhydride and 73.5 g of biphenyltetracarboxylic dianhydride was produced in the same manner as in the production example of the above (A2) to obtain a compound (A 8 ). The obtained compound had an acid value of 56 and a weight. The average molecular weight is 2,620 and the double bond equivalent is 216. 100 326\Patent specification (supplement)\94-03\93134393 1297694 (A9) The compound obtained by the following manufacturing example will be 9 , 9 - double (4 ' -Hydroxybenzene) bis diglycidyl etherate (epoxy equivalent 2 3 1 ) 100 parts, a reaction mixture of succinic anhydride and pentaerythritol triacrylate (the same as used in the production example of (A 2 ) above, acid Value 9 0 · 5 ) 2 7 3 · 2 parts, 0.19 parts of p-methoxyphenol, 7.4 parts of triphenylphosphine, and propylene glycol monoterpene ether acetate 3 6 8 parts were charged into the reaction vessel and stirred at a temperature of 90 ° C until the acid value reached 5 m g - Κ Ο H / g or less. For the acid value to reach the target, spend 10 hours (acid value 1.0). Next, the reaction liquid obtained by the above reaction was 80 parts, and 6 parts of propylene glycol monomethyl ether acetate was added thereto, and 9 parts of hexamethylene diisocyanate and 0.1 part of dibutyltin dilaurate were added thereto. The reaction was carried out at a temperature of 90 ° C for 3 hours, and then 3. 8 parts of trimellitic anhydride was added, and the reaction was carried out at a temperature of 90 ° C for 3 hours to obtain a polyphenylene having an acid value of 5 2 and measured by GPC. A solution of a compound (A 9 ) having a weight average molecular weight of 3,100 in terms of ethylene and a compound having a double bond equivalent of 199. (A 1 0 ) a resin having a phenol decane structure ("TCR1286" manufactured by Nippon Kayaku Co., Ltd., having an acid value of 101, a double bond equivalent of 315, and a di(ethylene glycol) monoethyl ether acetate solution) (A) 1 1 ) A compound obtained by the following production example (additional test of the acrylic resin described in Synthesis Example 3 of Japanese Patent Laid-Open Publication No. Hei No. Hei No. Hei No. 1 1 - 3 3 3 0 0) 2, 2' - 7 parts by weight of azobis(2,4-dimethylvaleronitrile) and 200 parts by weight of di(ethylene glycol) dioxime ether were placed in a flask equipped with a cooling tube and a stirrer. Then, 10 parts by weight of styrene, 20 parts by weight of methacrylic acid, 45 parts by weight of glycidyl acrylate, and 2,5,5,3,3,3,3,3,3 )\94-03\93134393 1297694 Parts by weight 'When using nitrogen to ventilate, slowly start to stir; mix. The temperature rises to 7 (TC, maintaining this temperature for 5 hours to obtain a polymer solution of the substance (A 1 1 ). The solid solution of the obtained polymer solution is 33%, and the weight average molecular weight of the polymer is 1,800. (A 1 2 ) The compound obtained by the following production examples is 57.5 g and 1,2,3,6-tetrahydroanthracene anhydride 43.1 g of "RIKACIDBT-100 Physicochemical Co., Ltd." which is a tetracarboxylic dianhydride. 2,3,6-tetrahydrophthalic anhydride 388 and biphenyltetracarboxylic dianhydride 73· were both produced in the same manner as in the production example of (A 2 ), and the compound obtained had an acid value of 55 and a weight average molecular weight of 4,450. (2): (C2) The ketone-containing acrylic acid-containing product of the above formula (VIIIc) (KAYARADP Μ 2 1): (F 1 ) melamine resin and its Modified resin (Sanhe Chemical r NIKALACK E-21 51)) (J 1 ) Fluorine-based surfactant (Otsuka Ink Chemical Industry r MEGAFAX F-4 7 5 j ) (Nl) Shi Xi Burning Coupler (Toray Dow Corning Co. Product" Subsequently, a spin coater was used to apply the coating liquid to a IT 0 film on a glass substrate having an IT 0 film. And drying on a hot plate for 3 minutes to form a coating film. The obtained coating film has nine circular openings each having a diameter of 5 to 2 0 // m and a pattern mask of each square opening portion. Under the exposure light, the intensity of the exposure gap of 365 nm is 32 mW/cm2 to expose the 326\patent specification (supplement)\94-03\93134393 102 to make the concentration of the copolymer contained in the solution (new Japanese 8 g instead of 5 g) In addition, (A 1 2 ) ° double bond equivalent 醯 oxy) company product company SH 6 0 4 0") surface formation 80 ° C temperature in the use of a side 5mm to 1 5 0 / m » The exposure can be performed in the manner of 1297694 6 0 m J / cm 2. The ultraviolet irradiation is performed under air. Secondly, 0.1% potassium hydroxide aqueous solution at 23 ° C is used, and the minimum development time is used. After spray development for 2 times, it was washed with pure water for 1 minute. Here, the minimum development time means that the unexposed portion is completely melted under the same development conditions. Part of the substrate formed with the spacer pattern in the oven Heat hardening at 30 ° C for 30 minutes, and obtain a plurality of spacer patterns having different bottom areas, and the height of the film portion (formed at a square opening of 5 mm or more on each side) is about 4 // m. With respect to the obtained spacer pattern, the adhesion and the compression characteristics were evaluated in accordance with the following methods, and the results are shown in Table 2. [3 - 2] Adhesion The adhesion evaluation was performed on Examples 8 to 1 1 and Comparative Examples 3 and 4. Regarding a spacer pattern having different bottom areas obtained from a pattern mask film having different mask opening diameters, eight or more patterns are formed in nine spacer patterns having the same pattern height of 3//m or more. The minimum pattern size (i.e., the pattern lacking one or less of the nine patterns that should be formed) defines the adhesion, and the bottom area is shown in Table 2. [3 - 3 ] Compression characteristics: Load using a micro hardness tester - In addition to the load test, the spacer pattern obtained above is used in an ultra-deep color 3D shape measuring microscope "VK - 9 5" manufactured by Kishins. Below 0 0", a longitudinal section through the axis of the spacer pattern is depicted. A line AA which is parallel to the substrate surface (substrate surface in the pattern of the spacer pattern) at a height of 90% from the substrate surface to the highest position point Q shown in the schematic diagram of FIG. 2 The length of ' is measured. Next, the straight line A A ' is the diameter of the 103 326 \ patent specification (supplement) \94·03\93134393 1297694 round area is set as the cross-sectional area above the spacer pattern. Among them, regarding one pattern having an upper sectional area of 80±10//m2, the load of the “Shimazu Dynamic Super Micro Hardness Tester DUH-W 2 0 1 S” was used to evaluate the compression. characteristic. The test conditions are set at a temperature of 2 3 °C, using a plane pressure of 50 @ // Hi, applying a load to the spacer at a certain speed (0.22 gf / sec), and maintaining the load when the load reaches 5 gf. 5 seconds, followed by the method of removing the load at this speed. According to the load-displacement curve obtained by this test (shown in Fig. 3), the maximum displacement Η [ ma X ], the final displacement Η [L ast ], and the recovery rate (%) = { Η [ 1 Ast ] / (pattern height before test) 丨x 1 0 0, elastic recovery rate (%) = {(H[max] -H[last])/H[max]}xlOO, the displacement at load is 0· When 25#πι is overweight N(gf), it is shown in Table 2. [3 - 4] Evaluation of spacer characteristics (evaluation of panel) A liquid crystal cell was prepared in accordance with the following method to evaluate the characteristics of the spacer. An electrode substrate A is prepared in which an IT 0 film and an electrode substrate B are integrally formed on one surface of a 2.5 cm square alkali-free glass substrate (Asa - 1 0 0). A 1 cm square IT0 film was formed on the central portion of one side of the same glass substrate of 2.5 cm square, and an output electrode of 2 mm width was connected thereto. The curable composition shown in each example was applied onto the electrode substrate A by spin coating, and heated on a hot plate at a temperature of 80 ° C for 3 minutes, using a portion having a central portion of 1 cm squared. The circular pattern of 80//Π12 can be arranged at 30°/cm X 3 /cm = 990 at equal intervals). The exposure mask is designed on the grid to press the exposure and light gap 1 5 0 // m to perform exposure. The irradiation energy is 326\patent specification (supplement)\94-03\93134393 104 1297694 6 0 m J / c m 2 . Subsequently, after developing with potassium hydroxide aqueous solution, it was washed with pure water, and fired at a temperature of 230 ° C in a hot air circulating furnace for 30 minutes. The coating conditions are adjusted so that the height of the spacer after firing can be 4 // m. Thus, an electrode substrate A in which a test pattern of spacers was formed at the center portion was prepared. Then, the alignment film (Nissan Chemical Co., Ltd. "S unever 7 4 9 2") was applied onto the electrode substrates A and B by spin coating, and then subjected to 1 1 Ο ° C for 1 minute on a hot plate. It was dried and then heated in a hot air circulating oven at a temperature of 200 ° C for 1 hour to form a coating film having a film thickness of 7 Ο nm. After applying the alignment treatment using a friction machine, an epoxy resin sealant containing ceria beads having a diameter of 4 // m was applied to the outer periphery of the surface of the electrode substrate B coated with the alignment film under the use of a dispenser. And the outer edge portion of the surface of the electrode substrate A on which the spacer test pattern is formed is disposed to be offset by 3 mm, and is heated at a temperature of 180 ° C in a hot air circulating furnace while being kept under pressure. 2 hours. With respect to the thus obtained empty unit, liquid crystal (Melk product Z L I - 4 7 9 2 ) was injected therein, and a peripheral portion of the UW was sealed with a U V hardening type sealant to prepare a test liquid crystal cell. An alternating voltage of 5 V, 6 Ο Η z was applied to the thus obtained liquid crystal cell, and the in-plane unevenness of the electro-optical response of the electrode forming portion was observed by a visual observation and a microscope. In the case where no in-plane unevenness was observed in both the visual and the microscope, it was evaluated as 〇, and it was evaluated as Δ in the case where the surface unevenness was not visually recognized but uneven in the surface of the microscope confirmation, and the unevenness in the surface was visually confirmed. The situation is rated as X and the results are shown in Table 2. 326\Patent specification (supplement)\94-03\93134393 105 1297694 |Comparative example 4 1 46.95 〇〇46. 95 T—H ◦· CO X 205.4 oo LO οα 1.26 t—CO ◦· CO oo inch 0.56 &lt; 1 Comparative Example 3 46.95 CO 46.95 CO CD &lt; 164.3 1 cd 1 1 1 1.30 0. 75 OO CNI inch cr&gt; CO o X Example 14| 46. 95 CO 46. 95 CO cz&gt;&lt; LO 〇〇CO 1 1.65 ο oo ◦· oo 0.38 〇|Example 13 | 46.95 CO 46.95 CO CD 〇1 155. 1 1 1 1.58 0. 74 2 oo times CO LO rH 呀 CD 〇|Example 121 46.95 CO 46.95 CO H ◦· 〇 1 136.6 1 1 1.40 0.59 LO oo oo LO CD CD ◦· 〇1 Example 111 46.95 CO 46.95 rH ◦· r—H &lt; 1 139.1 1 1 oi CNI 1.38 0.55 CD OO § CO CO ◦' 〇1 implementation Example ίο I 46.95 CO 46. 95 i 1 CD CO 〇 1 141.9 1 1 CD r—Η 1.39 0. 54 OO Z£&gt; oa CO Q· 〇 Example 9 46. 95 CO 46. 95 CO r—&lt; 〇· 〇r-i CD 呀Τ~Ή oo CO rH 1.42 CD oo g CLD 0.60 〇|Example 8 | 46. 95 CO 46.95 CO rH CD &lt; CD ai CO r-H CO csi 1.35 0.55 CO oo LO CO CD ◦· 〇(A2) (A8) 1 (A9) (A10) (A12) (A5) (All) (Bl) (Cl) (C2) (FI) HH (Nl) Save the stability of the composition of the whole double key equivalent cO Le w ίχί Last displacement H [last] ( // m) Recovery rate 00 Elastic recovery rate 00 ss LO ^ &gt; w Evaluation of the panel compound (B) polymerization initiator (C Ethylene unsaturated compound (F) surfactant (I) amine compound i (N) additive adhesion compression characteristics hair 趄 趄 哒荽 侧

9〇一® e6eKle6\eo46\(47}ii)_s^^*\9&lt;Ne 1297694 Although the present invention will be described in detail using specific aspects, it will be apparent to those skilled in the art that Variety. In addition, this case is based on the application for a patent (Purity 2 0 0 3 - 3 8 0 6 6 6 ) filed on January 1st, 2003, and the whole is used as a whole. &lt;Industrial Applicability&gt; The curable composition of the present invention is used for a printed wiring board, a liquid crystal display element, a plasma display device, a large-scale integrated circuit, a thin transistor, a semiconductor package, and color filter The formation of a solder mask, a coating film, and an insulating coating of various electronic parts in the fields of a sheet, an organic electric field illuminating mechanism, and the like is particularly suitable for use as a direct tracer using laser light. Further, 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 color filter, a black substrate, an overcoat layer, a rib, and a hardenable composition for a spacer. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing a drawing position when a spacer pattern is seen from above. 2 is a schematic view showing a longitudinal sectional view of a spacer pattern. Figure 3 is a schematic diagram showing the loading of the spacer - the load-displacement curve in addition to the load test. [Description of main component symbols] 1 spacer pattern 2 spacer pattern middle axis 3 drawing position 4 spacer pattern longitudinal section outline 107 326\patent specification (supplement)\94-03\93134393 1297694 5 from the substrate surface to the highest The height of the position 6 is 90% of the height from the substrate surface to the highest position. 7 The diameter of the upper section is AA'

326\Patent specification (supplement)\94-03\93134393 108

Claims (1)

1297694 X. Patent application scope: 1. A hardenable composition characterized by containing the following general formula (I) , 0—R— [In the formula (I), R 1 represents an alkylene group which may have a substituent, or an arylene group which may have a substituent; and R 2 represents a carbon atom which may have a substituent of 5 or more The carbonyloxy group having an ethylenically unsaturated group; R3 and R4 each independently represent an optional substituent; η is an integer of 0 to 10; and 4 benzene rings may further have a compound represented by a substituent]. 2. The sclerosing composition of claim 1, wherein R2 is the following formula (I I ) [In the formula (II), R7, R8 and R9 each independently represent a hydrogen atom or a methyl group, and Υ1 is an optional divalent group, wherein * represents a compound of the formula (I), -CH2- and R2 A carbonyloxy group having an ethylenically unsaturated group having 5 or more carbon atoms represented by a bond. 3. The sclerosing composition of claim 1 or 2, wherein R3 is a hydrogen atom; the following formula (Ilia) 109 326\patent specification (supplement)\94-03\93134393 1297694 〇II (ffla a C - R51 [In the formula (Ilia), R51 represents an alkyl group which may have a substituent, an alkenyl group which may have a substituent, a cycloalkyl group which may have a substituent, a cycloalkenyl group which may have a substituent, or a substituent represented by an aryl group which may have a substituent; and the following formula (mb) 〇|| H (rab) - C - N - R 5 2 [In the formula (Illb), R52 represents a substituent which may have a substituent The substituent represented by an alkyl group, an alkenyl group which may have a substituent, a cycloalkyl group which may have a substituent, a cycloalkenyl group which may have a substituent, or an aryl group which may have a substituent may be selected. 4. The sclerosing composition according to claim 1 or 2, wherein R4 is a formula (IV) R2 - ch2 - ch - CH2 - (〇R)) plant * I ο αν) I R3 [in In the formula (IV), the definitions of R1, R2, R3, and η are the same as those defined by the formula (I), and * in the formula (IV) represents the _0- and R4 of the compound of the formula (I). The substituent shown by the bond]. 5. If the sclerosing composition of claim 1 or 2 is applied, the 326\patent specification (supplement)\94-03\93134393 110