WO2018070535A1 - エポキシ樹脂、エポキシ樹脂組成物、エポキシ樹脂硬化物及び複合材料 - Google Patents
エポキシ樹脂、エポキシ樹脂組成物、エポキシ樹脂硬化物及び複合材料 Download PDFInfo
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- WO2018070535A1 WO2018070535A1 PCT/JP2017/037268 JP2017037268W WO2018070535A1 WO 2018070535 A1 WO2018070535 A1 WO 2018070535A1 JP 2017037268 W JP2017037268 W JP 2017037268W WO 2018070535 A1 WO2018070535 A1 WO 2018070535A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/226—Mixtures of di-epoxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
- C08G59/245—Di-epoxy compounds carbocyclic aromatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
Definitions
- the present invention relates to an epoxy resin, an epoxy resin composition, a cured epoxy resin, and a composite material.
- Epoxy resins are used in various applications by taking advantage of their excellent heat resistance. In recent years, in response to the increase in the actual use temperature of power devices using epoxy resins, studies on epoxy resins having excellent thermal conductivity have been underway.
- mesogen-containing epoxy resin An epoxy resin containing an epoxy compound having a mesogenic structure in the molecule (mesogen-containing epoxy resin) is known as an epoxy resin excellent in thermal conductivity.
- mesogen-containing epoxy resins generally have a higher viscosity than other epoxy resins, and sufficient fluidity may not be obtained during operation.
- an object of the present invention is to provide an epoxy resin and an epoxy resin composition excellent in handleability, and an epoxy resin cured product and a composite material obtained using these.
- Means for solving the above problems include the following embodiments. ⁇ 1> An epoxy resin comprising a first epoxy compound having a mesogenic structure and a second epoxy compound having two or more mesogenic structures having the same structure as the mesogenic structure, wherein the epoxy resin is obtained by liquid chromatography. The epoxy resin whose ratio of a 1st epoxy compound is 40 to 50% of the whole said epoxy resin.
- R 1 to R 4 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
- R 1 ⁇ R 4 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
- the second epoxy compound includes an epoxy compound having at least one selected from the group consisting of structures represented by the following general formulas (II-A) to (II-D): > The epoxy resin of any one of>.
- R 1 to R 4 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
- R 5 and R 6 each independently represent An alkyl group having 1 to 8 carbon atoms is shown.
- n and m each independently represents an integer of 0 to 4.
- Each X independently represents —O— or —NH—.
- An epoxy resin composition comprising the epoxy resin according to any one of ⁇ 1> to ⁇ 5> and a curing agent.
- An epoxy resin cured product which is a cured product of the epoxy resin composition according to ⁇ 6> or ⁇ 7>.
- a composite material comprising the cured epoxy resin according to ⁇ 8> and a reinforcing material.
- an epoxy resin and an epoxy resin composition excellent in handleability and an epoxy resin cured product and a composite material obtained by using these.
- the numerical values indicated by using “to” include numerical values described before and after “to” as the minimum value and the maximum value, respectively.
- the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of another numerical range. Good.
- the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples.
- the content rate or content of each component in the composition is such that when there are a plurality of substances corresponding to each component in the composition, the plurality of kinds present in the composition unless otherwise specified. It means the total content or content of substances.
- the “epoxy compound” means a compound having an epoxy group in the molecule.
- the “epoxy resin” is a concept that captures a plurality of epoxy compounds as an aggregate, and means an uncured state.
- the epoxy resin of the present embodiment is an epoxy resin comprising a first epoxy compound having a mesogenic structure and a second epoxy compound having two or more mesogenic structures having the same structure as the mesogenic structure,
- the ratio of the first epoxy compound obtained by lithography is 40% or more and 50% or less of the entire epoxy resin.
- an epoxy resin in which the proportion of the first epoxy compound obtained by liquid chromatography is 40% or more and 50% or less of the whole epoxy resin is such that the proportion of the first epoxy compound is that of the whole epoxy resin. It was found that the viscosity is likely to decrease at the time of temperature rise, and the handleability is excellent as compared with an epoxy resin exceeding 50%. The reason is not clear, but when the proportion of the first epoxy compound is 50% or less of the whole epoxy resin, the proportion of the epoxy resin is larger than the case where the proportion of the first epoxy compound exceeds 50% of the whole epoxy resin. This is presumably because the precipitation of crystals at a temperature below the melting temperature is suppressed. Moreover, it turned out that the epoxy resin whose ratio of a 1st epoxy compound is less than 40% of the whole epoxy resin has a high viscosity by molecular weight increase, and tends to be inferior to handleability.
- Liquid chromatography is performed at a sample concentration of 0.5% by mass, tetrahydrofuran as the mobile phase, and a flow rate of 1.0 ml / min.
- the measurement can be performed using, for example, a high performance liquid chromatograph “L6000” manufactured by Hitachi, Ltd. and a data analysis apparatus “C-R4A” manufactured by Shimadzu Corporation.
- As the column for example, “G2000HXL” and “G3000HXL” which are GPC columns manufactured by Tosoh Corporation can be used.
- the proportion of the first epoxy compound obtained by liquid chromatography is preferably 50% or less of the total epoxy resin, more preferably 49% or less, and 48% or less. More preferably it is.
- the ratio of the first epoxy compound obtained by liquid chromatography is not particularly limited as long as it is 40% or more of the entire epoxy resin, but it is 41% or more. Preferably, it is 42% or more.
- the epoxy resin may contain other epoxy compounds other than the first epoxy compound and the second epoxy compound.
- the ratio obtained by liquid chromatography of other epoxy compounds is preferably 10% or less of the entire epoxy resin.
- the epoxy resin of this embodiment includes an epoxy compound having a mesogenic structure. Therefore, a higher order structure is formed in the cured product obtained by reacting the epoxy resin with the curing agent. Therefore, the cured product has excellent thermal conductivity.
- the higher order structure means a structure including a higher order structure in which constituent elements are arranged to form a micro ordered structure, and corresponds to, for example, a crystal phase and a liquid crystal phase.
- the presence or absence of such a higher order structure can be determined by a polarizing microscope. That is, in the observation in the crossed Nicols state, it can be distinguished by seeing interference fringes due to depolarization.
- This higher order structure usually exists in an island shape in the cured product of the epoxy resin composition to form a domain structure, and one of the islands corresponds to one higher order structure.
- the constituent elements of this higher order structure are formed by covalent bonds.
- Examples of the higher order structure formed in the cured product include a nematic structure and a smectic structure.
- Each of the nematic structure and the smectic structure is a kind of liquid crystal structure.
- the nematic structure is a liquid crystal structure in which the molecular long axis is oriented in a uniform direction and has only an alignment order.
- the smectic structure is a liquid crystal structure having a one-dimensional positional order in addition to the orientation order and having a layer structure. The order is higher in the smectic structure than in the nematic structure. Therefore, from the viewpoint of thermal conductivity of the cured product, it is more preferable to form a higher order structure having a smectic structure.
- Whether a smectic structure is formed in the cured product obtained using the epoxy resin of the present embodiment can be determined by X-ray diffraction measurement of the cured product.
- X-ray diffraction measurement can be performed, for example, using an X-ray diffraction apparatus manufactured by Rigaku Corporation.
- the tube voltage is 40 kV
- the tube current is 20 mA
- the sampling width is 0.01 °
- 2 ⁇ 2 ° to 30 °
- a diffraction peak appears in the range of ⁇ 10 °.
- the first epoxy compound is not particularly limited as long as it is an epoxy compound having a mesogenic structure.
- the mesogen structure is a partial structure that contributes to the development of liquid crystallinity.
- Examples of the mesogen structure include a biphenyl structure, a phenylbenzoate structure, a cyclohexylbenzoate structure, an azobenzene structure, a stilbene structure, a terphenyl structure, a naphthalene structure, and an anthracene structure. And a structure in which two or more of these mesogenic structures are bonded via a bonding group.
- the first epoxy compound contained in the epoxy resin may be one kind or two or more kinds having different molecular structures.
- the molecular weight of the first epoxy compound is not particularly limited.
- it is preferably 800 or less, and 600 or less. More preferably. From the viewpoint of forming a higher order structure of the cured product, it is preferably 300 or more, and more preferably 350 or more.
- Preferred examples of the first epoxy compound include compounds represented by the following general formula (M).
- the compound represented by the general formula (M) reacts with the curing agent to form a smectic liquid crystal structure in the cured product.
- the first epoxy compound is a compound represented by the general formula (M)
- the compound represented by the general formula (M) may be one kind or two or more kinds.
- R 1 to R 4 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
- R 1 to R 4 are each independently preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom.
- 2 to 4 of R 1 to R 4 are hydrogen atoms, more preferably 3 or 4 are hydrogen atoms, and more preferably that all 4 are hydrogen atoms.
- any of R 1 to R 4 is an alkyl group having 1 to 3 carbon atoms
- at least one of R 1 and R 4 is preferably an alkyl group having 1 to 3 carbon atoms.
- the second epoxy compound is not particularly limited as long as it is an epoxy compound having two or more mesogenic structures having the same structure as the mesogenic structure of the first epoxy compound.
- the viscosity below the melting point of the epoxy compound tends to be lower than when the epoxy resin contains only the first epoxy compound. is there.
- the second epoxy compound is obtained by a reaction between the first epoxy compound and a compound having a functional group capable of reacting with the epoxy group of the first epoxy compound, Even those obtained by self-polymerization may be obtained by other methods.
- the number of mesogenic structures having the same structure as the mesogenic structure of the first epoxy compound contained in the second epoxy compound is not particularly limited. From the viewpoint of the intrinsic viscosity (melt viscosity), it is preferable that the number of mesogenic structures of the second epoxy compound that has the largest proportion obtained by liquid chromatography is 2.
- the second epoxy compound is obtained by a reaction between the first epoxy compound and a compound having a functional group capable of reacting with the epoxy group of the first epoxy compound, as the second epoxy compound.
- the compound which has a structure represented by the following general formula (A) or (B) is mentioned.
- * represents a bonding position with an adjacent atom.
- Adjacent atoms include oxygen and nitrogen atoms.
- R 1 to R 3 each independently represents an alkyl group having 1 to 8 carbon atoms.
- n, m and l each independently represents an integer of 0 to 4.
- n, m and l are each independently preferably an integer of 0 to 2, more preferably an integer of 0 to 1, and even more preferably 0.
- the structure represented by the general formula (A) or (B) is preferable.
- An epoxy compound having such a structure tends to have a linear molecular structure. For this reason, it is considered that the stacking property of molecules is high and higher-order structures are more easily formed.
- R 1 ⁇ R 3, n, m and l are * in formula (A) and (B), R 1 ⁇ R 3, n, The definition and preferred examples of m and l are the same.
- the second epoxy compound may be an epoxy compound having two or more structures represented by the following general formula (I).
- the second epoxy compound may be an epoxy compound having at least one selected from the group consisting of structures represented by the following general formulas (II-A) to (II-D).
- R 1 to R 4 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R 5 and R 6 each independently represent carbon.
- n and m each independently represents an integer of 0 to 4.
- X independently represents -0- or -NH-.
- R 1 to R 4 in general formulas (II-A) to (II-D) are the same as the specific examples of R 1 to R 4 in general formula (M), and preferred ranges thereof are also the same. .
- R 5 and R 6 each independently represents an alkyl group having 1 to 8 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, More preferably, it is a group.
- n and m each independently represent an integer of 0 to 4, preferably an integer of 0 to 2, and preferably an integer of 0 to 1. Is more preferred and 0 is even more preferred. That is, the benzene ring to which R 5 or R 6 is attached in the general formulas (II-A) to (II-D) preferably has 2 to 4 hydrogen atoms, and preferably 3 or 4 hydrogen atoms. More preferably, it has an atom, and further preferably has 4 hydrogen atoms.
- Formula (II-a) ⁇ R 1 ⁇ R 6 in (II-d), n, definition and preferred examples of m and X have the general formula (II-A) R 1 in the ⁇ (II-D) ⁇ R 6 , N, m and X are the same as defined and preferred examples.
- Examples of the case where the second epoxy compound is an epoxy compound (dimer compound) having two structures represented by the general formula (I) include the following general formulas (III-A) to (III to F). ) And at least one selected from the group consisting of epoxy compounds represented by:
- Formula (III-A) ⁇ R 1 in (III ⁇ F) ⁇ R 6 , n, the definition of m and X have the general formula (II-A) R 1 in the ⁇ (II-D) ⁇ R 6, n , M and X are the same, and the preferred range is also the same.
- Formula (III-a) ⁇ R 1 in (III ⁇ f) ⁇ R 6 , n, the definition of m and X have the general formula (III-A) R 1 in the ⁇ (III-F) ⁇ R 6, n , M and X are the same, and the preferred range is also the same.
- the method for synthesizing the second epoxy compound by reacting the first epoxy compound with a compound having a functional group capable of reacting with the epoxy group of the first epoxy compound is not particularly limited. Specifically, for example, a first epoxy compound, a compound having a functional group capable of reacting with the epoxy group of the first epoxy compound, and a reaction catalyst used as necessary are dissolved in a solvent and heated.
- the second epoxy compound can be synthesized by stirring while stirring.
- the first epoxy compound and the compound having a functional group capable of reacting with the epoxy group of the first epoxy compound are mixed without using a reaction catalyst and a solvent as necessary, and stirred while heating. By doing so, the second epoxy compound can be synthesized.
- the solvent is a solvent that can dissolve the first epoxy compound and the compound having a functional group capable of reacting with the epoxy group of the first epoxy compound and can be heated to a temperature necessary for the reaction of both compounds. If there is, there is no particular limitation. Specific examples include cyclohexanone, cyclopentanone, ethyl lactate, propylene glycol monomethyl ether, N-methylpyrrolidone, methyl cellosolve, ethyl cellosolve, propylene glycol monopropyl ether and the like.
- the quantity of a solvent is the quantity which can melt
- the solubility differs depending on the type of raw material before the reaction, the type of solvent, etc., for example, if the charged solid content concentration is 20% by mass to 60% by mass, the viscosity of the solution after the reaction is in a preferred range. There is a tendency.
- the compound having a functional group capable of reacting with the epoxy group of the first epoxy compound is not particularly limited. From the viewpoint of forming a smectic structure in the cured product, the compound having a functional group capable of reacting with the epoxy group of the first epoxy compound is a dihydroxybenzene compound having a structure in which two hydroxyl groups are bonded to one benzene ring, A diaminobenzene compound having a structure in which two amino groups are bonded to one benzene ring, a dihydroxybiphenyl compound having a structure in which one hydroxyl group is bonded to each of two benzene rings forming a biphenyl structure, and two forming a biphenyl structure It is preferably at least one selected from the group consisting of diaminobiphenyl compounds each having a structure in which one amino group is bonded to the benzene ring (hereinafter also referred to as a specific aromatic compound).
- a second epoxy compound having at least one can be synthesized.
- Examples of the dihydroxybenzene compound include 1,2-dihydroxybenzene (catechol), 1,3-dihydroxybenzene (resorcinol), 1,4-dihydroxybenzene (hydroquinone), and derivatives thereof.
- Examples of the diaminobenzene compound include 1,2-diaminobenzene, 1,3-diaminobenzene, 1,4-diaminobenzene, and derivatives thereof.
- Examples of the dihydroxybiphenyl compound include 3,3′-dihydroxybiphenyl, 3,4′-dihydroxybiphenyl, 4,4′-dihydroxybiphenyl, and derivatives thereof.
- Examples of the diaminobiphenyl compound include 3,3′-diaminobiphenyl, 3,4′-diaminobiphenyl, 4,4′-diaminobiphenyl, and derivatives thereof.
- Examples of the derivative of the specific aromatic compound include a compound in which a substituent such as an alkyl group having 1 to 8 carbon atoms is bonded to the benzene ring of the specific aromatic compound.
- a specific aromatic compound may be used individually by 1 type, and may use 2 or more types together.
- 1,4-dihydroxybenzene, 1,4-diaminobenzene, 4,4′-dihydroxybiphenyl and 4,4 are used as specific aromatic compounds.
- '-Diaminobiphenyl is preferred.
- the second epoxy compound obtained by reacting this with the first epoxy compound tends to have a linear structure. . For this reason, it is considered that the stacking property of the molecule is high and it is easy to form a smectic structure in the cured product.
- reaction catalyst is not particularly limited, and an appropriate one can be selected from the viewpoint of reaction rate, reaction temperature, storage stability, and the like. Specific examples include imidazole compounds, organophosphorus compounds, tertiary amines, and quaternary ammonium salts.
- a reaction catalyst may be used individually by 1 type, and may use 2 or more types together.
- an organic phosphorus compound is preferable as the reaction catalyst.
- the organic phosphorus compound include an organic phosphine compound, a compound having an intramolecular polarization formed by adding a compound having a ⁇ bond such as maleic anhydride, a quinone compound, diazophenylmethane, and a phenol resin to an organic phosphine compound, organic And a complex of a phosphine compound and an organic boron compound.
- organic phosphine compound examples include triphenylphosphine, diphenyl (p-tolyl) phosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, tris (alkylalkoxyphenyl) phosphine, tris (dialkylphenyl) phosphine, Tris (trialkylphenyl) phosphine, tris (tetraalkylphenyl) phosphine, tris (dialkoxyphenyl) phosphine, tris (trialkoxyphenyl) phosphine, tris (tetraalkoxyphenyl) phosphine, trialkylphosphine, dialkylarylphosphine, alkyldiaryl A phosphine etc. are mentioned.
- quinone compound examples include 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl- Examples include 1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, and phenyl-1,4-benzoquinone.
- organic boron compound examples include tetraphenyl borate, tetra-p-tolyl borate, and tetra-n-butyl borate.
- the amount of the reaction catalyst is not particularly limited. From the viewpoint of reaction rate and storage stability, 0.1 part by mass with respect to 100 parts by mass of the total of the first epoxy compound and the compound having a functional group capable of reacting with the epoxy group of the first epoxy compound.
- the content is preferably 1.5 parts by mass, more preferably 0.2 parts by mass to 1 part by mass.
- the synthesis of the second epoxy compound can be performed using a reaction vessel such as a flask for a small scale and a synthesis kettle for a large scale.
- a specific synthesis method is as follows, for example. First, a 1st epoxy compound is thrown into reaction container, a solvent is put as needed, and it heats to reaction temperature with an oil bath or a heat medium, and melt
- the reaction temperature is not particularly limited as long as the reaction proceeds between the epoxy group of the first epoxy compound and the functional group capable of reacting with the epoxy group, and is preferably in the range of 100 ° C. to 180 ° C., for example. More preferably, the temperature is in the range of 100 ° C to 150 ° C.
- the compounding ratio of the first epoxy compound used for the synthesis of the second epoxy compound and the compound having a functional group capable of reacting with the epoxy group is not particularly limited.
- the ratio (A / B) between the number of equivalents of epoxy groups (A) and the number of equivalents of functional groups capable of reacting with epoxy groups (A / B) is in the range of 100/100 to 100/1. Good. From the viewpoint of fracture toughness and heat resistance of the cured product, a blending ratio in which A / B is in the range of 100/50 to 100/1 is preferable.
- the structure of the second epoxy compound is, for example, the molecular weight of the second epoxy compound estimated to be obtained from the reaction between the first epoxy compound used for the synthesis and the compound having a functional group capable of reacting with the epoxy group. And the molecular weight of the target compound determined by liquid chromatography carried out using a liquid chromatograph equipped with UV and mass spectrum detectors.
- the epoxy equivalent of the epoxy resin is not particularly limited. From the viewpoint of achieving both the fluidity of the epoxy resin and the thermal conductivity of the cured product, it is preferably 245 g / eq to 500 g / eq, more preferably 250 g / eq to 450 g / eq, and more preferably 260 g / eq to More preferably, it is 400 g / eq. If the epoxy equivalent of the epoxy resin is 245 g / eq or more, the crystallinity of the epoxy resin does not become too high, and the fluidity of the epoxy resin tends not to decrease.
- the epoxy equivalent of the epoxy resin is 500 g / eq or less, the crosslinking density of the epoxy resin is unlikely to decrease, and the thermal conductivity of the molded product tends to increase.
- the epoxy equivalent of the epoxy resin is measured by a perchloric acid titration method.
- the number average molecular weight (Mn) and the weight average molecular weight (Mw) of the epoxy resin are not particularly limited and can be selected according to desired properties of the epoxy resin. From the viewpoint of viscosity, the weight average molecular weight (Mw) of the epoxy resin is preferably selected from the range of 1200 to 1550.
- the number average molecular weight (Mn) and the weight average molecular weight (Mw) of the epoxy resin are values obtained by liquid chromatography.
- Liquid chromatography is performed at a sample concentration of 0.5% by mass, tetrahydrofuran as the mobile phase, and a flow rate of 1.0 ml / min.
- a calibration curve is prepared using a polystyrene standard sample, and Mn and Mw are measured in terms of polystyrene using the calibration curve.
- the measurement can be performed using, for example, a high performance liquid chromatograph “L6000” manufactured by Hitachi, Ltd. and a data analysis apparatus “C-R4A” manufactured by Shimadzu Corporation.
- As the column for example, “G2000HXL” and “G3000HXL” which are GPC columns manufactured by Tosoh Corporation can be used.
- the epoxy resin composition of the present embodiment includes the epoxy resin of the above-described embodiment and a curing agent.
- the curing agent is not particularly limited as long as it is a compound capable of causing a curing reaction with the epoxy resin contained in the epoxy resin composition of the present embodiment.
- Specific examples of the curing agent include amine curing agents, phenol curing agents, acid anhydride curing agents, polymercaptan curing agents, polyaminoamide curing agents, isocyanate curing agents, and blocked isocyanate curing agents.
- curing agent may be used individually by 1 type, or may use 2 or more types together.
- the curing agent is preferably an amine curing agent or a phenol curing agent, and from the viewpoint of forming a higher-order structure of the cured product, an amine curing agent is more preferable.
- a compound having two or more amino groups directly bonded to the aromatic ring is more preferable.
- amine curing agents include 3,3′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 4,4′-diamino- 3,3′-dimethoxybiphenyl, 4,4′-diaminophenylbenzoate, 1,5-diaminonaphthalene, 1,3-diaminonaphthalene, 1,4-diaminonaphthalene, 1,8-diaminonaphthalene, 1,3-diamino Examples include benzene, 1,4-diaminobenzene, 4,4′-diaminobenzanilide, trimethylene-bis-4-aminobenzoate, and the like.
- Examples of the phenol curing agent include a low molecular phenol compound and a phenol novolac resin obtained by connecting a low molecular phenol compound with a methylene chain to form a novolac.
- Low molecular phenol compounds include monofunctional phenol compounds such as phenol, o-cresol, m-cresol, and p-cresol, bifunctional phenol compounds such as catechol, resorcinol, hydroquinone, 1,2,3-trihydroxybenzene, 1 , 2,4-trihydroxybenzene, trifunctional phenol compounds such as 1,3,5-trihydroxybenzene and the like.
- the content of the curing agent in the epoxy resin composition is not particularly limited. From the viewpoint of the efficiency of the curing reaction, the ratio between the number of active hydrogen equivalents (amine equivalent number) of the curing agent contained in the epoxy resin composition and the epoxy equivalent number of epoxy resin (amine equivalent number / epoxy equivalent number). Is preferably in an amount of 0.3 to 3.0, more preferably in an amount of 0.5 to 2.0.
- An epoxy resin composition may contain other components other than an epoxy resin and a hardening
- a curing catalyst and a filler may be included.
- Specific examples of the curing catalyst include compounds exemplified as reaction catalysts that can be used for the synthesis of multimers.
- the use of the epoxy resin composition of this embodiment is not particularly limited, it can be suitably used for a processing method involving relatively rapid heating of the epoxy resin composition.
- a processing method involving relatively rapid heating of the epoxy resin composition.
- suitable for the manufacture of FRP involving the step of impregnating the epoxy resin composition while heating the gap between the fibers, and the production of a sheet-like material involving the step of spreading the epoxy resin composition with a squeegee etc.
- the epoxy resin composition of this embodiment can also be suitably used in a processing method in which it is desired to omit or reduce the addition of a solvent for decreasing the viscosity from the viewpoint of suppressing the generation of voids in the cured product.
- the epoxy resin cured product of the present embodiment is obtained by curing the epoxy resin composition of the present embodiment.
- the composite material of this embodiment includes the epoxy resin cured product of this embodiment and a reinforcing material.
- the material of the reinforcing material included in the composite material is not particularly limited and can be selected according to the use of the composite material.
- Specific examples of the reinforcing material include carbon materials, glass, aromatic polyamide resins (for example, Kevlar (registered trademark)), ultrahigh molecular weight polyethylene, alumina, boron nitride, aluminum nitride, mica, silicon, and the like.
- the shape of the reinforcing material is not particularly limited, and examples thereof include fibrous and particulate (filler). Only one type or two or more types of reinforcing materials may be included in the composite material.
- the first epoxy compound used in the synthesis is powdery (crystalline phase) at room temperature, and transitions to a nematic phase at 150 ° C. and to an isotropic phase at 210 ° C.
- Japanese Patent No. 5471975 can be referred to for the production method and the like.
- the ratio of the peak area derived from the first epoxy compound to the entire epoxy resin was found to be 45%. Moreover, the number average molecular weight (Mn) of the resin 1 was 766, and the weight average molecular weight (Mw) was 1557.
- the first epoxy compound used for producing the epoxy resin had a peak top at 27.7 minutes.
- Liquid chromatography uses a liquid chromatograph equipped with UV and mass spectrum detectors (high performance liquid chromatograph “L6000” manufactured by Hitachi, Ltd.) and a data analysis device “C-R4A” manufactured by Shimadzu Corporation. went.
- As the column “G2000HXL” and “G3000HXL”, which are GPC columns manufactured by Tosoh Corporation, were used.
- the ratio of the first epoxy compound in the resin 6 was determined in the same manner as in the case of the resin 1, it was 51%. Further, the Mn of the resin 6 was 712, and the Mw was 1220.
- the viscosity behavior of the resins 1 to 6 was evaluated by measuring the dynamic shear viscosity (Pa ⁇ s).
- the dynamic shear viscosity (Pa ⁇ s) was measured in a vibration mode with a rheometer (MCR-301, manufactured by Anton Paar) in accordance with the standard of JIS K 7244-10.
- a parallel plate with a diameter of 12 mm was used, and the measurement conditions were a frequency of 1 Hz, a gap of 0.2 mm, and a strain of 2%.
- the epoxy resin is allowed to stand and melt at 150 ° C. for 3 minutes or more, and then the temperature is decreased from 150 ° C. to 30 ° C.
- Example 1 1.90 g of resin 1 and 1.90 g of 4,4′-diaminodiphenylsulfone (hereinafter referred to as DDS) as a curing agent were weighed and placed in a stainless steel dish. At this time, the blending amount was calculated so that the equivalent ratio of the epoxy group and the amino group derived from DDS was 1/1. It was heated to 180 ° C. with a hot plate, and the resin 1 and DDS in the stainless steel petri dish were melted while stirring with a spatula and heated for 1 hour. Furthermore, the temperature of the hot plate was raised to 230 ° C. and heated for 1 hour to obtain a cured product.
- DDS 4,4′-diaminodiphenylsulfone
- the cured product was taken out from the stainless steel petri dish, heated in an oven at 230 ° C. for 1 hour to complete the curing, and an epoxy resin cured product was obtained.
- This cured epoxy resin was cut into a 3.75 mm ⁇ 7.5 mm ⁇ 33 mm rectangular parallelepiped, and a test piece for fracture toughness evaluation was produced. Furthermore, the cured epoxy resin was cut into a 2 mm ⁇ 0.5 mm ⁇ 40 mm strip to prepare a test piece for glass transition temperature evaluation.
- Example 2 A cured epoxy resin was prepared in the same manner as in Example 1 except that the resin 1 was the same amount of the resin 2 and the DDS was 1.94 g, and test pieces for evaluation were prepared.
- Example 3 A cured epoxy resin was prepared in the same manner as in Example 1 except that the resin 1 was the same amount of the resin 3 and the DDS was 1.95 g, and test pieces for evaluation were prepared.
- Example 4 A cured epoxy resin was prepared in the same manner as in Example 1 except that the resin 1 was the same amount of resin 4 and the DDS was 1.81 g, and test pieces for evaluation were prepared.
- Example 1 A cured epoxy resin was prepared in the same manner as in Example 1 except that the resin 1 was the same amount of resin 5 and the DDS was 2.30 g, and test pieces for evaluation were prepared.
- ⁇ Comparative example 2> A cured epoxy resin was prepared in the same manner as in Example 1 except that the resin 1 was the same amount of the resin 6 and the DDS was 1.97 g, and test pieces for evaluation were prepared.
- Example 3 A cured epoxy resin was prepared in the same manner as in Example 1 except that the resin 1 was the same amount of the resin 7 and the DDS was 2.11 g, and test pieces for evaluation were prepared.
- a cured epoxy resin was prepared in the same manner as in Example 1 except that the resin 1 was the same amount of the resin 8 and the DDS was 1.81 g, and test pieces for evaluation were prepared.
- the fracture toughness value was used as an index indicating the fracture toughness of the test piece.
- the fracture toughness value of the test piece was calculated by performing a three-point bending measurement based on ASTM D5045. Instron 5948 (manufactured by Instron) was used as an evaluation apparatus. The results are shown in Table 1.
- the glass transition temperature was used as an index indicating the heat resistance of the test piece.
- the glass transition temperature of the test piece was calculated by performing dynamic viscoelasticity measurement in a tensile mode. The measurement conditions were vibration frequency: 10 Hz, temperature increase rate: 5 ° C./min, and strain: 0.1%. The peak of the obtained tan ⁇ chart was regarded as the glass transition temperature.
- RSA-G2 manufactured by TA Instruments
- the epoxy resin of the example in which the ratio of the first epoxy compound is 40% or more and 50% or less of the whole epoxy resin has a temporary viscosity during the temperature rising process in the measurement of the dynamic shear viscosity.
- the epoxy resin of Comparative Example 4 in which the proportion of the first epoxy compound was less than 40% had a dynamic shear viscosity measured at 90 ° C. exceeding 10,000 Pa ⁇ s, whereas the epoxy resin of the example was All were less than 1000 Pa ⁇ s and excellent in fluidity.
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Abstract
Description
本発明は上記状況に鑑み、取り扱い性に優れるエポキシ樹脂及びエポキシ樹脂組成物、並びにこれらを用いて得られるエポキシ樹脂硬化物及び複合材料を提供することを課題とする。
<1>メソゲン構造を有する第一のエポキシ化合物と、前記メソゲン構造と同じ構造のメソゲン構造を2つ以上有する第二のエポキシ化合物と、を含むエポキシ樹脂であって、液体クロマトグラフィーにより得られる前記第一のエポキシ化合物の割合が、前記エポキシ樹脂全体の40%以上50%以下である、エポキシ樹脂。
本明細書中に段階的に記載されている数値範囲において、一つの数値範囲で記載された上限値又は下限値は、他の段階的な記載の数値範囲の上限値又は下限値に置き換えてもよい。また、本明細書中に記載されている数値範囲において、その数値範囲の上限値又は下限値は、実施例に示されている値に置き換えてもよい。
本明細書において組成物中の各成分の含有率又は含有量は、組成物中に各成分に該当する物質が複数種存在する場合、特に断らない限り、組成物中に存在する当該複数種の物質の合計の含有率又は含有量を意味する。
本明細書において「エポキシ化合物」とは、分子中にエポキシ基を有する化合物を意味する。「エポキシ樹脂」とは、複数のエポキシ化合物を集合体として捉える概念であって硬化していない状態のものを意味する。
本実施形態のエポキシ樹脂は、メソゲン構造を有する第一のエポキシ化合物と、前記メソゲン構造と同じ構造のメソゲン構造を2つ以上有する第二のエポキシ化合物と、を含むエポキシ樹脂であって、液体クロマトグラフィーにより得られる前記第一のエポキシ化合物の割合が、前記エポキシ樹脂全体の40%以上50%以下である。
第一のエポキシ化合物に由来するピークの面積の割合(%)=(第一のエポキシ化合物に由来するピークの面積/全てのエポキシ化合物に由来するピークの合計面積)×100
第一のエポキシ化合物は、メソゲン構造を有するエポキシ化合物であれば特に制限されない。
メソゲン構造は液晶性の発現に寄与する部分構造であり、メソゲン構造としては、例えば、ビフェニル構造、フェニルベンゾエート構造、シクロヘキシルベンゾエート構造、アゾベンゼン構造、スチルベン構造、ターフェニル構造、ナフタレン構造、アントラセン構造、これらの誘導体、及びこれらのメソゲン構造の2つ以上が結合基を介して結合した構造が挙げられる。なお、メソゲン構造を有する化合物は、反応誘起で液晶性を示す場合もあるため、硬化物として液晶性を示すか否かが重要である。
エポキシ樹脂に含まれる第一のエポキシ化合物は、1種のみでも分子構造の異なる2種以上であってもよい。
第二のエポキシ化合物は、第一のエポキシ化合物が有するメソゲン構造と同じ構造のメソゲン構造を2つ以上有するエポキシ化合物であれば特に制限されない。
エポキシ樹脂が第一のエポキシ化合物に加えて第二のエポキシ化合物を含む場合は、エポキシ樹脂が第一のエポキシ化合物のみを含む場合に比べてエポキシ化合物の溶融点以下での粘度が低くなる傾向にある。
あるいは、例えば、第一のエポキシ化合物と、第一のエポキシ化合物のエポキシ基と反応しうる官能基を有する化合物を、必要に応じて用いる反応触媒と溶媒を用いずに混合し、加熱しながら撹拌することで、第二のエポキシ化合物を合成することができる。
ジアミノベンゼン化合物としては、1,2-ジアミノベンゼン、1,3-ジアミノベンゼン、1,4-ジアミノベンゼン、これらの誘導体等が挙げられる。
ジヒドロキシビフェニル化合物としては、3,3’-ジヒドロキシビフェニル、3,4’-ジヒドロキシビフェニル、4,4’-ジヒドロキシビフェニル、これらの誘導体等が挙げられる。
ジアミノビフェニル化合物としては、3,3’-ジアミノビフェニル、3,4’-ジアミノビフェニル、4,4’-ジアミノビフェニル、これらの誘導体等が挙げられる。
特定芳香族化合物の誘導体としては、特定芳香族化合物のベンゼン環に炭素数1~8のアルキル基等の置換基が結合した化合物が挙げられる。特定芳香族化合物は、1種を単独で用いてもよく、2種以上を併用してもよい。
有機リン化合物の好ましい例としては、有機ホスフィン化合物、有機ホスフィン化合物に無水マレイン酸、キノン化合物、ジアゾフェニルメタン、フェノール樹脂等のπ結合をもつ化合物を付加してなる分子内分極を有する化合物、有機ホスフィン化合物と有機ボロン化合物との錯体などが挙げられる。
まず、第一のエポキシ化合物を反応容器に投入し、必要に応じて溶媒を入れ、オイルバス又は熱媒により反応温度まで加温し、第一のエポキシ化合物を溶解する。そこに第一のエポキシ化合物のエポキシ基と反応しうる官能基を有する化合物を投入し、次いで必要に応じて反応触媒を投入し、反応を開始させる。次いで、必要に応じて減圧下で溶媒を留去することで、第二のエポキシ化合物が得られる。
液体クロマトグラフィーは、試料濃度を0.5質量%とし、移動相にテトラヒドロフランを用い、流速を1.0ml/minとして行う。検量線はポリスチレン標準サンプルを用いて作成し、それを用いてポリスチレン換算値でMn及びMwを測定する。
測定は、例えば、株式会社日立製作所製の高速液体クロマトグラフ「L6000」と、株式会社島津製作所製のデータ解析装置「C-R4A」を用いて行うことができる。カラムとしては、例えば、東ソー株式会社製のGPCカラムである「G2000HXL」及び「G3000HXL」を用いることができる。
本実施形態のエポキシ樹脂組成物は、上述した実施形態のエポキシ樹脂と、硬化剤と、を含む。
硬化剤は、本実施形態のエポキシ樹脂組成物に含まれるエポキシ樹脂と硬化反応を生じることができる化合物であれば、特に制限されない。硬化剤の具体例としては、アミン硬化剤、フェノール硬化剤、酸無水物硬化剤、ポリメルカプタン硬化剤、ポリアミノアミド硬化剤、イソシアネート硬化剤、ブロックイソシアネート硬化剤等が挙げられる。硬化剤は、1種を単独で用いても2種以上を併用してもよい。
エポキシ樹脂組成物は、必要に応じてエポキシ樹脂と硬化剤以外のその他の成分を含んでもよい。例えば、硬化触媒、フィラー等を含んでもよい。硬化触媒の具体例としては、多量体の合成に使用しうる反応触媒として例示した化合物が挙げられる。
本実施形態のエポキシ樹脂組成物の用途は特に制限されないが、エポキシ樹脂組成物の比較的急速な加温を伴う加工方法にも好適に用いることができる。例えば、繊維間の空隙にエポキシ樹脂組成物を加温しながら含浸する工程を伴うFRPの製造、エポキシ樹脂組成物を加温しながらスキージ等で広げる工程を伴うシート状物の製造などにも好適に用いることができる。
本実施形態のエポキシ樹脂組成物は、硬化物中のボイドの発生を抑制する観点から粘度低下のための溶剤の添加を省略又は低減することが望まれる加工方法にも好適に用いることができる。
本実施形態のエポキシ樹脂硬化物は、本実施形態のエポキシ樹脂組成物を硬化して得られる。本実施形態の複合材料は、本実施形態のエポキシ樹脂硬化物と、強化材と、を含む。
500mLの三口フラスコに、第一のエポキシ化合物(4-{4-(2,3-エポキシプロポキシ)フェニル}シクロヘキシル=4-(2,3-エポキシプロポキシ)ベンゾエート、下記構造、エポキシ当量:224g/eq)を50g量り取り、そこにプロピレングリコールモノメチルエーテル(和光純薬工業株式会社製)を100g添加した。三口フラスコに冷却管及び窒素導入管を設置し、溶媒に漬かるように撹拌羽を取り付けた。この三口フラスコを120℃のオイルバスに浸漬し、撹拌を開始した。エポキシモノマーが溶解し、透明な溶液になったことを確認した後、ヒドロキノン(和光純薬工業株式会社製、水酸基当量:55g/eq)をエポキシ基(A)とヒドロキノン由来のフェノール性水酸基(B)の当量比(A/B)が100/25となるように添加(3.07g)し、さらに反応触媒としてトリフェニルホスフィン(和光純薬工業株式会社製)を0.5g添加し、120℃のオイルバス温度で加熱を継続した。3時間加熱を継続した後に、反応溶液からプロピレングリコールモノメチルエーテルを減圧留去し、残渣を室温(25℃)まで冷却することにより、第一のエポキシ化合物の一部がヒドロキノンと反応して得られた第二のエポキシ化合物を含む樹脂1を得た。
合成に使用した第一のエポキシ化合物は室温では粉末状(結晶相)であり、150℃でネマチック相へ、210℃で等方相へと転移する。製造方法等については特許第5471975号を参照できる。
なお、エポキシ樹脂の作製に用いた第一のエポキシ化合物は、27.7分のところにピークトップを有していた。
固形分量(%)=(30分間放置した後の計測量/加熱前の計測量)×100
ヒドロキノンの代わりにレゾルシノール(和光純薬工業株式会社製、水酸基当量:55g/eq)を、エポキシ基(A)とレゾルシノール由来のフェノール性水酸基(B)の当量比(A/B)が100/25となるように添加(3.07g)したこと以外は実施例1と同様にして、第一のエポキシ化合物の一部がレゾルシノールと反応して得られた第二のエポキシ化合物を含む樹脂2を得た。
ヒドロキノンの代わりに、カテコール(東京化成工業株式会社製、水酸基当量:55g/eq)をエポキシ基(A)とカテコール由来のフェノール性水酸基(B)の当量比(A/B)が100/25となるように添加(3.07g)したこと以外は実施例1と同様にして、第一のエポキシ化合物の一部がカテコールと反応して得られた第二のエポキシ化合物を含む樹脂3を得た。
第一のエポキシ化合物の量を35gに、プロピレングリコールモノメチルエーテルの量を70gに、トリフェニルホスフィンの量を0.35gにそれぞれ変更したことと、ヒドロキノンの代わりに4,4’-ジヒドロキシビフェニル(和光純薬工業株式会社製、水酸基当量:93g/eq)をエポキシ基(A)と4,4’-ジヒドロキシビフェニル由来のフェノール性水酸基(B)の当量比(A/B)が100/25となるように添加(3.64g)したこと以外は実施例1と同様にして、第一のエポキシ化合物の一部が4,4’-ジヒドロキシビフェニルと反応して得られた第二のエポキシ化合物を含む樹脂4を得た。
ヒドロキノンを、エポキシ基(A)とヒドロキノン由来のフェノール性水酸基(B)の当量比(A/B)が100/13となるように添加(1.60g)した以外は実施例1と同様にして、第一のエポキシ化合物の一部がヒドロキノンと反応して得られた第二のエポキシ化合物を含む樹脂5を得た。
プロピレングリコールモノメチルエーテルの代わりにシクロヘキサノン(和光純薬工業株式会社製)を80g添加したことと、ヒドロキノンを、エポキシ基(A)とヒドロキノン由来のフェノール性水酸基(B)の当量比(A/B)が100/25となるように添加(3.07g)したことと、オイルバスの加熱温度を150℃としたこと以外は実施例1と同様にして、第一のエポキシ化合物の一部がヒドロキノンと反応して得られた第二のエポキシ化合物を含む樹脂6を得た。
レゾルシノールを、エポキシ基(A)とレゾルシノール由来のフェノール性水酸基(B)の当量比(A/B)が100/20となるように添加(2.5g)した以外は実施例2と同様にして、第一のエポキシ化合物の一部がレゾルシノールと反応して得られた第二のエポキシ化合物を含む樹脂7を得た。
レゾルシノールを、エポキシ基(A)とレゾルシノール由来のフェノール性水酸基(B)の当量比(A/B)が100/30となるように添加(3.7g)した以外は実施例2と同様にして、第一のエポキシ化合物の一部がレゾルシノールと反応して得られた第二のエポキシ化合物を含む樹脂8を得た。
樹脂1~6の粘度挙動の評価を、動的せん断粘度(Pa・s)を測定することにより行った。動的せん断粘度(Pa・s)は、JIS K 7244-10の規格に従い、レオメータ(MCR-301、アントンパール社製)により振動モードで測定した。測定には直径12mmの平行平板プレートを用い、測定条件は、周波数1Hz、ギャップ0.2mm、ひずみ2%とした。
具体的には、エポキシ樹脂を150℃で3分以上放置して溶融させた後、150℃から30℃まで2℃/分の速度で降温させ、続けて30℃から150℃まで2℃/分の速度で昇温させ、その間の動的せん断粘度を1点/℃以上の間隔で測定した。
30℃から150℃までの昇温過程において、粘度が一時的に増加する挙動が認められた場合は「有」、粘度が一時的に増加することなく粘度が低下した場合は「無」として評価した。結果を表1に示す。また、昇温過程において90℃で測定された動的せん断粘度(Pa・s)の値を表1に示す。
樹脂1を10gと、硬化剤として4,4’-ジアミノジフェニルスルホン(以下、DDSと記す)とを1.90g量り取り、ステンレスシャーレに入れた。このとき、配合量はエポキシ基とDDS由来のアミノ基の当量比が1/1となるように計算した。それをホットプレートで180℃に加熱し、ステンレスシャーレ内の樹脂1とDDSとをスパチュラでかき混ぜながら溶融させ、そのまま1時間加熱した。さらにホットプレートの温度を230℃に上げ、1時間加熱し、硬化物を得た。常温(25℃)まで冷却した後、ステンレスシャーレから硬化物を取り出し、オーブンにて230℃で1時間加熱して硬化を完了させて、エポキシ樹脂硬化物を得た。このエポキシ樹脂硬化物を3.75mm×7.5mm×33mmの直方体に切り出し、破壊靱性評価用の試験片を作製した。さらに、エポキシ樹脂硬化物を2mm×0.5mm×40mmの短冊状に切り出し、ガラス転移温度評価用の試験片を作製した。
樹脂1を同量の樹脂2とし、DDSを1.94gとした以外は実施例1と同様にしてエポキシ樹脂硬化物を作製し、評価用の試験片をそれぞれ作製した。
樹脂1を同量の樹脂3とし、DDSを1.95gとした以外は実施例1と同様にしてエポキシ樹脂硬化物を作製し、評価用の試験片をそれぞれ作製した。
樹脂1を同量の樹脂4とし、DDSを1.81gとした以外は実施例1と同様にしてエポキシ樹脂硬化物を作製し、評価用の試験片をそれぞれ作製した。
樹脂1を同量の樹脂5とし、DDSを2.30gとした以外は実施例1と同様にしてエポキシ樹脂硬化物を作製し、評価用の試験片をそれぞれ作製した。
樹脂1を同量の樹脂6とし、DDSを1.97gとした以外は実施例1と同様にしてエポキシ樹脂硬化物を作製し、評価用の試験片をそれぞれ作製した。
樹脂1を同量の樹脂7とし、DDSを2.11gとした以外は実施例1と同様にしてエポキシ樹脂硬化物を作製し、評価用の試験片をそれぞれ作製した。
樹脂1を同量の樹脂8とし、DDSを1.81gとした以外は実施例1と同様にしてエポキシ樹脂硬化物を作製し、評価用の試験片をそれぞれ作製した。
硬化物にスメクチック構造が形成されているか否かの確認をX線回折測定(株式会社リガク製のX線回折装置を使用)することにより行った。測定は、CuKα1線を用い、管電圧40kV、管電流20mA、サンプリング幅0.01°、走査速度1°/分、2θ=2°~30°の範囲で行った。2θ=2°~10°の範囲に回折ピークが現れた場合はスメクチック構造が形成されていると判断した。結果を表1に示す。
試験片の破壊靱性を示す指標として、破壊靱性値を用いた。試験片の破壊靱性値は、ASTM D5045に基づいて3点曲げ測定を行って算出した。評価装置としてはインストロン5948(インストロン社製)を用いた。結果を表1に示す。
試験片の耐熱性を示す指標として、ガラス転移温度を用いた。試験片のガラス転移温度は、引張りモードによる動的粘弾性測定を行って算出した。測定条件は、振動数:10Hz、昇温速度:5℃/min、歪み:0.1%とした。得られたtanδチャートのピークをガラス転移温度とみなした。評価装置としてはRSA-G2(ティー・エイ・インスツルメント社製)を用いた。結果を表1に示す。
以上より、本実施形態のエポキシ樹脂は、取り扱い性に優れていることがわかった。
また、実施例1~4で作製したエポキシ樹脂の硬化物は、いずれも高い破壊じん性値と高いガラス転移温度を示した。
本明細書に記載された全ての文献、特許出願、および技術規格は、個々の文献、特許出願、および技術規格が参照により取り込まれることが具体的かつ個々に記された場合と同程度に、本明細書中に援用されて取り込まれる。
Claims (9)
- メソゲン構造を有する第一のエポキシ化合物と、前記メソゲン構造と同じ構造のメソゲン構造を2つ以上有する第二のエポキシ化合物と、を含むエポキシ樹脂であって、液体クロマトグラフィーにより得られる前記第一のエポキシ化合物の割合が、前記エポキシ樹脂全体の40%以上50%以下である、エポキシ樹脂。
- 前記第二のエポキシ化合物が、前記一般式(I)で表される構造を2つ有するエポキシ化合物を含む、請求項3に記載のエポキシ樹脂。
- 請求項1~請求項5のいずれか1項に記載のエポキシ樹脂と、硬化剤と、を含む、エポキシ樹脂組成物。
- 硬化させた際にスメクチック構造を形成可能である、請求項6に記載のエポキシ樹脂組成物。
- 請求項6又は請求項7に記載のエポキシ樹脂組成物の硬化物である、エポキシ樹脂硬化物。
- 請求項8に記載のエポキシ樹脂硬化物と、強化材と、を含む複合材料。
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