TW201113241A - Hydrazide compound, method for producing the same, and curing agent, resin composition and cured product using the same - Google Patents

Abstract

To provide a hydrazide compound that has high activity to a resin containing an unsaturated bond, is stably reacted and is usable as a curing agent, a method for producing the same, a heat curing agent, a resin composition and a cured product. The hydrazide compound comprises a crystalline hydrazide compound containing at least one hydrazide group in the molecule and a metal element capable of forming a complex with the crystalline hydrazide compound. The curing agent for resins contains the hydrazide compound. The resin composition comprises the curing agent, a resin containing at least one unsaturated bond in one molecule and an epoxy resin. The cured product is obtained by curing the resin composition. The method for producing the hydrazide compound includes a step for heating a crystalline hydrazide compound containing at least one hydrazide group in the molecule and a metal element capable of forming a complex with the crystalline hydrazide compound to give a mixture, a step for isothermally treating the mixture and a step for cooling the mixture to give a solidified substance.

Description

[Technical Field] The present invention relates to a bismuth compound which can be used as a curing agent for a resin composition, a method for producing the same, and a curing agent, a resin composition and a cured product using the same . [Prior Art] When manufacturing electronic parts and the like, in order to perform high-precision position fixing of wirings, parts, etc., 'primary hardening by light irradiation such as ultraviolet rays (UV), false fixing, and secondary hardening by heating A fixed photothermographic resin composition is known. In general, the photothermographic resin composition is a composition of a resin having a (meth)acryl group as a photocuring component and a resin having an epoxy group as a heat curing component in an arbitrary ratio. As the photothermographic resin composition, for example, a method of dropping on a liquid crystal panel is used. This method can be used as a method for producing a liquid crystal display unit cell by dropping a liquid crystal on the inner side of the liquid crystal sealing agent formed on a substrate and then bonding the other substrate to produce a liquid crystal display cell. When a method of dropping a photothermographic resin composition onto a liquid crystal panel is used, insufficient hardening occurs in the light-shielding portion where the irradiated light does not rotate, and the channel is closed, and the panel is peeled off, and liquid crystal contamination occurs due to elution of the resin component. . In addition, in recent years, it is difficult to make the pitch of wirings and the like narrower and more precise, depending on the wiring or design. In recent years, it is difficult to increase the amount of light-shielding that is irradiated with light such as ultraviolet rays. The tendency is that even if there is a light-shielding portion that is hard to be irradiated with light, it is required to have no hardening agent which is insufficient in hardening. In order to solve the problem of insufficient hardening of the light-shielding portion into which the light does not rotate, for example, (1) a method of scattering light transmitted through the resin composition by adding a filler having a specific surface area (for example, Patent Document 1); (2) a method of adding a high-sensitivity photoinitiator or a photosensitizer to the resin composition; (3) adding a thermosetting agent of an acrylic resin to the resin composition, and performing secondary hardening by heat to improve the light-shielding portion An insufficient method of hardening once; (4) adding a thermosetting agent of an epoxy resin to the resin composition, and performing secondary hardening by heat to improve the insufficient hardening of the light-shielding portion. However, (1) by the light scattering method of the entangled material, since the hardening distance is related to the gap, and the light-shielding portion of 0·3 mm or more from the opening becomes hard to be hardened, there is a problem that design is limited. (2) A method of adding a high-sensitivity photoinitiator or a photosensitizer, which may cause contamination of the liquid crystal due to a component formed by a secondary reaction during the curing reaction. (3) A method of adding a thermosetting agent of an acrylic resin, using Organic peroxides are used as thermal hardeners, and such peroxides are easily dissolved in liquid crystals due to liquids, which tend to become a cause of contamination and cause seepage. Moreover, since organic peroxides are hardened by oxygen, there is a problem of poor hardening in the atmosphere. The organic peroxide-based thermal curing agent is, for example, a ketone peroxide, a peracetal, a hydrogen peroxide, a dialkyl peroxide, a dinonyl peroxide, a peroxyester or a peroxycarbonate. -6- 201113241 (4) A method of adding a thermosetting agent for an epoxy resin, using an amine compound, an acid anhydride, an antimony compound or the like as a thermosetting agent. Among these hardeners, since the amine compound has low-temperature curability, it is often used in the field where quick-curing property is required. However, the amine compound has a problem of poor moisture resistance or electrical properties and a short service life. Although it has the advantage of high transparency, it has only a problem of slightly poor moisture resistance. Here, as the amine compound, for example, a fatty acid polyamine such as diethylenetriamine 'triethylenetetramine or a modified polyamine such as an epoxy resin, acrylonitrile or ethylene oxide, or m-phenylenediamine is added to the aliphatic polyamine. An aromatic polyamine such as diaminodiphenylmethane or diaminodiphenylphosphonium. Further, as the acid anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl nalamic anhydride, trimellitic anhydride or the like is used. As the ruthenium compound, a dibasic acid bismuth such as diammonium adipate, dinonyl dodecanedioate or diterpene sebacate is used. In the epoxy resin thermal curing agent, the antimony compound (especially the dibasic acid diterpene compound) has superior storage stability, lower curing temperature, and shorter curing time than the amine compound or acid anhydride. Most of the advantages are used as a thermal hardener. Further, for example, it is proposed to add a dibasic acid diterpene compound (yttrium adipate; AD Η ) having an average particle diameter of 1 to 1 in a photothermographic resin composition as a heat hardening agent, in a heat hardening, in a matrix The hardener is uniformly added to improve the hardening of the shading portion. However, the typical hardening agent formed by the bismuth compound of the dibasic acid bismuth compound causes intense dissolution, viscosity decrease, and contamination of the adherend due to the single crystal of the organic compound, which is near the melting point 201113241. problem. In order to avoid this problem, when a low-temperature curable bismuth compound is used, there is a problem that the liquid stability is poor and the service life is poor. On the other hand, the bismuth compound having a good service life lacks low-temperature hardenability. [Patent Document 1] [Patent Document 1] JP-A-2006-5 8466 SUMMARY OF THE INVENTION An object of the present invention is to provide a high activity for a resin having an unsaturated bond and to shorten a low temperature of a curing temperature. And the sputum compound which is useful as a thermosetting agent, and the method of producing the same, and the curing agent, the resin composition, and the cured product thereof, which have been used for the purpose of solving the above problems, and the result of further in-depth review. It has been found that a resin having an unsaturated bond can be reacted by reacting a crystalline ruthenium compound having at least one fluorenyl group in the molecule and a metal element capable of forming a complex with the crystalline ruthenium compound. It is highly active and can be uniformly reacted, and the curing temperature can be lowered and the hardening time can be shortened, and a cerium compound which is useful as a curing agent which is stable in use life can be obtained. In other words, the invention is as follows. [1] A seed compound characterized by containing a crystalline germanium compound having at least one mercapto group in a molecule to form a complex metal compound with the crystalline germanium compound. [2] The X-ray diffraction spectrum of the ruthenium compound described in the above [1], which is on the Cu-Κα line 201113241 (wavelength 1.541A), at a Bragg angle of 20 (error 20 ± 〇. 2 °) 5_5. The range of ～7.5° has a peak 〇 [3] The oxime compound according to the above [1] or [2], wherein the melting point is from 60 to 2400. The oxime compound according to any one of the above [1] to [3] wherein the metal element is at least one selected from the group consisting of aluminum, titanium, tin, pin, zinc, iron, magnesium, cobalt, and nickel. , 铋, molybdenum, copper, niobium, tantalum, niobium, tantalum, niobium, tantalum, niobium, tantalum, niobium, calcium, silver, niobium, and gold. [5] As mentioned above [1]~[4] The cerium compound according to any one of the above [1] to [5], wherein the content of the metal element is 0.1 to 20.0% by mass based on the total of the crystalline cerium compound and the metal element. [6] The bismuth compound described in any one of the above [1] to [6], which contains the dibasic acid bismuth compound. [8] The ruthenium compound according to the above [6], wherein the two or more kinds of the crystalline ruthenium compounds are all bismuth bismuth compounds. [9] The ruthenium compound according to the above [6] or [8] The content of one type of crystalline ruthenium compound is from 1 to 99% by mass based on the total of two or more kinds of crystalline ruthenium compounds. [10] As in the above [1] to [9] The bismuth compound described in the above, wherein the average particle diameter is 0.5 to 20.0 #m. [11] A curing agent for a resin which is characterized by containing the ugly of any of the foregoing Π]~ -9 - 201113241 [1 ο ] [12] A resin composition comprising the curing agent according to [11] above, and a resin and/or an epoxy resin having at least one unsaturated bond in the molecule. [13] [12] The resin composition according to [12], wherein the resin having an unsaturated bond has a resin having at least one (meth) acrylonitrile group in the molecule. [14] A cured product characterized by the aforementioned [12] or [ 13] The resin composition described above is formed by curing. [15] A method for producing a ruthenium compound, which comprises a crystalline ruthenium compound having at least one fluorenyl group in a molecule, and a crystallization compound The cerium compound forms a metal element of the complex compound and is heated to obtain a mixture. The step of preparing the mixture after the constant temperature treatment, the step of subjecting the mixture to a constant temperature treatment, and then cooling the mixture to obtain a cured product. ] as described in [15] above And a step of pulverizing the solid into particles having an average particle diameter of 0.5 to 20. Ο/zm. [Effect of the invention] The ruthenium compound of the present invention is presumed to have at least one ruthenium in the molecule. The base crystalline bismuth compound and the metal element which can be formed by being misaligned with the crystalline ruthenium compound, at least a part of the crystalline ruthenium compound forms a complex with the metal element. Further, the activity becomes high in the case of the unsaturated bond. -10- 201113241 Moreover, since the ruthenium compound of the present invention tends to have a lower melting point than the crystalline ruthenium compound of the raw material, the heat of fusion is also small, so that it is lower. At a temperature, it reacts with an unsaturated bond (for example, (meth)acryl group) or an epoxy group, and does not cause a decrease in viscosity or contamination of the binder, and can be uniformly hardened and the hardening time is shortened. As described above, the ruthenium compound of the present invention can lower the curing temperature and shorten the curing time, and can be suitably used as a curing agent such as a resin having an unsaturated bond and/or an epoxy resin. The resin composition using the hydrazine compound of the present invention as a curing agent has a stable use period and good productivity. [Best Mode for Carrying Out the Invention] The ruthenium compound of the present invention contains a crystalline ruthenium compound having at least one fluorenyl group in the molecule, and a metal capable of forming a complex with the crystalline ruthenium compound. element. The crystalline cerium compound is not particularly limited as long as it has crystallinity and has at least one fluorenyl group in the molecule, and one fluorenyl group having one fluorenyl group in the molecule can be used. A dibasic acid bismuth having two fluorenyl groups, a tribasic acid bismuth having three fluorenyl groups in the molecule, and a polyfunctional fluorene having four or more fluorenyl groups in the molecule. Among them, in terms of heat resistance, it is preferred to use a polyfunctional ruthenium compound. As the crystalline ruthenium compound, one type of crystalline ruthenium compound may be used alone, or two or more kinds of crystalline ruthenium compounds may be arbitrarily combined. For the crystalline ruthenium compound of any combination, for example, one type of monobasic acid bismuth compound may be used alone, two or more types of monobasic acid hydrazine compound -11 - 201113241 may be used in combination, and the acid bismuth dibasic acid may be crystallized by two times. 1 One-component bismuth bismuth compound can be used alone, one bismuth compound and one bismuth bismuth compound can be used in combination, two or more kinds of cerium compounds can be used in combination, and a monobasic cerium compound can also be used in combination. And diterpene compounds and tribasic acid bismuth compounds. Among them, by combining a plurality of crystalline ruthenium compounds, since the melting point is lowered, the temperature adjustment of the constant temperature treatment is easier than that of the above. When two or more kinds of crystalline cerium compounds are used, the content of one type of crystalline cerium compound is preferably from 99 to 9% by mass, more preferably from 1 to 90% by mass, based on the total of two or more kinds of cerium compounds. 30 to 70% best. The crystalline hydrazine compound is, for example, a monobasic acid oxime represented by the general formula (1). 【化1】

(Formula aryl, number 3 substituted, in the methyl isobutylene 'R represents a hydrogen atom, an alkyl group, or a substituted or unsubstituted) alkyl group represented by R, such as methyl, ethyl, propyl a linear alkyl group having 1 to 12 carbon atoms such as a butyl group or a pentyl group or a cycloalkyl group having a carbon group of 12 to 12 such as a cyclohexyl group. Aryl groups such as phenyl, biphenyl, naphthyl and the like. a linear one having a carbon number of 1 to 4 such as a halogen atom group such as a hydroxyl group, a fluorine atom, a chlorine atom or a bromine atom, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a 3-butyl group or a group. Or a branched alkyl group or the like. A monobasic acid oxime represented by the general formula (1), specifically, for example, ethyl fluorenyl-12-201113241 醯肼' ytterbium propionate, bismuth valerate, bismuth laurate, cyclohexane carboxy oxime, water yang Barium acid, barium P-hydroxybenzoate, barium naphthalate, and the like. Other monobasic acids, such as, for example, phenylsulfonyl hydrazine. The crystalline ruthenium compound is, for example, a dibasic acid dioxime represented by the general formula (2). [Chemical 2]

&quot; (2) (wherein A represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, or a carbonyl group, and η represents an integer of 0 to 18) Alkylene group, such as methylene, ethyl, trimethylene, tetramethylene, pentamethylene 'hexamethylene, heptamethylene, octamethylene, ninth methylene A linear alkylene group having 1 to 12 carbon atoms such as a methyl group or an undecyl group. A substituent of an alkylene group such as a hydroxyl group or the like. An arylene group is, for example, a phenylene group, a biphenyl group, a naphthylene group, an anthranylene group, a phenanthrylene group or the like. The substituent of the arylene group is, for example, the same as the substituent of the aforementioned aryl group. The dibasic acid oxime represented by the general formula (2), specifically, for example, diammonium oxalate, diammonium malonate, diterpene succinate, diterpene adipic acid, diterpene trimellitate Bismuth, diammonium suberate, diterpene sebacate, diammonium azelate, dinonyl dodecanoate, diammonium hexadecandioate, diammonium isophthalate, Diphenyl phthalate and the like. Other dibasic acid diterpenes, such as, for example, carboxy hydrazine, diterpene maleate, diammonium fumarate, diammonium diglycolate, diterpenic tartrate, diammonium malate, 2 , 6_naphthoic acid diterpene, I,4-naphthoic acid diterpene, 4,4'-bisbenzoquinone, hydroquinone-13- 201113241 diglycolic acid diterpene, m-phenylene Phenol diglycolate diindole diethylene glycol diacetate, 4,4'-ethylidene bisphenol-diethylene glycol, 4,4'-vinylidene biguanide-diglycolic acid Second class. A tribasic acid hydrazine such as 1,3,5-parade (2-mercaptocarbonylacetate, etc. 1,3,5-gin(2-fluorenylcarbonylalkyl)isocyanate? For example, polyacrylic acid ruthenium, etc. The metal element is, for example, selected from the group consisting of aluminum, titanium, tin, pin 'zinc, cobalt, nickel, lanthanum, molybdenum, copper, lanthanum, cerium, boron, manganese, indium, lanthanum, cerium, calcium, silver. At least one metal element in the group of strontium, barium, and gold is at least one selected from the group consisting of aluminum, titanium, tin, antimony, zinc, iron, magnesium, antimony, molybdenum, copper, cerium, lanthanum, and boron. Further, one type or two or more types may be used in combination. Further, gold is used in the form of a metal oxide or a metal hydroxide. The content of the metal element is estimated to be 0.1 to 20.0 with respect to the total amount of the crystalline bismuth element. When the content of the metal element is 0.1 to 20% by mass based on the total of the crystalline bismuth compound, the metal element and the crystal compound form a good complex. The type, number, proportion, type, number, and proportion of crystalline bismuth compounds, visible hardened trees The type of the group, the use, the required hardening time, the hardening temperature, and the like are appropriately determined. Next, the bismuth catechol oxide, iron, magnesium, and the bismuth catechol compound of the present invention will be described. Cadmium and strontium are preferred. Cobalt, nickel, good. The metal elemental compound and gold are 1 · 0~ and the metal is deuterated into a complex compound and the physical properties. -14- 201113241 [Dimmering diffraction spectrum] The ruthenium compound of the present invention is presumed to be a crystalline ruthenium compound to form a ligand 'with a metal ion coordination bond'. At least a portion of the crystalline ruthenium compound is in conformity with the metal element. Things. Whether or not the crystalline ruthenium compound and the metal element form a complex compound tightly is not clear when the ruthenium compound of the present invention is compared with the one crystalline ruthenium compound of the raw material. In the diffraction spectrum, 1 at the Bragg angle 20 (error 20 ± 〇.2). The range of peaks with the highest intensity below becomes different. The X-ray diffraction spectrum of the raw material of one kind of crystalline bismuth compound has a peak in the range of 4.0 to 5.0 in the Bragg angle 20 (error 20 ± 〇.2) with respect to the X-ray diffraction spectrum of the Cu Κ α line. Further, the ruthenium compound of the present invention has a peak in the range of 5.5 to 7_5 of the Bragg angle 20 (error 20 ± 〇.2) in the X-ray diffraction spectrum of the CuK α line. When the ruthenium compound of the present invention is compared with a crystalline ruthenium compound of a raw material, it has a Bragg angle of 2 Θ. The maximum intensity peak below is shifted in the direction in which the distance between the grids becomes shorter. From this, it is presumed that at least a part of the crystalline ruthenium compound forms a complex with the metal element. The 醯肼 compound of the present invention has a peak in the range of 5. 5 to 7.5° of the Bragg angle 20 (error of 20 ± 0.2°) with respect to the X-ray diffraction spectrum of the CuK α line (wavelength of 1.541 Å). A crystalline metamorphic compound. The X-ray diffraction spectrum is measured by, for example, an X-ray diffraction apparatus (product name: -15-201113241 XRD-6 100, manufactured by Shimadzu Corporation). Further, the crystalline germanium compound containing no metal element is a compound containing two or more kinds of crystalline germanium compounds, and when compared with the peak of one crystalline germanium compound, there is a Bragg angle of 20 (error of 20 ± 0.2°). The tendency of the maximum intensity peak of 10° or less to shift in the direction of 5.5° of the Bragg angle. The ruthenium compound of the present invention has a Bragg angle of 20 (error 20 0 ± 0.2) of 20.0 to 25.0 with respect to the X-ray diffraction spectrum of the CuK α line (wavelength of 1.54 lA). The range is wider than that of the above-mentioned one-crystal crystalline ruthenium compound. As a result of the above, it is understood that the ruthenium compound of the present invention is a partially crystalline compound in which a metal compound and a partially crystalline ruthenium compound form a complex compound and a non-crystalline state and a crystalline state are mixed. [Melting point] The hydrazine compound of the present invention has preferably 60 to 260. (:, preferably 60 to 230 ° C, and the most preferable melting point in the range of 60 to 220 ° C.) The melting point of the hydrazine compound, for example, a differential scanning calorimeter (Pyris 6DSC, manufactured by Perkin-Elmer Co., Ltd., The term "Dsc" is used to determine the maximum peak temperature of the endotherm by melting as the melting point. The antimony compound of the present invention has a lower melting point when compared with the crystalline antimony compound containing no metal element. [The heat of fusion] -16-201113241 In addition, when the ruthenium compound of the present invention is compared with the crystalline ruthenium compound containing no raw material of a metal element, the heat of fusion becomes less than 15%. In the ruthenium compound of the invention, since the heat of fusion is smaller than that of the crystalline ruthenium compound of the raw material, the ruthenium compound is used as a resin having an unsaturated bond (for example, a heat hardener such as a (meth)acrylic resin or an epoxy resin. When the curing temperature is lowered, the curing time is shortened. Further, the heat of fusion is the same as that of the device for measuring the melting point, and the peak area of the endothermic peak by melting is obtained. Heat of fusion (J/g) [Form of ruthenium compound] The ruthenium compound of the present invention preferably has a pulverized particle form. For example, the ruthenium compound is pulverized to form a particulate form, and the ruthenium compound is used. When the ruthenium compound is used as a thermosetting agent, the reactivity with the resin can be further improved, and the curing time can be further shortened. The average particle diameter of the ruthenium compound is not particularly limited, and the ruthenium compound of the present invention is used as a resin. In the case of a hardener, the average particle diameter is preferably 0.5 to 20.0 μm, and more preferably 1.0 to 10. Oym. The average particle diameter of the cerium compound is less than 55/m, and it is preserved. The possibility that the stability is lowered is that the viscosity of the resin composition containing the antimony compound as the thermosetting agent is high, and therefore, the reactivity is low when the average particle diameter exceeds 2 0 · 0 // m. When used as a thermal hardener, the heat resistance and moisture resistance of the cured product are lowered due to the formation of a non-uniform hardening state, and -17-201113241 is not desirable. Moreover, the average particle diameter can be obtained by laser diffraction/scattering method. Particle size distribution The device was obtained, and the average particle diameter was measured as the mass average 値d5C measured by the particle size distribution of the laser diffraction/scattering method (the particle diameter when the cumulative mass of the d5G system was 50%, that is, the median diameter). . &lt;Curing Agent&gt; The ruthenium compound of the present invention has a high activity for a resin having an unsaturated bond because it is presumed that at least a part of the crystalline ruthenium compound forms a complex with a metal element. Further, the ruthenium compound of the present invention preferentially reacts with a resin having an unsaturated bond. Further, when the ruthenium compound of the present invention is compared with the crystalline ruthenium compound of the raw material, the melting point tends to decrease, and the heat of fusion becomes small, and the resin having an unsaturated bond and the epoxy resin are formed at a relatively low temperature. The reaction is carried out without causing a decrease in viscosity, contamination of the adherend, appearance of bleeding, etc., and can be uniformly hardened under a short hardening time. The bismuth compound of the present invention can be suitably used as a thermal curing agent such as a resin having an unsaturated bond or an epoxy resin, and can lower the curing temperature and shorten the curing time, and the liquid stability is also high, so the use period is stable. And high productivity. When the ruthenium compound of the present invention is used as the curing agent for the resin, one type or two or more types may be used in combination. When the hydrazine compound of the present invention is used as the resin curing agent, it is not particularly limited (different depending on the purpose), and is preferably 0.1 to 80 parts by mass, more preferably 1 to 50 parts by mass, per part by mass of the resin. -18-201113241 &lt;Resin composition&gt; The resin composition contains a ruthenium containing the present invention and a tree having at least one unsaturated bond in the molecule, for example, a resin having a molecular weight or Epoxy resin can also be used in combination with a plurality of epoxy resins. Epoxy resins can be used by conventional agents such as bis-bisphenol F-type epoxy resin, bisphenol AD-type epoxy resin, cresol novolac epoxy resin, glycidyl acrylate resin, ring An oxypropylamine epoxy resin, a urethane modified epoxy resin, or the like. Use bisphenol A epoxy resin, cresol novolac. It is also possible to use an epoxy group-containing resin with an epoxy group (meth)acrylic acid. The resin composition is preferably one having a molecule to a resin. A derivative having at least one unsaturated bond in the molecule. An ethylene derivative, a maleic imide-derived acid derivative, etc., among which an acrylic acid derivative having an acrylonitrile group in a molecule is preferably used. Specifically, an acrylic acid derivative such as (ethyl (meth)acrylate, (meth)acrylic acid isobutyl acrylate, (meth)acrylic acid 3-compound hardener, fat and/or epoxy resin at least 1 The unsaturated bond may also be an unsaturated bond containing a type A epoxy resin, a fat, a phenol novolac, a cyclic aliphatic epoxy resin, a heterocyclic ring, etc., in order to make an epoxy resin, etc. Preferably, the methyl group is a resin which is modified by acid to have one less unsaturated bond, such as a styrene or (meth) propylene having at least one methyl (meth) acrylate, n-butyl ester, (methyl) (Methyl) -19 - 201113241 butyl acrylate, etc.; alkyl (meth) acrylate such as phenyl (meth) acrylate or benzyl (meth) acrylate; methoxy (meth) acrylate An alkoxyalkyl (meth)acrylate such as ethyl ester, ethoxyethyl (meth)acrylate, propoxyethyl (meth)acrylate or butoxyethyl (meth)acrylate; Base) 2-hydroxyethyl acrylate, 3-hydroxypropyl (meth) acrylate, (A) a hydroxyl group-containing (meth) acrylate such as 2-hydroxypropyl acrylate or 4-hydroxybutyl (meth) acrylate; or an alicyclic alcohol such as cyclohexyl (meth) acrylate Base) acrylate and the like. Here, (meth)acrylic means both of acrylic acid and methacrylic acid. The amount of the epoxy resin and the resin having at least one unsaturated bond in the molecule can be appropriately determined depending on the purpose of curing the cured product. a resin having at least one unsaturated bond in the molecule, which is an acrylic acid derivative having at least one (meth) acrylonitrile group in the molecule, and is 0.1 to 9.0 equivalents based on 1 equivalent of the epoxy group. The propylene group is preferably a group, and more preferably 0.3 to 4.0 equivalents of the (meth) acrylonitrile group. In addition to the above-mentioned resin, the resin composition may contain an anthracene resin, a urethane resin, a quinone imine resin, glass, or the like as needed. Further, in the resin composition, an antioxidant, a UV absorber, a light stabilizer, a decane coupling agent, a coating surface improving agent, a thermal polymerization inhibiting agent, a leveling agent, a surfactant, a coloring agent may be blended as needed. As a variety of additives, the stabilizer, the plasticizer, the smoothing agent, the chelating agent, the inorganic particles, the anti-aging agent, the wetting improver, the antistatic agent and the like are stored. The resin composition containing the ruthenium compound of the present invention as a hardener, -20-201113241 The liquid composition stability of the resin composition is also good, and the viscosity change rate (liquid stability) within 1 week at 25 ° C becomes small. The period of use is also stable. For the measurement method of the liquid stability, for example, a RE-105U type viscometer (manufactured by Toki Sangyo Co., Ltd.) is used, and a 3° x R7.7 vertical roll is placed on the viscometer, and 0.1 ml of the resin composition to be measured is placed on the viscometer. The measurement was performed at 2.5 rpm, and the measurement object was allowed to stand at 25 ° C for one week, and the viscosity was measured to determine the rate of change of viscosity before and after standing for one week. <Sclerodables> The resin of the present invention was used. The cured product having a hardened composition is excellent in productivity because the curing temperature is lowered, the hardening time is shortened, and the service life is stabilized. Next, a method for producing the ruthenium compound of the present invention will be described. The method for producing a ruthenium compound according to the present invention includes a step of heating a metal ruthenium compound having at least one fluorenyl group in the molecule and a metal element which can be formed by interlacing the crystalline ruthenium compound to obtain a mixture. The step of subjecting the mixture to a constant temperature treatment, and the step of cooling the mixture and producing a cured product. The step of preparing a molten mixture is to first heat a crystalline cerium compound having at least one fluorenyl group in the molecule, and a metal element which can be formed by being mismatched with the crystalline cerium compound, and in a state of becoming a liquid, The crystalline cerium compound is dissolved to prepare a mixture. The temperature at which the crystalline cerium compound is heated is not particularly limited, and -21 to 201113241 is preferably a temperature at which a crystalline cerium compound forms a liquid state. Crystallization; the temperature at which the compound forms a liquid state, at a temperature near the melting point of the crystalline ruthenium compound, for example, a temperature lower than the melting point of the relatively crystalline ruthenium compound by 10 ° C to a higher temperature 〇 The temperature of °C is preferred. Next, the step of subjecting the mixture to a constant temperature treatment is carried out by subjecting the mixture to a constant temperature treatment at a constant temperature. Here, the constant temperature treatment means that the mixture is kept at a certain temperature (error range ± 101) for a certain period of time. The temperature of the constant temperature treatment is not particularly limited, and is preferably from 00 to 28 0 ° C, more preferably from 130 to 250 ° C. When the temperature of the constant temperature treatment is too high (for example, a temperature exceeding 28 ° C), the formation of a complex compound is intense, and it becomes difficult to control. In addition, when the temperature of the constant temperature treatment is too low (for example, the temperature is less than 100 ° C), the constant temperature treatment time becomes longer, and the production efficiency becomes lower, so there is no particular limitation on the time for the constant temperature treatment. It is 0 · 0 1~ 1 0 hours. The temperature of the constant temperature treatment varies depending on the temperature of the constant temperature treatment. The higher the temperature, the shorter the treatment time becomes. The lower the temperature, the longer the treatment time becomes, so that it can be used in accordance with the use as a hardener. The most suitable processing time for the purpose, etc. Then, the mixture was cooled to obtain a cured product. In the step of producing a cured product, the cooling rate is preferably from 0.01 ° C / min to 200 ° C / min, more preferably from 1 ° C / min to 1 0 0 ° c / min. Further, the cooling can be carried out in multiple stages, for example, in the first stage, the mixture is cooled to about 200 ° c ' and the crystal -22-201113241 is grown at this temperature, and then cooled to room temperature in the second stage. Further, the method for producing the ruthenium compound of the present invention comprises a step of pulverizing the cured product obtained by cooling and pulverizing into a particle shape having an average particle diameter of 0.5 to 20. Ομπι. In the pulverization method, the cured product is preferably pulverized, for example, by using a high-pressure pulverizer. The high-pressure pulverizer is, for example, a cross jet honing machine (manufactured by Kuriyuki Iron Co., Ltd.), a reverse blasting honing machine (manufactured by HOSOKAWAMICRON Co., Ltd.), a nano atomizer (manufactured by Aishin Nano Technologies Co., Ltd.), or the like. When the FT-IR image is measured by an FT-IR measuring apparatus (for example, Spectrum one, manufactured by Perkin-Elmer Co., Ltd.), the erbium compound produced by the production method of the present invention has a constant temperature treatment time, and is derived from the wavelength. The smaller the peak of NH stretching near SSOOcnr1. In addition, the peak of the CH stretching from the range of 2800 to 3000 cm·1 with a wavelength of almost no change. Moreover, when a ruthenium compound is produced, a gas is generated. This gas was collected, and when 1H-NMR was measured by a 1H-NMR measuring apparatus (for example, JNM-ECA600, manufactured by Sakamoto Electronics Co., Ltd.), it had a peak at 2.9592 ppm. This peak presents a peak representing water (H20). In the ruthenium compound of the present invention, it is confirmed by FT-IR that the peak size from the NH stretching is reduced, and it is confirmed by 1 H-NMR that water (H20) is generated in the gas released when the ruthenium compound is produced. At least a portion of the crystalline ruthenium compound forms a complex with the metal element. [Embodiment] -23- 201113241 In the following, the present invention will be specifically described by way of examples, but the present invention is not limited by the embodiments. [Examples] &lt;Two kinds of crystalline bismuth compounds and metal elements&gt; [Example 1] 500 parts by weight of dioxonium sebacate (manufactured by Otsuka Chemical Co., Ltd.) and dodecanedioic acid dioxime 500 parts by weight of DDH, manufactured by Otsuka Chemical Co., Ltd., and 20 parts by weight of titanium oxide (AEROXIDE P25, manufactured by Nippon Aerosil Co., Ltd.) (in an amount of 1.2% by mass) were placed in a 5000 ml separation flask and heated at 200 ° C. A mixture of two kinds of crystalline cerium compounds dissolved in an about liquid state was obtained. The mixture was subjected to a constant temperature treatment at 200 ° C for 2 hours. Then, the mixture was transferred to a glass plate made of Pyrex (registered trademark) which was preheated at 200 ° C, and placed in an oven at 200 ° C. Then, the mixture was cooled in an oven at a cooling rate of about 1 ° C /min to room temperature to obtain a cured product. The hardened material which was completely cooled to room temperature was subjected to coarse pulverization treatment by a coarse pulverizing mill (manufactured by Orient Co., Ltd.), and finally a high-pressure pulverizer (trade name: nano spray mill, Aishin Nano) was passed through a sieve of a mesh of 50,000 μm. (manufactured by Technologies, Inc.) to produce a ruthenium compound having an average particle diameter of 2.8 μm (hereinafter, the 醯肼 compound of Example 1 is referred to as "Τ 1 -2h" -24-201113241 [Example 2] 500 parts by weight of 肼 (SDH, manufactured by Otsuka Chemical Co., Ltd.), 500 parts by weight of dioxonium dodecanoate (DDH, manufactured by Otsuka Chemical Co., Ltd.), and 20 parts by weight of titanium oxide (AEROXIDE P25, manufactured by Nippon Aero Sil Co., Ltd.) The content of titanium was 1.2% by mass. The mixture was placed in a 5000 ml separation flask and heated at 200 ° C to obtain a mixture in which two kinds of crystalline cerium compounds were dissolved in an about liquid state. The mixture was subjected to constant temperature treatment at 200 ° C. 5 hours. Then, the mixture was transferred to a glass plate made of Pyrex (registered trademark) preheated at 200 ° C, and placed in an oven at 200 ° C. Then, the molten mixture was allowed to stand in the oven at about 1. Ot / min cooling The product was cooled to room temperature to obtain a cured product. The hardened product which was completely cooled to room temperature was coarsely pulverized by a coarse pulverization mill (manufactured by Orient Co., Ltd.), and finally a high-pressure pulverizer (trade name) was passed through a mesh of 500 μm. : Nano spray mill, manufactured by Aishi Nano Technologies Co., Ltd.), to produce a ruthenium compound having an average particle diameter of 3.4 μm (the ruthenium compound of the following Example 2 is referred to as "Τ 1 - 5 h") [Example 3] 500 parts by weight of diterpene sebacate (made by SDH, manufactured by Otsuka Chemical Co., Ltd.), 500 parts by weight of dioxonium dodecanoate (DDH, manufactured by Otsuka Chemical Co., Ltd.), and alumina (AEROXIDE AluC, manufactured by Nippon Aerosil Co., Ltd.) 50 parts by weight (the content of aluminum was 2.5% by mass) was added to 5 000 ml of -25-201113241. The flask was heated at 200 Torr to obtain a mixture in which two kinds of crystalline cerium compounds were dissolved in an about liquid state. The mixture was subjected to constant temperature treatment for 2 hours at 200 ° C. Then, the mixture was transferred to a Pyrex (registered trademark) glass dish preheated at 200 ° C, and placed in an oven at 2 ° C. Then, to melt The composition was cooled to room temperature in an oven at a cooling rate of about 1 ° C /min to obtain a cured product. The hardened product which was completely cooled to room temperature was coarsely pulverized by a coarse pulverization mill (manufactured by Orient Co., Ltd.). Finally, a sieve passing through a mesh of 5 ΟΟ/zm was pulverized by a high-pressure pulverizer (trade name: nano spray mill, manufactured by Aishi Nano Technologies Co., Ltd.) to produce a ruthenium compound having an average particle diameter of 2.5 μm (the following Example 3) The ruthenium compound is referred to as "C3-2h". [Example 4] 500 parts by weight of dioxonium sebacate (manufactured by Otsuka Chemical Co., Ltd.) and dioxonium dodecanoate (DDH, manufactured by Otsuka Chemical Co., Ltd.) 500 parts by weight, and 50 parts by weight of alumina (AEROXIDE AluC, manufactured by Nippon Aerosil Co., Ltd.) (2.5% by mass of aluminum) were placed in a 5000 ml separation flask and heated at 200 ° C to obtain two kinds of crystallinity. The hydrazine compound dissolves into a mixture of about liquid state. The mixture was subjected to a constant temperature treatment at 200 ° C for 2 hours. Then, the mixture was transferred to a Pyrex (registered trademark) glass plate preheated at 200 ° C, and placed in an oven at 200 ° C. Then, -26-201113241, the molten mixture was cooled in an oven at a cooling rate of about 1 ° C / min to 200 to 180 ° C, and the crystal was grown at 180 ° C for 5 hours. Further, it was cooled to room temperature at a cooling rate of about 1.0 ° C /min to obtain a cured product. The cured product which was completely cooled to room temperature was coarsely pulverized by a coarse pulverization mill (manufactured by Orient Co., Ltd.), and finally pulverized by a high-pressure pulverizer (trade name: nano spray mill, manufactured by Aishi Nano Technologies Co., Ltd.) to prepare an average particle diameter of 2.3 The compound of # m (the compound of the following Example 4 is referred to as "C3-2h-5Hold"). [Example 5] 500 parts by weight of dioxonium sebacate (manufactured by Otsuka Chemical Co., Ltd.), 500 parts by weight of dioxonium dodecanoate (DDH, manufactured by Otsuka Chemical Co., Ltd.), and zinc oxide (ZnO, 50 parts by weight (manufactured by CI KASEI Co., Ltd.) was added to a 5000 ml separation flask and heated at 200 ° C to obtain a mixture in which two kinds of crystalline cerium compounds were dissolved in an about liquid state. The mixture was subjected to a constant temperature treatment at 200 ° C for 2 hours. Then, the mixture was transferred to a glass plate made of Pyrex (registered trademark) which was preheated at 200 ° C, and fixed at 200. (: in the oven. Then, the mixture was cooled to room temperature in the oven at a cooling rate of about 1. 〇r / min to obtain a hardened material. The hardened material was completely cooled to room temperature with a coarse grinding mill (Orient The crude pulverization treatment was carried out, and finally pulverized by a high-pressure pulverizer (trade name: nano spray mill, manufactured by Aishi Nano Technologies Co., Ltd.) to produce a bismuth compound having a uniform particle diameter of 4·3 μηι (the following examples). (5) The compound (5) is exemplified as "E3-2h". [Example 6] 500 parts by weight of dioxonium sebacate (made by SDH, manufactured by Otsuka Chemical Co., Ltd.) and dioxonium dodecanoate (DDH, Daphnia) 500 parts by weight, and 50 parts by weight of tin oxide (manufactured by Sn02, CI KASEI) (the content of tin is 3.7% by mass) was placed in a 5000 ml separation flask and heated at 200 ° C to obtain two kinds. The crystalline cerium compound is dissolved into a mixture in a liquid state. The mixture is subjected to a constant temperature treatment at 200 ° C for 2 hours. Then, the mixture is transferred to a glass of Pyr ex (registered trademark) preheated at 200 ° C. On the plate, and fixed at 200 In the oven of C. Then, the molten mixture is cooled to room temperature in an oven at a cooling rate of about 1 · 〇 ° C / min to obtain a cured product. The hardened material is completely cooled to room temperature to be coarsely ground (Orient The product was subjected to a coarse pulverization treatment, and finally pulverized by a high-pressure pulverizer (trade name: nano spray mill, manufactured by Aishi Nano Technologies Co., Ltd.) to produce a ruthenium compound having an average particle diameter of 3.5 μm (the following Example 6) The compound is referred to as "F3-2h". [Example 7] 5 parts by weight of didecyl sebacate (SDH, manufactured by Otsuka Chemical Co., Ltd.), dioxonium dodecanoate (DDH, Otsuka Chemical Co., Ltd.) 5) 00 weight -28- 201113241 parts, with cerium oxide (yttria A, manufactured by Nippon Steel Co., Ltd.) 50 parts by weight (content of cerium is 4.3% by mass) added to a 5 000 ml separation flask at 200 ° The mixture was heated under C to prepare a mixture in which two kinds of crystalline cerium compounds were dissolved in an about liquid state. The mixture was subjected to constant temperature treatment at 200 ° C for 2 hours. Then, the mixture was transferred to Pyrex which was preheated at 200 ° C ( Registered trademark) on the glass plate And fixed in 20 (TC oven). Then, the mixture was cooled to room temperature in the oven at a cooling rate of about 1. ° C / min. to obtain a hardened material. The hardened material was completely cooled to room temperature. The coarse pulverization mill (manufactured by Orient Co., Ltd.) was subjected to coarse pulverization treatment, and finally pulverized by a high-pressure pulverizer (trade name: nano spray mill, manufactured by Aishi Nano Technologies Co., Ltd.) to produce a ruthenium compound having an average particle diameter of 2.6 am (the following examples) The compound at 7 is called "G3-2h"). [Example 8] 500 parts by weight of dioxonium sebacate (manufactured by Otsuka Chemical Co., Ltd.), 500 parts by weight of dioxonium dodecanoate (DDH, manufactured by Otsuka Chemical Co., Ltd.), and cobalt hydroxide 50 parts by weight (manufactured by Tanaka Chemical Research Institute Co., Ltd.) was added to a 5 〇〇〇 ml separation flask and heated at 200 ° C to obtain two kinds of crystalline bismuth compounds. A mixture of liquid states. The mixture was thermostated at 200 °C for 2 hours. Then, the mixture was transferred to a glass plate made of Pyrex ( -29-201113241 registered trademark) which was preheated at 200 ° C, and placed in an oven at 200 ° C. Then, the molten mixture was cooled in an oven at a cooling rate of about 1.0 Ot / min to room temperature to obtain a cured product. The cured product which was completely cooled to room temperature was coarsely pulverized by a coarse pulverization mill (manufactured by Orient Co., Ltd.), and finally pulverized by a high-pressure pulverizer (trade name: nano spray mill, manufactured by Aishi Nano Technologies Co., Ltd.) to prepare an average particle diameter of The compound of 3.3#m (the compound of the following Example 8 is referred to as "hX3-2h"). [Example 9] 500 parts by weight of dioxonium sebacate (made by SDH, manufactured by Otsuka Chemical Co., Ltd.), 500 parts by weight of dioxonium dodecanoate (DDH, manufactured by Otsuka Chemical Co., Ltd.), and nickel hydroxide ( 50 parts by weight (manufactured by Tanaka Chemical Research Institute Co., Ltd.) was added to a 5000 ml separation flask and heated at 200 ° C to obtain a mixture in which two kinds of crystalline cerium compounds were dissolved into a liquid state. . The mixture was thermostated at 200 ° C for 2 hours. Then, the mixture was transferred to a Pyrex (registered trademark) glass plate preheated at 200 ° C, and placed in an oven at 200 ° C. Then, the molten mixture was cooled in the oven at a cooling rate of about 〇 ° C / min to room temperature to obtain a cured product. The hardened product which was completely cooled to room temperature was coarsely pulverized by a coarse pulverization mill (manufactured by Orient Co., Ltd.), and finally pulverized by a high-pressure pulverizer (trade name: nano spray mill, manufactured by Aishi Nano Technologies Co., Ltd.) to produce a flat-30- 201113241 A ruthenium compound having a mean particle size of 2.6 // m (the ruthenium compound of the following Example 9 is referred to as "hY3-2h"). [Example 1] 500 parts by weight of dioxonium sebacate (made by SDH, manufactured by Otsuka Chemical Co., Ltd.) and 500 parts by weight of dioxonium dodecanoate (DDH, manufactured by Otsuka Chemical Co., Ltd.) and chromium hydroxide (Zirconium hydroxide 999-D, manufactured by Nippon Steel Co., Ltd.) 50 parts by weight (zirconium content: 2.6% by mass) was placed in a 500 ml separation flask to be heated at 200 ° C to obtain two kinds of crystallinity. The hydrazine compound dissolves into a mixture of about liquid state. The mixture was subjected to constant temperature treatment at 200 ° C for 2 hours. Then, the mixture was transferred to a Pyrex (registered trademark) glass plate preheated at 200 ° C, and fixed in an oven at 200 ° C. Then, the molten mixture was allowed to cool to room temperature in an oven at a cooling rate of about 1 〇 〇 t / minute to obtain a cured product. The cured product which was completely cooled to room temperature was coarsely pulverized by a coarse pulverization mill (manufactured by Orient Co., Ltd.), and finally pulverized by a high-pressure pulverizer (trade name: nano spray mill, manufactured by Aishi Nano Technologies Co., Ltd.) to prepare an average particle diameter of 2 · 9 μ m of the ruthenium compound (the compound of Example 10 below is referred to as "hZ3-2h"). &lt;One type of crystalline bismuth compound and metal element&gt; [Example 11] Dioxonium sebacate (SDH, manufactured by Otsuka Chemical Co., Ltd.) 1000 wt-31 - 201113241 parts, and alumina (AEROXIDE AluC, Japan) 50 parts by weight (manufactured by Aerosil Co., Ltd.) was added to a 5000 ml separation flask and heated at 200 ° C to obtain a mixture in which two kinds of crystalline cerium compounds were dissolved in an about liquid state. The mixture was subjected to constant temperature treatment at 200 ° C for 2 hours. Then, the mixture was transferred to a glass plate made of Pyrex (registered trademark) which was preheated at 200 ° C, and placed in an oven at 200 °C. Then, the molten mixture was cooled to room temperature in an oven at a cooling rate of about 1 · /min to obtain a cured product. The cured product which was completely cooled to room temperature was coarsely pulverized by a coarse pulverization mill (manufactured by Orient Co., Ltd.), and finally pulverized by a high-pressure pulverizer (trade name: nano spray mill, manufactured by Aishi Nano Technologies Co., Ltd.) to prepare an average particle diameter of The compound of 3.4 // m (the compound of the following Example 1 is referred to as "S-C3-2h"). &lt;3 kinds of crystalline bismuth compound and metal element&gt; 300 parts by weight of dioxonium sebacate (manufactured by Otsuka Chemical Co., Ltd.) and dioxonium dodecanoate (DDH, manufactured by Otsuka Chemical Co., Ltd.) 300 300 parts by weight of aluminum dioxime (IDH, manufactured by Otsuka Chemical Co., Ltd.) and 45 parts by weight of alumina (AEROXIDE AUC, manufactured by Nippon Aerosil Co., Ltd.) (2.5% by mass of aluminum) were added to 500 parts by weight. The separation flask was heated at 200 ° C to obtain a mixture in which three kinds of crystalline cerium compounds were dissolved in an about liquid state. The mixture was subjected to constant temperature treatment at 200 ° C for 2 hours. -32- 201113241 Then, the mixture was transferred to a glass plate made of Pyrex (registered trademark) preheated at 200 DC, and placed in an oven of 2001. Then, the molten mixture was cooled in an oven at a cooling rate of about 1 ° C /min to room temperature to obtain a cured product. The hardened material which was completely cooled to room temperature was subjected to coarse pulverization treatment with a coarse pulverization mill (manufactured by Orient Co., Ltd.), and finally pulverized by a high-pressure pulverizer (trade name: nano spray mill, manufactured by Aishi Nano Technologies Co., Ltd.) to prepare an average particle diameter of 3.0 m 醯肼 compound (the compound of Example 1 2 is referred to as "DSI-llll C3-2h"). [Comparative Example 1] Commercially available diterpene sebacate (SDH, manufactured by Otsuka Chemical Co., Ltd.) was used as Comparative Example 1. [Comparative Example 2] Commercially available dioxonium dodecanoate (DDH, manufactured by Otsuka Chemical Co., Ltd.) was used as Comparative Example 2. [Comparative Example 3] 500 parts by weight of didecyl sebacate (made by SDH, manufactured by Otsuka Chemical Co., Ltd.) and 50 parts by weight of dioxonium dodecanoate (DDH, manufactured by Otsuka Chemical Co., Ltd.) (hereinafter referred to as "SD55" is used as Comparative Example 3. [Comparative Example 4] -33-201113241 The mixture of Comparative Example 3 was heated to 200 °C, and after mixing into a liquid form, the mash of Comparative Example 4 was obtained in the same manner as in Example 4. The liquid crystal stability of Examples 1 to 2 and Comparative Examples 1 to 2 and 4, and the DSC of Examples 1 to 2 and Comparative Examples 1 to 3, the liquid stability of Examples 1 to 2, The measurement results of the measurements of Examples 1 to 12 and Comparative Examples 1 to 3, and the liquid, melting point, and heat of fusion are shown in Table 1. [X-ray diffraction spectrum] X-ray diffraction device (product name: XRD-6100, Shimadzu system), with X-ray output voltage: 4〇.OKV, X-ray output 4 0.0mA, scanning stage width: 0.02 degrees The measurement was carried out. [Differential Scanning Calorimetry (DSC)] Using a differential scanning calorimeter (Pyris 6DSC, manufactured by Elmer Co., Ltd.), the ruthenium compound of the measurement sample was sealed in aluminum, and the maximum peak temperature of the endotherm by melting was determined as the melting point. The peak area of the endothermic heat is used as the heat of fusion. [Liquid stability] Using the ruthenium compound of Examples 1 to 1 2 as a thermosetting agent, 15 parts by weight of the bismuth compound, bisphenol A type epoxy acrylate KR-8 5 0 CRP, manufactured by KSM Co., Ltd., 100 parts by weight, was produced. The resin melts the X curve of the ruthenium compound. In addition, stability is the public current:

Perkin- containers. Further, a resin (component - 34-201113241) is blended. Further, the bisphenol A type epoxy acrylate resin has an acryl oxime group of 1 equivalent based on 1 equivalent of the epoxy group. The resin composition is kept at a constant temperature at 25 ° C. For the treatment, a 3° x R7.7 vertical roll was placed on a RE-105U viscometer (manufactured by Toki Sangyo Co., Ltd.), and 0.15 ml of the resin composition of the object was placed in an upright roll, and 25 ° C was measured at 2.5 rpm. Viscosity of the resin composition. The resin composition to be measured was allowed to stand at 25 ° C for one week, and the viscosity of the resin composition after one week was measured by the above method, and the viscosity change rate after one week from the initial viscosity was calculated. (% /week ). When the measurement range is exceeded, the measurement cannot be performed. Moreover, the reference exceeding the measurement range is 1,20 〇, 〇〇〇mPa*s.

S-35-201113241 [Table I] Determination of stability (%/week) Heat of fusion (J/g) Melting point ro Example 1 Tl-2h 769.7 139.587 139.825 Example 2 Tl-5h 55.6 88.590 113.624 Example 3 C3-2h 569.3 114.985 133.222 Example 4 C3-2h-5Hold 9.6 54.012 184.480 Example 5 E3-2h 8.5 37.044 1-- 174.224 Example 6 F3-2h 33.6 139.627 Surface - a 157.456 Example 7 G3-2h 77.3 140.557 134.056 Example 8 hX3-2h 10.8 51.444 208.665 Example 9 hY3-2h 91.3 98.501 146.775 Example 10 hZ3-2h 171.0 150.076 131.417 Example 11 S-C3-2h 14.8 80.104 200.163 Example 12 DSI-lllC3-2h 38.6 38.317 63.858 Comparative Example 1 SDH - 339.669 195.922 Comparative Example 2 DDH - 295.923 193.401 Comparative Example 3 SD55 - 326.850 181.107 Comparative Example 4 N-2h-5Hold 143.0 137.500 139.530 As shown in Figures 1 to 2, the compounds of Examples 1 to 12 are relatively In the X-ray diffraction spectrum of the CuKa line (wavelength 1.541A), it is 5.5 to 7.5 at a Bragg angle of 20 (error 20 ± 〇 2). The range has a peak. Further, as shown in the first and fourth graphs, one of the crystalline ruthenium compounds of the materials of Comparative Examples 1 and 2 has a maximum intensity peak at 10° or less of the Bragg angle of 20 (error 20 ± 0.2°). In the range of 4.0 to 5.0° of the Prague angle 20 (error 20 ± 〇.2). When the ruthenium compound of Examples 1 to 12 was compared with one kind of crystalline ruthenium compound, it was 10 at a Bragg angle of 20 (error 20 ± 0.2). The following maximum intensity peaks are offset by a range of 5.5 to 7.5 degrees of a Bragg angle having a short distance between the grids. -36- 201113241 Furthermore, in Fig. 10, the peak at 2° around the Bragg angle 20 (error 20 ± 〇 · 2°) is scattered light, and there is no peak from X-ray diffraction. From the results shown in Figs. 1 to 2 and Table 1, it is presumed that the ruthenium compound of Examples 1 to 12 is at least partially crystalline ruthenium compound and a metal compound. Further, when the ruthenium compound of Examples 1 to 12 is compared with one of the crystalline ruthenium compounds of the materials of Comparative Examples 1 and 2, the Bragg angle is 20 (error 20 ± 〇.2) 5.5 to 7.5. . The peak intensity of the range is small, and it is estimated that the proportion of the amorphous material in the whole is increased. Further, the ruthenium compound of Examples 1 to 2 2 was 20.0 to 25.0 at a Bragg angle of 20 (error 20 ± 〇.2). The peaks in the range are wider than those of the one of the crystalline ruthenium compounds of the raw materials of Comparative Examples 1 and 2. From the results, it is understood that the ruthenium compound ' of Examples 1 to 12 at least partially forms a complex compound and is a partially crystalline compound in which an amorphous state and a crystalline state are mixed. Further, as shown in Fig. 15, the two kinds of crystalline ruthenium compounds of Comparative Example 4 have a Bragg angle of 20 (error of 20 ± 0.2). The following has the maximum intensity peak towards 5.5. The direction is shifted, but since there is no metal element, there is no peak from the complex formed by the ruthenium compound and the metal element. Further, the DSC curves of Figs. 16 to 30 and the enthalpy of the examples 1, 2, 3, 5 to 7, 9, 10, and 12 and the comparative examples 1 to 3 are shown in Table 1. When compared with a ruthenium compound, the melting point becomes low. Further, in the case of -37-201113241, the ruthenium compound of Examples 1 to 1 2 was compared with the ruthenium compound of Comparative Examples 1 to 3, and the heat of melting point was 45% or more. From the results, it was found that when the antimony compound of Examples 1 to 12 was used as the thermosetting agent, the curing temperature was lowered and the curing time was shortened. Further, in the ruthenium compounds of Examples 1 to 12, the number of liquid stability can be changed by changing the conditions (time, temperature, etc.) of the constant temperature treatment. Further, in the heat of fusion (J/g) of Comparative Example 4, the liquid stability could not be improved more than that of Example 4 in which the same constant temperature treatment was carried out. When a ruthenium compound is used as the thermosetting agent, a ruthenium compound can be formed by using a hardening resin or the like under conditions which change the temperature of the thermosetting treatment as a suitable thermosetting agent. When a ruthenium compound is used as the thermosetting agent, liquid stability (80% /week or less (more preferably 50% / week or less, and most preferably 30% / week or less) is formed.醯肼 醯肼 醯肼 & [ 实施 实施 实施 实施 SD SD SD SD SD SD SD SD SD SD SD SD SD SD SD SD SD SD SD SD SD SD SD SD SD SD SD SD SD SD SD SD SD SD SD SD SD SD SD SD SD SD 50 parts by weight of alumina (AEROXIDE AluC, manufactured by Nippon Aerosil Co., Ltd.) (2.5% by mass of aluminum) was placed in a 5000 ml separation flask and heated at 200 ° C. Two kinds of crystallinity were confirmed. The compound was completely melted to obtain a molten mixture, and the molten mixture was subjected to a constant temperature treatment at 200 ° C for ～3 hours, and sampled at 0, 1, 2, and 3 hours, and naturally cooled to obtain a ruthenium compound. Let each compound --38-201113241 be referred to as implementation 13-1 (C3-bl2-〇h, figure 31), implementation 13-2 (C3-bl2-lh, figure 32), implementation 13-3 (C3-bl2-2h, Fig. 33), and implementation of l3-4 (C3-bl2-3h, Fig. 34). [Example 14] 5 parts by weight of dioxonium diacid (SDH, manufactured by Otsuka Chemical Co., Ltd.), 500 parts by weight of dioxonium dodecanoate (DDH, manufactured by Otsuka Chemical Co., Ltd.), and titanium oxide (AEROXDE AluC, manufactured by Nippon Aerosil Co., Ltd.) 20 parts by weight (the content of aluminum is 1.2% by mass) was added to a 5000 ml separation flask to "heat at 2 ° C. It was confirmed that the two crystalline cerium compounds were completely melted" to obtain a molten mixture. The molten mixture was subjected to constant temperature treatment at 0 0 ° C for 0 to 5 hours, and sampled at 〇, 1, 2, 4, and 5 hours to carry out natural cooling to obtain a ruthenium compound. The ruthenium compounds are each referred to as "Tl-b5S-0h b5S-2h", "Tl-b5S-4h, , rj, "Tl-b5S-lh Tl-b5S-5h". T1 - each of the brewing compounds of Example 1 The calender diffraction spectrum was measured by the aforementioned method. The results are shown in Fig. 31 to Fig. 3. The FT-IR of each of the cake compounds of Example 4 was measured by the following method. Moreover, 'the composition of the gas collected in the constant temperature treatment is measured by 1H_NMR. The result is as follows. As shown in Fig. 36, the DSC curve of Examples 13 and 14 was also measured by omitting the figure $. [FT-IR] -39- 201113241 Determination of FT-IR using Spectrum One (manufactured by Perkin-Elmer) . [1H-NMR]]H-NMR was measured by using JNM-ECA600 (manufactured by JEOL Ltd.) at 50 °C, and acetone-d6 (re-hydrogenation rate: 99.9% or more) at 500 y was dissolved at 50//1. Sample. As shown in the figures 3 to 3, the ruthenium compound of Example 1 has a peak at a wavelength of 5.0° around the Bragg angle of 20 (error 2·0±〇.2°) at a constant temperature of 0 hours, and the constant temperature is confirmed. The longer the processing time, the tendency of the surface lattice spacing in the range of 5.5.0 to 7.5° of the Bragg angle 20 (error 20 ± 〇.2) to be shifted. From this result, it is presumed that the longer the temperature of the ruthenium compound of Example 13 is, the longer the ratio of the crystalline ruthenium compound to the metal element is formed. Moreover, the longer the time of the constant temperature treatment, the 23.0 to 24.0 at the Bragg angle of 20 (error 20 ± 〇. 2 °). The range has a reduced peak intensity. When the DSC curves of the ruthenium compounds of Examples 13 and 14 were measured, the heat of fusion of the ruthenium compounds of Examples 13 and 14 and the crystalline ruthenium compounds of the raw materials of Comparative Examples 1 to 3 were measured. When compared with the melting heat of s D Η, DD Η, and SD55), it is less than 70%. Further, in the heat of fusion of the ruthenium compound of Examples 13 and 14, the longer the constant temperature treatment time, the lower the heat of fusion tends to be. Further, since the curve pattern of the ruthenium compound of Examples 13 and 14 tends to be wider as the temperature is longer, the ratio of -10 to 201113241 tends to be wider, so that the proportion of the upper amorphous substance is estimated to be larger. As shown in Fig. 3, the longer the time of the constant temperature treatment of the ruthenium compound of Example 14, the smaller the peak of the NH stretching vibration from the vicinity of the wavelength of 3 3 00 CHT1. Further, there is almost no peak change of the CH stretching vibration from the range of 2800 to 3000 cm_1. As shown in Fig. 36, the h-NMR chart of the gas produced when the ruthenium compound was produced had a peak at 2.9592 ppm. This peak indicates the peak of water (h2o). From the results shown in Figs. 3 and 3, it is presumed that the ruthenium compound of the example is a crystalline ruthenium compound of at least a part of the raw material and a metal compound. [Example 15] The ruthenium compound (T 1 -2h ) of Example 1 was used as a thermosetting agent, and 15 parts by weight of the ruthenium compound was blended with a bisphenol A type epoxy acrylate resin (KR-850 CRP, manufactured by KSM Corporation). 100 parts by weight, a resin composition was produced. [Example 1 6] A resin composition was produced in the same manner as in Example 15 except that the hydrazine compound (Tl-5h) of Example 2 was used as a thermosetting agent. [Comparative Example 5] A resin composition was produced in the same manner as in Example 15 except that the 醯-41 - 201113241 肼 compound (SD55) obtained from the two kinds of crystalline ruthenium compounds of Comparative Example 3 was used as the curing agent. [Example 17] In addition to using the hydrazine compound (Tl-2h) of Example 1 as a thermosetting agent, 30 parts by weight of the cerium compound was blended, and bisphenol A type epoxy resin (850S, manufactured by DIC Corporation) was used. A resin composition was produced in parts by weight. [Example 18] A resin composition was produced in the same manner as in Example 17 except that the hydrazine compound (T 1 - 5 h) of Example 2 was used as a thermosetting agent. [Comparative Example 6] A resin composition was produced in the same manner as in Example 17 except that the indole compound (SD55) obtained from the two kinds of crystalline indole compounds of Comparative Example 3 was used as the curing agent. [Example 19] In addition to using the ruthenium compound (Tl-2h) of Example 1 as a thermosetting agent, 15 parts by weight of the ruthenium compound was blended with bisphenol A type epoxy resin (85 OS, manufactured by D 1C Co., Ltd.). A resin composition was produced in an amount of 1 part by weight of an epoxy acrylate resin modified with 100% acrylic acid. [Example 20] -42-201113241 A resin composition was produced in the same manner as in Example 19 except that the hydrazine compound (T1-5h) of Example 2 was used as a thermosetting agent. [Comparative Example 7] A resin composition was produced in the same manner as in Example 19 except that the anthraquinone compound (SD 5 5 ) obtained from the two kinds of crystalline ruthenium compounds of Comparative Example 3 was used as the curing agent. The curing start temperature of the resin compositions of Examples 1 to 2 and Comparative Examples 4 to 6 was measured using a differential scanning calorimeter (manufactured by Pyris6DSC Perkin-Elmer Co., Ltd.). The measurement method is the same as described above. The results are shown in Figures 37 to 45. The curing start temperature of the resin compositions of Examples 1 to 5 and Comparative Examples 5 and 6 was measured using a differential scanning calorimeter (Pyris 6DSC Perkin-Elmer). The measurement method is the same as described above. The results are shown in Figures 37 to 45. As shown in Fig. 37, the resin composition of Example 15 started to harden at around 105 °C, and as shown in Fig. 3, the resin composition of Example 16 began to harden at around 90 °C. Further, as shown in Fig. 3, the resin composition of Comparative Example 5 started to harden at around 150 °C. In the case of the resin composition of the first and the sixth, the resin composition of the sample of the first embodiment was found to have a lower temperature of 30 ° C or higher, and the reactivity was improved. As shown in Fig. 40, the resin composition of Example 17 began to harden at around 20 °C. Further, as shown in Fig. 41, the resin group of Example 18 -43 - 201113241 began to harden at around 108 °C. Further, as shown in Fig. 42, the resin composition of Comparative Example 5 started to harden at around 60 °C. In the case of the resin composition of the seventh embodiment and the resin composition of the comparative example 6, it was confirmed that the lowering temperature of the curing temperature was 30 °C or higher. As shown in Fig. 4, the resin composition of Example 19 started to harden at around 80 °C, as shown in Fig. 44. The resin composition of Example 20 began to harden at around 80 °C. Further, as shown in Fig. 45, the resin composition of Comparative Example 7 started to harden at around 1 l ° C. In the case of the resin composition of the first embodiment and the resin composition of the comparative example 7, it was confirmed that the curing temperature was 30 ° C or higher, and the reaction property was improved. The hydrazine compound of the present invention can be used as a curing agent which exhibits suitable liquid stability by changing the constant temperature treatment time. By the constant temperature treatment time, the effect of different liquid stability is confirmed as follows. [Comparative Example 8] The mixture of Comparative Example 3 was heated to 200 ° C to melt the mixture into a liquid state, and then cooled in the roasted phase at about 1.0 ° C / min. The temperature was cooled to room temperature to obtain a cured product. The cured product of Comparative Example 7 was obtained in the same manner as in Example 1 except that the cured product was obtained. With respect to the ruthenium compounds of Examples 1 to 4 and Comparative Examples 4 and 8, the heat of fusion (J/g) and the heat of dissolution of 肼-44 - 201113241 相对 compound with respect to Comparative Example 3 (SDH: raw material mixture), each 醯The reduction rate of the heat of dissolution of the hydrazine compound is shown in Table 2. L仏^ J Heating time (h) Melting heat 降低 Reduction rate of melting heat (%) Example 1 (Tl-2h) 2 139.6 57.3 Example 2 (Tl-5h) 5 88.6 72.9 Example 3 (C3-2h) 2 115.0 64.8 Example 4 (C3-2h-5Hold) 7 54.0 83.5 Comparative Example 8 (NS) 0 185.0 43.4 Comparative Example 4 (N-2h-5Hold) 7 137.5 57.9 Comparative Example 3 (raw material mixture: SD55) - 326.9 0.0 As shown in Table 2, the ruthenium compounds of Examples 1 to 4 were not related to the kind of the metal element, and the longer the constant temperature treatment time, the lower the heat of fusion and the higher the rate of decrease in heat of fusion. Further, in the ruthenium compound of the comparative example, the rate of decrease in the heat of fusion of the ruthenium compound of the Example did not become large even when the treatment time was constant. In other words, when the ruthenium compound of Examples 1 to 4 was compared with the ruthenium compound of Comparative Example 3 (raw material), the rate of decrease in heat of fusion was changed to 57.3 3 to 8 3 · 5 %. Further, in the case of Comparative Examples 4 and 8, the longer the constant temperature treatment time is, the lower the rate of decrease in the heat of fusion and the heat of fusion is obtained. However, in the case of Example 4 in which the same constant temperature treatment time is compared with Comparative Example 4, The reduction rate of the heat of fusion in Example 4 was 83.5%, and the rate of decrease in the heat of fusion of Comparative Example 4 was 57.9 %. Further, in the case of the hydrazine compound of the present invention, the longer the constant temperature treatment time, -45-201113241 can improve the liquid stability of the hydrazine compound of the present invention as a curing agent. When Example 1 and 2 of the same metal element were used, the stability of the Example 1 was improved by 92.8%. Moreover, with respect to Example 3, the liquid stability was improved by 98.3%. Further, in Comparative Examples 4 and 8, in Comparative Example 4 in which the constant temperature treatment time was long, in the case of the constant temperature treatment, the liquid stability was lowered in the case of Example 8, but there was a tendency to be practical. From the results, it is understood that the ruthenium compound-based compound of the present invention forms a suitable hardening agent depending on the type of the metal element of the complex compound, the temperature at which the temperature is treated, and the like. [Industrial use price 値] The ruthenium compound of the present invention has a high activity in the presence of unsaturation and can be stably reacted, so that the hardening and hardening time can be shortened, and the service life is also stabilized as heat. Therefore, the ruthenium compound of the present invention can be used, for example, as a heat-curing agent for use as a sealing material or a sealant for electronic parts such as devices. BRIEF DESCRIPTION OF THE DRAWINGS [Fig. 1] shows an X-ray diffraction spectrum of the ruthenium compound (2h) of the present invention. In the case of the liquid compositions of Examples 3 and 4, the ratio of the liquid to the comparative example is the opposite of that of the comparative example, and the resin of the constant temperature, and the time-lowering agent is useful for liquid crystal display of the fat composition. Example 1: T1- - 46-201113241 [Fig. 2] shows an X-ray diffraction spectrum of the ruthenium compound (Window, Shell 2: τ 1 5h) of the present invention.

[Fig. 3] shows an X-ray diffraction spectrum of the ruthenium compound (Example 3 2h) of the present invention. U

[Fig. 4] shows the X-ray diffraction spectrum of the ruthenium compound of the present invention (window, Example 4: c 3 2h-5Hold). [Fig. 5] shows an X-ray diffraction spectrum of the ruthenium compound (眚, Example 5: E 3 2h) of the present invention. _ [Fig. 6] shows the X-ray diffraction spectrum of the ruthenium compound of the present invention (Shenzhen &amp; 6, Example 6: F 3 2h). [Fig. 7] shows the X-ray diffraction spectrum of the ruthenium compound of the present invention (having her example 7: 〇 3 2h). [Fig. 8] shows an X-ray diffraction spectrum of the ruthenium compound of the present invention, which is orally cut (Example 8 · hX3-2h). [Fig. 9] shows an X-ray diffraction spectrum of the ruthenium compound σ (Cheng Shi Example 9: hY3-2h) of the present invention. ^ [Fig. 10] shows the X-ray diffraction spectrum of the ruthenium compound (Example ι 〇 hZ 3-2h) of the present invention. [Fig. 2] shows the X-ray diffraction spectrum of the ruthenium compound (Example ^ S-C3-2h) of the present invention. [Fig. 1 2] shows an X-ray diffraction spectrum of the ruthenium compound (Example 2 2: DSI-111 C3-2h) of the present invention. [Fig. 1 3] shows an X-ray diffraction spectrum of a crystalline ruthenium compound of Comparative Example (Comparative Example 1: SDH). -47-201113241 [Fig. 14] shows an X-ray diffraction spectrum of a crystalline ruthenium compound of Comparative Example (Comparative Example 2: DDH). [Fig. 15] shows the X-ray diffraction spectrum of the ruthenium compound of Comparative Example (Comparative Example 4: N-2h-5H〇ld). [Fig. 16] shows the D S C curve of the ruthenium compound '(Example 1: T 1 - 2 h) of the present invention. [Fig. 17] shows the D S C curve of the hydrazine compound of the present invention (Example 2: T 1 - 5 h). [Fig. 18] shows the D S C curve of the hydrazine compound of the present invention (Example 3: C 3 - 2 h). [Fig. 19] shows the DSC curve of the hydrazine compound of the present invention (Example 4: C3-2h-5Hold). [Fig. 2] shows the D S C curve of the hydrazine compound of the present invention (Example 5: E 3 - 2 h). [Fig. 21] shows the DSC curve of the hydrazine compound of the present invention (Example 6: F3-2h). [Fig. 22] is a D S C curve showing the hydrazine compound of the present invention (Example 7: G 3 - 2 h). [Fig. 23] shows the DSC curve of the hydrazine compound of the present invention (Example 8: hX3-2h). [Fig. 24] shows the D S C curve of the hydrazine compound of the present invention (Example 9: h Y 3 - 2 h). [Fig. 25] shows the D S C curve of the hydrazine compound of the present invention (Example 10: h Z 3 - 2 h). -48-201113241 [Fig. 26] shows the DSC curve of the hydrazine compound of the present invention (Example n: S-C3-2h). [Fig. 27] shows the DSC curve of the hydrazine compound of the present invention (Example 12: DSI-111 C3-2h). [Fig. 28] shows the D S C curve of the crystalline ruthenium compound of Comparative Example (Comparative Example 1: S D Η ). [Fig. 29] shows the DSC curve of the ruthenium compound of Comparative Example (Comparative Example 2: DDH). [Fig. 30] shows the DSC curve of the ruthenium compound of Comparative Example (Comparative Example 3: SD55). [Fig. 31] shows an X-ray diffraction spectrum of the ruthenium compound (Example I, C3-bl2-0h) of the present invention. [Fig. 32] shows an X-ray diffraction spectrum of the ruthenium compound (Example: C3-bl2-lh) of the present invention. (Example i3 (Example 13_4 (raw material blending, Tl'b5-5h) [Fig. 3] shows the X-ray diffraction spectrum of the oxime compound of the present invention: C3-bl2-2h). Figure 34 shows the X-ray diffraction spectrum of the ruthenium compound of the present invention: C3-bl2-3h). [Fig. 3] shows the FT-IR of the oxime compounds Tl-b5-0h, Tl-b5-lh, Tl-b5-2h, Tl-b5-4h of the present invention. [Fig. 36] shows the iH-NMR of the gas evolved in the production of the ruthenium compound of the present invention and the example t: Tl-2h). [Fig. 37] shows the DSC curve of the resin composition of the present invention (Example -49 - 201113241 Hardener T1 -2h). [Fig. 38] shows the D S C curve of the resin composition of the present invention (Example 16: Hardener T 1 - 5 h). [Fig. 39] shows the DSC curve of the resin composition of Comparative Example (Comparative Example 4: Hardener SD55) [Fig. 40] shows the resin composition of the present invention (Example 17: Hardener T 1 - 2 h) DSC curve. [Fig. 4 1] shows the D S C curve of the resin composition of the present invention (Example 18: hardener T 1 - 5 h). [Fig. 42] shows the DSC curve of the resin composition of Comparative Example (Comparative Example 5: hardener SD55). [Fig. 43] shows the DSC curve of the resin composition of the present invention (Example 19: hardener Tl-2h). [Fig. 44] shows the DSC curve of the resin composition of the present invention (Example 20: Tl-5h). [Fig. 45] shows the D S C curve of the resin composition of Comparative Example (Comparative Example 6: hardener S D 5 5 ). -50-

Claims (1)

201113241 VII. Patent Application Range: 1- An antimony compound characterized by containing a crystalline indole compound having at least one mercapto group in the molecule, and a metal element capable of forming a complex with the crystalline indole compound . 2. In the X-ray diffraction spectrum of the Cu-K α line (wavelength 1 · 541 A), in the X-ray diffraction spectrum of the Cu-K α line (wavelength 1 · 541 A), in the Bragg angle 26 (error 20 ± 〇. 2.) 5.5. ~7.5. The range has a peak. 3. A compound of the formula 1 or 2, wherein the melting point is 60 to 2400 °C. 4. The bismuth compound according to any one of claims 1 to 3, wherein the metal element is at least one selected from the group consisting of aluminum, titanium, tin, zirconium, zinc, iron, magnesium, cobalt, nickel, lanthanum, molybdenum, Copper, strontium, barium, boron, manganese, indium, bismuth, antimony, bismuth, antimony, calcium, silver, antimony, and gold. 5. The bismuth compound according to any one of the above-mentioned claims, wherein the content of the metal element is 0.1 to 20.0% by mass based on the total of the crystalline cerium compound and the metal element. 6. The ruthenium compound according to any one of claims 1 to 5, which contains two or more kinds of crystalline ruthenium compounds. 7. The bismuth compound according to any one of claims 1 to 6, which contains a dibasic acid bismuth compound. 8. The compound of claim 6, wherein two or more of the crystalline anthracene compounds are all dibasic acid bismuth compounds. 9 如 醯肼 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 . 10. The hydrazine compound according to any one of claims 1 to 9, wherein the average particle diameter is 0.5 to 20.0; / m»1 1 . A curing agent for a resin, characterized by containing the scope of the patent application An antimony compound of any one of items 1 to 10. A resin composition comprising a hardener according to claim 11 of the patent application, and a resin and/or an epoxy resin having at least one unsaturated bond in the molecule. The resin composition of claim 12, wherein the resin having an unsaturated bond has at least one (meth)acryl fluorenyl group in the molecule. 1 4 A cured product characterized by hardening a resin composition as disclosed in claim 12 or 13 of the patent application. A method for producing a ruthenium compound, which comprises a crystalline ruthenium compound having at least one fluorenyl group in a molecule, and a metal element capable of forming a complex with the crystalline ruthenium compound. The step of heating to obtain a mixture is a step of subjecting the mixture to a constant temperature treatment, and after the constant temperature treatment, the mixture is cooled to obtain a solid. 1 6 The manufacturing method according to claim 15 of the patent application, comprising the step of pulverizing the solid into particles having an average particle diameter of 0.5 to 20.0 μm - 52 -