TW200813107A - Linear (meth) acryloyl group-containing compound, star-shaped (meth) acryloyl group-containing compound and production processes thereof - Google Patents

Abstract

The present invention provides a linear (meth) acryloyl group-containing compound wherein the structural unit represented by the following general formula (1): (wherein, A represents a divalent hydrocarbon group which may or may not contain a hetero atom) has a structure which is coupled with the following general formula (2) or (3): (wherein, A in general formula (1) may be coupled by the same group or a different group), and the molecular terminal is an epoxy group, or a compound represented by the following general formula (4): (wherein, R represents a hydrogen atom or a methyl group, and B represents a monovalent hydrocarbon group); and, a total of 3 or more of the structural units represented by general formula (3) or (4) are contained on average in a single molecule, and the number average molecular weight is 500 to 10,000.

Description

200813107 IX. OBJECTS OF THE INVENTION: TECHNICAL FIELD The present invention relates to a (meth)acryl-containing fluorenyl compound, and a process for the preparation thereof. The (meth) propylene fluorenyl compound has an average of 3 in one molecule. One or more (meth) acrylonitrile groups are excellent in hardenability, and a material which is a curable resin composition can be widely used. [Prior Art] A compound having a (meth) acrylonitrile group is widely used as a material for using a curable resin composition of an active energy ray or a radical, or a thermosetting resin composition, or a material of a polymer compound. In particular, the heat resistance, chemical resistance, water resistance, adhesion, mechanical properties, and the like of the cured product obtained from the epoxy (meth) acrylate are compared with those obtained by using other (meth) acrylate. Because it is excellent, it is widely used as a coating resist, a printing ink, a UV curable resin, a molding resin, a film, an adhesive, a structural material, and a solder resist for a wiring base. Conventionally, the epoxy (meth) acrylate has a bifunctional substance using a bisphenol type epoxy resin as a raw material, and a polyfunctional substance using a resol type epoxy resin as a raw material, depending on the use or the The performance grade of the target hardened material is used separately. The bifunctional epoxy (meth) acrylate has fluidity at room temperature and has good handleability, but since the (meth) acrylonitrile group is present only at both ends of the epoxy resin of the raw material, it is hardenable or The hardening sensitivity is inferior to that of the polyfunctional epoxy (meth) acrylate, and in order to increase the crosslinking density of the cured product, a polyfunctional acrylic monomer or the like is used in combination, and troublesome composition preparation is required. Further, since it has only the 200813107 (meth) acrylonitrile group at the molecular terminal, the shrinkage at the time of hardening is large, and it is difficult to use it for applications such as adhesion to a substrate. On the other hand, a polyfunctional epoxy (meth) acrylate is a solid, and it is not easy to handle when a curable composition is prepared. Further, the polyfunctionality of the resole type epoxy resin as a raw material has one (meth) acrylonitrile group per one aromatic ring, and the obtained cured product has high crosslinking density and excellent corrosion resistance, etc. There is a tendency to be too hard and lack of toughness and brittleness. Further, many of the hydroxyl groups present in the resole type epoxy (meth) acrylate may cause adverse effects when used for precise electrical applications. In other words, in order to adjust the crosslinking density, the conventional epoxy (meth) acrylate has only been used in combination with other monomers, and has no handleability, curability, and cured product. A (meth)acryl-based compound containing a good balance of electrical properties and the like. Further, in the epoxy (meth) acrylate, it is necessary to introduce a functional group other than the (meth) acryl fluorenyl group for imparting other properties such as development, and for example, it is disclosed that it is present in epoxy (meth)acrylic acid. An acid side-side type epoxy (meth) acrylate in which a carboxyl group of the second stage of the ester is reacted with an acid anhydride or the like to introduce a carboxyl group (see, for example, Patent Documents 1 and 2). However, 'in the acid side-linked epoxy (meth) acrylate, basically as described above 'because the use of bifunctional epoxy (meth) acrylate, or polyfunctional epoxy (methyl) It is difficult to adjust the balance between the curability and the performance depending on the crosslink density of the cured product as the raw material of the acrylate. Further, the acid side-linked epoxy (meth) acrylate is obtained by reacting an epoxy resin with an unsaturated monovalent acid, and further reacting with a polyvalent acid anhydride or the like, and is obtained by using an epoxy (meth) propyl 200813107 enoic acid. There must be a minimum of two stages of reaction when the ester is introduced into other functional groups. By using an insufficient amount of the unsaturated monovalent acid to the epoxy group in the epoxy resin, a compound having a (meth)acrylonyl group and other functional groups (epoxy groups) in one molecule can be obtained, and also exists. There is a so-called half ester type epoxy (meth) acrylate. However, the epoxy (meth) acrylate of this type is very poor in storage stability and is easily known for high molecular weight (gelation). This is considered to be because the activity of the hydroxyl group produced by the reaction of the epoxy group with the unsaturated monovalent acid is high, and it can react with the epoxy group even at room temperature. In other words, it has an average of three or more (meth) acrylonitrile groups in one molecule by hardening or thermosetting of active energy rays, radicals, etc., and can be obtained by a one-stage reaction. The method for preparing a cation-hardened ring-and-base compound is conventionally absent. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei No. Hei No. Hei No. Hei No. 1 - 1 8 1 0 5 0 [Invention] [Problems to be Solved by the Invention] Based on the above-mentioned actual situation The problem to be solved by the present invention is to provide a (meth)acryl-containing fluorenyl group-containing compound having an average of three or more (meth) acrylonitrile groups in one molecule, which has good curability and is easy to adjust the obtained cured product. Crosslinking density, particularly a (meth)acryl-containing compound which is useful as a material capable of applying a resin composition of a cationic curing system, and an industrial process capable of easily producing the (meth)acryl-containing compound The method for preparing sulfhydryl compounds. [Means for Solving the Problems] In order to solve the above problems, the inventors of the present invention have found that the second-order hydroxyl groups which are mostly present in the linear or star-shaped epoxy resin have an average of three or more in one molecule. The compound obtained by introducing a (meth) acrylonitrile group is excellent in curability, and structurally adjusts the crosslink density of the cured product, and is introduced by using a specific catalyst at the second-order hydroxyl group (A) The reaction of the acrylonitrile group does not cause a side reaction such as high molecular weight (gelation), and a polyfunctional (meth)acryl-containing fluorenyl compound can be obtained, and in the epoxy resin as a raw material. The epoxy group can remain in the reaction product in a ring-free manner, and therefore, a compound having an epoxy group and a (meth)acryloyl group in one molecule can be obtained by a one-stage reaction, and the present invention is completed. invention. That is, the first aspect of the present invention provides a linear (meth)acrylonitrile-containing compound having the following general formula (1) [Chemical Formula 1], h2, 〇/A, 〇/CH2, ... (1) [In the formula (1), the A system may also contain a divalent hydrocarbon group of a hetero atom], and the structural unit represented by the following formula (2) or (3) [Chemical Formula 2]

200813107 [In the formula (3), R is a hydrogen atom or a structure in which a hydrogen atom is bonded to each other. [In the above formula (1), A may be the same or may be a different one.] The molecular terminal is an epoxy group, or the following formula (4) [Chemical Formula 3] produces ch2 o/C^o 丫\CHr〇, B (4) Η [in the formula (4), an R-based hydrogen atom or a methyl group , a compound of the above formula (3) or the above formula (4), wherein the total number of structural units represented by the above formula (3) or the above formula (4) is 3 or more on average, and the number average molecular weight is 500 to 500. Further, the second aspect of the present invention provides a star-type (meth)acryl-containing mercapto compound having a number average molecular weight of 800 to 10,000, which is represented by the following formula (5) [Chemical Formula 4]

200813107 [In the formula (5), R is a hydrogen atom or a methyl group, B is a valence group of a valence, and Y is a one selected from a polyfunctional epoxy resin having an average of n epoxy groups (where η is 3 or more). The residue after the epoxy group is represented by an integer of m or more (where m). Further, the third aspect of the present invention provides a method for producing a (meth)acryl-containing fluorenyl compound, which has three or more uses [Chemical Formula 5]

OH 〆, CHr 〒, CHT 〇, ...-(6) 环氧树脂 Unstructured units of epoxy resin (I), and (methyl) propyl succinic acid ester (π), in the polystannoxane The transesterification reaction is carried out in the presence of the medium (III), and an average of three or more (meth) acrylonitriles in one molecule is obtained by introducing a (meth) propyl storage group in the hydroxy group in the above formula (6). Base compound. [Effects of the Invention] The linear (meth)acryl-containing fluorenyl compound of the present invention has an average of three or more (meth) acrylonitrile groups in one molecule, and a conventional bifunctional linear ring When oxygen (meth) acrylate is compared, it has high hardenability and high sensitivity. Further, by selecting an epoxy resin as a raw material, the molecular weight of each (meth)acryl fluorenyl group [that is, the concentration of (meth) acrylonitrile group] can be easily prepared, even if it is not used in combination. Other acrylic monomers can also adjust the crosslink density of the cured product. Further, since the hydroxyl group remains in the molecule, it is also possible to use a material such as a precise electrical use. Further, since the star-type (meth)acryl-based mercapto compound of the present invention is multi-functional, it is excellent in hardenability or sensitivity. Moreover, when compared with the polyfunctional epoxy (meth) acrylate obtained by using a resole type epoxy resin as a raw material, there is one (methyl group) on one side chain extending from the center of the star shape. ) C. 醯 醯 ' 'easy to make the rules correctly cross-linked structure. Further, since the molecular weight of each (meth) propyl group is also large, a hardened material which is not too hard and has appropriate toughness can be obtained. Further, since the hydroxyl group can be left in the molecule, it is also possible to use a material such as a precise electrical use. Further, when the central portion of the star structure has an aromatic ring, it is also possible to impart a stacking capacity of 7 Γ - 7 分子 between molecules, and it is possible to improve heat resistance, corrosion resistance, mechanical strength, and the like of the cured product. As described above, the (meth)acryl-containing fluorenyl compound of the present invention is excellent in heat resistance, uranium resistance, mechanical strength, and the like, and can provide a cured product having excellent electrical properties. In addition, a (meth) acrylonitrile group and an epoxy group can be present in one molecule, and in this case, since a hydroxyl group which reacts with an epoxy group is not left, it is possible to use various curing systems which are excellent in storage stability. The resin composition is particularly a resin composition of a cationic curing system which is excellent in reactivity. Therefore, it can be used in a wide range of applications such as a coating resin, a printing ink, a UV curable resin, a cationic curable resin, a molding resin, an adhesive, and a solder resist for a wiring base. Further, the method for producing a (meth) acrylonitrile-containing compound of the present invention does not cause high-molecularization (gelation) due to a side reaction such as a methacryl addition reaction by the introduced (meth) acrylonitrile group. Further, it is possible to obtain a compound having an epoxy group and a (meth) acrylonitrile group in a one-stage reaction -12 to 200813107, which is highly useful as an industrial process. [Embodiment] In the present invention, a (meth) acrylonitrile group is a generic term for a propylene fluorenyl group and a (meth) acryl fluorenyl group, and a (meth) acryl fluorenyl group-containing compound may also contain two molecules in one molecule. base. Further, in the present invention, the linear (meth)acrylonitrile-containing compound means a moiety having the longest binding length in one molecule, and has a plurality of structural units represented by the above formula (1), and The terminal, the epoxy group having a molecular terminal structure or the group represented by the above formula (4), for example, may be a branching moiety in the hydrocarbon group (that is, having a carbon atom of 3 or 4), The hydrocarbon group having a trivalent or higher hetero atom such as a nitrogen atom or a phosphorus atom may have a branched structure at the hetero atom portion. Further, the star-type (meth) acrylonitrile-containing compound of the present invention means that there are two or more portions having the longest binding length in one molecule, and both ends of the respective portions have a ring having a molecular terminal structure. An oxy group or a group represented by the above formula (4). The linear (meth)acryl-containing fluorenyl compound of the first aspect of the present invention has the following general formula (1) [Chemical Formula 6] /CH2, 〇/A, /CH2, ... (1) [ In the formula (1), the A system may also contain a divalent hydrocarbon group of a hetero atom] The structural unit represented by the following formula (2) or (3) 200813107

[In the formula (3), a structure in which an R-based hydrogen atom or a methyl group is bonded] [wherein A in the above formula (1) may be formed by the same substance, or may be a different substance. a molecule, an end group of an epoxy group, or the following formula (4) [Chemical Formula 8]

In the formula (4), a compound represented by R, a hydrogen atom or a methyl group, and a B-valent monovalent hydrocarbon group, wherein the total of the structural units represented by the above formula (3) or the above formula (4) is 1 molecule The average content contains 3 or more, and the number average molecular weight is 5 00~1 〇, 〇〇〇. The (meth) acrylonitrile group in the linear (meth) acrylonitrile-containing compound of the present invention is present in the side chain portion with respect to the molecular chain having the longest binding length in one molecule, from hardening In terms of good sex or sensitivity, it is necessary to have an average of three or more in the molecule. The (meth) acrylonitrile group is a structural unit selected to constitute a linear portion, and the concentration in the molecule, that is, the molecular weight per one (meth) acryl fluorenyl group can be easily adjusted. For example, A in the above formula (1) is as described later, and when the residue of the two epoxy groups is removed from the bisphenol, it can be substantially the same as the conventional bifunctional epoxy (meth) acrylate. The concentration is a polyfunctional property, and at the same time, by setting the crosslinking density in an appropriate range, a cured product having both toughness and strength can be obtained. Further, since the (meth) acrylonitrile group is dispersed in the molecule, the shrinkage during curing is mild, and the adhesion to the substrate is also good, and cracks or the like are not generated in the cured product. This is a major feature not found in conventional epoxy (meth) acrylates. 'Because there is no need for troublesome begging of other acrylic monomers used for selective blending in order to adjust the performance balance of the cured product or prevent cracking or the like. , can also use 'so wide range of applications in the industry. Further, since the hydroxyl group in the above formula (2) has a low activity, it does not react with the terminal epoxy group at room temperature in the same manner as the second-order hydroxyl group in the epoxy resin, and the storage stability of the compound is also good. . Further, the linear (meth)acryl-containing mercapto compound of the present invention must have an average molecular weight of 500 to 10,000. When the number average molecular weight is less than 500, the heat resistance or corrosion resistance of the obtained cured product is insufficient, and when it is more than 10,000, when the method of the present invention described later is used, the epoxy resin of the raw material is not easily industrially obtained, and the softening point becomes too If it is high, it is incapable of maintaining the compatibility with the alkyl (meth) acrylate of the other raw material, and it is not easy to produce a transesterification reaction, which is not preferable. A particularly preferred number average molecular weight is from 1,500 to 5,000. Further, in the present invention, the number average molecular weight is determined by GPC (gel permeation chromatography), in which 1 g of the sample is dissolved in 10 ml of THF (tetrahydrofuran), and the liquid of 200813107 50 μl of the sample is injected into the column. A polystyrene of a known molecular weight is used as a standard substance. The fluorene system in the above formula (1) may contain a divalent hydrocarbon group such as a nitrogen atom, an oxygen atom or a phosphorus atom, and the aromatic compound is excellent in corrosion resistance and heat resistance of the obtained cured product. Further, it is preferable that the coloring of the cured product is a problem, and it is preferable to have an aliphatic cyclic structure. Further, when the softness of the cured product is emphasized, an alkyl chain or an alkyl chain may be selected. The A in the above formula (1) of the linear (meth)acryl-containing fluorenyl compound of the present invention may be a plurality of the same substances, or may be linked by a substance having a different structure, and may be a target. Use or the performance grade of the obtained hardened material, and use it as appropriate. The A in the above formula (1) can be used in various forms, and is not particularly limited, and examples thereof include those shown by the following structural formulas. [Chemical Formula 9] -16- 200813107 4cH2-CH2r〇)^CH2_CHr ch3 ch3 -{ch2-ch-o)^ch2-ch-

Q-ch.0-

Oi; ch3

OK>,

G~,

CHr ch3 -OtO, -c - I ch3

(In the formula, P and q are integers of 1 to 6 and may have a carbon number of 1 to 4 alkyl groups as a substituent in the ring.) Among the methods of the present invention described later, the raw material is used. In view of the fact that the epoxy resin is easily obtained industrially, it is preferable to remove the two hydroxyl groups from the bisphenol or the biphenol from the mechanical properties of the obtained cured product, particularly from the cured product. In terms of excellent heat resistance or flame retardancy, it is preferred to have a base having a xanthene skeleton. Further, R in the above formulas (3) and (4) is excellent in hardenability by an active energy ray, and a hydrogen atom is preferred. However, from the viewpoint of heat resistance, R in the above formulas (3) and (4) is preferably a methyl group, and in this case, it is preferred to use a heat curing system in accordance with the intended use or the type of curing system used. It is better to choose. The molecular terminal of the linear (meth)acryl-containing fluorenyl compound of the present invention has an epoxy group or a group represented by the above formula (4), and both ends of the molecule may be an epoxy group or may have only one side. It is an epoxy group, and the both ends of a molecule may also be the structure shown by the said General formula (4). Further, the epoxy group at the end of the molecule or the group represented by the above formula (4) is not directly bonded to the above-mentioned general description (2) or (3), but is bonded to the above formula (1). When the molecular terminal is an epoxy group, the compound having a (meth) acryloyl group and an epoxy group having a different nature and having a reactive functional group in one molecule can be used in addition to an active energy ray curing system, a radical polymerization system, a heat curing system, and a curing system using a cationic curing system, a curing reaction using a compound capable of reacting with an epoxy group and having a functional group such as an amine group, etc., may be used, and the curing device may be used according to the performance level of the intended use or the cured product. Various choices are made, such as the shape of the hardened material. Further, B in the above formula (4) which is a molecular terminal is not particularly limited as long as it is a monovalent hydrocarbon group, and examples thereof include those shown in the following structural formula. [Chemical Formula 10], ch3 *(CH2-CH2-〇)^CH2 - CH3 4cxj2-CH-ο Bu ch2-ch3

200813107 (In the formula, P and q are integers of 1 to 6 in which a carbon number of 1 to 4 alkyl groups may be substituted as a substituent in the ring). Among these, heat resistance and uranium resistance are obtained from the obtained cured product. In terms of excellent properties, a structure having an aromatic ring is preferred. The star-type (meth) propylene fluorenyl compound of the second aspect of the present invention has a number average molecular weight of 800 to 10, 〇〇〇, which is represented by the following formula (5) [Chemical Formula 1 1]

[In the formula (5), R is a hydrogen atom or a methyl group, B is a monovalent hydrocarbon, and Y is an epoxy resin obtained by removing an epoxy resin having an average of n epoxy groups (where n is 3 or more). The residue after the base is represented by an integer of 3 or more (where ng m)]. The (meth) acrylonitrile group contained in one molecule of the above-mentioned star-type (meth) acrylonitrile-based compound must have an average of three or more in terms of good curability. Therefore, when the epoxy resin to be used is trifunctional, it will be a compound having no epoxy group in one molecule. By having the structure represented by the above formula (5), compared with the polyfunctional epoxy (meth) acrylate obtained by using a resole type epoxy resin as a raw material, since it extends from the center of the star shape It has a (meth) acrylonitrile group on one side chain, making it easy to produce a regularly correct crosslinked structure. Moreover, since the molecular weight of each (meth) acrylonitrile group of -19-200813107 can be modulated by the structure of Y and B in the selection, the cured product can have both the multifunctional epoxy obtained from the epoxy resin ( Toughness and hardness obtained by the methyl methacrylate method. Can be used as a precision electrical material. Therefore, the above-mentioned linear (meth)acryl-containing fluorene-based group can be used in a wide range of industrial applications because it does not require troublesome bedding of other acrylic monomers which are used in combination for adjusting the properties of the cured product. The amount of the star-type (meth)acryl-containing mercapto compound of the present invention must be 800 to 1 0,0 0 0. When the molecular weight is less than 800 at a molecular weight of less than 8,000, the heat resistance of the obtained cured product is sufficient. When the molecular weight is more than 10,000, the ring-oxygen resin produced by the method of the present invention described later is not easily industrially obtained, and is softened. It is not preferable that the point change method maintains a transesterification reaction easily with the alkyl (meth) acrylate of the other raw material. The number of extra good is 1,500~5,000. Further, the number average molecular weight is determined in the same manner as the above-described mercapto) fluorenyl compound. The Y in the general formula (5) is, for example, the following structure: [Chemical Formula 12] The compound of the above formula (5), which is used for the gas-free use of the resol type ester, is also selected and used in the same manner, so the amount is Average score =, average number or uranium resistance from time to time, raw materials are too high, no compatibility, uneven molecular weight I chain-like inclusion (A formula. -20 - 200813107

a cHr〇

—ch2-o- 4^0—CH2—a ch2o

-ch2- 十o-ch2—(where the ring is also a” has a carbon number i~4, which is a substitute lane). When the central part of the star structure has an aromatic ring, it can also be intermolecular. The ability to impart 7 Γ - 7 Γ stacking capacity can improve the heat resistance, tamper resistance or mechanical strength of the cured product. Further, in the above formula (5), R ' is preferably a hydrogen atom from the viewpoint of good curability by an active energy ray. However, in the case of the cured product, R in the above formula (5) is preferably a methyl group. In this case, it is preferred to use a heat curing system, and it is preferably selected according to the intended use or the type of curing system to be used. Further, B in the above formula (5) is not particularly limited as long as it is a monovalent hydrocarbon group, and examples thereof include those represented by the following structural formulas. [Chemical Formula 13] 200813107 CH3 4cH2-CH: r〇)^CH2 - ch3 <ch2-0h-. Bu ch2-ch3 -o -c

,-0~cO,-〇£〇,ο,οο,

-σ ch2-

CH, -σο (wherein ρ and q are integers of 1 to 6 in which a carbon number of 1 to 4 alkyl groups may be substituted as a substituent in the ring), among these, heat resistance of the obtained cured product In terms of excellent corrosion resistance, a structure having an aromatic ring is preferred. The process for producing a (meth)acryl-containing fluorenyl compound of the present invention is characterized in that it has three or more of the following structural formulas (6) in one molecule by using [Chemical Formula 14].

OH .1 (6) 环氧树脂 The epoxy resin (I) and the alkyl (meth) acrylate (II) in the structural unit shown are transesterified in the presence of a polystannoxane catalyst (III). The (meth) acrylonitrile group is introduced into the hydroxyl group in the formula (6), and a compound having an average of three or more (meth) acrylonitrile groups in one molecule is obtained. Conventionally, a compound having a hydroxyl group and a alkyl (meth)acrylate are transesterified by a transesterification reaction, and a (meth)acryloyl group can be widely introduced into a hydroxyl group. However, the hydroxyl groups to be introduced in the present invention are particularly different in their position. That is, since the carbon atom to which the hydroxyl group is bonded bonds two oxygen atoms having a free electron pair by a methylene group, it can be easily estimated that the electron density around the hydroxyl group is high. This means that the hydrogen atom in the hydroxyl group has a charge of + and is not easily detached. In the past, it has been known that a 2-stage mesogenic group in an epoxy resin is very lacking in reactivity. That is, although a linear epoxy resin has a plurality of secondary hydroxyl groups, the epoxy group at the end reacts with the hydroxyl group to cause an increase in the epoxy equivalent during storage, which is usually not observed, and, for example, 'Normally, the hydroxyl group and the isocyanate group can react even at room temperature, but it can be seen that the reactivity is low from the case where the combination of the epoxy resin and the isocyanate compound is required to be heat-hardened. Further, 'in the above formula (6), when the oxygen atom of the main chain is bonded to the aromatic ring, 'because the carbon atom to which the hydroxyl group is bonded exists in the coating portion between the fe cloud formed by the linked aromatic ring' It is not susceptible to external attacks, and the reactivity of hydroxyl groups is low. Therefore, it is considered that it is extremely difficult to apply a reaction which is usually carried out in a hydroxyl group-containing compound to a hydroxyl group in an epoxy resin. Attempts to introduce a particularly reactive (meth)acrylonitrile group into a hydroxyl group in an epoxy resin in a manner that causes little side reaction, and also attempts to directly react an epoxy group having a very high reactivity in an epoxy resin. It is impossible to carry out the introduction of a (meth) acrylonitrile group into a hydroxyl group having a low reactivity. The epoxy resin (I) used in the present invention may have three or more of the above structural formula (6) in one molecule, and may be a commercially available product or may be a dihydroxy compound in a commercial product. A product obtained by performing an elongation reaction, -23-200813107 Further, a modified epoxy resin obtained by using a hydroxy compound to form a ring-opening epoxy resin may be used. An epoxy resin which can be used in the commercial product can provide a linear propylene-containing compound, and examples thereof include bisphenol A type epoxy resin F type epoxy resin, bisphenol S type epoxy resin, and double A bisphenol type epoxy resin such as a phenol ACP type ester or a bisphenol type A epoxy resin, a biphenyl oxy-resin, a hydrogenated bisphenol A type epoxy resin or the like has the structure represented by the above structural formula (6) in one molecule. Things. In addition, the elongation reaction described later can be carried out by using a dihydroxy compound or the like, and three or more structures represented by the above structural formula (6) can be used in the molecule, and an epoxy resin which provides a linear (meth)acryl-containing compound can be used. There are, for example, the aforementioned epoxy resins, and examples thereof include pentanediol diepoxypropyl ether, L4-butanediol diepoxypropyl ether, alcohol diepoxypropyl ether, and polypropylene glycol diepoxypropyl ether. Non-substituted xanthene diglycidyl ether, 3,6-bicyclic ring, such as diglycidyl ether, 2,7-diepoxypropyl hydroxyxanthene, 3,6-dicyclic hydroxyxanthene Substituted xanthene diglycidyl ethers such as hydroxy-9,9-dimethylxanthene, 2,7-diepoxypropylhydroxy-I, 3,4,5-methyl-9-phenylxanthene An epoxy resin having a xanthene skeleton such as dibenzoxanthene diether ether such as 2,1 1 -propylhydroxy-1 3 -biphenyldibenzoxanthene may be used singly or in combination. Among these, 'it is easy to obtain industrially, and it is preferable to use a bisphenol epoxy resin from the viewpoint of obtaining a hard mechanical material, etc., and it is also possible to obtain a cured product excellent in flame retardancy from heat resistance. The epoxy-based (methyl) lipid and the di-epoxyphenol-type ring have been used for the first time. The raw material of the ring has a new poly(ethylene oxide) oxypropyloxypropyl group, 6,8-hexacyclo ring. It is preferable to use an epoxy resin having a xanthene skeleton from -24 to 200813107. The dihydroxy compound used for the above-described elongation reaction is not particularly limited, and may, for example, be a divalent phenol such as a benzene group, a chlorophenol or a phenol, a bisphenol A, a bisphenol F or a bisphenol. Phenol AD, Si Mo, although 酣A and other bisphenol A, biphenol, tetramethylbiphenol and other biphenyl acids, 丨4·butanediol, ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, etc. Alcohols, etc., 2,7-dihydroxyxanthene, 3,6-dihydroxyxanthene, etc., unsubstituted xanthene dihydroxy compounds, 3,6-dihydroxy-9,9-dimethylxanthene, 2, 7 _ di-mercapto-1,3,4,5,6,8-hexamethyl-9-phenylxanthene, etc. substituted xanthene dihydroxy compound, 2,1 1 -mono-based-1 3 -biphenyl A diphenylxanthene type dihydroxy compound, dihydroxynaphthalene or dihydroxyanthracene such as dibenzoxanthene may be used alone or in combination of two or more. The epoxy resin obtained by elongating the epoxy resin or the epoxy resin obtained by stretching may further use a hydroxy compound to form a part or all of the epoxy group to be a modified epoxy resin, and then The raw material of the transesterification reaction described later. When the epoxy group is not present, the cured product cannot be obtained by using a cationic curing system. However, the obtained cured product is excellent in mechanical strength and the like, and is preferably selected and used depending on the use or the physical properties of the cured product. The hydroxy compound which can be used at this time is not particularly limited, and examples thereof include monovalent phenols such as phenol, butylphenol, nonylphenol, phenylphenol, and cumylphenol, and monovalent phenols such as ethanol and cyclohexanol. An alcohol or the like, a hydroxynaphthalene or a hydroxy hydrazine may be used alone or in combination of two or more. Among these, from the viewpoint of excellent heat resistance and corrosion resistance of the cured product, a compound having an aromatic ring is preferred. -25 - 200813107 Further, the 'star-type (meth) acryl-based fluorenyl compound can be used, for example, by using a naphthalene type tetrafunctional epoxy resin or a tetraphenol ethane type epoxy resin as a raw material, and the terminal epoxy group and The hydroxy compound is reacted to form a compound having three or more hydroxy groups by ring-opening of the epoxy group, and then obtained by a method of ester-reversion reaction described later. In addition, the commercially available tetraphenol ethane type epoxy resin also contains two or more molecules, and when used, the monomer can be extracted by a column or the like as a raw material of the present invention, and the product can be used according to the target performance. The products are used directly. By adjusting the reaction ratio of the above-mentioned hydroxy compound to the terminal epoxy group, the number of epoxy groups and (meth) fluorenyl groups in the obtained compound can be adjusted, and the reactivity can be introduced in one molecule at an arbitrary ratio. The method of the present invention is industrially useful in terms of two different functional groups. The commercially available epoxy resin is not particularly limited in a method of performing an elongation reaction using a dihydroxy compound or a method of ring-opening an epoxy resin using a hydroxy compound, and various methods can be used. For example, there is a method of heating and stirring at 120 to 220 ° C in the presence of a catalyst. The catalyst is not particularly limited, and examples thereof include a key salt, a phosphine, and an alkali metal hydroxide. The ratio of use of the epoxy resin and the dihydroxy compound or the hydroxy compound is appropriately selected in accordance with the epoxy equivalent of the target epoxy resin or the molecular weight of the modified epoxy equivalent, and the number of (meth)acrylonitrile groups introduced, and the like. It is better. The alkyl (meth)acrylate used in the transesterification reaction is not particularly limited, and from the viewpoint of good reactivity, an ester having an alkyl group having 1 to 6 carbon atoms is preferable, and for example, acrylic acid is exemplified. Methyl ester, ethyl acrylate, acrylic acid propyl-26 - 200813107 ester, methyl methacrylate, ethyl methacrylate, propyl methacrylate and the like. When the curable property of the (meth)acryl-containing fluorenyl group-containing compound is good, it is preferable to use an alkyl acrylate, and it is preferable to use the alkyl methacrylate when it is used for the heat resistance of the cured product. It is preferable to appropriately select according to the method of use or use of the obtained compound. In the process of the present invention, even if such (meth)acrylic acid alkyl ester (II) is used, during the transesterification reaction, almost no polymerization occurs between the (meth) acrylonitrile groups, and no generation occurs. High molecular weight (gelation). The polystannoxane catalyst (III) used as a transesterification catalyst in the present invention, the following general formula (7) [Chemical Formula 15]

[In the formula (7), R1 to R4 each independently represent a methyl group or an ethyl group, and X1 and X2 each independently represent an electron attracting group having an isolated electron pair on an atom bonded to a tin atom, and the r system The catalyst 1 shown in the integer of 1 to 8 is preferable from the viewpoint of exhibiting excellent catalyst activity and high yield of the transesterification reaction. The electron-attracting group having an isolated electron pair in the atom bonded to the tin atom in the above formula (7) includes a halogen atom such as a chlorine atom, a bromine atom or a fluorine atom, and a carbon atom number of 1 to A methoxy group, a hydroxyl group, a thiol group, a thiocyanate group or the like of 4. Among the polystannoxane catalysts represented by the above formula (7), in particular, -27-200813107 is a compound of the y system 1 or 2 in the above formula (7), after the transesterification reaction. It is preferable that the solubility in water during the extraction operation at the time of purification is good, and similarly, from the viewpoint of excellent solubility in water, R 1 to R 4 are preferably a methyl group. Further, in the above formula (7), X1 and X2 are preferably a halogen atom, a decyloxy group or a thiocyanate group, from the viewpoint of excellent catalyst activity. Therefore, the polystannoxane-based catalyst used in the present invention is a methyl group of R1 to R4 in the above formula (7), and a halogen atom of X1 and X2, a decyloxy group or a thiocyanate group. The distannoxane compound (r = i) or the tristannoxane compound (r = 2) is preferred.

The distannoxane compound may, for example, be Cl(CH3)2SnOSn(CH3)2Cl, Cl(CH3)2SnOSn(CH3)2OCOCH3, Cl(CH3)2SnOSn(CH3)2OCH3, CH3OCO(CH3)2SnOSn, (CH3) 2OCOCH3, Cl(CH3)2SnOSn(CH3)2OCOCH2CH3Cl(CH3)2SnOSn(CH3)2SCN, NCS(CH3)2SnOSn(CH3)2SCN, etc., and the tristannoxane compound may, for example, be Cl(Sn(CH3)20 2Sn(CH3)2Cl, Cl(Sn(CH3)20)2Sn(CH3)2 OCOCH3, Cl(Sn(CH3)20)2Sn(CH3)20CH3, CH30C0(Sn(CH3)20)2Sn(CH3)20C0CH3, Cl(Sn(CH3)2〇h Sn(CH3)20C0CH2CH3Cl(Sn(CH3)20)2Sn(CH3)2SCN, NCS(Sn(CH3)2 0)2SnCH3)2SCN, and the like. Further, it is preferred that the tristannoxane compound has good stability in water, does not easily cause hydrolysis in water, and can reduce the amount of residual organotin compound in the product. -28 - 200813107 Further, in the transesterification reaction of the present invention, the following general formula (8) [Chemical Formula 16] R5 X3 - Sn - X4 ... - (8) R6 [In the formula (8), R5 to R6 Each independently represents a methyl group or an ethyl group, and X3 and X4 each independently represent an electron attracting group having an isolated electron pair on an atom bonded to a tin atom. The tin compound and the alkali compound are added to the reaction system. A polystannoxane-based catalyst (III) is formed in the system to enable a transesterification reaction. In this case, when the epoxy group (I) to be used has an epoxy group, since the basic compound reacts with the epoxy group, the epoxy group is previously opened by a hydroxy compound as described above. The modified epoxy resin is preferred. The tin compound represented by the general formula (8) is Cl2Sn(CH3)2, Br2Sn(CH3)2, I2Sn(CH3)2, ClSn(CH3)2OH, ClSn(CH3)2SH, Cl2Sn(C2H5)2, Cl(CH3OCO) Sn(CH3)2, C 1 ( CH 3 CH 3 〇CO ) S n ( CH 3) 2 ,

Cl(NCS)Sn(CH3)2 is preferred, and the basic compound is an alkali metal or alkaline earth metal hydroxide such as sodium hydroxide, potassium hydroxide or calcium hydroxide, sodium methoxide or methoxide. A carbonate of an alkali metal or an alkaline earth metal such as potassium or calcium oxide, or a carbonate such as sodium carbonate or calcium carbonate. In the production method of the present invention, the use ratio of the above-mentioned tristannoxane compound (III) is usually 0. (H~1 (% by mass) in the range of 0.1 to 2.0 with respect to the quality of the epoxy resin as a raw material. The range of % by mass is more preferably. The transesterification reaction of the process of the present invention can be carried out in the presence of a solvent or -29 - 200813107 under the 'ester exchange reaction system to remove the alcohol formed by the reversible reaction to the outside of the system. The transesterification of the process of the present invention is characterized in that it is less likely to cause high molecular weight (gelation), and it is more preferable to suppress polymerization of a (meth)acrylic group, and it is preferred to use a polymerization inhibitor in combination. There may be mentioned, for example, benzoquinone, hydroquinone, phenol, diphenylphenylhydrazine, hydroquinone monomethyl ether, naphthoquinone, tert-butyl phenol, tert-butylphenol, dimethyl tert-butyl Phenol, tert-butyl cresol, thiophene, etc. The amount of the polymerization agent used depends on the amount of the reaction product and the amount of the raw material component, and the (meth) acryl-based compound containing the reaction product is usually based on the quality standard of 5 ~lOOOOppm, especially The range of 20 to 7000 ppm is preferred. The above transesterification reaction can be carried out under atmospheric pressure. Further, the reaction temperature conditions can be selected locally according to the raw materials used or the reaction solvent, and are preferably 20 to 15 Torr. That is, at a temperature of 20 ° C or higher, the reaction rate during the transesterification reaction is drastically increased, and the side reaction can be suppressed at a temperature of 150 ° C or lower, and the (meth) propylene can be suppressed. In the polymerization of sulfhydryl groups, it is preferably 70 to 120 ° C. Further, transesterification is carried out while continuously introducing oxygen-containing gas in an oxygen-containing gas atmosphere or in a reaction liquid surface or a reaction liquid. The method of the reaction 'is good because it can suppress the polymerization of the (meth) acrylonitrile group. Here, the oxygen-containing gas may also be air', but since the volume reference oxygen content is too high, there is a generation. The possibility of a gas explosion is high, and the color of the product -30-200813107 is easily caused, and a hot body having an oxygen content of 5 to 13% by volume is preferable. The gas having a content of 5 to 13% by volume can be borrowed. Mix empty by the way to meet this condition The oxygen gas and the inert gas are adjusted. Here, the inert gas may be nitrogen gas, argon gas or the like. The flow rate of the oxygen-containing gas continuously introduced into the reaction liquid surface or the reaction liquid is relative to 1 mol ( The alkyl (meth) acrylate (11)' is preferably 0. 1 to 30 ml/min. When the oxygen-containing gas is continuously introduced into the reaction liquid, 'there is a method in which the reaction liquid is as fine as possible. Further, in the transesterification reaction, the ratio of use of the epoxy resin (I) and the alkyl (meth)acrylate (II) is not particularly limited, and the epoxy resin is used. When a (meth)acrylonyl group is introduced into all of the second-order hydroxyl groups, the molar ratio of the second-order hydroxyl group to the alkyl (meth)acrylate (II) is usually 1 or more, particularly 1·1~ The range of 100 (Morbi) is better. Further, at this time, the amount of introduction of the (meth)acryl oxime group can be controlled by adjusting the amount of the alkyl (meth) acrylate (Π) used. The transesterification reaction of the present invention can be specifically carried out by the following method. That is, a method is as follows: first, a predetermined amount of the epoxy resin (I) and the alkyl (meth)acrylate (II) are added to a reactor equipped with a thermometer, a stirrer, a fractionation tube, and a dry air introduction tube. Then, a suitable amount of the polystannoxane-based catalyst (III) and the polymerization inhibitor are added to the reaction mixture, and the mixture is heated to the reflux temperature of the reaction system in the above-mentioned appropriate temperature range while stirring. Here, while stirring the reaction mixture, in order to complete the reaction, the alcohol produced by the transesterification reaction in the reaction and the excess (meth)acrylic acid 200813107 alkyl ester (II) or a reaction solvent are used as an azeotrope, from fractionation. Tube removal is preferred. Further, in order to suppress polymerization, it is preferred to carry out the reaction while adding the alkyl (meth)acrylate (Π) to the system. After the reaction is completed, the reaction liquid can be supplied to the next process for water extraction in the form of a crude reaction product, and the excess raw material (alkyl) (meth) acrylate (II) or the reaction solvent can also be removed from the reactor. After distilling off, the residue was used as a crude reaction product. Or, after the excess raw material (methyl) acrylic acid ester (11) or the reaction solvent is saturated from the reactor, a small amount of inert solvent such as toluene or heptane is added as a crude reaction product. . The target compound can be obtained by extracting the above-obtained crude reaction product using water and isolating the product-containing (meth)acryl-based compound from the organic layer. The method of segregation is preferably a method of distilling off the organic solution. In this case, in order to suppress the polymerization reaction of the product, it is usually preferred to add a polymerization inhibitor under reduced pressure. In this case, it is preferably carried out in an inert gas atmosphere having an oxygen content of 5 to 13% by volume. . Any of the foregoing may be used as the polymerization inhibitor to be used, and from the viewpoint of non-denaturing coloration, p-methoxyphenol is particularly preferred. The amount of the (meth)acrylonitrile-containing compound to be obtained is also preferably from 5 to 5,000 ppm, preferably from 50 to 2,500 ppm, based on the solution constituting the organic layer. As described above, according to the production method of the present invention, the (meth)acryl fluorenyl group can be introduced into the hydroxyl group of the epoxy resin having a secondary hydroxyl group efficiently and easily. In this case, when an epoxy group-containing epoxy resin is used as a raw material, a compound having an epoxy group and a (meth)acryl fluorenyl group can be obtained by a one-stage reaction, and it is highly useful in the industry of 32-200813107. . [Examples] Hereinafter, the present invention will be described in more detail by way of examples. However, the present invention is not limited to the following embodiments, and for example, constituent elements of the respective embodiments may be appropriately formed. Also, if not notified in advance, "%" means "Quality%". Synthesis Example 1 (Synthesis of a catalytic tristannoxane compound) A reaction vessel equipped with a stirrer, a thermometer, and a dropping funnel was charged with 16.48 g (75 mmol) of dichlorodimethyltin, K0 ml of water, and 45. Ethanol in milliliters, stir well to dissolve. Next, 10 g (1 0 0 mmol) of triethylamine was stirred and added dropwise from the dropping funnel. At this time, the reaction vessel was bathed in a water bath to maintain the contents at about 20 °C. After the completion of the dropwise addition, the mixture was further stirred at the same temperature for 3 hours. After the completion of the reaction, the white precipitate was filtered, washed with 1 ml of water and then 200 ml of ethanol, and then dried under reduced pressure at 1 〇 5 ° C to obtain 12.6 g of a white powder. Elemental analysis (BARIO EL manufactured by ELEMENTAL Co., Ltd.) showed that the tin was 64 〇/〇 and the chlorine was 13.0%, which is a theoretical 値 (tin) of hexamethylene-1·5-dichlorostannoxane shown by the following structural formula. 6 4.8%, chlorine 12.9%) The measurement error range (0.3%) is consistent. [Chemical Formula 17] ch3 ch3 ch3

Cl—Sn—ο—Sn—〇—Sn—Cl ch3 ch3 ^h3 Example 1 Transesterification of Bisphenol A Type Epoxy Resin (Synthesis of Acrylate) -33 - 200813107 With Mixer, Air Inlet, Thermometer In a reaction flask of a fractionation column, 10.0 g of bisphenol A type epoxy resin EPICLONAM-040-P (manufactured by Otsuka Ink Chemical Industry Co., Ltd., mass average molecular weight Mn = 2000, converted by styrene of GPC), 120.0 g of ethyl acrylate, 〇·6 g of the catalyst, the stannous oxyalkane compound obtained in the above-mentioned synthesis example, and 1.2 g of the polymerization inhibitor p-p-methoxyphenol were introduced into the air while the reaction was started. The ethanol produced at the reaction temperature of 9 5 to 9 8 ° C was refluxed while being mixed with a solution of ethyl acrylate, and the reaction was carried out for 24 hours. After completion of the reaction, excess ethyl acrylate was removed by distillation under reduced pressure, and a small amount of toluene was added to the residue, followed by distillation under reduced pressure to remove excess ethyl acrylate. The reaction mixture remaining by distillation under reduced pressure was added to a methanol solution of 300 ml, and the resulting white solid was separated. After dissolving the white solid in chloroform, it was again added to a methanol solution of 300 ml, and the white solid was separated. Then, it was dried under reduced pressure at 40 ° C to obtain 11.6 g of the target bisphenol A as the main skeleton of the following structural formula [Chemical Formula 18]

The linear (meth)acryl fluorenyl compound is shown. The obtained compound was measured for iH-NMR (manufactured by JEOL Ltd., AL3 00, 300 MHz, solvent CDC13), and the epoxy resin raw material and the product before and after the transesterification reaction were compared at -6.80 to 7.18 ppm- 34- 200813107 The integral ratio of aromatic hydrogen, propylene sulfhydryl hydrogen at 5.83 to 6.44 ppm, and epoxy hydrogen at 2.90 and 3.3 ppm, confirming that the introduction rate of propylene sulfhydryl groups introduced into the epoxy group is 99 moles. Above the ear %, the residual ratio of the oxy group is about 90% by mole. Further, the average enthalpy of t in the above structural formula was about 5.7, and the number of the obtained compounds was 2,300 on average, and the number of propylene groups per molecule was 5.7. Example 2 Transesterification of Bisphenol A Type Epoxy Resin (Synthesis of Methyl Ester) In Example 1, except that 120.0 g of ethyl acrylate was changed, Methyl methacrylate was changed at 1 〇〇 1 1 In the same manner as in Example 1, except that the mixed solution of ethanol and ethyl methacrylate was refluxed, the composition of the target bisphenol A as a main skeleton was obtained in the same manner. [Chemical Formula 19] 2.74 > Resin 2 terminal ring The number of repeating numbers is generated by acrylic r 135.0 and the following knot is implemented

H2c-o

A linear methacryl-containing mercapto compound is shown. The obtained compound was subjected to measurement by iH-NMR measurement. The product of the epoxy resin raw material and the product before and after the transesterification reaction was compared. The 99 mol% of the methyl methacrylate group introduced into the epoxy group 2 hydroxy group was confirmed. As described above, the residual ratio of the terminal epoxy group is about 87 moles, and the average number of repetitions t in the above structural formula is about 5.7, and the obtained ratio of h is obtained by the ratio. Further, the compound has a number average molecular weight of 2,380, and the number of methacryloyl groups per molecule is 5.7. Example 3 (3-1) Synthesis of xanthene-stranded biphenyl copolymerized epoxy resin 1. 15.55 g of the synthesized according to Examples 3 and 4 of JP-A-2000-203 1 3 3 3 Xanthene skeleton epoxy resin, 2.38 g (8 mmol) of diepoxypropylhydroxybiphenyl, 6.0 g (32 mmol) of 4,4'-dihydroxybiphenyl, and 0.106 g (0.2 mmol) A solution of ethyltriphenylvinylidene acetate in 70% methanol was added to 24.63 g of N,N-dimethylacetamide, and the mixture was heated and stirred at 130 ° C for 4 hours under a nitrogen atmosphere. After allowing to cool, it was diluted with 14.9 g of hydrazine, hydrazine-dimethylacetamide, and added dropwise to ice. The white precipitate was separated by suction filtration, and after washing with ice water, the precipitate was vigorously stirred in 2 liters of water and boiled for 3 minutes. After allowing to cool, the solid component obtained by decantation was pulverized and pulverized. Further, after washing with methanol, it was dried under reduced pressure at 60 ° C to obtain 23.3 g of xanthene-extended biphenyl copolymerized epoxy resin in a yield of 95%. (3-2) Transesterification reaction of xanthene-extended biphenyl copolymerized epoxy resin In Example 1, except that 14.0 g of the obtained xanthene-extended biphenyl copolymerized epoxy resin was used instead of 10.0 In the same manner as the transesterification reaction of Example 1, except for the Epiclon AM-040-P, the following structural formula in which a target xanthene-stranded biphenyl copolymerization type epoxy resin was used as a main skeleton and an acrylonitrile group was introduced was obtained. [Chemical Formula 20]

200813107 (wherein, the above structural formula uses a structural unit having an acrylonitrile group, and the xanthene skeleton and the extended biphenyl skeleton are bonded, and both ends of the structural unit may be bonded to the same skeleton. The epoxy propyl group at the molecular end may be Any one of the xanthene skeleton or the biphenyl skeleton may be the same or different at both ends. Also, since the xenon-containing skeleton epoxy resin used as a raw material has a repeating unit, the xanthene skeleton is also used by In the portion in which the epichlorohydrin residue is bonded, a linear acryl-containing fluorenyl compound is introduced into the second-order hydroxyl group of the epichlorohydrin residue portion, and the propylene fluorenyl group is introduced in the present formula. The results of iH-NMR measurement of the obtained compound in the same manner as in Example 1 were compared by comparing the epoxy resin raw materials before and after the transesterification reaction with the aromatic hydrogen, acrylonitrile hydrogen and epoxy hydrogen in the product. In the integral ratio, it was confirmed that the introduction ratio of the acrylonitrile group introduced into the hydroxyl group of the epoxy resin is 99 mol% or more, and the residual ratio of the terminal epoxy group is about 87 mol%. Further, the obtained compound had a number average molecular weight of 3,400 and a number of propylene groups per molecule of 8. Example 4 (4-1) Synthesis of xanthene-extended biphenyl copolymerized epoxy resin 2 According to Examples 3 and 4 of JP-A No. 2 00 3 -20 1 3 3 3, 1〇·2 Gb-containing skeleton epoxy resin, 2.6 g (14 mmol) 4,4'-dihydroxybiphenyl, 26.2 mg (0.1 mmol) triphenyl rust, and 13.4 g bismuth, fluorene-dimethyl In the acetamide, the mixture was heated and stirred at 130 ° C under a nitrogen atmosphere for 6 hours. After allowing to cool, the reaction solution was diluted with N,N-dimethylacetamide to a nonvolatile content of 15%, and added dropwise to 1 liter of water, and the obtained white turbid dispersion -37 - 200813107 was stirred at room temperature. hour. After centrifugation, the sinking source obtained by suction filtration was washed with methanol, and then dried under reduced pressure at 60 ° C to obtain 10.33 g of xanthene-extended benzene conjugated epoxy resin in a yield of 81%. (4-2) Transesterification reaction of xanthene-extended biphenyl copolymerized epoxy resin In Example 1 'In addition to using 9.7 g of the above-obtained xanthene-extended biphenyl copolymerized epoxy resin instead of 10.0 g EPICLON AM In the same manner as the transesterification reaction of the epoxy resin of Example 1, except that -040-P, the target xanthene-stranded biphenyl copolymerized epoxy resin was used as the main skeleton, and the following was introduced. Structural formula [Chemical Formula 21]

(Where, since the xenon-containing skeleton epoxy resin used as the raw material has a repeating unit, the xanthene skeleton also has a portion linked by epichlorohydrin residues in the part of the epichlorohydrin residue portion 2 The hydroxy group is also introduced with a propyl sulfonium group, and the linear propylene-containing fluorenyl compound shown in the present formula is omitted. The obtained compound was measured for iH-NMR in the same manner as in Example 1, and the epoxy resin raw material before and after the transesterification reaction was compared with the integral ratio of aromatic hydrogen and acrylonitrile hydrogen in the product to confirm the epoxy resin. The introduction ratio of the propylene fluorenyl group introduced into the hydroxyl group of the resin is two mol% or more. Further, the obtained compound had a number average molecular weight of 205 0 and a number of propylene groups per one molecule of 4. -38 - 200813107 Example 5 (5-1) Synthesis of xanthene-bisphenol A copolymerized epoxy resin In Example 3-1, except that it will be based on the special opening 20 0 3 - 2 0 1 3 3 3 1 5 · 5 5 g of xanthene-containing skeleton epoxy resin synthesized in Examples 3 and 4, 2 · 38 g (8 mmol) of diepoxypropyl hydroxybiphenyl, 6_0 g (32 mmol) 4,4'-dihydroxybiphenyl was changed in the same manner as in the synthesis of the epoxy resin of Example 3-1 except that it was changed to 19.44 g of a xanthene-containing skeleton epoxy resin and 7.8 g of bisphenol A (32 mmol). To obtain a xanthene-bisphenol A copolymerized epoxy resin. The yield of the obtained xanthene-bisphenol A copolymerized epoxy resin was 25.9 g, and the yield was 9 7% ° (5-2). The transesterification reaction of the xanthene-bisphenol A copolymerized epoxy resin was Example 1 was carried out in the same manner as in the transesterification reaction of Example 1 except that 10.3 g of xanthene-bisphenol A copolymerized epoxy resin was used instead of 1 〇. Ecklon AM-040-P. a ton-bisphenol A copolymerized epoxy resin as a main skeleton, and the following structural formula in which an acrylonitrile group is introduced [Chemical Formula 22]

(Where, since the xenon-containing skeleton epoxy resin used as the raw material has a repeating unit, the xanthene skeleton also has a portion joined by an epichlorohydrin residue, and in the epichlorohydrin residue portion 2 The hydroxy group is also introduced with an acryl fluorenyl group, and the linear propylene-containing fluorenyl compound shown in the above formula is omitted. -39 - 200813107 The obtained compound was measured for 1 Η-NM R in the same manner as in Example 1, and the integral of the epoxy resin raw material before and after the transesterification reaction and the aromatic hydrogen and acrylonitrile hydrogen in the product were compared. The ratio of the introduction rate of the acrylonitrile group introduced into the hydroxyl group of the epoxy resin to the second stage was 99 mol% or more, and the residual ratio of the terminal epoxy group was about 85 mol%. Further, the number average molecular weight of the obtained compound was 3,750, and the number of acrylonitrile groups per molecule was 8. Example 6 (6-1) xanthene-biphenyl-extension neopentane copolymerization type epoxy resin was synthesized in Example 3-1 except that 2.38 g (8 mmol) of 4,4'-diepoxy was used. The propyl hydroxybiphenyl was changed to 1.73 g (8 mmol) of neopentyl diol diglycidyl ether, and the same procedure as in the synthesis of the epoxy resin of Example 3-1 was carried out to obtain xanthene-biphenyl. - a neopentane copolymerized epoxy resin. The yield of the obtained ton-ton-biphenyl-nepentane copolymerized epoxy resin was 22.8 g, and the yield was 95%. (6-2) Transesterification reaction of xanthene-biphenyl-extension neopentane copolymerized epoxy resin In Example 1, except that the above-mentioned synthesized 8.6 g x-ton-biphenyl-extension pentane was used. The copolymerized epoxy resin was used in the same manner as the transesterification reaction of Example 1 except for the oxime EPICLON A Μ - 0 4 0 - oxime to obtain a target xanthene-bisphenol oxime copolymerized epoxy resin. As the main skeleton, the following structural formula in which a propylene group is introduced is introduced [Chemical Formula 23]

200813107 (wherein the above structural formula uses a structural unit having an acrylonitrile group to link a xanthene skeleton and a neopentane skeleton, and both ends of the structural unit may be bonded to the same skeleton. The epoxy hydroxy group at the molecular end may be linked to Any one of the xanthene skeleton or the neopentane skeleton may be the same or different at both ends. Also, since the xenon-containing skeleton epoxy resin used as a raw material has a repeating unit, the skeleton of the xanthene skeleton is also used. In the portion in which the chlorohydrin residue is bonded, a propylene group is introduced into the second-order hydroxyl group of the epichlorohydrin residue portion, and the linear propylene-containing fluorenyl compound shown in the present formula is omitted. The obtained compound was measured for 1 H-NMR in the same manner as in Example 1, and the integral ratio of the epoxy resin raw material before and after the transesterification reaction to the aromatic hydrogen and acrylonitrile hydrogen in the product was confirmed. The introduction ratio of the propylene group introduced into the hydroxyl group of the oxygen resin is 99 mol% or more, and the residual ratio of the terminal epoxy group is about 90 mol%. Further, the number average molecular weight of the obtained compound was 3,340, and the number of acrylonitrile groups per molecule was 8. Example 7 (7-1) xanthene-biphenyl-hydrogenated bisphenolphthalein copolymerized epoxy resin was synthesized in Example 3-1 except that 2·38 g (8 mmol) 4,4'-two The epoxypropyl hydroxybiphenyl was changed to 2.82 g (8 mmol) of hydrogenated bisphenol A (hereinafter abbreviated as hydrogenated BPA) diglycidyl ether, and the same procedure as in the synthesis of the epoxy resin of Example 3 was carried out. To obtain a xanthene-biphenyl-hydrogenated BPA copolymerized epoxy resin. The yield of the obtained bismuth-linked-gasified BPA copolymerized epoxy resin was 24.2 g, and the yield was 96%. -2) Transesterification of xanthene-biphenyl-hydrogenated biguanide A copolymerized epoxy resin -41 - 200813107 The reaction was carried out in Example 1, except that the above-mentioned 9-8 g xanthene-biphenyl-hydrogenation was used. In the same manner as the transesterification reaction of Example 1, except that 10.0 g of EPICLON AM-040-oxime was used instead of 10.0 g of EPICLON AM-040-oxime, the target xanthene-biphenyl-hydrogenated bisphenol A copolymerized epoxy resin was obtained. The main skeleton, the following structural formula in which an acrylonitrile group is introduced [Chemical Formula 24]

(The above structural formula uses a structural unit having an acrylonitrile group to bond a xanthene skeleton and a hydrogenated BPA skeleton, and both ends of the structural unit may be bonded to the same skeleton. The epoxy propyl group at the molecular end may be bonded to the xanthene Any of the skeleton or hydrogenated BPA skeleton may be the same or different at both ends. Also, since the xanthene-containing skeleton epoxy resin used as a raw material has a repeating unit, the xanthene skeleton is also depleted by epichlorohydrin. In the portion in which the group is bonded, a linear acryl-containing fluorenyl compound is introduced into the second-order hydroxyl group of the epichlorohydrin residue portion, and the propylene group is introduced in the present formula. The obtained compound was measured for 1 H-NMR in the same manner as in Example 1, and the integral ratio of the epoxy resin raw material before and after the transesterification reaction to the aromatic hydrogen and acrylonitrile hydrogen in the product was confirmed. The introduction ratio of the propylene group introduced into the hydroxyl group of the oxygen resin is 99 mol% or more, and the residual ratio of the terminal epoxy group is about 89 mol%. Further, the number of the obtained compounds was -42 - 200813107, and the average molecular weight was 3,450, and the number of acryl groups per molecule was 8. Example 8 Partial ring opening of an epoxy group (8-1) The synthesis of a biphenyl-modified bisphenol A type epoxy resin gave 18.7 g (20 meq) of £1 (:1^€^八1^040- ?, 1.28 g (7.5 mmol) of 4-phenylphenol, 0.26 ml (0.12 mol%) of 65% ethyltriphenyl iron acetate solution, and 50 ml of N,N-dimethylacetamide, The mixture was reacted for 6 hours at 1,200 ° C under a nitrogen atmosphere, and after cooling, it was added dropwise to 150 ml of water, and the obtained precipitate was washed twice with methanol, and then dried under reduced pressure at 60 ° C to obtain Biphenyl modified bisphenol bisphenol A epoxy resin. 1H-NMR measurement, by comparing the epoxy resin raw materials before and after the reaction with the aromatic hydrogen of the product bisphenol A and methyl hydrogen and epoxy hydrogen The integral ratio was confirmed to be about 5 4 mol% of the terminal epoxy group. The yield of the obtained compound was 19.9 g, and the yield was 1%. The obtained compound was measured 1H-NMR (Japan Electronics Co., Ltd.) The results of the company system, AL3 00, and 300 MHz) are as follows. The results of W-NMR (CDC13) are as follows: (5 (ppm): 7.55 to 6.75 (m), 4.4 0 to 3 · 9 0 (m), 3 · 3 3 (m), 2.89 (m ), 2.73 (m), 1.62 (s) (8-2) The transesterification reaction of biphenyl-modified bisphenol A epoxy resin is carried out in a reaction flask equipped with a stirrer, an air introduction tube, a thermometer, and a fractionation column. 12.0 g of the tristannoxane compound obtained in the above-mentioned Synthesis Example 1 of the biphenyl-modified bisphenol A type epoxy resin synthesized in the above (8-1), 12 0.0 g of ethyl acrylate, and 0.6 g of a catalyst, 1.2 g of a polymerization inhibitor of p-methoxyphenol, the reaction is started while introducing air. The reaction temperature at 95 to 98 ° C is -43 - 200813107, and the ethanol formed by the fractionation column is used, and mixed with ethyl acrylate. After the completion of the reaction, the excess ethyl acrylate was removed by distillation under reduced pressure, and a small amount of toluene was added to the residue, followed by distillation under reduced pressure to remove excess ethyl acrylate. The reaction mixture remaining by distillation under reduced pressure was added to a methanol solution of 300 ml, and the resulting white solid was separated. The white solid was dissolved in chloroform and then added to a methanol solution of 300 ml. In the separation, sink again The white solid matter was then dried under reduced pressure at 40 ° C to obtain 12.1 g of the following structural formula of a bisphenol A type epoxy resin having a ring-opening ring of one of the targets as a main skeleton [Chemical Formula 25]

The linear propylene-containing compound is shown to be linear. The obtained compound was subjected to 1H-NMR measurement, and the epoxy resin raw material and the product before and after the transesterification reaction were compared at 6.80 to 7.18 ppm of aromatic hydrogen, 5.83 to 6.44 ppm of acrylonitrile hydrogen, and In the integral ratio of the epoxy groups of 2.74, 2.90, and 3.33 ppm, it was confirmed that the introduction ratio of the propylene group introduced into the hydroxyl group of the epoxy resin was 99 mol% or more, and the residual ratio of the terminal epoxy group was About 5 2 mol%. Further, the obtained compound had an average molecular weight of 2,500 and the number of propylene groups per molecule was 6.7. Example 9 Introduction of a part of propylene sulfhydryl group -44- 200813107 (Transesterification reaction of epoxy resin) 9.3 g (10 meq) EPICLON AM-040-P, 100.0 g of ethyl acrylate, 0.5 g of catalyst was added. The p-stannoxane compound of the synthesis example 1 and the p-methoxy phenol of the 1 gram polymerization inhibitor were introduced into the air to start the reaction. Will be at 9 5~9 8. (The reaction temperature is the same as that of the ethyl acrylate, and the reaction is carried out by refluxing with a mixed solution of ethyl acrylate, and the amount of the ethanol is checked, and the reaction is carried out for about 6 hours, and the amount of the ethanol is 0. After completion of the reaction, the excess ethyl acrylate was removed by distillation under reduced pressure, and a small amount of toluene was added to the residue, followed by distillation under reduced pressure to remove excess ethyl acrylate. The reaction mixture remaining in the distillation was added to 300 ml of a methanol solution, and the resulting white solid was separated. The white solid was dissolved in chloroform, and then added again to 300 ml of a methanol solution, and separated again to precipitate. The white solid matter was then dried under reduced pressure at 40 ° C to obtain 11.1 g of the following structural formula in which a part of the hydroxyl group of the bisphenol A type epoxy resin was introduced with an acrylonitrile group [Chemical Formula 26]

(wherein the linear structural propylene-containing compound represented by the structural unit having an acryl fluorenyl group in the above structural formula and the structural unit having a hydroxyl group is bonded unnecessarily). -45 - 200813107 The results of the measurement of 1 Η - in the same manner as in Example 1 were carried out, and the epoxy resin raw materials and materials before and after the transesterification reaction were compared at 6.80 to 7.18 ppm of aromatic hydrogen at 5.83~. 6.44 ppm of olefinic hydrogen and the formation of 2.47, 2.90, and 3.33 ppm of epoxy hydrogen, and the introduction rate of the acryl fluorenyl group introduced into the epoxy group 2 grade hydroxyl group was confirmed to be ear %, and the residual ratio of the terminal epoxy group was It is about 9 5 mol%. Further, the obtained compound had a number average molecular weight of 2,150 and a number of propylene oximes per molecule of 3.1. Example 1 Partially ring-opening of an anthracene epoxy group and a part of an acryloyl group (transesterification reaction of an epoxy resin) In a reverse bottle equipped with a stirrer, an air introduction tube, a thermometer, and a fractionation column, 1 2 · 0 g was added. The tristannoxane compound obtained in the first example before the synthesis of the side chain biphenyl modified type A epoxy resin, 100.0 g of ethyl acrylate, and 5 g of the catalyst, and 1.0 g of the polymerization inhibitor obtained in the above Example 8. The methoxy phenol starts to react while introducing air. The ethanol produced by the fractionation column was used at a temperature of 95 to 98 ° C, and the reaction was confirmed while removing the ethanol. When the reaction was carried out for about 6 hours, the amount of deethanolation was 〇. 7 6 g The reaction was completed. After completion of the reaction, excess ethyl acrylate was added to the residue by vacuum distillation to remove a small amount of toluene, followed by distillation under reduced pressure to remove ethyl acrylate. The reaction mixture remaining by distillation under reduced pressure was added to a methanol solution of 300, and the resulting white solid was separated. After dissolving the white matter in chloroform, it was again added to a methanol solution of 300 ml of MeOH to produce a ratio of propylene h, and the introduction of 55 gram of the base should be burned to the opposite amount of the bisphenol, so that t was , excess milliliters of solid, sub-46-200813107 from the white solids again precipitated. Then by at 40. (: Drying under reduced pressure was carried out to obtain 13.7 g of the following structural formula in which a part of the bisphenol A type epoxy resin was introduced with an acrylonitrile group [Chemical Formula 27]

(wherein the linear structural propylene-containing compound represented by the structural unit having an acryl fluorenyl group in the above structural formula and the structural unit having a hydroxyl group is bonded unnecessarily). The obtained compound was subjected to measurement of 1 H-NMR in the same manner as in Example 1, and the epoxy resin raw material and the product before and after the transesterification reaction were compared at 6.80 to 7.18 ppm of aromatic hydrogen at 5.83 to 6.44 ppm. The integral ratio of the acrylonitrile hydrogen and the epoxy hydrogen at 2.74, 2.90, and 3.33 ppm was confirmed to be 57 mol% in the introduction of the propylene group introduced into the hydroxyl group of the epoxy resin, and the terminal epoxy group was The residual ratio is about 5 1 mol%. Further, the obtained compound had a number average molecular weight of 2,300 and a number of propylene groups per molecule of 3.1. Example 1 Synthesis of 1 (1 1 -1) biphenyl-modified bisphenol A epoxy resin 18.7 g (20 meq) EPICLON AM-040-P, 4.1 g (24 -47-200813107 mmol) 4-phenylphenol, 0.26 ml (0.12 mol%) of 65% ethyltriphenylselenyl acetate solution, and 50 ml of N,N-dimethylacetamide under nitrogen at 1 20 ° C reacted for 6 hours. After allowing to cool, it was added dropwise to 150 ml of water, and the obtained precipitate was washed twice with methanol, and then dried under reduced pressure at 60 ° C to obtain a biphenyl-modified bisphenol bisphenol A type epoxy resin. The yield of the obtained compound was 22.1 g, and the yield was 100%. The obtained compound was measured for 1H-NMR (manufactured by JEOL Ltd., AL300, 300 MHz), and the results of "H-NMR (CDC13) were as follows: δ (ppm): 7.55 to 6.75 (m) 4.40~3.90(m), 3.33(m), 1.62(s) (11-2) The transesterification reaction of biphenyl-modified bisphenol A epoxy resin is provided with a stirrer, an air introduction tube, a thermometer, and a fractionation column. In the reaction flask, 12.0 g of the triphenyl tin obtained by the above-mentioned (1 1 - 1 ) biphenyl-modified bisphenol A type epoxy resin, 120.0 g of ethyl acrylate, and 0.6 g of the catalyst of the above Synthesis Example 1 was added. The oxane compound and 1.2 g of a polymerization inhibitor of p-methoxyphenol were reacted while introducing air. The ethanol produced at a reaction temperature of 9 5 to 9 8 t was refluxed while being mixed with a solution of ethyl acrylate, and reacted for 24 hours. After completion of the reaction, excess ethyl acrylate was removed by distillation under reduced pressure, and a small amount of toluene was added to the residue, followed by distillation under reduced pressure to remove excess ethyl acrylate. The reaction mixture remaining by distillation under reduced pressure was added to 300 ml of a methanol solution, and the resulting white solid was separated. After dissolving the white solid -48-200813107 in chloroform, it was again added to a methanol solution of 300 ml, and the white solid which precipitated again was separated. Then, it was dried under reduced pressure at 40 ° C to obtain 13.6 g of the following biphenyl-modified bisphenol A type epoxy resin as a main skeleton, and the following structural formula in which an acrylonitrile group was introduced [Chemical Formula 28]

It does not contain a linear compound. In the same manner as in Example 1, the obtained compound was subjected to measurement of iH-NMR, and the epoxy resin raw material and the product before and after the transesterification reaction were compared at 6.80 to 7.18 ppm of aromatic hydrogen at 5.83 to 6.44 ppm. The integral ratio of propylene sulfhydryl hydrogen was confirmed to be 9 9 mol% in the introduction ratio of the acryl fluorenyl group introduced into the hydroxyl group of the epoxy resin. Further, the obtained compound had an average molecular weight of 2,750 and the number of acrylonitrile groups per molecule was 7.7. Example 1 2 Transesterification of a polystannoxane catalyst formed in the system In Example 11-2, except that 0.6 g of dimethyltin dichloride and 0.3 g of sodium methoxide were used instead of ruthenium. 6 g of Synthesis Example 1 The transesterification reaction of the biphenyl-modified bisphenol A type epoxy resin of the above-mentioned Example (11-2) was carried out in the same manner as the obtained tristannoxane to obtain a biphenyl-modified bisphenol A type epoxy. A linear propylene-containing fluorenyl compound represented by the above structural formula in which a resin is a main skeleton and an acrylonitrile group is introduced. In the same manner as in Example 1, the obtained compound was subjected to measurement of iH-NMR, and the epoxy resin raw material before and after the transesterification reaction was compared with the formation of -49-200813107 at 6.80 to 7.18 ppm of aromatic hydrogen, at 5 The integral ratio of propylenesulfonyl hydrogen of 8 3 to 6.44 ppm was confirmed to be the same as that of the compound obtained in the above Example (丨2). Example 1 Synthesis of 3 (1 3 · 1) epoxy resin containing biphenyl modified xanthene skeleton 9.7 2 g of the xanthene-biphenyl copolymerized epoxy resin obtained in Example 3-1, 4 1 g (24 mmol) of 4-phenylphenol, 26.2 mg (0.1 mmol) of triphenyl iron, and 50 ml of hydrazine, hydrazine-dimethylacetamide in a nitrogen atmosphere 'at 1 The mixture was stirred under heating at 30 ° C for 6 hours. After cooling, it was added dropwise to 100 ml of water, and the precipitate was washed twice with methanol, and then dried under reduced pressure at 6 ° C to obtain an epoxy resin containing a biphenyl-modified xanthene skeleton. The yield was 13.2 grams, yield 99%. The epoxy resin containing the biphenyl-modified xanthene skeleton was measured by j-NMR (manufactured by JEOL Ltd., AL300, 300 MHz), and the results of W-NMR (CDC13) measurement were as follows: 5 ( Ppm): 7.54 to 7.00 (m), 5.21 (s), 4.35 to 3.80 (m), 2·40 to 2.08 (m) (1 3 -2) ester of epoxy resin containing biphenyl modified xanthene skeleton The exchange reaction was carried out in Example 11-2 except that 9.7 g of the epoxy resin containing the biphenyl-modified xanthene skeleton synthesized in the above (13-1) was used instead of 1 2.0 g of the biphenyl-modified bisphenol A type epoxy resin. In the same manner as the transesterification reaction of the epoxy resin of Example 11, the epoxy resin having the target biphenyl-modified xanthene skeleton was used as the main skeleton, and the following structural formula in which the acrylonitrile group was introduced was carried out -50-200813107 [Chemical Formula 2 9 ]

(Which 'because the xenon-containing skeleton epoxy resin used as a raw material has a repeating unit', the portion of the xanthene skeleton is also linked by an epichlorohydrin residue, in the part of the epichlorohydrin residue. The hydroxy group is also introduced with an acryl fluorenyl group, and the linear propylene-containing fluorenyl compound shown in the above formula is omitted. The obtained compound was measured for 1 H-NMR in the same manner as in Example 1, and the integral ratio of the epoxy resin raw material before and after the transesterification reaction to the aromatic hydrogen and acrylonitrile hydrogen in the product was confirmed. The introduction ratio of the propylene group introduced into the hydroxyl group of the oxygen resin is 9 9 mol% or more. Further, the obtained compound had a number average molecular weight of 2,500, and the number of propylene groups per molecule was 6. Example 1 Synthesis of an epoxy resin containing a bisphenol A-biphenyl modified xanthene skeleton in Example 13 except that 9·8 g of xanthene synthesized according to Example 5-1 was used. - bisphenol A copolymerized epoxy resin was used in the same manner as in the synthesis of the epoxy resin of Example 13-1 except that 9.72 g of the xanthene-biphenyl copolymerized epoxy resin synthesized in accordance with Example 3-1 was used. The yield of the epoxy resin containing bisphenol A-biphenyl modified 咕200813107 ton skeleton was 13.3 g, and the yield was 97%. The results of 1H-NMR (AL300, 300 MHz, manufactured by Nippon Denshi Co., Ltd.) of the epoxy resin containing the diacid-containing A-biphenyl-modified xanthene skeleton were measured as follows, and h-NMR (CDC13) was measured. Results: δ (ppm): 7.54 to 6.60 (m), 5.21 (s), 4.35 to 3.80 (m), 2.40 to 2.08 (m), 1.62 (s) (14-2) containing bisphenol A - The transesterification reaction of the epoxy resin of the biphenyl modified xanthene skeleton is carried out in Example 10 except that the bisphenol A-biphenyl modified xanthene skeleton synthesized by the above (i 4 - 1) is used. An epoxy resin was used in the same manner as the transesterification reaction of the epoxy resin of Example 1 except that 12.0 g of a biphenyl-modified bisphenol A type epoxy resin was used, and the target bisphenol A-biphenyl modified oxime was obtained. The epoxy resin of the ton skeleton is used as the main skeleton, and the following structural formula in which an acrylonitrile group is introduced [Chemical Formula 30]

(Where, since the xenon-containing skeleton epoxy resin used as the raw material has a repeating unit, the xanthene skeleton also has a portion joined by an epichlorohydrin residue, and in the epichlorohydrin residue portion 2 The hydroxy group is also introduced with an acrylonitrile group, and -52-200813107 omits the linear propylene-containing fluorenyl compound shown in the present formula. The obtained compound was measured for 1 H-NMR in the same manner as in Example 1, and the integral ratio of the epoxy resin raw material before and after the transesterification reaction to the aromatic hydrogen and acrylonitrile hydrogen in the product was confirmed. The introduction ratio of the propylene group introduced into the hydroxyl group of the oxygen resin is 99 mol% or more. Further, the obtained compound had a number average molecular weight of 4,200 and the number of propylene groups per molecule was 1 Å. Example 1 Synthesis of 5 (1 5 -1 ) biphenyl-containing tetraphenolethane-type epoxy resin 9.8 g (50 meq, epoxy equivalent 196) JAPAN EPOXY RESIN AG, trade name jER1031S [tetraphenol Ethyl type epoxy resin], 11.9 g (70 mmol) of 4-phenylphenol, 0.21 ml (0.1 mol%) of 65% ethyl acetate triphenyl iron ethanol solution, and 40 ml of hydrazine, hydrazine -Dimethylacetamide was reacted at 160 ° C for 4 hours under a nitrogen atmosphere. After allowing to cool, it was added dropwise to 1 〇 ml of water, and the obtained precipitate was washed twice with methanol, and then dried under reduced pressure at 70 ° C to obtain a biphenyl-modified tetraphenol-ethane-type epoxy resin. The yield of the obtained product was 17.6 g, and the yield was 96%. (15-2) Transesterification reaction of a biphenyl-modified tetraphenol ethane type epoxy resin (synthesis of acrylic acid) In Example 1, except that 1 gram of the above-mentioned (1 5 - 1 ) was used. An epoxy resin of a biphenyl-modified tetraphenol-ethane type epoxy resin was used in the same manner as the transesterification reaction of the epoxy resin of Example 1 except for 1 0.0 g of EPICLON AM-040-P, and the following were obtained. Structural Formula -53- 200813107 [Chemical Formula 31]

1 H-NMR was measured in the same manner as in Example 1, and the integral ratio of the epoxy resin raw material before and after the transesterification reaction to the aromatic hydrogen and acrylonitrile hydrogen in the product was compared. It was confirmed that the introduction ratio of the acrylonitrile group introduced into the hydroxyl group of the epoxy resin level 2 was 99 mol% or more. Further, the average enthalpy of the number of repetitions t in the above structural formula is about 2 · 0, the number average molecular weight of the obtained compound is 2,300, and the number of fluorenyl groups per molecule is 5.5. Example 16 Transesterification reaction of tetraphenol ethane type epoxy resin (synthesis of methyl acrylate) In Example 1, except that the epoxy resin system was used, 1 克. 7 g of Example 1 5 - 1 was obtained. Si-Yi-type epoxy resin, replacing 1 2 0 · 0 g of ethyl acrylate with 1 3 5 · 0 g of methyl propyl methacrylate, will be generated at a reaction temperature of 10 0 to 110 ° C The ethanol was refluxed in the same manner as in the mixed solution of ethyl methacrylate, and the same procedure as in the transesterification reaction of Example 1 was carried out to obtain the following structural formula [Chemical Formula 32] -54 - 200813107

The star type shown contains a methacryl oxime compound. The obtained compound was measured for 1 Η-NM R in the same manner as in Example 1, and the integral ratio of the epoxy resin raw material before and after the transesterification reaction to the aromatic hydrogen and methacrylonitrile hydrogen in the product was compared. It was confirmed that the introduction ratio of the methacrylinyl group introduced into the hydroxyl group of the epoxy resin is yy mol% or more, and the average enthalpy of the number t of repetitions in the above structural formula is about 2 · 〇, and the number of the obtained compound The average molecular weight was 2,380, and the number of methacrylamido groups per molecule was 5.5. Comparative Example In a reaction flask equipped with a stirrer, an air introduction tube, a thermometer, and a fractionation column, 5.0 g of EPICLONAM-040-P, 40 g of chloroform, 3.3 g of pyridine, and 1.2 g of a polymerization inhibitor of p-methoxyphenol were added. The reaction mixture was dissolved by stirring. Then, 1.92 g (21.2 mmol) of propylene chloride was added dropwise from the dropping funnel while stirring. At this time, after dropping using an ice bath, the mixture was further stirred at 40 ° C for 8 hours to complete the reaction. After the reaction was completed, 40 ml of chloroform was added to dilute the reaction solution. Then, it was washed with a 1 ml of a 5% aqueous solution of hydrochloric acid, a saturated aqueous solution of sodium hydrogencarbonate, and a saturated aqueous solution of sodium chloride, and dried over magnesium sulfate. The solid matter was washed with methanol for several times, and then filtered and dried under reduced pressure at 40 ° C to give a solid material of 5. 5 g. 1H-NMR measurement was carried out in the same manner as in Example 1. As a result, a small amount of epoxy hydrogen was observed in the vicinity of -55 - 200813107 2.74, 2.90, and 3.33 ppm, but it was not confirmed that propylene sulfhydryl hydrogen was in the vicinity of 5.86 to 6.44 ppm. . From this, it was found that the propylene group was not introduced into the hydroxyl group. Test Example 1 and Comparative Test Example 1 : Comparison of Curability of Radical Polymerization Using a linear propylene-containing fluorenyl compound having bisphenol A synthesized in Example 1 as a main skeleton and having an epoxy group at the end (hereinafter referred to as Compound 1) It is compared with the bisphenol A type propylene oxide modified epoxy resin diacrylate BP4PA (manufactured by Kyoeisha Chemical Co., Ltd.) by the curability of radical polymerization. [Table 1] Table 1 Preparation of radical polymerizable composition (mixing ratio/quality part) Composition 1 Comparative composition 1 Compound 1 100 BP4PA 100 Ethyl acetate 40 1-651 1 1 Footnote of Table 1 : 1-651 : Free Base polymerization catalyst, test method manufactured by CIBA GEIGY Co., Ltd.: The above composition was formed into a film on a glass slope surface using a bar coater #5. Under a cold mirror, a high-pressure mercury lamp (120 watts) was used, and polymerization was carried out by 50 mJ/time of irradiation intensity, and the number of times of irradiation of the surface of the coating film without adhesiveness was measured. -56- 200813107 [Table 2] Table 2 Hardening test composition Test Example 1 Comparative test example 1 Number of times without adhesiveness (times) 1 7 Test Example 2 and Comparative Test Example 2: Comparison of hardenability by cationic polymerization In the same manner as in the test example 1 and the comparative test example 1, the preparation of the cationically polymerizable composition of the curable property of the two types of the propylene-containing fluorenyl compound containing bisphenol A as a main skeleton by cationic polymerization (mixing ratio/quality) was carried out. Composition 1 Comparative composition 1 Compound 1 100 BP4PA 100 Ethyl acetate 40 UVI-6990 2 2 Footnote of Table 3: UVI-6990: Cationic polymerization catalyst, test method manufactured by CIBAGEIGY Co., Ltd.: Coating on a glass slope using a rod The above composition was formed into a film. Under a cold mirror, polymerization was carried out by using a metal halide lamp (80 watts) by 50 mJ/time of irradiation intensity, and the number of times of coating surface hardening without adhesiveness was measured. -57 - 200813107 [Table 4] Table 4 Hardening test composition Test example 1 Comparative test example 1 Number of times without adhesiveness (times) 2 1 〇 < (unhardened) From the above results, it was confirmed that the present invention contained The (meth)acrylonitrile compound has excellent radical hardenability and cationic hardenability. [Industrial Applicability] The linear (meth)acryl-containing fluorenyl compound of the present invention has an average of three or more (meth) acrylonitrile groups in one molecule, and the conventional bifunctional linear lock When the epoxy (meth) acrylate is compared, it has high hardenability and high sensitivity. Further, by selecting an epoxy resin as a raw material, the molecular weight of each (meth)acryl fluorenyl group [that is, the concentration of (meth) acrylonitrile group] can be easily prepared, even if it is not used in combination. Other acrylic monomers can also adjust the crosslink density of the cured product. Further, since the hydroxyl group can be left in the molecule, it is also possible to use a material such as a precise electrical use. Further, since the star-containing (meth) acrylonitrile-based compound of the present invention is multi-functional, it has excellent curability or sensitivity. Further, since the molecular weight of each (meth) propylene fluorenyl group is also large, a hard acid which is not too hard and has appropriate toughness can be obtained. Further, since the hydroxyl group can be left in the molecule, it can be used as a material for precise electrical use. Further, when the central portion of the star structure has an aromatic ring, it is also possible to impart a ^ - π stacking ability between molecules, and it is possible to improve heat resistance, corrosion resistance, mechanical strength, and the like of the cured product, and is of great industrial significance. •58- 200813107 [Simple description of the diagram and 〇 J\\\ [Component symbol description 4FH1 〇

Claims (1)

200813107 X. Patent application scope: ' 1. A linear (meth) propylene fluorenyl compound having the following formula (1) [Chemical Formula 1] /CH2, 〇/A\〇, 2 (1) [In the formula (1), the A system may also contain a divalent hydrocarbon group of a hetero atom] The structural unit represented by the following formula (2) or (3) [Chemical Formula 2] R [In the formula (3), a structure in which R is a hydrogen atom or a methyl group] is bonded to each other. [In the formula (1), A may be the same thing or may be a different substance. ], the molecular terminal is an epoxy group, or the following formula (4) [Chemical Formula 3] Η [In the formula (4), a R-based hydrogen atom or a methyl group, a fluorene-based monovalent hydrocarbon group], wherein -60 - 200813107 is a structural unit represented by the formula (3) or the formula (4) The total amount is 3 or more on average in one molecule, and the number average molecular weight is 500 to 10,000. 2. The linear (meth)acryl-containing mercapto compound according to claim 1, wherein the A in the formula (1) is selected from the group consisting of the following: [Chemical Formula 4] CH3 ch3 4ch plant ch2 -o)^ch2- ch2 - -{ch2-ch-o^ch2-ch— (In the formula, p and q are an integer of 1 to 6 and may have a C 1 to 4 alkyl group as a substituent in the ring). 3. The linear (meth)-propyl-containing fluorenyl compound according to claim 1, wherein the B-form in the formula (4) is selected from the group consisting of 'Chemical Formula 5】 -61 - 200813107 Ch3 fine 2-〇12_〇沴〇02-ch3, such as h24h-c^ch2_ch3 (In the formula, P and q are an integer of 1 to 6 and may have a carbon number of 1 to 4 alkyl groups as a substituent). 4. A linear (meth)acryl-containing fluorenyl compound according to claim 1, wherein the molecular terminal is an epoxy group. The linear (meth)acryl-containing mercapto compound according to any one of claims 1 to 4, wherein R in the formulas (3) and (4) is a hydrogen atom. 6. Star-type (meth) propylene fluorenyl compound characterized by the following general formula (5) [Chemical Formula 6] [In the formula (5), R is a hydrogen atom or a methyl group, b is a monovalent hydrocarbon group, and γ is a polyfunctional epoxy resin having an average of n epoxy groups (11 or more of which are 11 or more) from 200813107. The residue of the group, m is an integer of 3 or more (where 'n - m)], and the number average molecular weight is 800 to 1,000,000. 7. The star-type (meth)acryl-based fluorenyl compound according to item 6 of the patent application, wherein the B group in the formula (5) is selected from the group consisting of the following: [Chemical Formula 7] (wherein p and q are integers of 1 to 6 in which "the ring may have a carbon number of 1 to 4 as a substituent"), and the star type (methyl)-propyl group as in claim 6 a stilbene-based compound, wherein the oxime in the formula (5) is selected from the group consisting of 'Chemical Formula 8】 -63 - 200813107 -CH2- a ch2_o 〇~ch2- 0—CH 2 — —h〇—CH 2 — (wherein the ring may have an alkyl group having 1 to 4 carbon atoms as a substituent). 9. The star-type (meth)acryl-containing mercapto compound according to any one of claims 6 to 8, wherein R in the formula (5) is a hydrogen atom. 1 〇 a method for producing a (meth) acrylonitrile-based compound, which is characterized in that it has three or more structural formulas (6) below in one molecule, [Chemical Formula 9] The epoxy resin (I) and the alkyl (meth)acrylate (π) in the structural unit shown are subjected to a transesterification reaction in the presence of a polyoxystannane (p〇iystannoxane) catalyst (ΠΙ). When a (meth) acrylonitrile group is introduced into the hydroxyl group in the above formula (6), a compound having an average of three or more (meth) acrylonitrile groups in one molecule is obtained. 1 1 · The method for preparing a (meth) propyl-based compound according to claim 10 of the patent scope, wherein the epoxy resin (I) is a bisphenol type epoxy resin and a tetraphenol ethane type -64-200813107 An epoxy resin, an epoxy resin having a xanthene skeleton, or an epoxy resin obtained by subjecting such epoxy resins to an elongation reaction by a dihydroxy compound. 1 2 · The method for producing a (meth) acrylonitrile compound according to claim 10, wherein the epoxy resin (I) is a bisphenol epoxy resin or a tetraphenol ethane epoxy resin An epoxy resin having a xanthene skeleton or an epoxy resin obtained by subjecting the epoxy resin to an elongation reaction by a dihydroxy compound, and further modifying the epoxy group by a hydroxy compound Epoxy resin. 13. The process for producing a (meth)acrylonitrile compound according to claim 10, wherein the alkyl group of the alkyl (meth)acrylate (11) is an alkyl group having 1 to 6 carbon atoms, (Methyl) acrylonitrile-based acrylonitrile. The method for producing a (meth)acryl-based fluorenyl compound according to any one of claims 10 to 13, wherein the polystannoxane-based catalyst (III) has the following formula (7) ) the catalyst shown, [Chemical Formula 10] In the formula (7), R1 to R4 each independently represent a methyl group, an ethyl group, and an anthracene and an X2 group each independently represent an electron attracting group having an isolated electron pair on an atom bonded to a tin atom, and the r system An integer from 1 to 8]. 15. The method for producing a (meth) acrylonitrile-based compound according to claim 12, wherein a tin compound represented by the following formula (8) and a basic compound are added to the reaction system during the transesterification reaction, -65- 200813107 [Chemical Formula 1 1] R5 X3—Sn—X4 (8) [In the formula (8), R5 to R6 each independently represent a methyl group or an ethyl group, and X3 and X4 are each independently represented by a tin atom. The bonded atom has an electron attracting group of an isolated electron pair. A polystannoxane-based catalyst (ΙΠ) is formed in the system to carry out a transesterification reaction. -66- 200813107 VII. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: Μ 〇 j\ \\ 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: