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  • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
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  • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
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  • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
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Definitions

• the present invention relates to a curable resin having a specific structure, a curable resin composition containing the curable resin, and a cured product obtained from the curable resin composition.
• vinyl group-containing curable resins having various chemical structures have been conventionally proposed.
• a curable resin for example, a curable resin such as bisphenol divinylbenzyl ether or novolak polyvinylbenzyl ether has been proposed (see, for example, Patent Documents 1 and 2).
• these vinylbenzyl ethers cannot give a cured product having sufficiently small dielectric properties, and the obtained cured product has a problem in stable use in a high frequency band, and further, bisphenol divinylbenzyl ether. Was not sufficiently high in heat resistance.
• the conventional curable resin containing a vinyl group containing polyvinylbenzyl ether can withstand the low dielectric loss tangent required for electrical insulating material applications, especially for high frequency electrical insulating materials, and lead-free soldering. It did not give a cured product having both heat resistance.
• Japanese Unexamined Patent Publication No. 63-68537 Japanese Unexamined Patent Publication No. 64-65110 Special Table 1-503238 Gazette Japanese Unexamined Patent Publication No. 9-31006 Japanese Unexamined Patent Publication No. 2005-314556
• an object to be solved by the present invention is to provide a cured product having excellent heat resistance (high glass transition temperature) and low dielectric property by using a curable resin having a specific structure. ..
• the present inventors have obtained a curable resin that can contribute to heat resistance and low dielectric properties, and a curable resin composition containing the curable resin. It has been found that the obtained cured product is excellent in heat resistance and low dielectric property, and the present invention has been completed.
• the present invention is characterized by having a structural unit (1) represented by the following general formula (1) and a terminal structure (2) represented by the following general formula (2). Regarding.
• R 1 independently represents an alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group, or a cycloalkyl group
• k is 1 to 3
• R 2 independently represents a hydrogen atom or a methyl group
• X represents a (meth) acryloyloxy group, a vinylbenzyl ether group, or an allyl ether group, respectively.
• R 3 independently represents an alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group, a cycloalkyl group, or an alkenyl group.
• the above general formula (1) is preferably represented by the following general formula (1-1).
• the above general formula (2) is preferably represented by the following general formula (2-1).
• R 4 represents a hydrogen atom, a methyl group, or a phenyl group
• R 5 represents an alkyl group having 1 to 4 carbon atoms.
• the general formula (1) is represented by the following general formula (1-2), and the general formula (2) is represented by the following general formula (2-2) or (2-2-). It is preferably represented by 3).
• R 6 independently has a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group, and an aralkyl group, respectively. , Or a cycloalkyl group.
• the curable resin of the present invention preferably has a weight average molecular weight of 500 to 50,000.
• the present invention relates to a curable resin composition containing the curable resin.
• the present invention relates to a cured product obtained by subjecting the curable resin composition to a curing reaction.
• the curable resin of the present invention can contribute to heat resistance and low dielectric properties
• the cured product obtained from the curable resin composition containing the curable resin has heat resistance and low dielectric properties (particularly). Excellent in low dielectric loss tangent) and useful.
• the present invention relates to a curable resin having a structural unit (1) represented by the following general formula (1) and a terminal structure (2) represented by the following general formula (2).
• R 1 independently represents an alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group, or a cycloalkyl group, and k has 1 to 3 carbon atoms.
• R 2 independently represents a hydrogen atom or a methyl group
• X represents a (meth) acryloyloxy group, a vinylbenzyl ether group, or an allyl ether group, and the above general formula (2).
• R 3 independently represents an alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group, a cycloalkyl group, or an alkenyl group.
• the curable resin Since the curable resin has a specific structure in the terminal structure and the main chain structure, the proportion of polar functional groups in the structure of the curable resin is reduced, and the curable resin is used.
• the produced cured product is preferable because it has excellent low dielectric properties. Further, by having a cross-linking group in the curable resin, the obtained cured product has excellent heat resistance and is preferable.
• R 1 independently represents an alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group, or a cycloalkyl group, and preferably an alkyl group having 1 to 6 carbon atoms. , Aryl group, or cycloalkyl group. Since R 1 is an alkyl group having 1 to 12 carbon atoms or the like, the flatness in the vicinity of the benzene ring in the general formula (1) is lowered, and the crystallinity is lowered, so that the solvent solubility is improved and the solvent solubility is improved. The melting point is lowered, which is a preferable embodiment.
• k represents an integer of 1 to 3, preferably an integer of 1 to 2.
• R 2 is independently a hydrogen atom or a methyl group. Since R 2 is a hydrogen atom or the like, the dielectric constant is lowered, which is a preferable embodiment.
• X is a (meth) acryloyloxy group, a vinylbenzyl ether group, or an allyl ether group, preferably a (meth) acryloyloxy group, and more preferably a methacryloyloxy group.
• the crosslinking group in the curable resin a cured product having a low dielectric loss tangent can be obtained, which is a preferable embodiment.
• the methacryloyloxy group contains a methyl group in the structure of the curable resin as compared with other cross-linking groups (for example, an ether group which is a polar group such as a vinylbenzyl ether group or an allyl ether group).
• a bridging group X is also a polar group, by adjacent R 1 is a substituent, it is sterically hindered, is molecular mobility of X is inhibited, the dielectric loss tangent of the cured product obtained is low This is a preferred embodiment.
• R 3 independently represents an alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group, a cycloalkyl group, or an alkenyl group, and preferably has 1 to 10 carbon atoms. Alkyl group, aryl group, or cycloalkyl group.
• R 3 is an alkyl group having 1 to 12 carbon atoms or the like, the flatness in the vicinity of the benzene ring in the general formula (2) is lowered, and the crystallinity is lowered, so that the solvent solubility is improved and the solvent solubility is improved. The melting point is lowered, which is a preferable embodiment.
• a bridging group X is also a polar group, by which the R 3 is a substituent adjacent, becomes sterically hindered, is molecular mobility of X is inhibited, the dielectric loss tangent of the cured product obtained is low This is a preferred embodiment.
• the curable resin of the present invention is characterized by containing the above general formulas (1) and (2), has a structure in which the above structural unit (1) is repeated, and has a terminal structure based on the above general formula (2).
• a phenylethylidene skeleton (structure), an indan skeleton (structure), a dicyclopentadiene skeleton (structure) It may contain a structure (or a structural unit) such as an aralkyl group (structure) having a substituent. That is, the structural unit (1) may form a block structure, and may form a random structure together with other structural units as long as it does not affect the characteristics of the present invention.
• the phenylethylidene skeleton (structure) other than the structural unit (1) and the terminal structure (2) has a small polarity and does not have a structure that increases the dielectric constant or the dielectric loss tangent. Does not affect.
• the above general formula (1) is preferably represented by the following general formula (1-1).
• the above general formula (2) is preferably represented by the following general formula (2-1).
• R 4 is preferably represented by a hydrogen atom, a methyl group, or a phenyl group, more preferably a hydrogen atom or a methyl group
• R 5 is the number of carbon atoms. It is preferably represented by an alkyl group of 1 to 4, and more preferably an alkyl group having 1 to 2 carbon atoms.
• the dielectric loss tangent is low, which is a preferable embodiment
• the R 5 is the alkyl group or the like, the dielectric loss tangent is low, which is a preferable embodiment.
• the general formula (1) is represented by the following general formula (1-2), and the general formula (2) is represented by the following general formula (2-2) or (2-3). It is preferably represented by.
• R 6 independently has a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group, and an aralkyl group, respectively. Alternatively, it is preferably represented by a cycloalkyl group, and more preferably represented by a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group, or a cycloalkyl group. Since the R 6 is a hydrogen atom or the like, the dielectric loss tangent is lowered, which is a preferable embodiment.
• Examples of the method for producing the intermediate phenol compound include an aralkyl compound represented by the following general formula (3-1) or (3-2) (hereinafter, may be referred to as “compound (a)”) and the following general.
• a structural unit represented by the following general formula by reacting an aralkyl compound represented by the following general formula (5-1) or (5-2) hereinafter, may be referred to as “compound (d)”).
• the intermediate phenol compound having (6) and the terminal structure represented by the following general formula (7) can be obtained.
• Y in the above general formula (3-1) is preferably a halogen atom, a hydroxyl group, or an oxyalkyl group, and more preferably a hydroxyl group.
• the compound (a) include 1,2-di (chloromethyl) benzene, 1,2-di (bromomethyl) benzene, 1,3-di (chloromethyl) benzene, and 1,3-di (fluoro).
• the compound (a) may be used alone or in combination of two or more.
• the compound (a) is, for example, p-xylene glycol, m-xylene glycol, 1,3-bis ( ⁇ -hydroxyisopropyl) benzene, 1,4 from the viewpoint of industrial availability. It is more preferable to use -bis ( ⁇ -hydroxyisopropyl) benzene, p-divinylbenzene, or m-divinylbenzene.
• the compound (b) is not particularly limited, but specifically, cresols such as o-cresol, m-cresol, p-cresol; 2,3-xylenol, 2,4-xylenol, 2,5-xylenol.
• ethylphenol such as o-ethyl
• These compounds (b) may be used alone or in combination of two or more. Above all, from the viewpoint of easy industrial availability, it is more preferable to use, for example, cresol or xylenol as the compound (b). However, if the steric disorder is too large, there is a concern that the reactivity of the intermediate phenol compound during synthesis may be hindered. Therefore, for example, the compound (b) having a methyl group, an ethyl group, a cyclohexyl group and a phenyl group is used. It is preferable to do so.
• the compound (a) and the compound (b) are used, and the molar ratio of the compound (b) to the compound (a) (compound (b) / compound (a)) is used.
• the molar ratio of the compound (b) to the compound (a) is used.
• Examples of the acid catalyst used in the reaction include inorganic acids such as phosphoric acid, hydrochloric acid and sulfuric acid, oxalic acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid, fluoromethanesulfonic acid and other organic acids, and active white clay.
• Acidic white clay, silica alumina, zeolite, solid acids such as strongly acidic ion exchange resin, heteropolyrates, etc. can be mentioned, but with a uniform catalyst that can be easily removed by neutralization with a base and washing with water after the reaction. It is preferable to use certain oxalic acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid, and fluoromethanesulfonic acid.
• the blending amount of the acid catalyst is in the range of 0.001 to 40 parts by mass with respect to 100 parts by mass of the compound (a) and the compound (b), which are the raw materials to be charged first. From the viewpoint of handleability and economy, 0.001 to 25 parts by mass is preferable.
• the reaction temperature may be usually in the range of 80 to 200 ° C., but in order to suppress the formation of isomer structures, avoid side reactions such as thermal decomposition, and obtain a high-purity intermediate phenol compound, 100 ⁇ 150 ° C. is preferable.
• the reaction time the reaction does not proceed completely in a short time, and side reactions such as a thermal decomposition reaction of the product occur when the reaction time is long. Therefore, under the reaction temperature conditions, the total is usually 0. It is in the range of .5 to 24 hours, but preferably in the range of 0.5 to 15 hours in total.
• the compound (d) (which functions as an end-capping agent) are not particularly limited, but specifically, styrene, styrene dimer, ⁇ -methylstyrene, ⁇ -methylstyrene dimer, methylstyrene, and the like.
• Vinyl toluene), styrene or styrene derivatives such as ethylstyrene and t-butylstyrene, vinylnaphthalene, vinylbiphenyl, diphenylethylene, 1-octene and the like can be mentioned.
• the blending amount of the compound (d) is in the range of 1 to 200 parts by mass with respect to 100 parts by mass of the total amount of the compound (a) and the compound (b) as the raw materials to be charged first. From the viewpoint of reactivity, 10 to 100 parts by mass is preferable.
• the reaction temperature of the compound (b) and the reaction product (c) may be usually in the range of 80 to 200 ° C., but the formation of an isomer structure is suppressed, side reactions such as thermal decomposition are avoided, and the reaction temperature is high. In order to obtain an intermediate phenol compound of purity, 100 to 150 ° C. is preferable.
• the reaction time the reaction does not proceed completely in a short time, and side reactions such as a thermal decomposition reaction of the product occur when the reaction time is long. Therefore, under the reaction temperature conditions, the total is usually 0. It is in the range of .5 to 24 hours, but preferably in the range of 0.5 to 15 hours in total.
• the acid catalyst used in the reaction of the compound (a) and the compound (b) described above may be similarly used. can.
• the raw material since the raw material may also serve as a solvent, it is not always necessary to use another solvent, but it is also possible to use a solvent. Further, as for the solvent generated during the reaction (for example, methanol), a method of distilling off the solvent and then carrying out the reaction within the above reaction temperature range may be adopted.
• the solvent generated during the reaction for example, methanol
• Examples of the organic solvent used for synthesizing the intermediate phenol compound include ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, cyclohexanone and acetophenone, alcohols such as 2-ethoxyethanol and methanol, N, Aprotonic solvents such as N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, acetonitrile and sulfolane, cyclic ethers such as dioxane and tetrahydrofuran, esters such as ethyl acetate and butyl acetate. Examples thereof include aromatic solvents such as benzene, toluene and xylene, and these may be used alone or in combination.
• ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, cyclohe
• the hydroxyl group equivalent (phenol equivalent) of the intermediate phenol compound is preferably 100 to 1000 g / eq, and more preferably 200 to 500 g / eq, from the viewpoint of heat resistance.
• the hydroxyl group equivalent (phenol equivalent) of the intermediate phenol compound is calculated by a titration method, and refers to a neutralization titration method based on JIS K0070.
• the curable resin may be added to the intermediate phenol compound with anhydrous (meth) acrylic acid, (meth) acrylic acid chloride, chloromethylstyrene, chlorostyrene, allyl chloride, or It can be obtained by a known method such as reaction with allyl bromide or the like (hereinafter, may be referred to as “compound (e)”).
• compound (e) By reacting these, a cross-linking group (X) can be introduced into the intermediate phenol compound, and the thermosetting property has a low dielectric constant and a low dielectric loss tangent, which is a preferable embodiment.
• Examples of the anhydrous (meth) acrylic acid as the compound (e) (functioning as a cross-linking group-introducing agent) include methacrylic anhydride and methacrylic anhydride.
• Examples of the (meth) acrylic acid chloride include methacrylic acid chloride and acrylic acid chloride.
• Examples of chloromethylstyrene include p-chloromethylstyrene and m-chloromethylstyrene
• examples of chlorostyrene include p-chlorostyrene and m-chlorostyrene
• examples of chlorostyrene include allyl chloride.
• 3-chloro-1-propene can be mentioned, and examples of the allyl bromide include 3-bromo-1-propene. These may be used alone or in combination. Above all, it is preferable to use methacrylic anhydride or methacrylic acid chloride, which can obtain a cured product having a lower dielectric loss tangent.
• the basic catalyst include dimethylaminopyridine, alkaline earth metal hydroxide, alkali metal carbonate, and alkali metal hydroxide.
• the acidic catalyst include sulfuric acid and methanesulfonic acid.
• dimethylaminopyridine is excellent in terms of catalytic activity.
• reaction between the intermediate phenol compound and the compound (e) 1 to 10 mol of the compound (e) is added to 1 mol of the hydroxyl group contained in the intermediate phenol compound, and 0.01 to 0 is added.
• examples thereof include a method of reacting at a temperature of 30 to 150 ° C. for 1 to 40 hours while adding 2 mol of the basic catalyst in a batch or gradually.
• the reaction rate in the synthesis of the curable resin can be increased.
• the organic solvent is not particularly limited, but for example, ketones such as acetone and methyl ethyl ketone, alcohols such as methanol, ethanol, 1-propyl alcohol, isopropyl alcohol, 1-butanol, secondary butanol and tertiary butanol, and methyl.
• Examples include cellosolves such as cellosolve and ethyl cellosolve, ethers such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxane and diethoxyethane, aprotic polar solvents such as acetonitrile, dimethylsulfoxide and dimethylformamide, and toluene. Be done. Each of these organic solvents may be used alone, or two or more kinds may be used in combination as appropriate for adjusting the polarity.
• the reaction product After completion of the reaction with the above-mentioned compound (e) (introduction of a cross-linking group), the reaction product is reprecipitated in a poor solvent, and then the precipitate is prepared in a poor solvent at a temperature of 20 to 100 ° C. from 0.1 to
• the desired curable resin can be obtained by stirring for 5 hours, filtering under reduced pressure, and then drying the precipitate at a temperature of 40 to 80 ° C. for 1 to 10 hours.
• the poor solvent include hexane and the like.
• the curable resin of the present invention is characterized by containing the above general formulas (1) and (2), has a structure in which the above structural unit (1) is repeated, and is based on the above general formula (2). Although it is preferably a terminal structure, even if a structure other than these structural units (1) and the terminal structure (2) is included as a side reaction by the above-mentioned production method, the characteristics of the curable resin in the present invention are affected. If it is not given, there is no particular problem.
• the curable resin of the present invention preferably has a weight average molecular weight (Mw) of 500 to 50,000, more preferably 500 to 20,000, and even more preferably 800 to 10,000.
• Mw weight average molecular weight
• the weight average molecular weight of the curable resin is within the above range, it is preferable because it is excellent in workability and molding processability.
• the softening point of the curable resin is preferably 150 ° C. or lower, more preferably 50 to 100 ° C. It is preferable that the softening point of the curable resin is within the above range because it is excellent in processability.
• the curable resin composition of the present invention preferably contains the curable resin. Since the curable resin has a substituent R 1 in its structure and -C (CH 3 ) R 3 R 3 in its terminal structure, the molecular motility of the cross-linking group is suppressed and it is excellent in low dielectric loss tangent. In addition, by having -CR 2 R 2- C 6 H 4- CR 2 R 2- in the structural unit, the free volume is small, the low dielectric constant is excellent, the flexibility is exhibited, and the solvent solubility is achieved.
• the curable resin composition is excellent, the curable resin composition is easy to prepare, the handleability is excellent, and the proportion of polar functional groups in the structure of the curable resin is small, the cured product obtained by using the curable resin composition can be obtained. It has excellent low dielectric properties and is a preferable embodiment.
• the curable resin composition of the present invention in addition to the curable resin, other resins, curing agents, curing accelerators and the like can be used without particular limitation as long as the object of the present invention is not impaired.
• a cured product can be obtained by heating or the like without blending a curing agent.
• a curing agent or a curing accelerator can be obtained. Etc. can be mixed and used.
• the curable resin composition of the present invention contains the curable resin.
• X when X is an allyl ether group, X is a (meth) acryloyloxy group or a vinylbenzyl ether group. Unlike, it cannot be homopolymerized (crosslinked) (a cured product cannot be obtained by itself), so when the X is an allyl ether group, it is necessary to use a curing agent, a curing accelerator, or the like. ..
• alkenyl group-containing compounds such as bismaleimides, allyl ether compounds, allylamine compounds, triallyl cyanurates, alkenylphenol compounds, vinyl group-containing polyolefin compounds and the like can be added.
• other thermosetting resins such as a thermosetting polyimide resin, an epoxy resin, a phenol resin, an active ester resin, a benzoxazine resin, and a cyanate resin can also be appropriately blended depending on the intended purpose.
• curing agent examples include amine compounds, amide compounds, acid anhydride compounds, phenolic compounds, cyanate ester compounds and the like. These curing agents may be used alone or in combination of two or more.
• curing accelerator various substances can be used, and examples thereof include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, amine complex salts and the like.
• phosphorus compounds such as triphenylphosphine or imidazoles are preferable because they are excellent in curability, heat resistance, electrical properties, moisture resistance reliability and the like.
• These curing accelerators can be used alone or in combination of two or more.
• a flame retardant can be added to the curable resin composition of the present invention in order to exhibit flame retardancy, if necessary, and among them, a non-halogen flame retardant that does not substantially contain a halogen atom is used. It is preferable to mix.
• the non-halogen flame retardant include phosphorus-based flame retardants, nitrogen-based flame retardants, silicone-based flame retardants, inorganic flame retardants, organic metal salt-based flame retardants, and the like. You may use more than one type.
• An inorganic filler can be added to the curable resin composition of the present invention, if necessary.
• the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, aluminum hydroxide and the like.
• fused silica When the blending amount of the inorganic filler is particularly large, it is preferable to use fused silica.
• the molten silica can be used in either a crushed form or a spherical shape, but in order to increase the blending amount of the molten silica and suppress the increase in the melt viscosity of the molding material, it is better to mainly use the spherical one. preferable.
• a conductive filler such as silver powder or copper powder can be used.
• Various compounding agents such as a silane coupling agent, a mold release agent, a pigment, and an emulsifier can be added to the curable resin composition of the present invention, if necessary.
• the cured product of the present invention is preferably obtained by subjecting the curable resin composition to a curing reaction.
• the curable resin composition is obtained by uniformly mixing each component such as the above-mentioned curing agent in addition to the above-mentioned curable resin alone or the above-mentioned curable resin, and is the same as a conventionally known method. Can be easily made into a cured product by the above method.
• Examples of the cured product include molded products such as laminates, cast products, adhesive layers, coating films, and films.
• thermosetting and ultraviolet curing reactions examples include thermosetting and ultraviolet curing reactions.
• the thermosetting reaction is easily carried out even under a non-catalyst, but if a faster reaction is desired, an organic peroxide or an azo compound is used. It is effective to add a polymerization initiator such as, a phosphine compound, or a basic catalyst such as a tertiary amine. Examples thereof include benzoyl peroxide, dicumyl peroxide, azobisisobutyronitrile, triphenylphosphine, triethylamine, imidazoles and the like.
• the cured product obtained from the curable resin composition of the present invention is excellent in heat resistance and low dielectric properties, it can be suitably used for heat-resistant members and electronic members.
• it can be suitably used for prepregs, circuit boards, semiconductor encapsulants, semiconductor devices, build-up films, build-up boards, adhesives, resist materials and the like.
• it can be suitably used for a matrix resin of a fiber reinforced resin, and is particularly suitable as a prepreg having high heat resistance.
• the curable resin contained in the curable resin composition can be made into a paint because it exhibits excellent solubility in various solvents.
• the heat-resistant members and electronic members thus obtained can be suitably used for various purposes, for example, industrial mechanical parts, general mechanical parts, automobile / railroad / vehicle parts, space / aviation-related parts, electronic / electrical parts, and the like.
• Examples include, but are not limited to, building materials, containers / packaging materials, daily necessities, sports / leisure products, and housing materials for wind power generation.
• Measuring device "HLC-8320 GPC” manufactured by Tosoh Corporation Column: Guard column “HXL-L” manufactured by Tosoh Corporation + “TSK-GEL G2000HXL” manufactured by Tosoh Corporation + “TSK-GEL G2000HXL” manufactured by Tosoh Corporation + “TSK-GEL G3000HXL” manufactured by Tosoh Corporation + Tosoh Corporation Made by “TSK-GEL G4000HXL” Detector: RI (Differential Refractometer) Data processing: "GPC Workstation EcoSEC-WorkStation” manufactured by Tosoh Corporation Measurement conditions: Column temperature 40 ° C Developing solvent Tetrahydrofuran Flow rate 1.0 ml / min Standard: The following monodisperse polystyrene with a known molecular weight was used in accordance with the measurement manual of the above-mentioned "GPC workstation EcoSEC-WorkStation".
• Example 1 324.4 g of o-cresol, 276.3 g of p-xylylene glycol, and p-toluenesulfonic acid monohydrate in a 3 L, 4-port separable flask equipped with a stirrer, a condenser, a nitrogen introduction tube, and a thermometer. 19.0 g was charged, the temperature was raised to 150 ° C. with stirring, and the reaction was carried out for 5 hours. During this period, methanol produced by the reaction was removed from the system. Then, the temperature was lowered to 120 ° C., and 260.4 g of styrene was added dropwise over 5 hours to react to obtain an intermediate phenol compound.
• Example 2 324.4 g of o-cresol, 388.5 g of 1,3-bis ( ⁇ -hydroxyisopropyl) benzene, and p- in a 3 L, 4-port separable flask equipped with a stirrer, condenser, nitrogen introduction tube, and thermometer. 19.0 g of toluenesulfonic acid monohydrate was charged, the temperature was raised to 150 ° C. with stirring, and the reaction was carried out for 5 hours. During this period, the water produced by the reaction was removed from the system. Then, the temperature was lowered to 120 ° C., and 260.4 g of styrene was added dropwise over 5 hours to react to obtain an intermediate phenol compound.
• Example 3 324.4 g of o-cresol, 332.4 g of 1,4-bis (1-hydroxyethyl) benzene, and p- in a 3 L, 4-port separable flask equipped with a stirrer, condenser, nitrogen introduction tube, and thermometer. 19.0 g of toluenesulfonic acid monohydrate was charged, the temperature was raised to 150 ° C. with stirring, and the reaction was carried out for 5 hours. During this period, the water produced by the reaction was removed from the system. Then, the temperature was lowered to 120 ° C., and 260.4 g of styrene was added dropwise over 5 hours to react to obtain an intermediate phenol compound.
• Example 4 Synthesis was carried out in the same manner as in Example 3 except that 260.4 g of styrene of Example 3 was changed to ⁇ -methylstyrene 295.5 g, and a curable resin (Mw: 2000) was obtained.
• Example 5 Synthesis was carried out in the same manner as in Example 3 except that 260.4 g of styrene in Example 3 was changed to 295.5 g of 4-methylstyrene to obtain a curable resin (Mw: 1900).
• Example 6 Synthesis was carried out in the same manner as in Example 3 except that 260.4 g of styrene in Example 3 was changed to 450.8 g of 1,1-diphenylethylene to obtain a curable resin (Mw: 1900).
• Example 7 The synthesis was carried out in the same manner as in Example 3 except that 260.4 g of styrene of Example 3 was changed to 280.6 g of 1-octene to obtain a curable resin (Mw: 1800).
• Example 8 The synthesis was carried out in the same manner as in Example 3 except that 324.4 g of o-cresol in Example 3 was changed to 366.5 g of 2-ethylphenol to obtain a curable resin (Mw: 1800).
• Example 9 The synthesis was carried out in the same manner as in Example 3 except that 324.4 g of o-cresol in Example 3 was changed to 510.6 g of 2-phenylphenol to obtain a curable resin (Mw: 1800).
• Example 10 The synthesis was carried out in the same manner as in Example 3 except that 324.4 g of o-cresol in Example 3 was changed to 528.8 g of 2-cyclohexylphenol to obtain a curable resin (Mw: 1900).
• Example 11 The synthesis was carried out in the same manner as in Example 3 except that 324.4 g of o-cresol in Example 3 was changed to 324.4 g of p-cresol to obtain a curable resin (Mw: 2600).
• Example 12 Examples except that 9.2 g of 4-chloromethylstyrene in Example 3 was changed to 9.3 g of methacrylic anhydride and 7.0 g of a 48% potassium hydroxide aqueous solution was changed to 0.2 g of 4-dimethylaminopyridine. The synthesis was carried out in the same manner as in No. 3 to obtain a curable resin (Mw: 2200).
• Example 13 324.4 g of o-cresol and 19.0 g of p-toluenesulfonic acid monohydrate were placed in a 3 L, 4-port separable flask equipped with a stirrer, a cooling tube, a nitrogen introduction tube, and a thermometer, and 120 g while stirring. The temperature was raised to ° C., and 280.4 g of divinylbenzene was added dropwise over 5 hours for reaction. Then, 260.4 g of styrene was added dropwise over 5 hours and reacted to obtain an intermediate phenol compound.
• Example 14 The synthesis was carried out in the same manner as in Example 3 except that 324.4 g of o-cresol in Example 3 was changed to 266.49 g of 2,5-xylenol to obtain a curable resin (Mw: 2300).
• Example 15 The synthesis was carried out in the same manner as in Example 3 except that 324.4 g of o-cresol in Example 3 was changed to 408.54 g of 2,3,5-trimethylphenol, and a curable resin (Mw: 2500) was used. Obtained.
• Example 16 The same method as in Example 3 except that 9.2 g of 4-chloromethylstyrene of Example 3 was changed to 7.3 g of acrylic bromide and 7.0 g of a 48% potassium hydroxide aqueous solution was changed to 20.0 g of potassium carbonate. The synthesis was carried out in 1 to obtain a curable resin (Mw: 1800).
• Example 16 In Example 16 (X is an allyl ether group), homopolymerization (crosslinking) of the curable resin alone does not proceed, so only the production confirmation of the curable resin is performed, and the following resin film (cured product) is used. No evaluation based on this is done.
• the dielectric constant and dielectric loss tangent at a frequency of 10 GHz by the split post dielectric resonator method using a network analyzer N5247A manufactured by Keysight Technology Co., Ltd. was measured.
• the dielectric loss tangent if it is 10 ⁇ 10 -3 or less, there is no practical problem, preferably 5.5 ⁇ 10 -3 or less, and more preferably 4.5 ⁇ 10 -3 or less. ..
• the dielectric constant is 3 or less, there is no problem in practical use, and it is preferably 2.8 or less, more preferably 2.6 or less.
• R 1 in Table 1 above has a methyl group or the like at the ortho position with respect to the cross-linking group X in Examples 1 to 10, 12 and 13. Further, Example 11 has a methyl group at the ortho position with respect to the cross-linking group X, and Example 14 has a methyl group at the ortho-position (2-) and the meta-position (5-) with respect to the cross-linking group X. Example 15 has a methyl group at the ortho-position (2-), the meta-position (3-), and the meta-position (5-) with respect to the cross-linking group X.
• Ph represents a phenyl group and Cy represents a cyclohexyl group.
• the cured product obtained by using the curable resin can achieve both heat resistance and low dielectric properties, and is practically available. It was confirmed that there was no problem.
• the cured product obtained by using the curable resin of the present invention is excellent in heat resistance and dielectric properties, and therefore can be suitably used for heat-resistant members and electronic members.
• prepregs, semiconductor encapsulants, and circuits It can be suitably used for substrates, build-up films, build-up substrates, etc., adhesives and resist materials. Further, it can be suitably used for a matrix resin of a fiber reinforced resin, and is suitable as a prepreg having high heat resistance.

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