TW201000491A - Silanol-group-containing curable cage-type silsesquioxane compound, cage-structure-containing curable silicone copolymer, processes for producing these, and curable resin composition - Google Patents

Abstract

A curable cage-type silsesquioxane compound containing a silanol group; a copolymer containing the compound introduced into the main chain; processes for producing the compound and copolymer; and a curable resin composition containing the copolymer. The curable compound is a compound represented by the general formula [R1SiO3/2]n[HO1/2]m which is obtained by cleaving one or more of the siloxane bonds of a curable cage-type silsesquioxane compound represented by the general formula [R1SiO3/2]n in the presence of a basic compound in an organic solvent comprising one or both of a nonpolar solvent and a polar solvent, bonding a counter cation derived from the basic compound to each cleaved part, and then treating the resultant compound with an acid to convert the cleaved part into a hydroxy group. This compound is condensed with a compound represented by general formula (7) to obtain a copolymer. The curable resin composition contains this copolymer.

Description

201000491 VI. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a copolymer of a sclerosing cage type sesquitaine compound of a new type, a copolymer obtained by using the sclerosing cage type sesquiterpoxide compound, The manufacturing method and the curable resin composition of the present invention are detailed in the case of a cage type sesquifer compound which can be suitably used for an electronic material, an optical material, an electro-optical material or the like because of a complex curable functional group. The curable fluorenone copolymer having a cage structure, and the method for producing the same, and further relates to a curable resin composition containing the curable fluorenone copolymer having the cage structure. [Prior Art] To date, there have been many studies on the use of a polymer having a cage structure of sesquiterpene or a derivative thereof. This polymer is expected to have excellent heat resistance, weather resistance, optical properties, dimensional stability, and the like. For example, in Non-Patent Document 1, a sesquioxane having an incompletely condensed structure (a non-complete octahedral structure, at least one structure having at least one crack and a space unclosed) is disclosed as a copolymer linked by a siloxane coupling. Manufacturing method. This production method is a method of crosslinking with an aromatic quinone imine compound or a phenyl ether after the introduction of an amine or the like by an incomplete cage sesquiterpene. Further, Non-Patent Document 2 discloses a method for producing a copolymer of a silyard alcohol group and an amine decane which are incomplete cage sesquioxanes. Further, 'Non-patent document 3' discloses an example in which a vinyl group-containing sesquifer and a sesquioxane containing a hydrogen-containing cleavage group are formed. However, these resins are all straight and non---500-201000491 fragile materials. In particular, in the case of an electronic material, an optical material, or the like, heat resistance, durability, and moldability are required to be improved in transparency, weather resistance, and the like depending on the portion to be used. However, in the conventional sesquioxane copolymer, the structure is unclear and lacks stability 'and' enables the cage sesquioxane to be graft-polymerized on the main chain 'because it becomes a crosslinking point' for colloid It is difficult to obtain a structure that satisfies these characteristics. Therefore, it is desirable to use a copolymer having excellent heat resistance, weather resistance, optical properties, and the like, which is mainly composed of a cage-type sesquiterpene oxide and having a well-defined bondability, but is preferably incorporated in the main chain. There are few examples of copolymers of cage sesquioxanes. In the following Patent Documents 1 and 2, it is disclosed that a decane compound having a 3-functional hydrolyzable group is hydrolyzed in an organic solvent in the presence of a monovalent alkali metal hydroxide, and synthesis of Si-ONa as an inactive group is incomplete. After the cage-type sesquifers, the incomplete cage-type sesquisole is reacted with a functional chlorine-based garden to obtain a copolymer obtained by copolymerizing various compounds. However, the inventors know that there is no disclosure of the method other than the above, and that the method has a side chain which has a cage-type sesquiterpene skeleton and is not hardenable, so that heat resistance is deteriorated. After that. However, an optical material such as a substrate for a liquid crystal display device, an optical lens, a sealing material for a light-emitting diode, or the like is a material having a low birefringence and a small photoelastic coefficient and high optical transparency. Further, in the case of a material such as a substrate for a liquid crystal display device or an optical lens, the material used in the manufacturing process requires high heat resistance. Materials that meet this requirement have used glass and the like in the past. However, in recent years, for example, an optical lens has been used as a curved surface, and a substrate for liquid crystal display in 201000491 has been required to be thinned, and a glass used in the prior art has a high degree of brittleness. A material having high toughness such as a high molecular material 'but generally a polymer material has low heat resistance. For example, an acrylate resin may be colored by heat due to its low heat resistance. Therefore, the introduction of the aromatic skeleton into the means for exhibiting high heat resistance has been discussed. On the other hand, it is difficult to achieve high heat resistance and optical performance because the birefringence is high and the photoelastic coefficient is increased. [Patent Document 1] JP-A-2006-26 5243 [Patent Document 2] WO2003/024870 [Non-Patent Document 1] Chem. Mater. 2003, 15, 264-268 [Non-Patent Document 2] Macromolecules. 1993, 26 2141-2142 [Non-Patent Document 3] J. Am. Chem. Soc. 1998, 120, 8380-83 9 1 [Problems to be Solved by the Invention] As described above, if the molecular weight can be arbitrarily controlled, The material can be designed to meet the purpose, and the degree of freedom in forming the electronic material or the optical material should be increased. However, the synthesis of the copolymer in which the cage structure is introduced into the main chain is rare, and the specific characteristics of the copolymer are not known. Accordingly, an object of the present invention is to provide a sulfanol group-containing curable cage sesquiterpoxysilane compound and a copolymer which is introduced into the main chain. Further, it is a method for producing a curable cage type sesquiterpoxide containing a stanol group and a copolymer of the copolymer introduced into the main chain. Further, a curable resin composition of a molded article which is excellent in heat resistance, optical characteristics, and dimensionality and excellent in toughness is provided. [Means for Solving the Problems] As a result of efforts to solve the above problems, the present inventors have found that a curable cage-type sesquiterpene oxide compound containing a stanol group can be obtained under specific reaction conditions, and is introduced into the main chain. Further, the curable resin composition containing such a copolymer has been found to provide a cured product excellent in heat resistance, optical properties, and dimensional stability, and completed the present invention. That is, the present invention is the following general formula (2) [R1 Si〇3/2]n [HO 1 /2] m (2 ) (except, R1 is a vinyl group, an alkyl group, a phenyl group, a (methyl group) The propylene fluorenyl group, the allyl group, or the group having an oxirane ring may be the same or different from each other, and at least one of R1 contained in one molecule is an alkyl group or a (meth) propyl group. Any one of the base, the propyl group or the group having an epoxy oxime ring, and η is a number of 6 to 14, and m is a number of 1 to 4. The sulfoalkyl group-containing hardenable cage sesquiterpoxide compound is characterized by the following general formula (π [R^iOa/iln (1) (only 'R1 is a vinyl group, an alkyl group, a phenyl group , (meth) propylene fluorenyl, allyl or a group having an epoxy ring, although mutually identical or different, at least one of R1 contained in one molecule is an alkyl group, (methyl Any one of a propyl fluorenyl group, an allyl group or a group having an oxirane ring, η is a number of from 6 to 14). The sclerosing cage type sesquiterpene oxide compound represented by the test compound is present In a non-polar solvent and a polar solvent, or in an organic solvent containing two kinds, the heptane is bonded to one or a plurality of cracks, and the counter cation and the cleavage bond from the test compound -8-201000491 are bonded. Thereafter, it is treated with an acid to convert the cleavage portion into a hydroxyl group. Further, the present invention is the following general formula (2) [R1Si03/2] „[H01/2] m (2) (only, R1 is a vinyl group) Or an alkyl group, a phenyl group, a (meth) propylene fluorenyl group, an allyl group or a group having an oxirane ring, which may be the same or different from each other, and at least one of R1 contained in the i molecule Any one of a vinyl group, a (meth) acryl fluorenyl group, an allyl group or a group having an oxirane ring, and η is a number of 6 to 14 and m is a number of 1 to 4). A method for producing a sulfanyl group-containing hardenable cage sesquiterpoxide compound characterized by the following general formula (1) [R 1 S ΐ Ο 3 /2 ] η (1) (except that R1 is a vinyl group) , an alkyl group, a phenyl group, a (meth) propylene fluorenyl group, an allyl group or a group having an oxirane ring, which may be the same or different from each other, and at least one of R1 contained in one molecule is ethylene. Any of the (meth)acrylonitrile groups, allyl groups or groups having an oxirane ring, and n is a number from 6 to 14). The hardenable cage sesquiterpoxide compound represented by the group. In the presence of a basic compound, in a non-polar solvent and a polar solvent, or in an organic solvent containing two or more, the azide is bonded to one or a plurality of cracks, and the counter cation from the basic compound is bonded to the cracking portion. Thereafter, the treatment with an acid converts the cleavage portion into a hydroxyl group. Further, the present invention is a sclerosing fluorenone copolymer having a cage structure, which has the following characteristics General formula (3) -9- 201000491 Y-[Z-(R]Si〇3/2)n]lZY (3) [R, R1 is a vinyl group, an alkyl group, a phenyl group, a (meth) acrylonitrile group , allyl or a group having an oxirane ring, although mutually identical or different, at least one of R1 contained in one molecule is a vinyl group, a (meth) acryl fluorenyl group, an allyl group or Any one of the groups having an oxirane ring, η is a number of 6 to 14 and 1 is a number of 1 to 2000, and Ζ is the following general formula (4) [Chemical 1] > i-0

(4) ~ 〇 1/2 (except that R 2 is a hydrogen atom, a vinyl group, an alkyl group, a phenyl group, a (meth) acryl fluorenyl group, an allyl group or a group having an oxirane ring, which may be the same as each other Or different, again, a is a number from 0 to 30). The two-valent group represented, Y is the following general formula (5 ') HO./2- (5,) or the following general formula (5) - [R1Si03/2] „[H〇i/2]m (5) (R1, R1 is a vinyl group, an alkyl group, a phenyl group, a (meth) acrylonitrile group, an allyl group or a group having an oxirane ring, and although they may be the same or different from each other, 1 At least one of R1 contained in the molecule is any one of a vinyl group, a (meth) acryl fluorenyl group, an allyl group or a group having an oxirane ring, and η is a number of 6 to 14, and m is 1 〜4的数) or the following general formula (6) -10- 201000491 【化2】 R3

, I R3—Si—01/2— | 1/2 (6) R3 (only 'R3 is hydrogen, vinyl, alkyl, phenyl, (meth)acryloyl, allyl or has epoxy B The base of the alkane ring can be the same or different from each other). It is not a one-price base. The constituent units indicated. Further, the present invention is a method for producing a curable anthrone copolymer containing a cage structure, which is characterized by the following general formula (2) [R1Si03/2]n[H01/2]m (2) R1 is a vinyl group, an alkyl group, a phenyl group, a (meth) acrylonitrile group, an allyl group or a group having an oxirane ring, and although they may be the same or different from each other, the R1 contained in the i molecule At least one of a vinyl group, a (meth) acryl fluorenyl group, a propylene group or a group having an epoxy ring, and η is a number of 6 to 14, and m is a number of 1 to 4. The curable cage-type sesquifere compound containing a stanol group and the following general formula (7) [Chemical 3]

(R2, R2 is a hydrogen atom, a vinyl group, an alkyl group, a phenyl group, a (meth) propylene-11 - 201000491 fluorenyl group, an allyl group or an oxirane ring, and further, X is a hydrogen atom or a halogen atom. The difference, and then b is a number from 0 to 30), or, in turn, with the following general formula: R3 R3-Si-CI ... | (8) R3 (only, R3 is a hydrogen atom, ethylene Base, thiol, allyl or having an oxirane ring). The compound represented is condensed 3)

Y-[Z-(R1Si03/2)„]i-Z-Y

[Rf, however, R1 is a vinyl group, an alkyl group, a phenylpropyl group or a group having an oxirane ring, although at least one of R1 contained in the molecule is a group, an allyl group or a group having an oxirane ring The number, 1 is a number from 1 to 2000, Z is the lower group, and may be the same or different or alkoxy groups, and the compounds represented by the same or ° may be subjected to a condensation group, a phenyl group, a (meth) group. The propylene groups may be the same or different from each other to obtain the following general formula ((3), (meth) propylene fluorenyl group, olefin may be the same or different from each other, 1 vinyl group, (methyl) Any one of acrylonitrile, and η is 6 to 14 (4) [Chemical 5] f \ R2 〇1/2-| -Si-O-一| 〇1/2— \ / a I R2 ( 4 201000491 (However, R2 is a hydrogen atom, a butyl group, a propyl group or a group having an epoxy group, an alkyl group, a phenyl group or a (meth) propylene ring, which may be the same or different from each other, Further, a is a number from 0 to 30. The two-valent group represented by Y is represented by the following general formula (5') HO 1/2- (5,) or the following general formula (5) - [RS ϊ Ο 3 / 2 ] η [ Η Ο 1 / 2 ] m . (However, R1 is a vinyl base, a yard base a group or at least a group of R1 contained in a molecule having an oxirane ring, an allyl group or an ethylene oxide 1 (5) 'phenyl group, a (meth) acrylonitrile group 'ene group, although Any one of the same or different ones is a group of vinyl or (meth) propylene arsenic, and η is 6 to 14 or the following general formula (6)

The number, m is a number from 1 to 4) [Chemical 6] R3 R3—Si-〇1/2-R3 (only 'R3 is hydrogen, B-base, yard-based, phenyl, (methyl)-propyl vinegar a monovalent group represented by a group, an allyl group or a group having an oxirane ring which may be the same or different from each other. A hardenable fluorenone copolymer having a cage structure represented by the constituent units. Further, the present invention is a curable resin composition characterized by the following general formula (3) -13 - 201000491 Y-[Z-(R1Si〇3/2)n]iZY (3) (described in the formula a curable fluorenone copolymer having a cage structure in the same manner as described above, in combination with either or both of a hydrogenation catalyst and a radical initiator, and having at least one germanium atom Any one or both of a hydrogen atom-soluble compound of a hydrogen atom and a compound having an unsaturated group in the molecule. In addition, the present invention is a cured product (molded body) obtained by molding and curing the curable resin composition, and specifically, a cured product (molded body) obtained by hydrogenating and radically polymerizing the curable resin composition. Specific examples of the hardenable cage sesquioxane compound of the sand-containing alcohol group represented by the general formula (2) are represented by the following structural formulae (9) to (15), respectively. The structural formula (9) is n - 6 ' ' (1〇) is n_7 ' m = 3 ' (11) -1 and (Η) -2 is n = 8' m = 2, (12) is n = 9, m=1, (13) is π1〇, m = 2 ' (14) is n=12 ' m = 2 ' (U) is n=l 4, m = 2. However, the structural unit represented by the general formula (2) is not limited to those shown by the structural formulas (9) to (15). Further, in the structural formulae (9) to (15), R1 is the same as the general formula (2). -14- (9) 201000491 【化7】

OH PH .Si'pi Ί R 0 (10) R1, 丨

Si

Si——〇—Si-R1 | •R1 〇 R1-huyiyi〇~7Si iy°

/〇H,R1 (11)-2 201000491 【化8 R1 R丨

-SU

R1 /° ? rV ? R, Si_j-o-Si—[Ο* I Si—O—丨-Si, D 0/^1 0 / R IP R IP , Si—0-Si R1 L

〇\ ,R1 ^s,\ OH (12) R1ο o 丨 O—Si· , R1 R1 -l

\ .R1 ,Si—OH (13) R1..m Ο n ;sr〇H R1,〇”〆〇 R1 / R1

o \io- 1RS R1.si_ o

R , 9 >s. o 0 1 \°JS I ·1 1 s R 1/ R1 olv ;/?si1 rvsi' "—¥i,o \ ζο so R1/c 3 / -R1 -sloro-si H R1o H o VR1 4

Γ or 1 1 ' s-o-j-s'- R R one. L-ri \0^\0-~ IR'sisauolf/ J RR1 R

5, legalized paraffin oxygen-making sand half-polymerization type cage 嗣 [4 矽 性 硬 hard hardening of the structure of the structure 3 cage 1 containing C of the same type of hair to make a first head 6 201000491 , in the presence of a basic compound, in an organic solvent containing one or two of a non-polar solvent and a polar solvent, one or more of the xanthene linkages are cleaved, and the crack is maintained by the counter cation from the basic compound Thereafter, the neutralization is carried out to convert to a hydroxyl group, and the sulfoalkyl group-containing curable cage sesquiterpoxide compound represented by the above general formula (2) is obtained. A basic compound used in the synthesis of a sulfanol group-containing curable cage sesquiterpoxide compound represented by the general formula (2), for example, tetramethylammonium hydroxide, tetraethylammonium hydroxide, or oxyhydroxide One-valent alkali metal hydroxide such as tetrabutylammonium, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, etc., ammonium hydroxide, lithium hydroxide, sodium hydroxide, potassium hydroxide, etc. . Among these, ammonium hydroxide is preferred in order to effectively act as a counter cation. A preferred example of the ammonium hydroxide salt is tetramethylammonium hydroxide. The amount of the basic compound to be used is preferably 1 mol with respect to the structural unit represented by the general formula (1), preferably 0.5 to 3 mol, preferably 1.5 to 2.5 mol. In the case of this reaction, when the amount of the basic compound used is less than 0.5 mole, the reaction does not proceed. In addition, if it is more than 3 moles, the cracking reaction of the cage structure is excessively promoted to cause decomposition. Further, an alkaline compound is generally used as an alcohol solution. The alcohol solution used, for example, methanol, ethanol, propanol, isopropanol. Among them, methanol is preferred. The organic solvent used for the synthesis of the sulfhydryl group-containing curable cage sesquioxane compound represented by the general formula (2) is a solvent containing one or two kinds of a nonpolar solvent and a polar solvent. Here, specific examples of the nonpolar solvent include hydrocarbon solvents such as hexane, toluene, xylene, and benzene. Specific examples of the polar solvent include an ether solvent such as diethyl ether or tetrahydrofuran, -17-201000491, an ester solvent such as ethyl acetate, an alcohol solvent such as methanol, ethanol or isopropanol, acetone or methyl b. A ketone solvent such as a ketone. Among these, a polar solvent is preferred from the viewpoint of imparting a structure control effect of the solvent affinity, and tetrahydrofuran is more preferable. The organic solvent is preferably used in an amount of 1 mol based on the structural unit represented by the general formula (1), preferably in a molar concentration (mol/1 : Μ) of 0.01 to 10 Torr, preferably 0.01 to 1 Torr. Regarding the amount of the non-polar solvent and/or the polar solvent to be added to the organic solvent, a non-polar solvent is preferably a small amount relative to the polar solvent. Preferably, the ratio of the relative polar solvent is 10 0 to 1 00, the nonpolar solvent is 1, preferably the relative polar solvent is 5 0 to 1 0 0, and the nonpolar solvent is 1. a reaction condition for reacting a curable cage type sesquiterpoxide compound represented by the general formula (1) in an organic solvent containing one or two kinds of a nonpolar solvent and a polar solvent in the presence of a basic compound, and reacting The temperature is preferably 0 to 60 ° C, more preferably 20 to 40 ° C. When the reaction temperature is lower than 0 °c, the reaction rate becomes slow and remains in the state of the uncracked completely caged sesquiterpene gas, which requires a large reaction time. Further, when the temperature is higher than 60 °C, the reaction rate is too fast, and a complicated condensation reaction is carried out, and as a result, high molecular weight is promoted. The reaction time varies depending on the substituent R1 of the structure represented by the above general formula (1), and is usually from several minutes to several hours, preferably from 1 to 3 hours. After the reaction was completed, the reaction solution was neutralized with a weakly acidic solution. After neutral or acidic treatment, the water or aqueous reaction solvent is separated. The separation of the water or the aqueous reaction solvent may be carried out by washing the solution with salt water or the like to sufficiently remove water or other impurities, followed by drying with a drying agent such as anhydrous magnesium sulfate. When a polar solvent is used, the hands of -18-201000491 such as vacuum evaporation may be used, and after removing the polar solvent, a non-polar solvent is added to dissolve the polycondensate, and then washed and dried as described above. As the weakly acidic solution, a sulfuric acid dilution solution, a hydrochloric acid dilution solution, a citric acid dilution solution, acetic acid, an aqueous ammonium chloride solution, a malic acid solution, an oxalic acid solution or the like can be used. Although the non-polar solvent separates the recoverable reaction product by evaporation or the like, if the non-polar solvent can be used as the non-polar solvent for the next reaction, the separation is not required. The above-obtained stanol-containing hardening cage is obtained. The sesquiterpene oxide compound can be represented by the following general formula (2). [R1Si〇3/2]n[H01/2]m (2) (However, R1 is a vinyl group, an alkyl group, a phenyl group, a (meth)acryloyl group, an allyl group, or an oxirane ring At least one of R1 contained in one molecule is a group having a vinyl group, a (meth)acryl fluorenyl group, an allyl group or an oxirane ring, although they may be the same or different from each other. A curable functional group. η is a number from 6 to 14, and m is a number from 1 to 4. The sulfoalkyl group-containing hardenable cage sesquiterpoxide compound represented by the general formula (2) has a partial sterol group at the terminal and does not completely form a closed space, and is an incomplete condensation type. Semi-oxane. Next, the sulfoalkyl group-containing hardenable cage sesquiterpene oxide compound represented by the general formula (2) is the following general formula (7).

-19- 201000491 (However, R2 is a hydrogen atom, an ethylene group, a hospital group, a phenyl group, a (meth)propenyl group, an allyl group or a group having an oxirane ring, which may be the same or each other X is a hydrogen atom, a halogen atom, or an alkoxy group, and may be the same or different from each other. b is a number of 〇~30). The compound represented by the condensation reaction can be obtained by the following general formula (3) -1 YMZ-WSiOmKh-Z-Y1 (3)-1 (except that R1 is an alkyl group, a phenyl group, a phenyl group, a methyl group The propylene group, the propyl group or the epoxide group having the oxirane ring may be the same or different from each other, and at least one of the compounds of the general formula (3)-1 has a vinyl group (methyl group). Any one of a propylene group, an allyl group, or a curable functional group having an oxirane ring group. Further, η is a number of 6 to 14, and 1 is a number of 1 to 2,000. A sclerosing fluorenone copolymer having a cage structure as a constituent unit. Here, Ζ is the following general formula (4) [Chemical 1 〇]

(4) (However, R2 is hydrogen, vinyl, alkyl, phenyl, (meth)acryloyl group, allyl or group having an oxirane ring' may be the same or different from each other. a is 0 ~3 0 number). The two-valent base represented. Further, Y1 is represented by the following general formula (5 ') ΗΟ, /2- (5. -20- 201000491 or the following general formula (5) - [R1Si〇3/2]n [HOI/2] ml (5) (R1, R1 is a vinyl group, an alkyl group, a phenyl group, a (fluorenyl) acrylonitrile group, an allyl group or a group having an oxirane ring, although they may be the same or different from each other, and are contained in one molecule. At least one of R1 is a vinyl group, a (meth) acryl fluorenyl group, an allyl group or a group having an oxirane ring group, and a number of η is 6 to 14 and a number of m is 1 to 4. The hardening of the cage-containing structure obtained by the condensation reaction of the sulfanol group-containing hardenable cage sesquioxane compound represented by the general formula (2) with the compound represented by the general formula (7) In the method for producing a ketone ketone copolymer, as described below, the production method differs depending on the type of the substituent X of the compound represented by the general formula (7). When the compound represented by the formula (7) is chlorine, it is chlorine. 'This is the following general formula (1 6) [Chemical 1 1]

(R2, R2 is a hydrogen atom, a vinyl group, an alkyl group, a phenyl group, a (meth)acryloyl group, an allyl group or a group having an oxirane ring' may be the same or different from each other. b is 0. When the number is -30, the sulfoalkyl group-containing hardening cage-type sesquioxane compound 1 moler represented by the general formula (2) is 0 5 to 10 mol, preferably 0.5 to 3.0. The range of Moer is one of the above-mentioned general formula (-21 - 201000491 16), which is represented by the dichlorinated sand or the α, ω-dichloro-salt, under the test conditions, in the non-polar solvent and the ether solvent. The reaction may be carried out in a solvent of two or more kinds to obtain a curable fluorenone copolymer having a cage structure represented by a general formula (3)-1. The curable cage sesquiterpoxide compound containing a stanol group represented by the general formula (2), the dichlorodecane represented by the general formula (16), or the α,ω-dichloroadenine. Specific reaction conditions, for example, dissolving dichlorosilane or α,ω-dichlorodecane in a solvent containing one or two kinds of a non-polar solvent and an ether solvent, and relative to dichlorosilane or α, Ω-dichlorodecane is added to a mixed solution of 1 equivalent or more of triethylamine or a mixture of a solvent and a base in an amine solvent to form a stanol-containing hardenable cage sesquiterpene oxide. The compound is dissolved in a solvent of one type or two kinds of solvents in a non-polar solvent and an ether solvent, and is added dropwise at room temperature under an inert gas atmosphere such as nitrogen, and then it is preferably stirred at room temperature for 2 hours or more. At this time, if the reaction time is short, there is a case where the reaction cannot be completed. After completion of the reaction, toluene and water are added to dissolve the curable fluorenone copolymer containing the cage structure represented by the general formula (3)-1 in toluene, and the excess chlorine sands, the by-produced hydrochloric acid And the hydrochloride is dissolved in the aqueous layer to remove. Further, the organic layer is dried with a desiccant such as magnesium sulfate, and the base and solvent to be used are removed by concentration under reduced pressure. Specific examples of the general formula (16) 'b is the dichlorosilane represented by 0', such as propyl propyl chlorinated sand, propyl hexyl chlorinated sand, burned propyl methyl dichloro decane, allyl Phenyldichlorodecane, methyldichlorosilane, dimethyldichloroindole, ethyl dichloride, methyl ethyl chlorinated sand, ethyl-22- 201000491 monoethyl chloride Sand yard, diethoxydichloropurine, diallyldichloropurine methyl dichlorodecane, ethoxymethyldichlorosilane, monoethyl chlorin, methyl propyl dichloromethane Alkane, butylmethyldichlorodecane, phenyldichlorodecane, methylpentyldichlorodecane, dichlorodecane, hexylmethyldichloromethyldichlorodecane-2-norbornyl, 3-methylpropene oxime Oxypropyl propyl, dibutyl chlorodecane, methyl dichloro decane, t-butyl phenyl dimethyl phenyl dichloro decane, cyclohexyl methyl sane, phenyl vinyl dichloro decane, 6 _ , 2-methyldichloroindenyl norbornene-chloromethylnonane, heptylmethyldichloroindenyl-β-phenethyldichlorodecane, methyloctylchlorodecane, mercaptomethyldichlorodecane Second Silane chloride group, a group of their own sand-chloro-firing, dodecyl cut hospital hospital methyldichlorosilane, methyl dichloro silane-octadecyl and the like. With respect to the general formula (16), b is a specific example of the α,ω-dichloroadenine represented, for example, 1,1,3,3·tetramethyl-;[,3-dichlorodecane, l ,l,3j-tetracyclopentyl-1,3-dichlorodecane, m3,·tetraisopropyl·,3···················· - /, methyl - hydrazine, 5 · dichloro III. Cascade, 1,1,3,3,5,5,7,7-octamethyl-1,7-dichlorotetraoxane, and the like. The organic solvent used in the case where X of the compound represented by the general formula (7) is chlorine may be optionally selected from the group consisting of p-dichloromethane or a, co-dichloromethane oxide, and may be optionally selected. A specific example of a non-polar solvent is a hydrocarbon-based solvent such as hexane, toluene or xylene 'benzene. Specific examples of the ether solvent include diethyl ether and tetrahydrofuran. Among these, an ether solvent is preferred from the viewpoint of controlling the structure of the solvent and the effect, and tetrahydrofuran is more preferable. Further, as the solvent and the alkali, the amine solvent may be used singly or as a mixed solution. Specific examples of the amine solvent include pyridinium, diethylamine, -23-201000491 aniline, and N,N-diisopropylamine. In the case where an amine solvent is not used, a base such as triethylamine is added. The solvent is preferably used in an amount of from 1 mol to the sulfanol group-containing hardenable cage sesquiterpene structural unit represented by the general formula (2), preferably in the range of 0.01 to 10 M, preferably 0.01 to 0.01. 1M. Further, when X of the compound represented by the general formula (7) is an alkoxy group, that is, the following general formula (17) [Chemical Formula 1]

(R2) R2 is a group having a hydrogen, a vinyl group, an alkyl group, a phenyl group, a (meth)acryloyl group, an allyl group, an alkoxy group or an oxirane ring, and may be the same or different from each other. R4 is a methyl group, an ethyl group, or a propyl group, and may be the same or different from each other. When b is a number of 0 to 30), it is a doubler than the sulfoalkyl group-containing hardening cage type represented by the general formula (2). The semi-oxane compound 1 mole, in the range of 0.5 to 10 moles, preferably 〇 5 to 3.0 moles, of the dialkoxy decane represented by the above general formula (17), or α, ω - The dialkoxy oxirane is reacted in a solvent containing one or two kinds of a non-polar solvent and an ether solvent in the presence of a catalyst to obtain a composition represented by the general formula (3)-1. A unit of a sclerosing fluorenone copolymer containing a cage structure. The sulfoalkyl group-containing hardenable cage sesquiterpoxide compound represented by the general formula (2) and the dialkoxy decane represented by the general formula (17) or α, ω-dialkoxy fluorene Specific reaction conditions of the oxane, for example, a sulfoalkyl group-containing hardenable cage sesquiterpoxide compound represented by the formula (2), a dialkoxy decane, or α, ω- A case where a dialkoxy oxirane and a catalyst are dissolved in a solvent containing one or both of a non-polar solvent and an ether solvent. The concentration is relative to a sulfonate-containing hardenable cage sesquiterpoxide compound. , with 0. 1~2 · 0 Μ is better. The reaction temperature is 〇1 to 130. (: Preferably, 80 to 1 1 〇 ° C is more preferable. When the reaction temperature is lower, the reaction rate becomes slower and becomes more reaction time. In addition, when it is higher than 130 ° C, a cage structure is produced. The cracking reaction, as a result of the complicated condensation reaction, forms a colloidal solid. The reaction time is preferably 2 hours or more. At this time, if the reaction time is short, the reaction may not be completed. After the reaction is completed, the reaction solution is allowed to be completed. After neutral or acidic treatment, the water or the aqueous reaction solvent is separated. The separation of the water or the aqueous reaction solvent may be carried out by washing the solution with salt water or the like to sufficiently remove water or other impurities, followed by anhydrous magnesium sulfate or the like. When the ether solvent is used, the ether solvent may be used, and after removing the ether solvent, the non-polar solvent may be added to dissolve the polycondensate, and then washed and dried as described above. With respect to the general formula (17), b is a specific example of the dialkoxy decane represented by 0, such as dimethoxy dimethyl decane, diethoxymethyl decane, diethoxy vinyl decane, and Ethoxygen Diethyldecane, dimethyldipropoxydecane, dimethoxymethylphenyldecane, 3-glycidoxypropylmethyldiethoxydecane, 3-glycidoxypropyl Methyldimethoxydecane, 3-methylpropenyloxypropylmethyldimethoxydecane, diethoxymethylphenylnonane, 3-methylpropenyloxypropylmethyldiethyl Oxydecane, dimethyl-25-201000491 oxydiphenyl decane, diethoxydodecylmethyl decane, etc. With respect to the general formula (17), b is α, ω_ represented by 1 to 30 Specific examples of oxirane, such as 1,3-dimethoxytetramethyl bis 7 oxo '1,3-diethoxytetramethyldioxane, 1,5-dimethyl Oxy hexamethyl trioxaxane, 1,7-dimethoxyoctamethyltetraoxane, 1,5-diethoxy hexamethyltrioxane, 1,7-diethoxy VIII Methyltetraoxane, etc. 1. The organic solvent used in the case where the oxime used for the compound represented by the general formula (7) is an oxime oxime may be optionally selected from alkoxy decane' or α, ω-Ζ: fire The oxy oxane is inactive, and specific examples of the non-polar solvent, such as A hydrocarbon-based solvent such as an alkane, toluene'xylene or benzene. Specific examples of the ether solvent include diethyl ether and tetrahydrofuran. Among them, toluene is preferred as the solvent. Alternatively, it may be an ether solvent and a non-polar solvent. The solvent is preferably used in an amount of from 1 to 10 mol per unit of the structural unit represented by the general formula (2), preferably from 0.01 to 10 Torr, more preferably from 1 to 1 Torr. The catalyst used when X of the compound represented by the general formula (7) is an alkoxy group, such as an alkali metal hydroxide such as potassium hydroxide, sodium hydroxide or hydroxide, or tetramethylammonium hydroxide. Ammonium hydroxide salt of tetraethylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide and benzyltriethylammonium hydroxide, tetraethoxytitanium, tetrabutoxytitanium , tin oxide, dibutyltin oxide, zinc acetate dihydrate, lead acetate trihydrate, lead oxide, aluminum acetate, manganese acetate tetrahydrate, cobalt acetate tetrahydrate, cadmium acetate, dibutyl tin laurel Acid salt, dibutyl tin maleate, dioctyl tin mercaptide, stannous octoate, octanoic acid, etc. Organometallic catalyst, trivinyldiamine, tetramethylguanidine, 2-(dimethylaminomethyl)phenol, -26 - 201000491 氺:^,>1',:^-tetramethyl hexane -1,6-diamine, 1,8-diazabicyclo[5.4.0]undecene-7, p-toluenesulfonic acid, and acetic acid trifluoride. Among these, tetramethylammonium hydroxide is preferred from the viewpoint of high catalyst activity. Further, when X of the compound represented by the general formula (7) is a hydrogen atom, that is, the following general formula (18) [Chemical Formula 1]

(R2, R2 is a hydrogen atom, a vinyl group, an alkyl group, a phenyl group, a (meth)acryloyl group, an allyl group, an alkoxy group or a group having an oxirane ring, which may be the same or different from each other. b is a number from 0 to 3 0). In the case of the sulfoalkyl group-containing hardenable cage sesquioxane compound 1 mol represented by the general formula (2), it is in the range of 55 to 10 mol, preferably 0.5 to 3.0 mol. The dihydrononane or α,ω-dihydrofuranyl represented by the above general formula (17) is reacted in a solvent containing one or both of a non-polar solvent and an ether solvent in the presence of a catalyst. 'A sclerosing fluorenone copolymer having a cage structure having a constituent unit represented by the general formula (3) -1 can be obtained. The specific reaction of the sulfanol group-containing sclerosing cage sesquioxane compound represented by the general formula (2) with the general formula (17) represented by dihydro decane or α, ω-dihydroioxane The condition, for example, the sulfoalkyl group-containing hardenable cage sesquiterpoxide compound represented by the general formula (2) and dihydro decane, or α,ω-dihydrophthaloxane and a catalyst are dissolved in a non-polar In the case of a solvent and an ether system -27-201000491, in the case of a solvent of one or both of the solvents, the concentration is based on the sulfoalkyl group-containing hardenable cage sesquioxane compound represented by the general formula (2). 0.1 to 2.0M is preferred. The reaction temperature is 〇~1〇〇. Preferably, 20 to 80 ° C is better. When the reaction temperature is lower than 0 °C, the reaction rate becomes slow and it takes a lot of reaction time. Further, if it is higher than 100 ° C, the reaction rate is too fast and a complicated condensation reaction is carried out to form a colloidal solid. The reaction time is preferably 2 hours or more. At this time, if the reaction time is short, there is a case where the reaction cannot be completed. After completion of the reaction, the reaction solution is subjected to neutral or acidic treatment to separate water or an aqueous reaction solvent. At this time, the terminal group non-stanol group is converted into a stanol group by hydrolysis. The separation of the water or the aqueous reaction solvent may be carried out by washing the solution with salt water or the like to sufficiently remove water or other impurities, followed by drying with a drying agent such as anhydrous magnesium sulfate. When an ether solvent is used, the ether solvent may be removed by a method such as evaporation under reduced pressure, and then the non-polar solvent is added, and then the polycondensate is dissolved, and then washed and dried as described above. Regarding the general formula (18), b is a specific example of the dihydrogen sand court represented by 0, such as diethyl decane, diphenyl decane or the like. With respect to the general formula (18), b is a specific example of α,ω-dioxane represented by 1 to 30, such as 1,1,3,3-tetramethyldioxane, 1,1 , 3,3-tetracyclopentyldioxane, 1,1,3,3-tetraisopropyldioxane, hydrazine, 3,3,5,5-hexamethyltrioxane, 1 1,3,3,5,5,7,7-octamethyltetraoxane, and the like. The organic solvent used when X of the compound represented by the general formula (7) is a hydrogen atom can be arbitrarily selected from those in which dihydrofurfurane or α,ω-dihydroindoleoxy-28-201000491 is inactive. Specific examples of the non-polar solvent are hydrocarbon solvents such as hexagram, toluene, xylene, and benzene. Specific examples of the ether solvent include diethyl ether and tetrahydrofuran. Among them, toluene is preferred as the solvent. Further, it may be a mixture of a polar solvent and an ether solvent. The organic solvent is preferably used in an amount of from 0.01 to 10 M, preferably from 0.1 to 1 M, per 1 mol of the structural unit represented by the general formula (2). Further, the catalyst used when X of the compound represented by the general formula (7) is a hydrogen atom may, for example, be tetraethoxytitanium, tetrabutoxytitanium, hydroxylamine, N-methylhydroxylamine, or N. a hydroxylamine compound such as N-dimethylhydroxylamine, N-ethylhydroxylamine or N,N-diethylhydroxylamine. Among these, N, N-diethylhydroxylamine is preferably used. Further, by making the curable fluorenone copolymer having a cage structure represented by the general formula (3)-1 and the following general formula (8), R3 R3-Si-Cl I (8) R3 ( However, R3 is hydrogen, vinyl, alkyl, phenyl, (meth)acrylonitrile, allyl or a group having an oxirane ring, which may be the same or different from each other). The compound represented by the condensation reaction may also have the following general formula (3)-2 Y2-[Z-(R* Si03/2)n]iZ-Y2 (3)-2 (only, R1 is a vinyl group) , an alkyl group, a phenyl group, a (meth) propylene fluorenyl group, an allyl group, or a group having an oxirane ring, which may be the same or different from each other, -29- 201000491 1 R1 contained in the molecule At least one group, allyl or with an oxirane ring, 1 is a number from 1 to 2000. Further, z is any of vinyl, (meth) propylene, and η is 6~ The number of 14 is the following general formula (4) [Chemical 1 5]

(R2 is a hydrogen atom, a vinyl fluorenyl group, an allyl group or an epoxy group, and a is a number from 0 to 30). The formula (5 ') Η〇ι/2- (5,) or the following general formula (6) (4), the base, the phenyl, the (methyl) propyl can be used as a base Interrogating or different; showing the divalent base, Υ2 is as follows - [Chemical 1 6] R3 (6) R3 - Si - 01/2 - R3 (only, R3 is a hydrogen atom, a vinyl fluorenyl group, an olefin Propyl or with epoxy). The one-valent base represented). a sclerosing fluorenone copolymer. , the base of the base, the base of the phenyl, (meth) propyl can be the same as the cage structure of the unit represented by the same or different -30- 201000491 Here, relative to the general formula (3) - The sclerosing fluorenone copolymer having a cage structure represented by 1 is 1 mol, and the chlorodecane represented by the above general formula (8) in the range of 2 to 100 m under the alkaline condition The polar solvent is reacted with one or two kinds of solvents in a polar solvent to obtain a curable fluorenone copolymer having a cage structure represented by the general formula (3)-2. The preferred use amount of chlorodecane is preferably 2 to 30 moles per mole of the curable fluorenone copolymer having a cage structure represented by the general formula (3)-1. Specific reaction conditions of the sulfonated fluorenone copolymer having a cage structure represented by the general formula (3) -1 and the chlorodecane represented by the general formula (8), for example, a chlorodecane in a nonpolar solvent Dissolving in one or two solvents of a polar solvent, adding a mixture of triethylamine of 1 equivalent or more with respect to chlorodecane, or dissolving chlorodecane in a mixture of pyridine as a solvent and a base. A solution of a stanol-containing sclerosing cage sesquioxane compound dissolved in a solvent containing one or both of a non-polar solvent and a polar solvent is allowed to drip at room temperature under an inert gas atmosphere such as nitrogen. After that, it is preferred to carry out the stirring at room temperature for 2 hours or more. At this time, if the reaction time is short, the reaction cannot be completed. After completion of the reaction, toluene and water are added. The curable fluorenone copolymer having a cage structure represented by the general formula (3)-2 is dissolved in toluene to cause excess chlorodecane, by-produced hydrochloric acid, And the hydrochloride is dissolved in the aqueous layer to remove. Further, the organic layer is dried with a desiccant such as magnesium sulfate, and the base and the solvent to be used are concentrated under reduced pressure to give a hardenable fluorenone copolymer having a cage structure represented by the general formula (3)-2. -31 - 201000491 It is limited to the sulfanol group-containing hardening cage sesquiterpene oxide compound represented by the general formula (2) and the dichlorohydrazine compound represented by the general formula (16), or α, ω-dichloro When the oxirane is reacted to obtain the general formula (3)-1, it is not necessary to take out the general formula (3)-1, and the chlorosilane represented by the general formula (8) is added to the reaction system to carry out a reaction, and a general formula can be obtained. (3) A curable fluorenone copolymer having a cage structure as a constituent unit represented by -2. The specific conditions for obtaining the reaction of the curable fluorenone copolymer having a cage structure represented by the general formula (3) - 2 are such that the chlorosilane represented by the general formula (8) is dissolved in a non-polar solvent and a polar group. One or two kinds of solvents in the solvent, a mixed solution of 1 equivalent or more of triethylamine to chlorodecane or a mixture of chlorosilane represented by the general formula (7) in pyridine as a solvent and a base. The dichlorosilane is added dropwise to the sulfhydryl group-containing sulfenyl sesquioxane compound, and after stirring for 2 hours or more, the adjusted chlorosilane solution is preferably dropped, and further stirred at room temperature for 2 hours or more. At this time, if the reaction time is short, there is a case where the reaction cannot be completed. After completion of the reaction, toluene and water are added to dissolve the curable fluorenone copolymer having a cage structure represented by the general formula (3)-2 in toluene, and excess chlorodecane, by-produced hydrochloric acid, And the hydrochloride is dissolved in the aqueous layer to remove. The organic layer is dried with a desiccant such as magnesium sulfate, and the base and solvent to be used are concentrated under reduced pressure to give a curable fluorene copolymer having a cage structure represented by the general formula (3)-2. Specific examples of the chlorodecane represented by the general formula (8), such as trimethylchlorodecane, allyldimethylchlorodecane, dimethylpropyl chlorodecane, dimethyl isopropyl gas sands, t- Butyl monomethyl chloride sand, diethyl chlorin, di-32- 201000491 methyl phenyl chlorodecane, benzyl dimethyl chlorodecane, tripropyl chlorodecane, tributyl chlorodecane, diphenyl Vinyl chlorodecane, triphenylchlorodecane, and the like. Further, in the present invention, the curable fluorenone copolymer having a cage structure represented by the general formula (3) may be used in combination with either or both of a hydrogenation catalyst and a radical initiator. Further, a curable resin composition is obtained by combining any one or both of a hydrogen group-containing compound having a hydrogen atom and at least one atom having an unsaturated group in the molecule. Then, the curable resin composition is thermally cured or photocured, and then subjected to hydrazine hydrogenation or radical polymerization to obtain a cured product (molded body). In other words, the purpose of promoting the reaction by the purpose of curing the curable resin to obtain a molded body or improving the physical properties of the obtained molded article is to match the hydrogenation catalyst, the thermal polymerization initiator, the thermal polymerization promoter, and the light. A curing initiator, a photoinitiating aid, a sensitizer, and the like are used to obtain a curable resin composition. In the curable resin composition, a compound having a hydrogen atom on a ruthenium atom for use in a sclerosing fluorenone copolymer having a cage structure represented by the general formula (3) is at least one or more hydrogen hydride in a molecule. An oligomer having a hydrogen atom and a monomer on a helium atom. Here, as the oligomer having a hydrogen atom on the ruthenium atom, there may be mentioned polyhydrogen oxiranes, polydimethylhydroquinone oxiranes and copolymers thereof, and dimethylhydroquinone at the end. Oxyoxy modified alkane. Further, examples of the monomer having a hydrogen atom on the ruthenium atom include a cyclic oxirane such as tetramethylcyclotetraoxane or pentamethylcyclopentadiene, and dihydrodioxane. Trihydromonodecanes, dihydromonodecanes, monohydromonodecanes, dimethyloxymethoxyoxanes, etc., or these two or more types may be mixed. -33- 201000491 Further, a curable resin composition The compound having an unsaturated group used together with the curable fluorenone copolymer having a cage structure represented by the general formula (3) is roughly classified into a polymer having a repeating number of structural units of from 2 to 20 A oligomer with a low molecular weight and low viscosity reactive monomer. Further, it can be roughly classified into a monofunctional unsaturated compound having one unsaturated group and a polyfunctional unsaturated compound having two or more unsaturated groups. Here, as the reactive oligomer, there may be mentioned, for example, polyvinyl siloxanes, polydimethylvinyl decyloxy siloxanes, copolymers thereof, and dimethylvinyl oxime at the end. Base modified siloxanes, epoxy acrylates, epoxidized oil acrylates, polyurethane acrylates, unsaturated polyesters, polyester acrylates, polyether acrylates, vinyl acrylates, polyolefins / mercaptan, anthrone acrylate, polybutadiene, polystyryl ethyl methacrylate, and the like. Among these, there are monofunctional unsaturated compounds and polyfunctional unsaturated compounds. The reactive monofunctional monomer may, for example, be a vinyl-substituted fluorene compound such as triethylvinyl decane or triphenyl vinyl decane, or a cyclic olefin such as cyclohexene, styrene or vinyl acetate. Ester, N-vinylpyrrolidone, butyl acrylate, 2-ethylhexyl acrylate, η-hexyl acrylate, cyclohexyl acrylate, η_mercapto acrylate, isobornyl acrylate, dicyclopentenyloxyethylacrylat, phenoxy Ethylpropionate, trifluoroethyl methacrylate, and the like. The reactive polyfunctional monomer may, for example, be a vinyl-substituted anthracene compound such as tetravinylnonane or divinyltetramethyldioxane, tetramethyltetravinylcyclotetraoxane or pentylene. -5-201000491 vinyl-substituted cyclic anthracene compound, acetylene derivative of bis(trimethyldecyl)acetylene, diphenylacetylene, norbornadiene, bicyclic ring a cyclic polyene such as pentadiene or cyclooctadiene, a vinyl-substituted cyclic olefin such as vinylcyclohexene, a divinylbenzene, a diacetylenylbenzene or a trimethylolpropanediene Ether, pentaerythritol triallyl ether, tripropylene glycol diacrylate, 1,6-hexanediol diacrylate, bisphenol A diglycidyl ether diacrylate, tetraethylene glycol diacrylate, hydroxyl Neopentyl glycol neopentyl glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dimethylol-tricyclodecane diacrylate, 1 ,3-dimethylpropenyloxymethyl-1,1,3,3-tetramethyl Oxane, 1,3-bis(3-methylpropenyloxypropyl)-1,1,3,3-tetramethyldioxane, 1,3 -dipropenyloxymethyl- Acrylic acid such as l,l,3,3-tetramethyldioxane, l,3-bis(3-propenyloxypropyl)-1,1,3,3-tetramethyldioxane Esters. In terms of the compound having an unsaturated group in the molecule, various reactive oligomers and monomers can be used in addition to the above examples. Further, these reactive oligomers or monomers may be used singly or in combination of two or more kinds. The compound having a hydrogen atom on the ruthenium atom and the compound having an unsaturated group in the molecule used in the present invention may be used singly or in combination of two or more kinds. As described above, the curable resin composition of the present invention can be used in combination with a sulfonated fluorenone copolymer having a cage structure represented by the general formula (3), a hydrogenation catalyst, a radical initiator or the like. A compound containing a hydrogen atom or a compound having an unsaturated group. The cured product (molded body) of the present invention can be obtained by subjecting the curable resin composition to form curing. In other words, a hardened product (molded body) can be obtained by subjecting the curable resin composition to hydrogenation hardening and radical polymerization. When the hydrazine-based hydrogenation catalyst is used, the amount thereof is added in the range of 1 to 100 ppm, preferably 20 to 500 ppm, based on the weight of the curable fluorenone copolymer having a cage structure represented by the general formula (3). It is better. Further, in the case of a radical polymerization initiator in combination with a photopolymerization initiator or a thermal polymerization initiator, the amount of addition is 1 〇〇 by weight of the curable anthrone copolymer containing the cage structure represented by the general formula (3). The fraction is preferably in the range of 〇1 to 10 parts by weight, more preferably in the range of 0.1 to 5 parts by weight. When the amount is less than 0.1 part by weight, the curing is insufficient, and the strength or rigidity of the obtained molded body is lowered. On the other hand, when it exceeds 10 parts by weight, there is a problem that coloring of the molded body or the like occurs. Further, the hydrogenation catalyst and the radical initiator may be used singly or in two types. The hydrogenation catalyst may, for example, be platonic chloride, chloroplatinic acid (H2PtCU·6H2〇), chloroauric acid and alcohol, aldehyde, ketone complex, chlorination. A complex of leuco acid and an olefin, a complex of platinum and a vinyl siloxane, a dicarbonyl chloroplatin, a palladium catalyst, or a lanthanum-based metal catalyst. Among these, from the viewpoint of catalyst activity, a complex of chloroplatinic acid, a mixed solution of chloroauric acid and an olefin, and a complex of platinum and vinyl alkane is preferred. Further, these may be used alone or in combination of two or more types. The photopolymerization initiator used in the case where the curable resin composition is a photocurable resin composition is preferably an acetophenone type, a benzoin system, a diphenyl-36-201000491 formamidine system, a thioxanthone system, or a thiol group. A compound of a phosphine oxide system. Specifically, for example, trichloroacetamidine, diethoxyethyl benzene, phenyl -2-hydroxy-2-methylpropan-1-one, hydroxycyclohexyl phenyl ketone, 2- Methyl-1-(4-methylthiophenyl)-2-morphinol propane-butanone, benzoin methyl ether, benzyldimethylketal, benzophenone, thioxanthone, 2,4 , 6-trimethyl benzamidine diphenylphosphine oxide, methyl phenyl glyoxylic acid, camphorquinone, benzyl, awake, rice bran, and the like. Further, a photoinitiator or a sensitizer which exerts an effect in combination with a photopolymerization initiator may be used in combination. For the thermal polymerization initiator used for the above purpose, a ketone peroxide system, a peroxy S system, a hydroperoxide system, a monobasic peroxide system, a dimercapto peroxide system, and the like are suitable. Various organic peroxides such as oxydicarbonate and peroxyester. Specifically, cyclohexanone peroxide, 1,1-bis(t-hexylperoxy)cyclohexanone, cumene hydroperoxide, diisopropylbenzene peroxide, benzamidine peroxidation can be exemplified. And diisopropyl peroxide, t-butylperoxy 2-ethylhexanoic acid vinegar, etc., but are not limited thereto. Further, these thermal polymerization initiators may be used singly or in combination of two or more kinds. In the curable resin composition, various additives may be added without departing from the object of the present invention. The various additives may, for example, be organic/inorganic grave materials, plasticizers, flame retardants, heat stabilizers, antioxidants, light stabilizers, ultraviolet absorbers, slip agents, antistatic agents, release agents, foaming agents, A nucleating agent, a coloring agent, a crosslinking agent, a dispersing aid, a resin component, and the like. The shaped body formed by the curable fluorenone copolymer containing the cage structure represented by the general formula (3) of the present invention may be any one of the ruthenium-containing hydrogenation catalyst or the radical polymerization initiator, or the like Both of the curable resin compositions - 37 - 201000491 are produced by heating or light irradiation and then hardening. In the case where a cured product (formed body) is produced by heating, the forming temperature can be selected from a wide range of from room temperature to 200 ° C depending on the selection of the thermal polymerization initiator and the accelerator. At this time, the cured product (molded body) of a desired shape can be obtained by solidifying the polymerization in a mold or a steel strip. More specifically, a general forming processing method in which all of the so-called injection molding, extrusion molding, compression molding, transfer molding, roll forming, and casting (injection molding) are applied can be applied. Further, when a cured product (molded body) is produced by light irradiation, a molded body can be obtained by irradiating ultraviolet rays having a wavelength of 100 to 400 nm or visible light having a wavelength of 400 to 700 nm. Although the wavelength of the light used is not particularly limited, it is preferable to use a near-ultraviolet light having a wavelength of 200 to 40 nm. Examples of the lamp usable as the ultraviolet light generating source include a low pressure mercury lamp (output: 0.4 to 4 W/cm), a high pressure mercury lamp (40 to 1 60 W/cm), an ultrahigh pressure mercury lamp (1 73 to 43 5 W/cm), and a metal halide. Lamp (80 to 160 W/cm), pulsed xenon lamp (80 to 120 W/cm), electrodeless discharge lamp (80 to 120 W/cm), and the like. These ultraviolet lamps are characterized by their respective spectral distributions, and are selected depending on the type of photoinitiator to be used. In the method of obtaining a cured product (molded body) by light irradiation, for example, a mold having a rectangular shape and a transparent material such as quartz glass is injected into the mold, and the ultraviolet light is irradiated with ultraviolet rays to carry out polymerization hardening, and then the mold is released. And a method of producing a molded body of a desired shape, or applying a curable resin composition of the present invention, for example, on a moving steel strip using a doctor blade or a roll coater, when the mold is not used, A method in which an ultraviolet lamp is polymerized and cured to produce a sheet-like formed body. Further, in the present invention -38 to 201000491, a method of obtaining a molded body by heating and light irradiation may be combined. [Effects of the Invention] The present invention provides a side chain of a sand-oxygen skeleton having a strong polyhedral structure (cage structure) in a molecular structure in which the opposite physical properties exhibiting low thermal expansion and high toughness can be provided. The curable resin having a reactive functional group is incorporated into the main chain of the anthrone to polymerize the copolymer, and a method for producing the same can be provided. In other words, by using the cage-type sclerosing fluorenone copolymer represented by the general formula (3) of the present invention, in addition to the fluorenone characteristics excellent in heat resistance and transparency, it is possible to produce both low thermal expansion properties and A molded body of opposite physical properties with high toughness. Therefore, it is possible to obtain an optically transparent material which has an imperfect heat resistance or a high dimensional stability which is formed by a hydrocarbon-based component and which is difficult to achieve in glass. According to the curable resin composition of the present invention, a cured product excellent in heat resistance, optical properties, and dimensional stability can be obtained. Then, the obtained cured product is used for various applications such as a touch panel substrate, a flat panel display substrate, a lens, a optical disk, an optical fiber, and the like, and can be used for various applications such as various transportation machinery or window materials for houses, and the like. It can be used as a lightweight transparent member, and it can be used as a substitute for various types of glass used so far, and its use range is wide, and the industrial use price is extremely high. Further, according to the production method of the present invention, a cage-type sesquiterpoxysilane compound containing a stanol group represented by the general formula (2) having a reactive stanol group is used as a starting material, as described above. The useful novel compounds of the characteristics are the first, and the molecular design of the indole chain main chain into the cage structure becomes easy. -39- 201000491 Further, a plurality of functional groups or other groups selected for the purpose can be easily introduced into the cage structure and the indole chain main chain. [Embodiment] [Best Mode for Carrying Out the Invention] Hereinafter, the present invention will be more specifically described by way of examples. [Examples] [Reference Example 1] This synthesis example was produced by a j-method described in JP-A-2004-143449, which is a cage-type octadecane sesquifer with a structural formula (C^HsSiO3/2) 8. To a reaction vessel equipped with a stirrer, a dropping funnel, and a thermometer, 20 g of a solvent of 2-propanol (IP A ) 6 0 0 m 1 and an alkaline catalyst 5% aqueous solution of tetramethylammonium hydroxide (TMAH aqueous solution) were added. To the dropping funnel, 150 ml of IPA and 51 g of trimethoxyvinyl decane were added, and the reaction vessel was stirred, and an IPA solution of trimethoxyvinyl decane was added dropwise at 〇 °C for 1 hour. After the dropwise addition of trimethoxyvinyl decane, it was slowly returned to room temperature, and stirred without heating for 6 hours. After stirring, the IPA was removed under reduced pressure and dissolved in toluene 1 000 ml. Next, 25 g of the sesquioxane obtained above, and 600 g of toluene and 3.2 g of a 5% TMAH aqueous solution were added to a reaction solvent equipped with a stirrer, a Dean-Stark apparatus, and a cooling tube, and the water was distilled off at 1200 ° C. The toluene is heated under reflux to carry out a recondensation reaction. After refluxing with toluene for 3 hours, the 'return to room temperature' was terminated. The reaction solution was neutralized with 1 〇 % citric acid 3 8 g, and then washed with saturated brine and dehydrated with anhydrous magnesium sulfate -40-201000491. Anhydrous magnesium sulfate was filtered off and concentrated to give a recondensate 2 4.5 g. The mass analysis of the obtained white powder was confirmed to be a cage type octavinylsesquioxane. [Example 1] A curable cage type represented by the following general formula (1) [R1Si03/2]n (1) obtained by the same synthesis method as in the above Reference Example 1 was added in order to a reaction vessel equipped with a stirrer. a semi-oxane compound (R1 is a vinyl group, n = 8) 20 g, tetrahydrofuran 520 ml, 25% oxidized tetramethyl sulphate (methanol solution) (hereinafter referred to as TMAH methanol solution) 23.08 g, under nitrogen atmosphere, room temperature Stir for 2 hours. After stirring for 2 hours, 100 ml of a 10% aqueous citric acid solution and 200 ml of toluene were added for neutralization. After the organic layer was taken out, it was washed three times with distilled water and twice with saturated brine, and dehydrated with anhydrous magnesium sulfate. Anhydrous magnesium sulfate was filtered off and concentrated to obtain 19.92 g (yield: 97%) of a colorless viscous liquid which was dissolved in various organic solvents. The GPC measurement results of the above-mentioned colorless viscous liquid are shown in Fig. 1. From Fig. 1, it is confirmed that Mw = l 00 5 and Mw / Mn = 1.225. Among them, the peak of the low molecular side of 70% of the area ratio is Mw = 668 and Mw/Mn = 1.020. Next, the results of measuring fNMR are shown in Fig. 2. The peak of the multiple of the vinyl group of 5.8 to 6.2 ppm and the peak integral ratio of the hexanol group of 1.6 ppm with respect to the vinyl group 1, the decyl alcohol group was 0.174. On the other hand, if the compound estimated by the Mw and the integral ratio of the main peak of the main peak is the following general formula (2) [R1Si03/2] „[H01/2]m (2) -41 - 201000491, η is 8. and m is 2. In order to confirm the presence of the stanol group of the colorless viscous liquid obtained above, IR measurement is carried out. As a result, since a broad peak derived from a stanol group is present at 3100 to 3400 cm·1, the presence of a stanol group is confirmed. From the above results, it was judged that the structure of the colorless viscous liquid obtained was a sulfanol group-containing curable cage sesquiterpene oxide compound represented by the above general formula (2) (R1 is a vinyl group). Further, The results of electrospray ionization mass spectrometry (ESI-MS) of the sulfanol group-containing curable cage sesquiterpoxysilane compound (R1 is a vinyl group) represented by the above general formula (2) are shown in the table. In Table 1, one 倂 indicates the main peak detected by mass analysis and the number m of m and η. The detected peak m/z is the molecular weight of the general formula (2), and the enthalpy of the ammonium ion (Mw18) is added. The results of this mass analysis also show that a portion of the helium oxide bond forming the cage structure is cracked and The terminal portion has a structure having a stanol group. [Table 1] The detected peak m / z η m 58 1.3 6 2 598.4 7 3 65 1.3 8 2 73 8.0 9 1 827.5 10 2 985.5 12 2 1142.0 14 2 [Implementation Example 2] A curable cage type sesquifer compound compound represented by the above general formula (1) obtained by the same synthesis method as that of Reference Example 1 (Ri is an alkyl group: -42 - 201000491 Ethyl = 1 : 1. η = 8 ) 2 0 g, the reaction was carried out in the same manner as in Example 1 to obtain 19.79 g (recovery rate: 97%) of a colorless viscous liquid which was soluble in various organic solvents. The colorless viscous liquid obtained above The GPC measurement results showed that Mw=1101 and Mw/Mn=l.1 57. Among them, the area ratio accounted for 73% of the peak on the low molecular side, M w = 63 4 ' Mw / Mn = 1.072. Next, I ^ NMR was measured. The peak integration ratio of the 5.8 to 6.2 ppm vinyl multiple peak to the 1.6 ppm stanol group relative to the vinyl group 1, the stanol group is 〇· 5 4 1. However, the Mw and the integral of the low molecular side of the main peak When the general formula (2) is used, the ratio of η is 8 and m is 2. The colorless viscous liquid obtained above is a sterol group. When it was found, IR was measured. As a result, a broad peak derived from a stanol group was observed at 3,100 to 3,400 cm·1, and the presence of a stanol group was confirmed. From the above results, it was judged that the structure of the obtained colorless viscous liquid was a general formula (2). The sulfoalkyl group-containing hardenable cage sesquiterpoxide compound (R1 is a vinyl group: ethyl = 1 : 1 ). [Example 3] A curable cage sesquiterpene oxide compound represented by the above general formula (1) obtained by the same synthesis method as that of Reference Example 1 (R1 is a vinyl group: methyl propyl storage group = 1: The reaction was carried out in the same manner as in Example 1 except for 20 g of 20 g (available in the same manner as in Example 1) to obtain 19.91 g (recovery rate: 98%) of a colorless viscous liquid which was soluble in various organic solvents. GP C measurement result of the above-mentioned colorless viscous liquid, Mw = 1 3 5 5, -43- 201000491

Mw / Mn = 1.201. Among them, the area ratio accounts for 67% of the peaks on the low molecular side, Mw = 994, Mw / Mn = 1.04. Next, i^NMR was measured, and the peak-to-peak ratio of the sigma group of 5.8 to 6.2 ppm to the peak of the 1.6 ppm of the sand-based alcohol group was 0.489 with respect to the vinyl group 1, and the stanol group. On the other hand, when the Mw and the integral ratio of the main peak of the main peak are estimated to be the above general formula (2), η is 8 and m is 2. The IR measurement was carried out to confirm the presence of the stanol group of the colorless viscous liquid obtained above. As a result, a broad peak derived from a stanol group was observed at 3100 to 340 (^1^1, so the presence of a stanol group was confirmed. From the above results, the structural judgment of the obtained colorless viscous liquid was expressed by the general formula (2). A curable cage type sesquiterpoxide compound containing a stanol group (R 1 is a vinyl group: methacryl group = 1 : 1 ). [Example 4] The above general procedure was carried out except that the same synthesis method as Reference Example 1 was used. The reaction was carried out in the same manner as in Example 1 except that the curable cage sesquiterpoxide compound represented by the formula (1) (R1 was a vinyl group: a glycidoxypropyl group = 1:1.11 = 8) 20 g. 19.76 g (recovery rate: 98%) of a colorless viscous liquid which is soluble in various organic solvents is obtained. The GP C measurement result of the colorless viscous liquid obtained above, M w = 1 3 5 5 , Mw / Mn = 1.201 Among them, the area ratio is 69% of the low molecular side peak, Mw = 954, Mw / Mn = 1.043. Next, I ^ NMR is measured. 5.8 ~ 6.2 ppm of vinyl multiple peak and 1.6 ppm of stanol The peak integration ratio is 0.5 1 9 with respect to vinyl 1, and the low molecular side M w and product of the peak of the dominant wave -44-201000491 When the ratio of the compound to be estimated is the above formula (2), η is 8 and m is 2. In order to confirm the presence of the stanol group of the colorless viscous liquid obtained above, IR measurement is carried out, and as a result, it is 3100 to 3400 (^-1 has From the broad peak of stanol, the presence of a stanol group was confirmed. From the above results, the structure of the colorless viscous liquid was judged to be a seromeric cage-type sesquiterpoxide compound represented by the general formula (2). (R1 is ethylene glycidoxypropyl group = 1 : 1). [Example 5] In a reaction vessel equipped with a stirrer and a dropping funnel, a methyldichloromethane 1 · 9 9 g, pyridine 1 5 was weighed. 3 8 m 1 and nitrogen substitution. The sulfanol group-containing hardenable cage sesquiterpoxide compound represented by the general formula obtained in the same manner as in Example 1 was vinyl, n=8. , m = 2) 5.0 g, and pyridine 98 mL, dripped at room temperature for one hour. After the completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours. 2 After stirring, 50 mL of toluene and 50 mL of distilled water were added to separate the organic layer. After extraction, the solution was washed three times with distilled water and twice with saturated brine. Dehydrated with anhydrous magnesium sulfate. Anhydrous sulfur was filtered off and concentrated to obtain 5.25 g of a colorless viscous solid (yield: 89%). The GPC measurement result of the colorless viscous solid obtained above is shown in Fig. 3. 3 ' Mw = 4 5 1 , 620 , Mw / Mn = l 04.89. Further, the I ^ NMR results are shown in Figure 4. The multiple peaks of the 5.8 to 6.2 ppm vinyl group and the multiple peak integration ratio of the methyl group of 0.3 Ppm relative to the vinyl 1, A The base of the resulting base is generally carried out: in drops (2) (R1 b for 1.5 hours with water and magnesium strontium sulphate from the graph of the knot 0 7 ~ base is -45- 201000491 0.37. This 値 shows the ratio of the 3 protons of the ethylene group to the 6 protons of the methyl group. However, in order to compare the ratio of the cage structure to the sand-oxygen chain, it is necessary to express the methyl integral 値 as the three protons. On the other hand, relative to vinyl 1, the methyl proton ratio became 0.185. Then, the ratio of n of the compound of the cage structure represented by the general formula (2) estimated above to the dimethyl methoxyoxane corresponding to the above formula (2) was 1.48. Further, Mw = 451, 620' obtained by GPC with a molecular weight of 757·5 of a cage structure of η of 8 and dimethyloxane 1.48 is taught as a unit of 596 repeating structures. Further, the structure of the obtained colorless viscous solid is judged to be a cage having a constituent unit represented by the following general formula (3) - 1 Y'-tZ-iR'SiOa/ainli-Z-Y1 (3)-1 The structure of the sclerosing fluorenone copolymer [Rl is an acetamyl group] 11 is 8' 1 is 596' Z is the following general formula (4) [Chem. 1 7]

(4) (r2 is methyl 'a is 0.48), and 'Y1 is the following general formula (5') H〇i/2- (5,) [Example 6] In a reaction vessel equipped with a stirrer and a dropping funnel The middle portion was charged with 1.19 g of dimethyldichlorodecane, 2.14 ml of triethylamine, and 9.3 ml -46 - 201000491 of tetrahydrofuran and subjected to nitrogen substitution. A sulfanol group-containing hardenable cage sesquiterpoxide compound represented by the general formula (2) obtained in the same manner as in Example 1 was added to the dropping funnel (Ri is a vinyl group, n = 8, m = 2). 3.0 g and 46.2 ml of tetrahydrofuran were dripped at room temperature for 30 minutes. After the completion of the dropwise addition, stirring was carried out for 2 hours at room temperature. After that, 1.5 g of a sulfoalkyl group-containing curable cage sesquiterpoxide compound (R1 is a vinyl group) represented by the general formula (2) and 20 ml of tetrahydrofuran were added dropwise, and after completion of the dropwise addition, it was carried out at room temperature. Stir for hours. After stirring for 2 hours, 20 ml of a 1% citric acid aqueous solution and 20 ml of toluene were added to carry out neutralization. After the organic layer was taken out, the mixture was washed three times with distilled water and twice with saturated brine. The mixture was dehydrated with anhydrous magnesium sulfate. Anhydrous magnesium sulfate was filtered off and concentrated to give a colorless viscous liquid of 3.7 3 g (yield: 7 4 %). The GPC measurement results of the colorless viscous liquid obtained above were Mw = 3,910 and Mw/Mn = 2.891. Further, the multiple peak integration ratio of the multiple peak of the vinyl group of '5·8 to 6.2 ppm and the methyl group of 0_07 to 〇.3 ppm of the Hi NMR measurement result was 0 · 3 5 ° with respect to the ethyl group 1 'methyl group and the examples (5) The structure of the colorless viscous liquid obtained in the same manner was judged to be a sclerosing fluorenone copolymer having a cage structure represented by the above-mentioned general formula (3)-1. , n is 8' 1 is 5' Z is the above general formula (4) (R2 is a methyl group, a is 0.4), and Υ1 is the following general formula (5') Η〇!/2- (5,) [Implementation Example 7] -47-201000491 A cage containing a stanol group represented by the general formula (2) obtained in the same manner as in Example 1 was added to a reaction vessel equipped with a machine and a cooling tube. The oxoxane compound (R1 is a vinyl group, n = 8, m = 2) 5.0 g, 1.14 g of dimethyldiethoxydecane, 0.14 g of a TMAH methanol solution, and 77 ml of toluene were stirred at 9 (TC for 1 hour). After that, the Dean-Stark apparatus was placed in a reaction vessel, and the mixture was heated to l〇〇°C while heating and stirring while removing methanol and ethanol. After heating and stirring for 2 hours, the reaction was dissolved. The solution was returned to room temperature, and 30 ml of a 10% aqueous citric acid solution was added for neutralization. After the organic layer was taken out, the mixture was washed three times with distilled water and twice with saturated brine, and dried over anhydrous magnesium sulfate. Magnesium sulfate was concentrated to obtain 5.03 g of a colorless viscous liquid (recovery rate: 91%). The GPC measurement result of the colorless viscous liquid obtained above, Mw = 12, 4 8 5 , Mw / Mn = 5.5 6 7. Further, fNMR As a result of the measurement, the multiple peak integration ratio of the multiplex peak of 5.8 to 6.2 ppm of the vinyl group and the methyl group of 0.07 to 0.3 ppm was 0.44 with respect to the vinyl group 1, and the result of analysis was carried out in the same manner as in Example 5. The structure of the colorless viscous liquid is judged to be a sclerosing fluorenone copolymer having a cage structure represented by the above general formula (3)-1 (R1 is a vinyl group, η is 8, and 1 is 16, and Z is The above general formula (4) (R2 is a methyl group, a is 0.76) 'Y1 is the following general formula (5,) H〇i/2- (5,) [Example 8] is provided with a stirrer, and a cooling tube In the reaction vessel, the amount represented by the general formula (2) obtained in the same manner as in Example 1 of -48 - 201000491 was added. a stanol-based cage sesquiterpoxide compound (R1 is a vinyl group, n = 8, m = 2) 5.0 g, diphenyl decane 1.42 g, hydrazine, hydrazine-diethylhydroxylamine 〇. 7 g and toluene 7 7 ml was stirred at 50 ° C for 3 hours. After heating and stirring for 3 hours, the reaction solution was returned to room temperature, and 30 ml of a 10% aqueous citric acid solution was added for neutralization. After the organic layer was taken out, the mixture was washed three times with distilled water and twice with saturated brine, and then dried over anhydrous magnesium sulfate. Anhydrous magnesium sulfate was filtered off and concentrated to give a colorless viscous liquid 5 J2 g (yield: 93%). The GPC measurement results of the colorless viscous liquid obtained above were Mw = 18, 3 54 and Mw / Mn = 4.995. Further, as a result of I^NMR measurement, the multiple peak integration ratio of the pentad of 5.8 to 6.2 ppm of the vinyl group and the phenyl group of 7.3 to 7.8 ppm was 0.56 with respect to the vinyl group. As a result of the analysis in the same manner as in Example 5, the structure of the obtained colorless viscous liquid was judged to be a sclerosing fluorenone copolymer having a cage structure represented by the above general formula (3)-1 (R1 is Vinyl, η is 8, and 1 is 20, Z is the above general formula (4) (R2 is a methyl group, a is 0.35), and Y1 is the following general formula (5') H〇i/2- (5,) [Example 9] The cage-structured hardenable fluorenone copolymer 5 having the constituent unit represented by the general formula (3)-1 obtained in Example 7 was weighed in a reaction vessel equipped with a stirrer and a cooling tube. 0 g and pyridine 30 ml, and nitrogen substitution. Trimethylchloromethane 5 was added to the dropping funnel. 〇g and pyridine 20 ml '-49- 201000491 were dropped at room temperature for 30 minutes, and stirred for 2 hours. 2, 30 mL of toluene and 30 mL of distilled water were added, and the organic layer was separated, and then washed with distilled water three times, and washed twice with saturated sodium sulfate, and dehydrated with anhydrous magnesium sulfate. The anhydrous sulfur was filtered off to obtain a colorless viscosity. Liquid 4.82g (recovery rate 96%) GPC measurement result of the above-mentioned colorless viscous liquid, Mw/Mn = 5.32 7. Further, in the measurement results, 5.8, the multiple peak of the vinyl group and the methyl group of 〇·〇7~〇.3 ppm are more than the vinyl group 1, and the methyl group is 〇.41. Further, the IR measurement is performed for the disappearance of the base. The broad peaks from 3100 to 3400 CITT1 disappeared. Therefore, the colorless viscous liquid obtained by the following formula (3) -2 Y2-[Z-(R1Si〇3/2)n]i'Z-Y2 ( 3) - 2 represents the sclerosing sulphonyl vinyl group having a cage structure, η is 8, and 1 is 16, and Z is the above general formula (4 base, a is 0.64), and Y2 is the following general formula (6) [Chem. 1 8] R3

I R3—Si—01/2—(6) R3 (R3 is methyl)]. [Example 1 〇] After stirring for an hour, the water layer was used. There is a salt and magnesium salt and 〇Mw=12,656" 6.2ppm double peak integration ratio confirms that the stanol is determined from the stanol structure as a polymer [R1 is) (R2 is A-50 - 201000491 with a blender and a dropping funnel In the reaction vessel, 1.99 g of dimethyldichloromethane and 15.38 m of pyridine were added and nitrogen substitution was carried out, and the content represented by the general formula (2) obtained in the same manner as in Example 1 was added to the dropping funnel. A sterol-based sclerosing cage sesquiterpoxide compound (R1 is a vinyl group, n=8, m = 2) 5.0 g, and pyridine 77 mL, which was dropped at room temperature for 5 hours. After stirring for 2 hours, the mixture was stirred for 2 hours, and then 5.0 g of trimethylchloromethane and 20 ml of pyridine were added thereto, and the mixture was stirred at room temperature for 2 hours. After stirring for 2 hours, toluene 5 〇 niL and distilled water 50 mL were added. The organic layer and the aqueous layer were separated, and the organic layer was extracted three times with distilled water and twice with saturated brine, and dried over anhydrous magnesium sulfate. Anhydrous magnesium sulfate was filtered and concentrated to give colorless 4.88g of solid (97% recovery). GPC measurement results of colorless viscous liquid, Mw=128, 350, 1^! Reviews/1^11 = 38.486. Also, 1'14>/111 measurement results, 5.8~6.2ppm vinyl multiple peaks and 〇. The multiple peak integral ratio of the methyl group of 〇7 to 0.3 ppm is 〇.44 with respect to the vinyl group 1. Further, in order to confirm the disappearance of the stanol group, IR measurement is performed. 3100 to 3 WOcnT1 is broad from the stanol group. The peak disappears, so that the structure of the colorless viscous solid obtained is judged to be a sclerosing fluorenone copolymer having a cage structure having the above-mentioned constituent unit represented by the general formula (3) - 2 [Rl is a vinyl' η of 8 '1 is 165, Ζ is the above general formula (4) (R2 is methyl 'a is 0.76) 'Y2 is the above general formula (6) (R3 is methyl)]. [Example 11] -51 - 201000491 In a reaction vessel equipped with a stirrer and a dropping funnel, 94 g of 1,1,3,3-tetramethyl-1,3-dichlorodecane oxime and 9.23 mi of pyridine were added thereto, and nitrogen substitution was carried out. A stanol-containing hardening cage-type sesquiterpene oxide compound represented by the general formula (2) obtained in the same manner as in Example ( is added (R1) Vinyl, n = 8, m = 2) 3 _ 〇 g, and shame steep 4 6 _ 2 m L, drenched at room temperature for 1.5 hours. After the completion of the dropwise addition, stirring at room temperature for 2 hours. 2 hours After stirring, 3 mL of toluene and 30 mL of distilled water were added to separate the organic layer and the aqueous layer. After the organic layer was taken out, the mixture was washed three times with distilled water and twice with saturated brine, and dried over anhydrous magnesium sulfate. . Anhydrous magnesium sulfate was filtered off and concentrated to give a colorless viscous solid, 3.18 g (yield: 8 8 %). The GPC measurement result of the colorless viscous solid obtained above was Mw = 8 5, 3 4 〇 and Mw / Mn = 2 8.3 8 5 . Further, as a result of fNMR measurement, the multiple peak integration ratio of the double peak of the 5.8 to 6.2 ppm of the susceptor group and the methyl group of 0.07 to 0.3 ppm was 0.58 with respect to the vinyl group. As a result of the analysis in the same manner as in Example 5, the structure of the obtained colorless viscous liquid was judged to be a sclerosing fluorenone copolymer having a cage structure represented by the above general formula (3)-1 [R1 is Vinyl, η is 8 '1 is 104, Ζ is the above general formula (4) (R2 is methyl, a is 1.32) 'Υ1 is the following general formula (5') Η Ο 1 /2 - (5 ') [0] [Example 12] A cage containing a stanol group represented by the general formula (2) obtained in the same manner as in Example 1 of -52-201000491 was added to a reaction vessel equipped with a stirrer and a cooling tube. a semi-oxane compound (R1 is a vinyl group, n=8, m = 2) 3.0 g, 1,3-dimethoxydimethyldioxane 0.9 g, TMAH solution 0.084 g, and toluene 46.2 ml. Stirring was carried out at 90 ° C for 1 hour. Thereafter, a Dean-Stark apparatus was placed in a reaction vessel, and the mixture was heated to l ° ° C, and then heated and stirred while removing methanol. After the heating and stirring operation for 2 hours, the reaction solution was returned to room temperature, and 20 ml of a 10% aqueous citric acid solution was added thereto for neutralization. After the organic layer was taken out, the mixture was washed three times with distilled water and twice with saturated brine, and dried over anhydrous magnesium sulfate. Anhydrous magnesium sulfate was filtered off and concentrated to give a colorless viscous liquid (3.1 g) (yield: 84%). The GPC measurement result of the colorless viscous solid obtained above was Mw = 14,844 and Mw / Mn = 5.145. Further, as a result of i NMR measurement, the multiple peak integration ratio of the multiple peak of the vinyl group of 5.8 to 6.2 ppm to the methyl group of 0.07 to 0.3 ppm was 〇.6 相对 with respect to the vinyl group 1. As a result of the analysis in the same manner as in the example 5, the structure of the colorless viscous liquid obtained was judged to be a sclerosing fluorenone copolymer having a cage structure represented by the above-mentioned general formula (3) < It is an ethylene group 'η is 8' 1 is 18' Z is the above general formula (4) (R2 is a methyl group, a is 1.4), and Y1 is the following general formula (5') H〇i/2- (5). [Example 1 3] The stanol group represented by the general formula (2) obtained in the same manner as in Example 1 of -53-201000491 was added to a reaction vessel equipped with a stirrer and a cooling tube. Cage sesquioxane compound (R1 is vinyl, n = 8, m = 2) 3_0g, tetramethyldioxane 〇.62g, hydrazine, hydrazine-diethylhydroxylamine 〇.3g and toluene 45ml 'Agitate at 50 ° C for 3 hours. After heating and stirring for 3 hours, the reaction solution was returned to room temperature, and 10% of a 10% aqueous citric acid solution was added to carry out neutralization. After the organic layer was taken out, it was washed three times with distilled water, twice with saturated brine, and dried over anhydrous magnesium sulfate. Anhydrous magnesium sulfate was filtered off and concentrated to give a colorless viscous liquid (3%) (yield: 86%). The GPC measurement results of the colorless viscous solids obtained above, Mw = 15,782, Mw / Mn = 6.113. Further, as a result of HiNMR measurement, the multiple peak integration ratio of the multiplex peak of 5.8 to 6.2 ppm of the vinyl group and the methyl group of 0·07 to 〇.3 ppm was 0·5 3 with respect to the vinyl 1 'methyl group. As a result of the analysis in the same manner as in Example 5, the structure of the obtained colorless viscous liquid was judged to be a curable chopone copolymer having a cage structure represented by the above general formula (3)-1 [R1 is The vinyl 'n' is 8'1 is 20, Z is the above general formula (4) (R2 is a methyl group, a is 1.12), and Y1 is the following general formula (5') HOi/2- [Example 14] 3.0 g of a curable fluorenone copolymer having a cage structure represented by the general formula (3) -1 obtained in Example 12 was reacted in the same manner as in Example 9, and reacted with 3.0 g of trimethylchloromethane. The colorless adhesive-54-201000491 liquid was obtained 2.89 g (recovery rate 96%). The GPC measurement results of the colorless viscous liquid obtained above were Mw = 14,973 and Mw/Mn = 5.345. Further, as a result of fNMR measurement, the multiple peak integration ratio of the multiple peak of the vinyl group of 5.8 to 6.2 ppm to the methyl group of 0.1 to 0.4 ppm was 0.61 with respect to the vinyl group. Further, in order to confirm the disappearance of the stanol group, IR measurement was carried out. The broad peak from the stanol group of 3100 to 3400 CHT1 disappears, and the structure of the obtained colorless viscous liquid is judged to be a sclerosing fluorenone copolymer having a cage structure represented by the above general formula (3)-2. [R1 is a vinyl group, η is 8, and 1 is 18, Z is the above general formula (4) (R2 is a methyl group, a is 1.4), and Υ2 is the above general formula (6) (R3 is a methyl group). [Example 15] The result of the same experiment was obtained by changing 1.99 g of dimethyldichloromethane used in Example 10 to 1,1,3,3-tetramethyl-1,3-dichlorodecane 1.578. Colorless viscous liquid 5 · 1 2 g (recovery rate 8 5 %). The G P C measurement result of the colorless viscous liquid obtained above was M w = 1 16 6 598 and Mw / Mn = 45.496. Further, as a result of i NMR measurement, the multiple peak integration ratio of the pentads of 5.8 to 6.2 ppm of the vinyl group and the methyl group of 〇.〇7 to 〇.3 ppm was 0.59 with respect to the vinyl group. Further, in order to confirm the disappearance of the alcohol base of the sand yard, IR measurement was carried out. The broad peak from the stanol group of 3100 to 3400 cm-1 disappears, and the structure of the obtained colorless viscous liquid is judged to be a sclerosing ketone containing a cage structure represented by the above general formula (3)-2. Copolymer [R1 is a vinyl group, η is 8, 1 is 142-55-201000491, z is the above general formula (4) (R2 is a methyl group, a is 1.36), and Υ2 is the above general formula (6) (R3 is methyl)]. [Example 16] In a reaction vessel equipped with a stirrer and a dropping funnel, 8.9 g of dimethyldichloromethane oxime and 15.38 ml of pyridine were added thereto, and nitrogen substitution was carried out. A sulfanol group-containing hardenable cage sesquiterpene oxide compound represented by the general formula (2) obtained in the same manner as in Example 1 was added to the dropping funnel (R1 was a vinyl group 'n = 8, m = 2 5.0 g, and pyridine 77 mL, dripped at room temperature for 1.5 hours. After the completion of the dropwise addition, stirring was carried out for 2 hours at room temperature. After stirring for 2 hours, 50 mL of toluene and 50 mL of distilled water were added, and the organic layer and the aqueous layer were separated. After the organic layer was taken out, the mixture was washed three times with distilled water and twice with saturated brine, and dried over anhydrous magnesium sulfate. The anhydrous sulfuric acid was filtered off and concentrated to give 5.07 g (yield: 94%) as a colorless viscous solid. From the obtained GPC of the colorless viscous solid and the Η 1N MR measurement result 'determined as the following general formula (3) - 2 Y2-[Z-(R1Si〇3/2)n]iZ-Y2 (3)- 2 A sclerosing fluorenone copolymer containing a cage structure [R1 is a vinyl group, n is 8, and 1 is 235, and z is the following general formula (4) [Chem. 19]

-56 - 201000491 (R2 is a methyl group, a is 0.33) 'Y1 is the following general formula (5) - [R 1 S i 〇3/2 ] η [ Η Ο 1/2 ] m - 1 (5) ( R1 is a vinyl group, η = 8, m = 2)]. [Example 17] In a reaction vessel equipped with a stirrer and a cooling tube, 5.0 g of a curable fluorenone copolymer containing a cage structure represented by the general formula (3)-1 obtained in the above Example 5 was weighed and pyridine was added. 30 ml and nitrogen substitution. To the dropping funnel, 5.0 g of trimethylchloromethane and 20 ml of pyridine were added, and the mixture was dropped at room temperature for 3 minutes, and stirred for 2 hours. After stirring for 2 hours, 30 mL of toluene and 30 mL of distilled water were added, and the organic layer and the aqueous layer were separated. After the organic layer was taken out, the mixture was washed three times with distilled water and twice with saturated brine, and dried over anhydrous magnesium sulfate. Anhydrous magnesium sulfate was filtered off and concentrated to obtain 4.82 g of a colorless viscous liquid (yield: 9.6 %). The structure of the obtained colorless viscous liquid was judged by GPC and HMMR measurement results as follows: (3) -3 Y3-[Z-(R! Si〇3/2)n]iZ-Y3 (3 a hardening fluorenone copolymer containing a cage structure represented by -3 [R1 is a vinyl group, η is 8, and 1 is 596, and z is the above general formula (4) (R2 is a methyl group, and a is 0_48) ), Y3 is the following general formula (6) [Chemical 2 0] R3 R3—Si-〇1/2~ R3 -57- (6) 201000491 (R3 is methyl)]. [Example 18] 10 parts by weight, 1, 3, 5, 7 - of the hardening fluorenone copolymer containing the cage structure represented by the general formula (3) _ 1 obtained by the same synthesis method as in the above Example 5 30 parts by weight of tetramethyl-1,3,5,7-tetraacetylene ring tetraxole, and di-t-butyl peroxide as a thermal polymerization initiator (PERBUTYL D manufactured by Sakamoto Oil Co., Ltd.) 5 parts by weight of 'a transparent curable resin composition was obtained. Then, the curable resin group and the obtained product obtained by the above-described method are used to carry out casting (extension) so as to be thicker than 5 mm using a light coater'. The temperature is raised from 100 ° C to 5 ° C / min to 100 ° C. 160 ° C, further 'heating from 16 ° ° C at 1 ° C / mi η to 200 ° C, then cooling at 1 · 5 ° C / m 丨 n to 50 ° c thermal hardening program, and get A curable fluorenone resin molded body having a cage structure of Example 18 having a specific thickness. [Example 1 9] 10 parts by weight, 1, 3, 5 of a hardening fluorenone copolymer having a cage structure represented by the general formula (3)-2 obtained by the same synthesis method as in the above Example 16. 30 parts by weight of 7-tetramethyl-1,3,5,7-tetravinylcyclotetraoxane, and dibutyl peroxide as a thermal polymerization initiator (PERBUTYL D manufactured by Nippon Oil & Fat Co., Ltd.) 5 parts by weight to obtain a transparent curable resin composition. -58 - 201000491 Then, the curable resin composition obtained above was cast (extended) so as to have a thickness of 0-5 mm by a roll coater, and the temperature was raised from 0 ° C to 0 · 5 t /min. To a temperature of 1 60 ° C, further, from 1 60 ° C to 1 ° C / min to 200 ° C, then cooled to a temperature of 50 ° C at a temperature of 1.5 ° C / min to obtain a specific thickness The curable fluorenone resin molded body of the cage structure of Example 19. [Example 20] 100 parts by weight, 1, 3, 5 of the curable fluorenone copolymer containing the cage structure represented by the general formula (3)-3 obtained by the same synthesis method as in the above Example 17. 30 parts by weight of 7-tetramethyl-1,3,5,7-tetravinylcyclotetraoxane, and di-t-butyl peroxide as a thermal polymerization initiator (PERBUTYL D manufactured by Nippon Oil & Fat Co., Ltd.) 5 parts by weight, a transparent curable resin composition was obtained. Then, the curable resin composition obtained as described above was cast (extending) so as to be thicker than 5 mm using a roll coater'. The temperature was raised from 100 Torr to 160 t at 100 ° C. Further, from 160 ° C was heated to 200 ° C at 1 ° C /min, and then cooled to a thermal hardening program of 50 ° C at 1.51: /min to obtain a sclerosing fluorenone resin containing cage structure of Example 20 having a specific thickness. body. [Example 21] 100 parts by weight of the curable fluorenone copolymer containing the cage structure represented by the general formula (3)-3 obtained by the same synthesis method as in the above-mentioned Example 17, -59-201000491 1,3, 30 parts by weight of 5,7-tetramethyl-1,3,5,7-tetravinylcyclotetraoxane, as a thermal polymerization initiator, t-butyl peroxide (PERBUTYL, manufactured by Nippon Oil & Fat Co., Ltd.) D) 2_5 parts by weight, and 2-hydroxy-2-methyl-1-phenyl-propan-1-one as a photoinitiator (Dal o cur e 1 1 7 3 by CIBASPECIALTY CHEMICALSK·.K.) 2 · 5 parts by weight, a transparent curable resin composition was obtained. Then, the curable resin composition obtained above was cast (extended) so as to have a thickness of 5 mm using a roll coater, and hardened by a total of 2000 mJ/cm 2 using a high-pressure mercury lamp of 30 W/cm. Then, the temperature is raised from 100 ° C to ° 5 ° C / min to 160 ° C 'further, from 1 60 ° C at 1 ° C / min to 20 ° C, then 1.5 ° C / min The thermosetting step of cooling to 50 ° C was carried out to obtain a curable fluorenone resin molded body containing the cage structure of Example 21 having a specific thickness. [Example 22] 100 parts by weight of the curable fluorenone copolymer containing the cage structure represented by the general formula (3)-3 obtained by the same synthesis method as in the above Example 17 was mixed, 1, 3, 5, 7- 30 parts by weight of tetramethyl-I,3,5,7-tetraethylene ring tetrachad, and platinum-vinyl oxime complex (SIP 6 8 3 0.3 by azmax Co., Ltd.) 〇. 5 The transparent curable resin composition was obtained in the form of a weight portion, and then the curable resin composition obtained above was cast (extended) so as to have a thickness of 0.5 mm using a roll coater, respectively, at 100 t: The calcined fluorenone resin molded body containing the cage structure of Example 2 2 having a specific thickness was obtained by heating at -40 ° C, 1 hour', and 1 80 ° C for 1 hour. [Comparative Example 1] 100 parts by weight of 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetraoxane and a dibutyl butyl peroxide as a thermal polymerization initiator The product (PERBUTYL D manufactured by Nippon Oil & Fat Co., Ltd.) was obtained in an amount of 5 parts by weight to obtain a transparent curable resin composition. Then, the curable resin composition obtained above was cast (extruded) to a thickness of 5 mm using a roll coater, and was carried out from 1 0 0 ° (: 〇 _ 5 ° C / min) The temperature was raised to 160 ° C. Further, the temperature was raised from 160 ° C to 1 ° C / min to 200 ° C, and then the temperature was cooled to 1.5 ° C at 1.5 ° C / min to obtain a specific thickness of Comparative Example 1 [Comparative Example 2] Mixed dicyclopentyl diacrylate (LIGHT-ACRYLATEDCP-A, manufactured by Kyoei Chemical Co., Ltd.) 100 parts by weight, and photopolymerization 5 parts by weight of a starting agent of hydroxycyclohexyl phenyl ketone (IRGACURE 1 84 manufactured by CIBASPECIALTY CHEMICALSK..K.) to obtain a transparent curable resin composition. Next, a roll coater was used to obtain the above-obtained The curable resin composition was cast (cast) in a thickness of 〇 5 mm, and a cylinder pressure mercury lamp of 3 〇 W/cm was used, and the exposure amount was 2000 mJ/cm 2 to harden -61 - 201000491 to obtain a specific thickness. The flaky shaped body of Comparative Example 2 was evaluated for the above Examples 18 to 22 and compared. The physical properties of the obtained molded body of 1 to 2 are shown in Table 2. Here, C TE represents a linear expansion coefficient of 50 ° C to 150 ° C. The physical properties of the molded body were evaluated by the following methods. (1) Heat resistance test (a) Line expansion coefficient: measured by a thermomechanical analysis method at a temperature increase rate of 5 ° C / min. (b) Transmittance: After heating at 200 ° C for 3 hours, Hitachi Co., Ltd. was used. The U4000 manufactured by the company measures the transmittance of light with a wavelength of 400 nm. (2) After the test piece is formed on a test piece of 10 cm square and 0.5 mm thick, it is judged that the crack-free one is 〇 and the other is X. 2] _ CTE (ppm/K) Transmittance at 400 nm (%) Cracking Example 18 35 88.5 〇 Example 19 37 88.6 〇 Example 20 32 89.5 〇 Example 21 45 90.1 〇 Example 22 40 87.4 〇 Comparison Example 1 52 85.6 X Comparative Example 2 81 54.2 〇 [Industrial Applicability] -62 - 201000491 According to the cage-containing hardenable ketene copolymer of the present invention, it is possible to obtain an anthrone characteristic which is excellent in heat resistance or transparency. a hardened substance having both physical properties of low thermal expansion and high toughness A transparent material which is resistant to heat and high dimensional stability which is not possible in a plastic formed by using a hydrocarbon-based component, and which is difficult to achieve in glass. Therefore, the obtained cured product can be used for, for example, a touch panel substrate. In addition to optical applications such as flat panel display substrates, lenses, optical discs, and optical fibers, it can be used in various applications such as window materials for transportation machinery and houses, and can also be used as a lightweight transparent member. Various types of glass are used instead of materials. BRIEF DESCRIPTION OF THE DRAWINGS [Fig. 1] Fig. 1 is a GPC chart of a cage sesquioxane compound containing a stanol group obtained in Example 1. Fig. 2 is a NMR chart of a cage sesquioxane compound containing a stanol group obtained in Example 1. Fig. 3 is a GPC chart of the cage-structured hardenable fluorenone copolymer YMzjR^SiOhdnh-Z-Y1 obtained in Example 5. Fig. 4 is a NMR chart of the cage-structured hardenable ketene copolymer YMz^RisiOhJn]丨-Z-Y2 obtained in Example 5. -63-

Claims (1)

201000491 VII. Patent application scope: 1. A stanol-containing sesquiterpene oxide compound represented by the general formula (2) [R1Si〇3/2]n[H01/2]m (2) ( R1 is a vinyl group, an alkyl group, a phenyl group, a (meth)propylpropyl group, or a group having an oxirane ring, and may be mutually identical, but at least one of R1 contained in one molecule is a vinyl group, a rare one Any of 6 to 14 having a mercapto group, a propyl group or a group having an epoxy ring, m is a number of 1 to 4, and is characterized by the following general formula (1) [R1Si03/2]n (1) (R1) R1 is a vinyl group, an alkyl group, a phenyl group, a (meth)propylpropyl group or a group having an oxirane ring, and at least one of R1 contained in the same molecule may be a vinyl group. a curable cage sesquiterpoxide compound represented by (methyl, allyl or any group having an oxirane ring, η is) in a base, in a nonpolar solvent and a polar solvent In one or a solvent, one or a plurality of decane bonds are bonded, and the counter cation of the product is bonded to the cleavage portion, and then converted to a hydroxyl group by an acid. The first item of the first range is the general formula (2, a sulfonate-containing hardening cage sesquiterpoxide compound, the average molecular weight Μη in the range of 500 to 10000, the molecular weight fraction average molecular weight) / Μη] in the range of 1.0 to 2.0 The range of the sclerosing olefin group, the olefin or the dissimilar, (meth) propyl, and η is the number of the olefinic group, the olefin 5, the 1 group) acryl oxime 6~1 4 The compound contains two kinds of organic self-alkalinization, which are represented by the cracking), and the number of flat divergence [Mw (-64 - 201000491 3_) is a general formula (2) cage type sesquiterpene oxide compound [R1Si03/2]n[H〇1/2]m (except that R1 is a vinyl group, an alkyl group, a propyl group, or an olefin group having an oxirane ring but R1 contained in one molecule, Allyl or a number having an epoxy group of 6 to 14, m is a number of 1 to 4, and the following general formula (1) [R1 Si〇3/2]n (1 ) (except that R1 is a vinyl group, an alkyl group, a propyl group or a hardenable cage represented by a propyl group having at least one group of R1 contained in a molecule of an oxirane ring, an allyl group or an oxirane ring, in the presence of a non-polar Solvent and; In the solvent, the counter cation of the siloxane coupling compound and the cracking cleavage portion are converted into a hydroxyl group. 4. The structural unit represented by the manufacture of the first sesquioxane compound of the patent application range 1) 5. A hardening method comprising a stanol group represented by a hard 1 containing a cage structure, (2) a phenyl group, a (meth) acryl fluorenyl group, an alkenyl group, which may be the same or different from each other. Any one of which is a group of a vinyl group or a (meth)propane ring, and η is), which may be characterized by being a phenyl group, a (meth) propylene group or an ene group. Any one of the same or different, but one of the bases of the phenyl group and the (meth) acetonium group, and η is one of the 6 to 14 times sesquioxalyl compounds in the alkaline hydrating solvent. Or one or two of the two types of cracking, so that after the bonding of the basic part, the acid is treated to make the hardening cage method containing the stanol group of the three items, which is relative to the general formula ( ί uses 0.5~ 3 molar range of alkali t-fluorenone copolymers, characterized by -65- (3) 201000491 has the following General formula (3) Y-[Z-(R1Si〇3/2)n]lZY [However, R1 is a vinyl group, an alkyl group, a propyl group or an R1 contained in a molecule having an oxirane ring; The number of at least one group, allyl group or oxirane ring, 1 is a number from 1 to 2000, Z [Chemical 1] (However, R2 is a hydrogen atom, a vinyl fluorenyl group, an allyl group or an epoxy group, and 'a is a number from 0 to 30.) General formula (5 ') H〇i/2- (5,) or The following general formula (5) -[RISi〇3/2]n[H01/2]m.1 (except that R1 is a vinyl group, an alkyl group, a propyl group or a molecule having an oxirane ring; If at least one of the phenyl group, the (meth) acryl fluorenyl group and the rare sulphur group containing R1 are the same or different from each other, any one of the bases of the stimulating group and the (meth) acryl oxime is further η is 6 to 14 is a divalent group represented by the following general formula (4) (4), an alkyl group, a phenyl group, or a (meth) propylene can be the same or a divalent group represented by a phase, γ The following (5) phenyl, (meth) acryl fluorenyl, alkene, although mutually identical or different, but a vinyl, (meth) acryl fluorenyl, allyl or epoxy Any one of the groups of the ethane ring, η is a number of 6 to 14 -66 - 201000491, m is a number of 1 to 4) or the following general formula (6) [Chemical 2] R3 R3 - 〒卜〇1 /2— (However, R3 is hydrogen, vinyl, alkyl, phenyl, (meth) acrylonitrile, propylene Or a group having an oxirane ring, the person may be the same or different each other) of a monovalent group represented] The constituent units represented. 6 - The manufacture of a sclerosing fluorenone copolymer containing a cage structure is characterized by the following general formula (2) [R'SiOa/ilntHOwa], (2) (only, R1 is a vinyl group, an alkyl group, a phenyl group, a (meth) acrylonitrile group, a dilute propyl group or a group having an oxirane ring, which may be the same or different from each other, but at least one of R1 contained in one molecule Any one of a vinyl group, a (meth)acrylase group, an allyl group or a group having an oxirane ring, which is represented by a number of 6 to 14 and a number of m of 1 to 4) a stilbenyl-containing sclerosing cage sesquiterpene oxide compound and the following general formula (7) [Chemical 3] 201000491 (However, R2 is a hydrogen atom, a vinyl group, an alkyl group, a phenyl group, a (meth)acryloyl group, an allyl group or a group having an oxirane ring, which may be the same or different from each other, X is a hydrogen atom, a halogen atom or an alkoxy group, which may be the same or different from each other, and b is a compound represented by the number of 0 to 30, or a general reaction formula (8) 4] R3 (8) R3—Si-CI I R3 (only fluorenyl), R3 is a hydrogen atom, a vinyl group, an alkyl group, a phenyl group, a (methyl propylene) propylene group, an allyl group or an epoxy group The group of the alkane ring can be condensed by the same compound represented by the same π & ”% different, and the following 〜@ @, Y-[Z-(RlSi03/2)n]iZY (3) is obtained. [However, R1 is a vinyl 'alkyl group, a phenyl group, a (meth) propylene group or a group having an oxirane ring, which may be at least the same or different from each other. Any one of a group of a vinyl group, a (meth) group, an allyl group or an oxirane ring, and a number of n, and a number of 1 to 2000 'Z is the following general formula (4) ) 【化5】 -68- 201000491 (However, R2 is a hydrogen atom, a vinyl group, an alkyl group, a phenyl '(methyl)propancanyl group, an allyl group or a group having an oxirane ring' may be the same or different from each other Again, a is the number of 〇~30). The two-valent group represented by γ is the following general formula (5) HOi/2- (5,) or the following general formula (5) - [R 1 S i 〇 3/2 ] η [Η Ο 1/ 2 ] m - 1 (5) (However, R1 is a vinyl group, an alkyl group, a phenyl group, a (meth) acrylonitrile group, an allyl group or a group having an epoxy ring, although they may be the same or each other Any one, but at least one of R1 contained in the i molecule is a vinyl group, a (meth) acryl fluorenyl group, an allyl group or a group having an oxirane ring, and the 'n' η is 6 to 14 The number, πι is a number from 1 to 4, or the following general formula (Ο6) R3 I R3—Si-〇1/2—, | 1/2 (6) R3 (only, R3 is hydrogen, A composition represented by a vinyl group, an alkyl group, a phenyl group, a (meth) acrylonitrile group, an allyl group or a group having an oxirane ring, which may be the same or different from each other) A sclerosing fluorenone copolymer containing a cage structure of the unit. 7. A method for producing a sclerosing fluorenone copolymer containing a cage structure according to claim 6 of the patent application, wherein, for the general formula (2), 69- 201000491 Sulfhydryl-based sclerosing cage sesquiterpene oxide compound 1 mol, for the condensation reaction of the compound represented by the general formula (7) in the range of 5 to 10 mol. 8 · The manufacture of the curable anthrone copolymer containing the cage structure as claimed in claim 6 The method wherein the sulfoalkyl group-containing hardenable cage sesquioxane compound 1 mol represented by the general formula (2) is represented by a general formula (7) in a range of 0.5 to 10 mol The compound is subjected to a condensation reaction with a compound represented by the general formula (8) in the range of 2 to 100 mol. 9 - A curable resin composition characterized by having the following general formula (3) y-[Z-( R1Si〇3/2)„]iZY (3) [Rf, R1 is a vinyl group, an alkyl group, a phenyl group, a (meth) acrylonitrile group, a dilute propyl group or a group having an oxirane ring, although Any one of the same or different, but in the case of R1, having at least one of ethylene, (meth)acryloyl, allyl or an oxirane ring in one molecule, , n stomach 6 to 14 number, 1 is a number from 1 to 2000, Z is the following general formula (4) [Chem. 7] (However, R 2 is a hydrogen atom, a B-group, a phenyl group, a (meth)propenyl group, an allyl group or a group having an oxirane ring may be the same or different from each other, 201000491, Further, a is a divalent group represented by the number of 〇30, and γ is the following general formula (5') Η〇ι/2- (5,) or the following general formula (5) - [R1Si〇 3/2]n[H01/2]mi (5) (only 'R1 is a vinyl group, an alkyl group, a phenyl group, a (methyl) fluorene group, a propyl group or a group having an oxirane ring' Although they may be the same or different from each other, in the case of R1, at least one of them is a vinyl group, a (meth)acryloyl group, an allyl group or a group having an oxirane ring. Further, n is a number of 6 to 14, m is a number of 1 to 4) or the following general formula (6) [Chemical 8] R3 R3—Si—〇1/2—I 1/2 (6) R3 ( However, 'R3 is hydrogen, an alkyl group, a phenyl group, a phenyl group, a (meth) acryl fluorenyl group, an allyl group or a group having an oxirane ring, which may be the same or different from each other) a hardening ketone copolymer containing a cage structure represented by a monovalent group, with a hydrogenation catalyst Either or both of the radical initiators and the at least one helium atom having a hydrogen atom and a compound having an unsaturated group in the molecule or both may be used. 10' The curable resin composition of claim 9, wherein the hydrazine-reducing compound having a hydrogen atom and having a hydrogen atom is 矽-71 - 201000491 oxane or decane. 1 1. A molded body characterized by being formed by curing a curable resin composition of claim 9 or 10 of the patent application. -72-