WO2019198703A1 - 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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- WO2019198703A1 WO2019198703A1 PCT/JP2019/015427 JP2019015427W WO2019198703A1 WO 2019198703 A1 WO2019198703 A1 WO 2019198703A1 JP 2019015427 W JP2019015427 W JP 2019015427W WO 2019198703 A1 WO2019198703 A1 WO 2019198703A1
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- WIPO (PCT)
- Prior art keywords
- epoxy
- epoxy resin
- mesogenic
- epoxy compound
- compound
- Prior art date
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- 125000003700 epoxy group Chemical group 0.000 claims description 45
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 230000028161 membrane depolarization Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- PKXSNWGPLBAAJQ-UHFFFAOYSA-N naphthalene-1,3-diamine Chemical compound C1=CC=CC2=CC(N)=CC(N)=C21 PKXSNWGPLBAAJQ-UHFFFAOYSA-N 0.000 description 1
- OKBVMLGZPNDWJK-UHFFFAOYSA-N naphthalene-1,4-diamine Chemical compound C1=CC=C2C(N)=CC=C(N)C2=C1 OKBVMLGZPNDWJK-UHFFFAOYSA-N 0.000 description 1
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- FCJSHPDYVMKCHI-UHFFFAOYSA-N phenyl benzoate Chemical group C=1C=CC=CC=1C(=O)OC1=CC=CC=C1 FCJSHPDYVMKCHI-UHFFFAOYSA-N 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical group C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/38—Polymers
- C09K19/3833—Polymers with mesogenic groups in the side chain
- C09K19/3876—Polyoxyalkylene polymers
- C09K19/388—Polyepoxides
-
- 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
- C08G59/223—Di-epoxy compounds together with monoepoxy 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
- C08G59/40—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
- C08G59/5033—Amines aromatic
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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
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
- C08G59/063—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with epihalohydrins
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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
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- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
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- C08G59/066—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with chain extension or advancing agents
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- 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
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
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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
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
- C08J5/243—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using carbon fibres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
- C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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- C08J5/246—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using polymer based synthetic fibres
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/247—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using fibres of at least two types
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- 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
-
- 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
- C08G59/182—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 using pre-adducts of epoxy compounds with curing agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; 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 resin is widely used as a matrix resin for fiber reinforced plastic (FRP). Recently, epoxy resins have also been used as matrix resins for FRP used in aerospace applications that require high levels of physical properties such as fracture toughness, elasticity, and heat resistance. However, thermosetting resins such as epoxy resins tend to be inferior in fracture toughness while being excellent in heat resistance as compared to thermoplastic resins.
- Epoxy resins having a mesogen structure in the molecule (hereinafter also referred to as mesogen-containing epoxy resins) generally have higher crystallinity and higher viscosity than other epoxy resins. For this reason, sufficient fluidity may not be obtained during work.
- the mesogen-containing epoxy resin described in Patent Document 1 has a low softening point, but is still highly crystalline and has a high viscosity under working temperature conditions, so that it is difficult to apply without solvent. There is room for improvement from the viewpoint of process compatibility. In addition, even if the viscosity can be reduced under the temperature conditions at the time of operation, other factors (for example, if the resin is sheared in the mold and flowed while shearing, the molecules are oriented and the viscosity increases). It is also necessary to consider the possibility of affecting the process compatibility of the epoxy resin. In view of the above situation, an object of the present invention is to provide an epoxy resin and an epoxy resin composition excellent in process compatibility, and an epoxy resin cured product and a composite material obtained by using them.
- Means for solving the above problems include the following embodiments.
- An epoxy compound having a mesogenic structure is included, and in the measurement of dynamic shear viscosity, the initial dynamic shear viscosity is ⁇ ′1 (Pa ⁇ s), and the maximum value of the dynamic shear viscosity during measurement is ⁇ ′.
- the epoxy resin according to ⁇ 1> including an epoxy compound represented by the following general formula (1).
- R 1 , R 2 and R 3 each independently represent a monovalent group, and at least one of the monovalent groups represented by R 1 , R 2 and R 3 has a mesogenic structure. In addition, at least one of the monovalent groups represented by R 1 , R 2 and R 3 has an epoxy group. ⁇ 3> including an epoxy compound A having two or more mesogenic structures and one or more phenylene groups, and an epoxy compound B having two or more mesogenic structures and one or more divalent biphenyl groups The epoxy resin as described in ⁇ 1>.
- ⁇ 4> two aromatic rings forming a divalent biphenyl structure, and a mesogenic structure bonded to each of the two aromatic rings, wherein at least one of the mesogenic structures is a molecular axis of the divalent biphenyl structure
- the epoxy resin according to ⁇ 1> comprising an epoxy compound that is bonded to the aromatic ring at an angle.
- ⁇ 5> The epoxy resin according to any one of ⁇ 1> to ⁇ 4>, wherein the initial dynamic shear viscosity ⁇ ′1 is 200 Pa ⁇ s or less.
- R 1 , R 2 and R 3 each independently represent a monovalent group, and at least one of the monovalent groups represented by R 1 , R 2 and R 3 has a mesogenic structure. In addition, at least one of the monovalent groups represented by R 1 , R 2 and R 3 has an epoxy group.
- ⁇ 8> An epoxy resin composition comprising the epoxy resin according to any one of ⁇ 1> to ⁇ 7> and a curing agent.
- ⁇ 9> An epoxy resin containing an epoxy compound having a mesogenic structure and a curing agent. In the measurement of the dynamic shear viscosity, the initial dynamic shear viscosity is ⁇ ′3 (Pa ⁇ s), and the measurement is in progress.
- ⁇ 10> A cured epoxy resin obtained by curing the epoxy resin composition according to ⁇ 8> or ⁇ 9>.
- ⁇ 11> A composite material comprising the cured epoxy resin according to ⁇ 10> and a reinforcing material.
- an epoxy resin and an epoxy resin composition excellent in process compatibility and an epoxy resin cured product and a composite material obtained by using these.
- the term “process” includes a process that is independent of other processes and includes the process if the purpose of the process is achieved even if it cannot be clearly distinguished from the other processes.
- numerical ranges indicated 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 description.
- the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples.
- each component may contain a plurality of corresponding substances.
- the content or content of each component is the total content or content of the multiple types of substances present in the composition unless otherwise specified.
- a plurality of particles corresponding to each component may be included.
- the particle diameter of each component means a value for a mixture of the multiple types of particles present in the composition unless otherwise specified.
- 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 first embodiment includes an epoxy compound having a mesogenic structure (hereinafter also referred to as a mesogen-containing epoxy compound), and the initial dynamic shear viscosity is ⁇ ′1 (Pa ⁇ s) in the measurement of the dynamic shear viscosity. ), And the maximum value of the dynamic shear viscosity during the measurement is ⁇ ′2 (Pa ⁇ s), the value of ⁇ ′2 / ⁇ ′1 is 3 or less.
- the epoxy resin having the above configuration is excellent in process compatibility. More specifically, the present inventors have clarified that the viscosity of an epoxy resin having a mesogenic structure may increase regardless of temperature conditions when shear stress is applied. Further investigation based on this finding revealed that the epoxy resin having a value of ⁇ ′2 / ⁇ ′1 of 3 or less obtained by measuring the dynamic shear viscosity suppressed an increase in viscosity even when a shear stress was applied. Therefore, it has been found that good fluidity can be maintained even when a process of applying a shear stress before curing such as kneading and coating is involved. Therefore, the epoxy resin of the present disclosure is excellent in adaptability to various processes.
- the dynamic shear viscosity of the epoxy resin can be measured using a viscoelasticity measuring device. Specifically, the gap between the parallel plate and the stage of the viscoelasticity measuring device: 0.05 mm, frequency: 0.5 Hz, strain: 8000%, measurement temperature: 80 ° C. (constant), and continuously measured for 80 minutes. Do.
- the viscoelasticity measuring device for example, MCR-301 manufactured by Anton Paar can be used.
- ⁇ ′2 / ⁇ ′1 is not particularly limited as long as it is 3 or less, but it can be said that the smaller the value, the better the viscosity stability when applying a shear stress and the better the process suitability.
- the value of ⁇ ′2 / ⁇ ′1 is preferably 2.5 or less, and more preferably 2 or less.
- the absolute value of the dynamic shear viscosity in the above measurement is not particularly limited.
- the initial dynamic shear viscosity ⁇ ′1 is preferably 200 Pa ⁇ s or less, more preferably 100 Pa ⁇ s or less, and further preferably 50 Pa ⁇ s or less. preferable.
- the method for obtaining an epoxy resin having a value of ⁇ ′2 / ⁇ ′1 of 3 or less obtained in the dynamic viscoelasticity measurement is not particularly limited. For example, it can be obtained by appropriately controlling the structure of the mesogen-containing epoxy compound contained in the epoxy resin.
- the mesogen structure of the mesogen-containing epoxy compound include a biphenyl structure, a phenylbenzoate structure, a cyclohexylbenzoate structure, an azobenzene structure, a stilbene structure, a terphenyl structure, an anthracene structure, derivatives thereof, and two or more of these mesogen structures.
- bonded through the coupling group are mentioned.
- the mesogen-containing epoxy compound Since the mesogen-containing epoxy compound has a linear and rigid molecular structure, the mesogen-containing epoxy compound has a property of easily forming a higher order structure in the cured product by aligning molecules in a certain direction.
- 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 state 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, it is more preferable to form a higher-order structure having a smectic structure from the viewpoint of thermal conductivity and fracture toughness of the cured product.
- Whether or not a smectic structure is formed in the cured epoxy resin can also be determined by performing X-ray diffraction measurement in addition to the above-mentioned observation with a polarizing microscope.
- X-ray diffraction measurement can be performed, for example, using an X-ray diffraction apparatus manufactured by Rigaku Corporation.
- the mesogen structure of the mesogen-containing epoxy compound may be a structure represented by the following general formula (M).
- X represents a single bond or at least one linking group selected from the group (A) consisting of the following divalent groups.
- Y independently represents an aliphatic hydrocarbon group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, or an acetyl group.
- n independently represents an integer of 0 to 4. * Represents a bonding site with an adjacent atom.
- each Y independently represents an aliphatic hydrocarbon group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, or a nitro group.
- n independently represents an integer of 0 to 4
- k represents an integer of 0 to 7
- m represents an integer of 0 to 8
- l represents an integer of 0 to 12.
- each Y is independently not present (n, k, m or l is 0) or preferably an alkyl group having 1 to 3 carbon atoms, and may be absent or a methyl group. More preferably, it is more preferable that it does not exist.
- X is at least one linking group selected from the group (A) consisting of the above divalent groups, the group consisting of the following divalent groups (Aa And at least one linking group selected from the group (Aa), and more preferably a linking group containing at least one cyclic structure.
- each Y independently represents an aliphatic hydrocarbon group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, or a nitro group.
- n independently represents an integer of 0 to 4
- k represents an integer of 0 to 7
- m represents an integer of 0 to 8
- l represents an integer of 0 to 12.
- each Y is independently not present (n, k, m or l is 0) or preferably an alkyl group having 1 to 3 carbon atoms, and may be absent or a methyl group. More preferably, it is more preferable that it does not exist.
- the mesogenic structure represented by the general formula (M) is preferably a mesogenic structure represented by the following general formula (M-1).
- Preferable examples of the mesogen structure represented by the general formula (M) include a biphenyl structure and a structure in which three or more 6-membered ring groups are connected in a straight chain, and more preferable examples include the following general formula (M -2) to mesogenic structures represented by formula (M-4).
- M-2 general formulas (M-2) to (M-4)
- the definitions and preferred examples of Y, n and * are the same as the definitions and preferred examples of Y, n and * in general formula (M).
- the epoxy resin preferably contains a multimer (preferably a dimer) of a mesogen-containing epoxy compound.
- a multimer preferably a dimer
- an epoxy compound having a plurality of the same mesogenic structures in the molecule is referred to as “multimer”
- an epoxy compound having two of the same mesogenic structures in the molecule is referred to as “dimer”.
- the multimer of the mesogen-containing epoxy compound may be, for example, a reaction product of a mesogen-containing epoxy compound and a compound having a functional group (hydroxyl group, amino group, etc.) that can react with the epoxy group of the mesogen-containing epoxy compound. Good.
- the epoxy resin may contain a mesogen-containing epoxy compound having one mesogen structure in the molecule (hereinafter also referred to as mesogen epoxy monomer).
- mesogen epoxy monomer examples include an epoxy compound having a structure represented by the following general formula (1-m).
- the epoxy compound represented by the general formula (1-m) is an epoxy compound having a structure represented by the following general formula (2-m). preferable.
- epoxy compound represented by the general formula (1-m) include epoxy compounds having structures represented by the following general formula (3-m) to general formula (5-m).
- the epoxy resin may include both mesogenic epoxy monomers and multimers (preferably dimers) of mesogenic epoxy monomers as mesogen-containing epoxy compounds.
- the epoxy resin of this indication is not restricted to these. Also, the details and preferred embodiments described in each exemplary embodiment can be applied to other exemplary embodiments where possible.
- the mesogen-containing epoxy compound may be an epoxy compound represented by the following general formula (1) (hereinafter also referred to as a specific epoxy compound 1).
- R 1 , R 2 and R 3 each independently represent a monovalent group, and at least one of the monovalent groups represented by R 1 , R 2 and R 3 has a mesogenic structure. In addition, at least one of the monovalent groups represented by R 1 , R 2 and R 3 has an epoxy group.
- the epoxy resin containing the specific epoxy compound 1 is suppressed in viscosity increase even when a shear stress is applied, and is excellent in viscosity stability.
- the reason for this is not necessarily clear, but it is presumed that part of the linearity of the molecular structure of the specific epoxy compound 1 is broken by the branch (portion indicated by R 3 ), and the molecular orientation during shearing is suppressed. Is done.
- the specific epoxy compound 1 includes at least one monovalent group represented by R 1 , R 2, and R 3 in the general formula (1) includes a mesogen structure, and is represented by R 1 , R 2, and R 3.
- the structure is not particularly limited as long as at least one monovalent group has an epoxy group.
- the monovalent group represented by R 1 , R 2 and R 3 may or may not have an epoxy group.
- the monovalent group represented by R 1 , R 2 and R 3 contains a mesogenic structure, the monovalent group is a combination of a mesogenic structure and another structure, even if the monovalent group consists of only a mesogenic structure. Also good.
- the monovalent group represented by R 1 , R 2 and R 3 has an epoxy group, the position of the epoxy group in the monovalent group is not particularly limited. For example, you may have at the terminal.
- the number of epoxy groups that the monovalent group has is not particularly limited, and may be one or more.
- the number of mesogenic structures that the specific epoxy compound 1 has in the molecule may be one or two or more. When the specific epoxy compound 1 has two or more mesogenic structures in the molecule, these mesogenic structures may be the same or different.
- the monovalent group represented by R 1 , R 2 and R 3 does not contain a mesogenic structure
- the monovalent group includes an aliphatic hydrocarbon group, an aliphatic hydrocarbon oxy group, and an aromatic hydrocarbon group.
- aromatic hydrocarbon oxy groups include an alkyl group and an alkenyl group
- examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group.
- the number of carbon atoms of the monovalent group is not particularly limited, but may be 20 or less, for example, 15 or less. There may be.
- the monovalent group represented by R 1 , R 2 and R 3 may be unsubstituted or may have a substituent.
- the specific epoxy compound 1 may be such that at least a monovalent group represented by R 1 and R 2 includes a mesogenic structure, and a monovalent group represented by R 1 , R 2, and R 3. All of the groups may contain a mesogenic structure.
- the specific epoxy compound 1 may be one in which at least a monovalent group represented by R 1 and R 2 has an epoxy group at the terminal, and is represented by R 1 , R 2, and R 3. All of the monovalent groups may have an epoxy group at the terminal.
- the epoxy resin contains the specific epoxy compound 1 can be confirmed, for example, by whether or not a peak derived from the specific epoxy compound 1 appears in a chart obtained by gel permeation chromatography (GPC). .
- the content rate of the specific epoxy compound 1 contained in the epoxy resin is not particularly limited.
- the ratio of the area of the peak derived from the specific epoxy compound 1 to the total area of the peak derived from the epoxy compound containing two or more mesogenic structures in the main chain is 3% or more.
- the content may be as high as possible.
- the content is preferably such that the ratio is 4% or more, and more preferably 5% or more.
- the upper limit of the content rate of the specific epoxy compound 1 is not particularly limited, the content rate is preferably such that the ratio is 25% or less from the viewpoint of suppressing the increase in viscosity and the epoxy functional group concentration (epoxy equivalent).
- the total area A of peaks derived from an epoxy compound having a main chain containing two or more mesogenic structures is detected by detecting the absorbance at a wavelength of 280 nm of the epoxy resin to be measured, for example. It is obtained by subtracting the area of the peak derived from the epoxy compound having only one mesogenic structure (mesogenic epoxy monomer) from the total area of all the peaks.
- GPC measurement conditions are not particularly limited as long as a desired result can be obtained. For example, it can be set as the measurement conditions described in the Example mentioned later.
- Examples of the “main chain including two or more mesogenic structures” possessed by the epoxy compound include a structure in which two or more mesogenic structures are bonded via a divalent linking group such as an aromatic group.
- Examples of the “branch” possessed by the epoxy compound include a structure formed by a reaction of a functional group such as a divalent hydroxyl group generated at the bonding site of the structural unit forming the main chain of the epoxy compound with another compound.
- the “branch” of the epoxy compound may or may not include a mesogenic structure, and may or may not have an epoxy group.
- the excellent viscosity stability at the time of imparting shear of the epoxy resin containing the specific epoxy compound 1 can be obtained by containing an epoxy compound having at least one branch in the molecule at a predetermined ratio. Therefore, the specific structure of the epoxy compound having a branch is not particularly limited. For convenience, an epoxy compound having a specific structure (for example, an epoxy compound having a main chain including two mesogenic structures and one branch) is used. You may estimate the content rate of the specific epoxy compound 1 on the basis of the ratio of the area of the peak derived.
- the mesogen-containing epoxy compound includes an epoxy compound A having two or more mesogenic structures and one or more phenylene groups, an epoxy compound B having two or more mesogenic structures and one or more divalent biphenyl groups, and Or a combination thereof (hereinafter also referred to as a specific epoxy compound 2).
- the phenylene group when two or more mesogenic structures of the epoxy compound A include a phenylene group, the phenylene group is different from “one or more phenylene groups”.
- the divalent biphenyl group is different from “one or more divalent biphenyl groups”.
- the epoxy compound A and the epoxy compound B contained in the epoxy resin may each be one type or two or more types. Moreover, the mesogenic structure which the epoxy compound A and the epoxy compound B have may be the same or different.
- the epoxy resin containing both the epoxy compound A and the epoxy compound B has a small increase in viscosity when applied with shear stress compared to the epoxy resin containing only the epoxy compound B, and the viscosity stability is improved. I found it excellent. This is because the epoxy compound B having a biphenyl group in the molecule has a property that the molecule tends to be oriented with physical stimulation such as shear stress as compared with the epoxy compound A having a phenylene group in the molecule. By using the epoxy compound A together with the epoxy compound B, it is considered that an increase in viscosity at the time of applying shear stress is suppressed.
- the mass ratio of the epoxy compound A and the epoxy compound B in the epoxy resin is not particularly limited. From the viewpoint of achieving both low viscosity in the temperature range during work and viscosity stability under the condition where shear stress is continuously applied, the ratio of epoxy compound A to epoxy compound B (epoxy compound A: epoxy compound) B) is preferably 1: 9 to 9: 1, more preferably 3: 7 to 9: 1, still more preferably 4: 6 to 8: 2, and 6: 4 to 8: 2 is particularly preferred.
- the structures of the epoxy compound A and the epoxy compound B are not particularly limited as long as they have two or more mesogenic structures and one or more phenylene groups or divalent biphenyl groups. Further, two or more mesogenic structures contained in one molecule of the epoxy compound A and the epoxy compound B may be different or the same.
- Examples of the monovalent substituent represented by R 1 and R 2 include a monovalent hydrocarbon group and a halogen atom.
- Examples of the monovalent hydrocarbon group include an alkyl group, preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and further preferably a methyl group.
- Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom, and a fluorine atom is preferable.
- M is each independently preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0.
- the structure represented by the general formula (5A) is preferable.
- the structure represented by the following general formula (5B) is preferable.
- a structure is preferred. 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 2 and m have the general formula (5A) and the general formula (5B) *, R 1, R 2 and m This is the same as the definition and preferred examples.
- the epoxy compound A and the epoxy compound B preferably have a structure in which one phenylene group or divalent biphenyl group is arranged between two mesogenic structures.
- the epoxy compound A and the epoxy compound B may be an epoxy compound having a structure represented by the following general formula (6-1) or general formula (6-2).
- the number of mesogenic structures that the epoxy compound A and the epoxy compound B have is not particularly limited as long as it is 2 or more. From the viewpoint of reducing the viscosity during work, it is preferable that at least a part of the epoxy compound A and the epoxy compound B is a compound having two mesogenic structures (dimer).
- Examples of the structure when the epoxy compound A and the epoxy compound B are dimers include compounds represented by the following general formula (7-1) or the following general formula (7-2).
- the mesogen-containing epoxy compound has two aromatic rings forming a divalent biphenyl structure, and a mesogen structure bonded to each of the two aromatic rings, and at least one of the mesogen structures is the divalent biphenyl structure.
- An epoxy compound hereinafter also referred to as a specific epoxy compound 3) bonded to the aromatic ring at an angle with respect to the molecular axis.
- the epoxy resin containing the specific epoxy compound 3 was suppressed in the increase in viscosity even when shear stress was applied, and was excellent in viscosity stability.
- the reason for this is not necessarily clear, but at least one of the mesogen-containing epoxy compounds bonded to two aromatic rings having a divalent biphenyl structure forms an angle with the molecular axis of the biphenyl structure, whereby the molecular structure of the epoxy compound This is presumed to be caused by twisting.
- the “molecular axis of a bivalent biphenyl structure” means a carbon atom that contributes to bonding between aromatic rings that form a biphenyl structure, and a carbon of each aromatic ring that is para to the carbon atom. A line connecting atoms.
- “at least one of the mesogenic structures is bonded to the aromatic ring at an angle with the molecular axis of the divalent biphenyl structure” means that at least one of the mesogenic structures and the aromatic that forms the divalent biphenyl structure. This means that the bonding position with the ring is not on the molecular axis of the divalent biphenyl structure. More specifically, the bonding position between at least one of the mesogenic structures and the aromatic ring forming the divalent biphenyl structure is a carbon atom contributing to the bonding between the aromatic ring and another aromatic ring. On the other hand, it means a state that is ortho or meta.
- the mode in which the mesogen structure is bonded to the aromatic ring forming the divalent biphenyl structure is not particularly limited.
- the atom itself forming the mesogenic structure may be directly bonded to the aromatic ring or indirectly bonded through a linking group.
- the mesogenic structure may include a biphenyl structure. In this case, the biphenyl structure contained in the mesogenic structure is different from the biphenyl structure described above.
- divalent biphenyl structure contained in the specific epoxy compound 3 include structures represented by the following general formulas (BP1) to (BP5).
- the three-dimensional positional relationship between the two aromatic rings forming the divalent biphenyl structure is not particularly limited, and the surfaces formed by the aromatic rings may be on the same plane or different planes.
- * represents a bonding position with an adjacent atom.
- R 1 and R 2 each independently represents a monovalent substituent.
- Each m independently represents an integer of 0 to 4.
- Examples of the monovalent substituent represented by R 1 and R 2 include a monovalent hydrocarbon group and a halogen atom.
- Examples of the monovalent hydrocarbon group include an alkyl group, preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and further preferably a methyl group.
- Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom, and a fluorine atom is preferable.
- M is each independently preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0.
- both * are in the ortho position or the meta position with respect to the carbon atom contributing to the bond between the aromatic rings (that is, the general formula (BP1 ), (BP3) or (BP5)).
- At least one of * is in the ortho position with respect to the carbon atom contributing to the bond between the aromatic rings (that is, the general formula (BP1) to (A structure represented by any one of (BP3)), and both * are ortho positions with respect to the carbon atom contributing to the bond between the aromatic rings (that is, in the general formula (BP1)). It is more preferable that it is a structure represented.
- the specific epoxy compound 3 has a molecular axis of the divalent biphenyl structure with respect to an aromatic ring in which at least one of Z forms a divalent biphenyl structure in the structure represented by the general formula (6-2).
- a compound bonded at an angle may also be used. That is, at least one of Z is a compound in which an aromatic ring forming a divalent biphenyl structure is bonded in an ortho position or a meta position with respect to a carbon atom contributing to the bond between the aromatic rings. May be.
- both Z's are an aromatic ring that forms a divalent biphenyl structure.
- the divalent biphenyl structure is preferably bonded at an angle to the molecular axis. That is, it is preferable that both Z are bonded to the aromatic ring forming a divalent biphenyl structure at the ortho position or the meta position with respect to the carbon atom contributing to the bonding between the aromatic rings.
- X, Y, n, R 1 , R 2 , m and Z are X, Y, n, R 1 , R 2 , m in the general formula (6-2). And Z are the same as those defined and preferred examples.
- the number of mesogenic structures in the specific epoxy compound 3 is not particularly limited as long as it is 2 or more. From the viewpoint of reducing the viscosity of the epoxy resin, it is preferable that at least a part of the specific epoxy compound 3 is a compound (dimer) containing two mesogenic structures.
- At least one of Z is an aromatic ring forming a divalent biphenyl structure.
- Examples thereof include a structure in which the divalent biphenyl structure is bonded at an angle to the molecular axis. That is, a structure in which at least one of Z is bonded to an aromatic ring forming a divalent biphenyl structure in an ortho position or a meta position with respect to a carbon atom contributing to the bonding between the aromatic rings. .
- the epoxy resin of 2nd Embodiment contains the epoxy compound represented by following General formula (1). That is, the epoxy resin of 2nd Embodiment contains the specific epoxy compound 1 mentioned above as a mesogen containing epoxy compound.
- R 1 , R 2 and R 3 each independently represent a monovalent group, and at least one of the monovalent groups represented by R 1 , R 2 and R 3 has a mesogenic structure. In addition, at least one of the monovalent groups represented by R 1 , R 2 and R 3 has an epoxy group.
- An epoxy resin satisfying the above conditions is suppressed in viscosity increase even when shearing is applied, and is excellent in viscosity stability. For this reason, it is excellent in process adaptability. The reason for this is not necessarily clear, but it is presumed that part of the linearity of the molecular structure of the epoxy compound contained in the epoxy resin is broken by branching and the molecular orientation due to the application of shear is suppressed.
- the content of the epoxy compound represented by the general formula (1) contained in the epoxy resin is not particularly limited.
- the ratio of the area of the peak derived from the epoxy compound represented by the general formula (1) to the total area of the peak derived from the epoxy compound containing two or more mesogenic structures in the main chain The content may be 3% or more.
- the epoxy resin of the third embodiment includes an epoxy compound having a main chain including two mesogenic structures and one branch, and has two or more mesogenic structures in a chart obtained by gel permeation chromatography (GPC).
- the ratio of the area B of the peak derived from the epoxy compound in the total area A of the peaks derived from the epoxy compound having the main chain is 3% or more.
- the ratio of the area B to the total area A is not particularly limited as long as it is 3% or more. From the viewpoint of viscosity stability at the time of applying shear, it is preferably 4% or more, and more preferably 5% or more. The upper limit of the ratio is not particularly limited. From the viewpoint of suppression of viscosity increase and epoxy functional group concentration (epoxy equivalent), it is preferably 25% or less.
- An epoxy resin satisfying the above conditions is suppressed in viscosity increase even when shearing is applied, and is excellent in viscosity stability. For this reason, it is excellent in process adaptability. The reason for this is not necessarily clear, but it is presumed that a part of the linearity of the molecular structure of the epoxy compound is broken by branching and the molecular orientation due to the application of shear is suppressed.
- the total area A of peaks derived from an epoxy compound having a main chain containing two or more mesogenic structures is detected by detecting the absorbance at a wavelength of 280 nm of the epoxy resin to be measured, for example. It is obtained by subtracting the area of the peak derived from the epoxy compound having only one mesogen structure from the total area of all the peaks.
- GPC measurement conditions are not particularly limited as long as a desired result can be obtained. For example, it can be set as the measurement conditions described in the Example mentioned later.
- Examples of the “main chain containing two or more mesogen structures” of the epoxy compound include a structure in which two or more mesogen structures are bonded via a divalent linking group such as an aromatic group as necessary. Can be mentioned.
- Examples of the “branch” possessed by the epoxy compound include a structure formed by a reaction of a functional group such as a secondary hydroxyl group generated at the bonding site of the structural unit forming the main chain of the epoxy compound with another compound.
- the “branch” of the epoxy compound may or may not include a mesogenic structure, and may or may not have an epoxy group.
- the excellent viscosity stability at the time of applying shear to the epoxy resin of this embodiment can be obtained by including an epoxy compound having at least one branch in a molecule at a predetermined ratio.
- the specific structure of the epoxy compound having a branch is not particularly limited, but for convenience, the ratio of the epoxy compound having a main chain including two mesogenic structures and one branch is used as a reference.
- the epoxy resin of this embodiment may include an epoxy compound (specific epoxy compound 1) represented by the general formula (1) as a mesogen-containing epoxy compound.
- the method for synthesizing the mesogen-containing epoxy compound is not particularly limited. For example, it is obtained by reacting an epoxy compound (mesogen epoxy monomer) having a mesogen structure corresponding to the mesogen structure of the mesogen-containing epoxy compound with a compound having a functional group capable of reacting with the epoxy group of the mesogen epoxy monomer. May be.
- the mesogenic epoxy monomer may be, for example, an epoxy compound having a structure represented by the general formula (1-m) described above.
- a method for synthesizing a mesogen-containing epoxy compound by reacting a mesogen epoxy monomer with a compound having a functional group capable of reacting with an epoxy group of the mesogen epoxy monomer is not particularly limited. Specifically, for example, a mesogenic epoxy monomer, a compound having a functional group capable of reacting with the epoxy group of the mesogenic epoxy monomer, and a reaction catalyst used as necessary are dissolved in a solvent and stirred while heating. Thus, a mesogen-containing epoxy compound can be synthesized.
- a mesogen-containing epoxy compound can be synthesized by mixing a mesogenic epoxy monomer and a compound having a functional group capable of reacting with the epoxy group of the mesogenic epoxy monomer without using a solvent, and stirring while heating. it can.
- the method for introducing the structure (branch) represented by R 3 in the general formula (1) is not particularly limited.
- a secondary hydroxyl group produced by reacting a mesogenic epoxy monomer having a structure corresponding to R 1 and R 2 with a compound having a hydroxyl group as a functional group capable of reacting with an epoxy group has a structure corresponding to R 3. It can introduce
- the progress of the reaction for introducing the structure represented by R 3 into the reaction product can be controlled, for example, by appropriately selecting the type of reaction catalyst used in the reaction. That is, when a reaction catalyst having a relatively low activity is used, the reaction between the epoxy group and the hydroxyl group of the mesogenic epoxy monomer having a structure corresponding to R 1 and R 2 proceeds, while the secondary produced by the reaction. The reaction between the hydroxyl group and the epoxy group of the mesogenic epoxy monomer having a structure corresponding to R 3 does not proceed, and the ratio of the epoxy compound having a structure corresponding to R 3 is likely to be low.
- the solvent used for the synthesis is a solvent that can dissolve the mesogenic epoxy monomer and the compound having a functional group capable of reacting with the epoxy group of the mesogenic epoxy monomer, 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 amount of the solvent is not particularly limited as long as it can dissolve the mesogenic epoxy monomer, the compound having a functional group capable of reacting with the epoxy group of the mesogenic epoxy monomer, and the reaction catalyst used as necessary at the reaction temperature.
- 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 kind of the compound having a functional group capable of reacting with the epoxy group of the mesogenic epoxy monomer is not particularly limited. From the viewpoint of heat resistance of the cured product, a compound having one or more benzene rings (aromatic compound) is preferable.
- 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
- It consists of a dihydroxybiphenyl compound having a structure in which one hydroxyl group is bonded to each of two benzene rings forming a biphenyl structure, and a diaminobiphenyl compound having a structure in which one amino group is bonded to each of two benzene rings forming a biphenyl structure. It is preferably at least one selected from the group (hereinafter also referred to as a specific aromatic compound).
- dihydroxybenzene compound examples include catechol, resorcinol, hydroquinone, and derivatives thereof.
- diaminobenzene compound examples include 1,2-diaminobenzene, 1,3-diaminobenzene, 1,4-diaminobenzene, and derivatives thereof.
- Dihydroxybiphenyl compounds include 2,2′-dihydroxybiphenyl, 2,3′-dihydroxybiphenyl, 2,4′-dihydroxybiphenyl, 3,3′-dihydroxybiphenyl, 3,4′-dihydroxybiphenyl, 4,4 ′ -Dihydroxybiphenyl, derivatives thereof and the like.
- Diaminobiphenyl compounds include 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 2,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 3,4'-diaminobiphenyl, 4,4 ' -Diaminobiphenyl, derivatives thereof and the like.
- 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 or a halogen atom 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.
- 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 (tributylphosphine, etc.), Dialkyl Examples include aryl phosphine and alkyldiaryl phosphine.
- 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, phenyl-1,4-benzoquinone, hydroquinone and the like.
- 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 the reaction rate and storage stability, 0.1 to 1.5 parts by mass with respect to 100 parts by mass of the total mass of the mesogenic epoxy monomer and the compound having a functional group capable of reacting with the epoxy group of the mesogenic epoxy monomer.
- the amount is preferably part by mass, more preferably 0.2 part by mass to 1 part by mass.
- the synthesis of the mesogen-containing 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 mesogenic epoxy monomer is put into a reaction vessel, a solvent is put in if necessary, and heated to a reaction temperature with an oil bath or a heat medium to dissolve the mesogenic epoxy monomer. A compound having a functional group capable of reacting with the epoxy group of the mesogenic epoxy monomer is added thereto, and then a reaction catalyst is introduced as necessary to start the reaction. Subsequently, the mesogen containing epoxy compound is obtained by distilling a solvent off under reduced pressure as needed.
- the reaction temperature is not particularly limited as long as the reaction between the epoxy group of the mesogenic epoxy monomer and the functional group capable of reacting with the epoxy group of the mesogenic epoxy monomer proceeds.
- the reaction temperature is in the range of 100 ° C to 180 ° C. Is preferable, and the range of 100 ° C. to 150 ° C. is more preferable.
- the compounding ratio of the mesogenic epoxy monomer and the compound having a functional group capable of reacting with the epoxy group of the mesogenic epoxy monomer is not particularly limited.
- the mixing ratio in which the ratio (A: B) of the number of equivalents (A) of epoxy groups to the number of equivalents (B) of functional groups capable of reacting with epoxy groups is in the range of 10: 0.01 to 10:10 It is good.
- a blending ratio in which A: B is in the range of 10: 0.1 to 10: 5 is preferable.
- the ratio (A: B) of the number of equivalents of epoxy groups (A) to the number of equivalents of functional groups capable of reacting with epoxy groups (A: B) is 10: 1.6 to 10 :
- a blending ratio in the range of 3.0 is preferable, a blending ratio in the range of 10: 1.8 to 10: 2.9 is more preferable, and a blending ratio in the range of 10: 2.0 to 10: 2.8
- the ratio is further preferred.
- the structure of the specific epoxy compound is, for example, the molecular weight of the specific epoxy compound estimated to be obtained from the reaction between the mesogenic epoxy monomer used for the synthesis and the compound having a functional group capable of reacting with the epoxy group of the mesogenic epoxy monomer, It can be determined by comparing the molecular weight of the target compound determined by liquid chromatography performed using a liquid chromatograph equipped with UV and mass spectrum detectors.
- the weight average molecular weight (Mw) of the epoxy resin is not particularly limited. From the viewpoint of lowering the viscosity, the weight average molecular weight (Mw) of the epoxy resin is preferably selected from the range of 800 to 1300.
- 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 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 360 g / eq, more preferably 250 g / eq to 355 g / eq, and more preferably 260 g / eq to More preferably, it is 350 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 360 g / eq or less, the crosslink 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.
- Epoxy resin composition (first embodiment)>
- the epoxy resin composition of 1st Embodiment contains the epoxy resin mentioned above and a hardening
- the epoxy resin composition of the second embodiment includes an epoxy resin containing an epoxy compound having a mesogenic structure and a curing agent.
- the initial dynamic shear viscosity is ⁇ ′3 (Pa S)
- the maximum value of the dynamic shear viscosity during measurement is ⁇ ′4 (Pa ⁇ s)
- the value of ⁇ ′4 / ⁇ ′3 is 3 or less.
- the epoxy resin composition of the present embodiment is excellent in process suitability because an increase in viscosity when shear stress is applied even when the epoxy resin contains an epoxy compound having a mesogenic structure is suppressed.
- the measurement of the dynamic shear viscosity of the epoxy resin composition can be performed using a viscoelasticity measuring apparatus.
- the gap between the parallel plate and the stage of the viscoelasticity measuring apparatus is 0.2 mm
- the frequency is 1 Hz
- the strain is 1000%
- the measurement temperature is 80 ° C. (constant).
- the viscoelasticity measuring device for example, MCR-301 manufactured by Anton Paar can be used.
- ⁇ ′4 / ⁇ ′3 is not particularly limited as long as it is 3 or less, but it can be said that the smaller the value, the better the viscosity stability when applying a shear stress and the better the process suitability.
- the value of ⁇ ′4 / ⁇ ′3 is preferably 2.5 or less, more preferably 2 or less.
- the absolute value of the dynamic shear viscosity in the above measurement is not particularly limited.
- the initial dynamic shear viscosity ⁇ ′3 is preferably 500 Pa ⁇ s or less, more preferably 300 Pa ⁇ s or less, and further preferably 100 Pa ⁇ s or less. preferable.
- the epoxy resin contained in the epoxy resin composition of the present embodiment is not particularly limited as long as it contains an epoxy compound having a mesogenic structure.
- the mesogen-containing epoxy compound described above may be included.
- the type of curing agent contained in the epoxy resin composition of each of the above embodiments is not particularly limited. Specific examples 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 epoxy resin composition is preferably capable of forming a higher order structure in the cured product, and more preferably capable of forming a smectic structure.
- an amine curing agent and a phenol curing agent are preferable, and an amine curing agent is more preferable.
- amine curing agent those usually used can be used without particular limitation, and may be commercially available. Among these, from the viewpoint of heat resistance, it is preferable to use an amine curing agent having a benzene ring or a naphthalene ring, and it is more preferable to use an amine curing agent having an amino group on the benzene ring or naphthalene ring. From the viewpoint of curability, it is preferable to use a polyfunctional amine curing agent having two or more amino groups.
- amine curing agents examples include 3,3′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenylmethane, 3,3′-diethyl-4,4′-diaminodiphenylmethane, 4, 4'-diaminodiphenyl ether, 4,4'-diamino-3,3'-dimethoxybiphenyl, 4,4'-diaminophenylbenzoate, 1,5-diaminonaphthalene, 1,3-diaminonaphthalene, 1,2-phenylenediamine 1,3-phenylenediamine, 1,4-phenylenediamine, 4,4′-diaminobenzanilide, 3,3′-diaminobenzanilide, trimethylene-bis-4-aminobenzoate, 1,4-diaminonaphthalene, And 1,8-d
- the phenol curing agent examples 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.
- the low molecular weight phenol compound examples include monofunctional phenol compounds such as phenol, o-cresol, m-cresol, and p-cresol, bifunctional phenol compounds such as catechol, resorcinol, and 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 equivalent number A of the functional group of the curing agent (active hydrogen in the case of an amine curing agent) contained in the epoxy resin composition and the equivalent number B of the epoxy group of the epoxy resin.
- the amount that (A / B) is 0.3 to 3.0 is preferable, and the amount that is 0.5 to 2.0 is more preferable.
- 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 a specific epoxy compound.
- the use of the epoxy resin composition is not particularly limited, but it can be suitably used for a processing method that is required to have excellent fluidity at the time of operation because an increase in viscosity when shear stress is applied is suppressed. it can.
- it involves the production of fiber reinforced plastic (FRP) involving the step of impregnating the epoxy resin composition with heating in the voids between the fibers, and the step of spreading the epoxy resin composition with a squeegee while heating the epoxy resin composition. It can be suitably used for production of sheet-like materials.
- FRP fiber reinforced plastic
- the epoxy resin cured product of the present disclosure is obtained by curing the epoxy resin composition of the above-described embodiment.
- the composite material of the present disclosure includes the cured epoxy resin of the present disclosure 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). From the viewpoint of the strength of the composite material, the reinforcing material is preferably a carbon material, and more preferably a carbon fiber.
- the reinforcing material contained in the composite material may be one type or two or more types.
- Example 2 An epoxy resin (prepolymer) was obtained in the same manner as in Example 1 except that the same amount of addition reaction product of triphenylphosphine and hydroquinone (the following structure, molecular weight: 370.35) was used as the reaction catalyst.
- Example 3 An epoxy resin containing the specific epoxy compound 2 as a mesogen-containing epoxy compound was synthesized as follows. In a 500 ml three-necked flask, 50 g of the same mesogenic epoxy monomer as in Example 1 was weighed, and 80 g of propylene glycol monomethyl ether as a synthesis solvent was added thereto. A cooling tube and a nitrogen introducing tube were installed in the three-necked flask, and a stirring blade was attached so as to be immersed in the solvent. This three-necked flask was immersed in a 120 ° C. oil bath, and stirring was started.
- An epoxy resin containing a specific epoxy compound 2 was obtained by mixing 35.0 g of an epoxy resin containing an epoxy compound A and 15.0 g of an epoxy resin containing an epoxy compound B.
- Example 4 An epoxy resin containing the specific epoxy compound 3 as a mesogen-containing epoxy compound was synthesized as follows. To a 500 ml three-necked flask, 50 g of the same mesogenic epoxy monomer as in Example 1 was weighed, and 100 g of propylene glycol monomethyl ether as a synthesis solvent was added thereto. A cooling tube and a nitrogen introducing tube were installed in the three-necked flask, and a stirring blade was attached so as to be immersed in the solvent. This three-necked flask was immersed in an oil bath at 150 ° C., and stirring was started.
- Comparative Example 1 A multimer formed by reacting a mesogenic epoxy monomer with 4,4′-biphenol in the same manner as in Example 1 except that the reaction catalyst was changed from an addition reaction product of tributylphosphine and hydroquinone to the same amount of triphenylphosphine. And an epoxy resin (prepolymer) containing unreacted mesogenic epoxy monomer.
- the dynamic shear viscosity of the epoxy resin was measured using a viscoelasticity measuring device. Specifically, the gap between the parallel plate and the stage of the viscoelasticity measuring device (Anton Paar MCR-301): 0.05 mm, frequency: 0.5 Hz, strain: 8000%, measurement temperature: 80 ° C. (constant) In the measurement performed continuously for 80 minutes, the dynamic shear viscosity ⁇ ′1 (Pa ⁇ s) at the initial stage (immediately after the start of measurement) and the maximum value ⁇ ′2 (Pa ⁇ s) of the dynamic shear viscosity during measurement ) And measured.
- the dynamic shear viscosity of the epoxy resin composition was measured using a viscoelasticity measuring device. Specifically, the gap between the parallel plate and the stage of the viscoelasticity measuring apparatus (MCR-301 manufactured by Anton Paar): 0.2 mm, frequency: 1 Hz, strain: 1000%, measurement temperature: 80 ° C. (constant), In the measurement carried out continuously for 120 minutes, the dynamic shear viscosity ⁇ ′3 (Pa ⁇ s) at the initial stage (immediately after the start of measurement) and the maximum value ⁇ ′4 (Pa ⁇ s) of the dynamic shear viscosity during measurement was measured.
- MCR-301 manufactured by Anton Paar
- the bending elastic modulus was measured as an index for evaluating the elastic modulus of the cured epoxy resin. Specifically, the three-point bending measurement was performed on the produced test piece based on ASTM D790. Instron 5948 (Instron) was used as the evaluation device. The distance between fulcrums was 32 mm, and the test speed was 1 mm / min. The results are shown in Table 1.
- the fracture toughness value (MPa ⁇ m 1/2 ) was measured as an index for evaluating the toughness of the cured epoxy resin. Specifically, it was calculated by performing a three-point bending measurement based on ASTM D5045 for the prepared test piece. Instron 5948 (Instron) was used as the evaluation device. The results are shown in Table 1.
- the ratio of the epoxy compound having a branch contained in the synthesized epoxy resin was calculated by GPC. Specifically, the absorbance at a wavelength of 280 nm of the epoxy resin to be measured is detected, the following area A and area B are calculated from the total area of all detected peaks, and the ratio of area B to area A (%) was calculated.
- Area A Area obtained by subtracting the area of the peak derived from an epoxy compound having one mesogenic structure (unreacted mesogenic epoxy monomer) from the total area of all peaks appearing on the GPC chart (specifying the mesogenic epoxy monomer) Total area of peaks derived from multimers obtained by reaction with aromatic compounds).
- GPC measurement uses “G2000HXL” and “3000HXL” manufactured by Tosoh Corporation as analytical GPC columns, tetrahydrofuran is used for the mobile phase, the sample concentration is 0.2 mass%, and the flow rate is 1.0 ml / min. went.
- a calibration curve was prepared using a polystyrene standard sample, and Mn was calculated as a polystyrene equivalent value.
- the ratio of the number of equivalents of active hydrogen in the curing agent to the number of equivalents of epoxy groups in the epoxy resin is 1: 1.
- the epoxy resin composition is prepared by putting it into a stirring vessel of a planetary mixer and heating it to 80 ° C. to melt the resin, followed by stirring for 60 minutes at 20 rpm. did.
- the 3,3′-diaminodiphenyl sulfone was pretreated by pulverization so as to obtain a powder having an average particle diameter of 8 ⁇ m in advance.
- paintability of the epoxy resin composition was evaluated as follows. A stainless steel plate was placed on a hot plate heated to 90 ° C. and sufficiently heated, and then a PET film was placed on the stainless steel plate and fixed. Next, about 3 g of the epoxy resin composition was placed on the PET film and melted. Thereafter, the applicator heated to 90 ° C. in advance was swept with a gap of 100 ⁇ m, and the epoxy resin was stretched on the PET film. The applicability of the epoxy resin at this time was evaluated according to the following evaluation criteria. The results are shown in Table 1. A: Epoxy resin maintains fluidity and can sweep 10 cm with a uniform appearance.
- B The epoxy resin maintains fluidity to a certain extent and can be swept by 10 cm, but is partially faint.
- C The epoxy resin becomes lumpy and cannot be swept uniformly, or the viscosity is too high to sweep over 10 cm, or it cannot be swept at all.
- the epoxy resin synthesized in the comparative example and the epoxy resin composition containing the epoxy resin and the curing agent have a large viscosity increase rate when a shear stress is applied, and the viscosity increases significantly when stirred using a planetary mixer. It was not possible to apply without showing.
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Abstract
Description
分子中にメソゲン構造を有するエポキシ樹脂(以下、メソゲン含有エポキシ樹脂とも称する)は、一般に他のエポキシ樹脂に比べて結晶性が強く、粘度が高い。このため、作業時に充分な流動性が得られない場合がある。そこで、メソゲン含有エポキシ樹脂の流動性を向上する方法として、メソゲン構造を有するエポキシモノマーと2価フェノール化合物とを反応させて、特定範囲の分子量のエポキシ化合物の状態にする技術が提案されている(例えば、特許文献1参照)。
本発明は上記状況に鑑み、プロセス適合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エポキシ化合物を含み、動的せん断粘度の測定において、初期の動的せん断粘度をη’1(Pa・s)とし、測定中の動的せん断粘度の最大値をη’2(Pa・s)としたとき、η’2/η’1の値が3以下である、エポキシ樹脂。
<2>下記一般式(1)で表されるエポキシ化合物を含む、<1>に記載のエポキシ樹脂。
<3>2つ以上のメソゲン構造と1つ以上のフェニレン基とを有するエポキシ化合物Aと、2つ以上のメソゲン構造と1つ以上の2価のビフェニル基とを有するエポキシ化合物Bと、を含む、<1>に記載のエポキシ樹脂。
<4>2価のビフェニル構造を形成する2つの芳香環と、前記2つの芳香環のそれぞれに結合したメソゲン構造とを有し、前記メソゲン構造の少なくとも一方が前記2価のビフェニル構造の分子軸と角度をなして前記芳香環に結合しているエポキシ化合物を含む、<1>に記載のエポキシ樹脂。
<5>初期の動的せん断粘度η’1が200Pa・s以下である、<1>~<4>のいずれか1項に記載のエポキシ樹脂。
<6>下記一般式(1)で表されるエポキシ化合物を含む、エポキシ樹脂。
<7>2つのメソゲン構造を含む主鎖と1つの分岐とを有するエポキシ化合物を含み、ゲルパーミエーションクロマトグラフィー(GPC)により得られるチャートにおいて、2つ以上のメソゲン構造を含む主鎖を有するエポキシ化合物に由来するピークの合計面積Aに占める前記エポキシ化合物に由来するピークの面積Bの割合が3%以上である、エポキシ樹脂。
<8><1>~<7>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。
<9>メソゲン構造を有するエポキシ化合物を含むエポキシ樹脂と、硬化剤と、を含み、動的せん断粘度の測定において、初期の動的せん断粘度をη’3(Pa・s)とし、測定中の動的せん断粘度の最大値をη’4(Pa・s)としたとき、η’4/η’3の値が3以下である、エポキシ樹脂組成物。
<10><8>又は<9>に記載のエポキシ樹脂組成物を硬化して得られる、エポキシ樹脂硬化物。
<11><10>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。
本開示において「~」を用いて示された数値範囲には、「~」の前後に記載される数値がそれぞれ最小値及び最大値として含まれる。
本開示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、本開示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。
本開示において各成分は該当する物質を複数種含んでいてもよい。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、各成分の含有率又は含有量は、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。
本開示において各成分に該当する粒子は複数種含んでいてもよい。組成物中に各成分に該当する粒子が複数種存在する場合、各成分の粒子径は、特に断らない限り、組成物中に存在する当該複数種の粒子の混合物についての値を意味する。
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。
第1実施形態のエポキシ樹脂は、メソゲン構造を有するエポキシ化合物(以下、メソゲン含有エポキシ化合物とも称する)を含み、動的せん断粘度の測定において、初期の動的せん断粘度をη’1(Pa・s)とし、測定中の動的せん断粘度の最大値をη’2(Pa・s)としたとき、η’2/η’1の値が3以下である。
本開示では分子中に同じメソゲン構造を複数個有するエポキシ化合物を「多量体」と称し、分子中に同じメソゲン構造を2個有するエポキシ化合物を「二量体」と称する。
メソゲン含有エポキシ化合物は、下記一般式(1)で表されるエポキシ化合物(以下、特定エポキシ化合物1とも称する)であってもよい。
R1、R2及びR3で表される1価の基がメソゲン構造を含む場合、当該1価の基はメソゲン構造のみからなっていても、メソゲン構造と他の構造との組合せであってもよい。
R1、R2及びR3で表される1価の基がエポキシ基を有する場合、当該1価の基におけるエポキシ基の位置は特に制限されない。例えば、末端に有していてもよい。また、当該1価の基が有するエポキシ基の数は特に制限されず、1つでも複数であってもよい。
特定エポキシ化合物1の含有率の上限は特に制限されないが、粘度上昇の抑制及びエポキシ官能基濃度(エポキシ当量)の観点からは上記割合が25%以下となるような含有率であることが好ましい。
メソゲン含有エポキシ化合物は、2つ以上のメソゲン構造と1つ以上のフェニレン基とを有するエポキシ化合物Aと、2つ以上のメソゲン構造と1つ以上の2価のビフェニル基とを有するエポキシ化合物Bと、の組合せ(以下、特定エポキシ化合物2ともいう)であってもよい。
メソゲン含有エポキシ化合物は、2価のビフェニル構造を形成する2つの芳香環と、前記2つの芳香環のそれぞれに結合したメソゲン構造とを有し、前記メソゲン構造の少なくとも一方が前記2価のビフェニル構造の分子軸と角度をなして前記芳香環に結合しているエポキシ化合物(以下、特定エポキシ化合物3とも称する)であってもよい。
第2実施形態のエポキシ樹脂は、下記一般式(1)で表されるエポキシ化合物を含む。すなわち、第2実施形態のエポキシ樹脂は、メソゲン含有エポキシ化合物として上述した特定エポキシ化合物1を含む。
第3実施形態のエポキシ樹脂は、2つのメソゲン構造を含む主鎖と1つの分岐とを有するエポキシ化合物を含み、ゲルパーミエーションクロマトグラフィー(GPC)により得られるチャートにおいて、2つ以上のメソゲン構造を含む主鎖を有するエポキシ化合物に由来するピークの合計面積Aに占める前記エポキシ化合物に由来するピークの面積Bの割合が3%以上である。
本実施形態のエポキシ樹脂は、メソゲン含有エポキシ化合物として一般式(1)で表されるエポキシ化合物(特定エポキシ化合物1)を含むものであってもよい。
メソゲン含有エポキシ化合物を合成する方法は、特に制限されない。例えば、メソゲン含有エポキシ化合物が有するメソゲン構造に相当するメソゲン構造を含有するエポキシ化合物(メソゲンエポキシモノマー)と、当該メソゲンエポキシシモノマーのエポキシ基と反応しうる官能基を有する化合物とを反応させて得てもよい。メソゲンエポキシシモノマーは、例えば、上述した一般式(1-m)で表される構造を有するエポキシ化合物であってもよい。
すなわち、比較的活性の低い反応触媒を用いた場合は、R1及びR2に相当する構造を有するメソゲンエポキシモノマーのエポキシ基と水酸基との反応が進行する一方で、当該反応により生成する2級水酸基とR3に相当する構造を有するメソゲンエポキシモノマーのエポキシ基との反応は進まず、R3に相当する構造を有するエポキシ化合物の生成する割合が低い傾向にある。
これに対し、比較的活性の高い反応触媒を用いた場合は、R1及びR2に相当する構造を有するメソゲンエポキシモノマーのエポキシ基と水酸基との反応に加え、当該反応により生成する2級水酸基とR3に相当する構造を有するメソゲンエポキシモノマーのエポキシ基との反応が進み、R3に相当する構造を効率よく導入することができる。
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。
ジアミノビフェニル化合物としては、2,2’-ジアミノビフェニル、2,3’-ジアミノビフェニル、2,4’-ジアミノビフェニル、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。
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、メソゲンエポキシモノマー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、メソゲンエポキシモノマーを溶解する。そこにメソゲンエポキシモノマー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、メソゲン含有エポキシ化合物が得られる。
エポキシ樹脂の取り扱い性の観点からは、エポキシ基の当量数(A)と、エポキシ基と反応しうる官能基の当量数(B)との比(A:B)が10:1.6~10:3.0の範囲となる配合比が好ましく、10:1.8~10:2.9の範囲となる配合比がより好ましく、10:2.0~10:2.8の範囲となる配合比がさらに好ましい。
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。
第1実施形態のエポキシ樹脂組成物は、上述したエポキシ樹脂と、硬化剤と、を含む。
本実施形態のエポキシ樹脂組成物は、上述したエポキシ樹脂を含むため、プロセス適合性に優れている。
第2実施形態のエポキシ樹脂組成物は、メソゲン構造を有するエポキシ化合物を含むエポキシ樹脂と、硬化剤と、を含み、動的せん断粘度の測定において、初期の動的せん断粘度をη’3(Pa・s)とし、測定中の動的せん断粘度の最大値をη’4(Pa・s)としたとき、η’4/η’3の値が3以下である。
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、特定エポキシ化合物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。
エポキシ樹脂組成物の用途は特に制限されないが、せん断応力を付与したときの粘度上昇が抑制されるため、作業時の流動性に優れていることが要求される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繊維強化プラスチック(Fiber Reinforced Plastic、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。
本開示のエポキシ樹脂硬化物は、上述した実施形態のエポキシ樹脂組成物を硬化して得られる。本開示の複合材料は、本開示のエポキシ樹脂硬化物と、強化材と、を含む。
(実施例1)
メソゲン含有エポキシ化合物として特定エポキシ化合物1を含むエポキシ樹脂を、下記のようにして合成した。
500mLの三口フラスコに、メソゲンエポキシモノマーとして(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:227g/eq)を50g量り取り、そこに合成溶媒(シクロヘキサノン)を80g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160℃のオイルバスに浸漬し、撹拌を開始した。
反応触媒として同量のトリフェニルホスフィンとヒドロキノンの付加反応物(下記構造、分子量:370.35)を用いたこと以外は実施例1と同様にして、エポキシ樹脂(プレポリマ)を得た。
メソゲン含有エポキシ化合物として特定エポキシ化合物2を含むエポキシ樹脂を、下記のようにして合成した。
500mlの三口フラスコに、実施例1と同じメソゲンエポキシモノマーを50g量り取り、そこに合成溶媒としてプロピレングリコールモノメチルエーテルを80g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。メソゲン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、特定芳香族化合物として4,4’-ビフェノールを5.2g、反応触媒としてトリフェニルホスフィンを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、メソゲンエポキシモノマーが4,4’-ビフェノールと反応して生成した多量体(エポキシ化合物A)と、未反応のメソゲンエポキシモノマーとを含むエポキシ樹脂(プレポリマ)を得た。
メソゲン含有エポキシ化合物として特定エポキシ化合物3を含むエポキシ樹脂を、下記のようにして合成した。
500mlの三口フラスコに、実施例1と同じメソゲンエポキシモノマーを50g量り取り、そこに合成溶媒としてプロピレングリコールモノメチルエーテルを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150℃のオイルバスに浸漬し、撹拌を開始した。メソゲン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、特定芳香族化合物として2,2’-ビフェノールを、メソゲンエポキシモノマーのエポキシ基(A)と2,2’-ビフェノールの水酸基(B)の当量数比(A:B)が10:2.5となるように添加し、反応触媒としてトリフェニルホスフィンを0.5g添加し、150℃のオイルバス温度で還流しながら加熱を継続した。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、メソゲンエポキシモノマーが2,2’-ビフェノールと反応して生成した多量体と、未反応のメソゲンエポキシモノマーとを含むエポキシ樹脂(プレポリマ)を得た。
反応触媒をトリブチルホスフィンとヒドロキノンの付加反応物から同量のトリフェニルホスフィンに変更したこと以外は実施例1と同様にして、メソゲンエポキシモノマーが4,4’-ビフェノールと反応して生成した多量体と、未反応のメソゲンエポキシモノマーとを含むエポキシ樹脂(プレポリマ)を得た。
エポキシ樹脂の動的せん断粘度の測定を、粘弾性測定装置を用いて行った。具体的には、粘弾性測定装置(アントンパール社のMCR-301)のパラレルプレートとステージ間のギャップ:0.05mm、周波数:0.5Hz、歪み:8000%、測定温度:80℃(一定)とし、80分間連続して行った測定において、初期(測定開始直後)の動的せん断粘度η’1(Pa・s)と、測定中の動的せん断粘度の最大値η’2(Pa・s)とを測定した。
各実施例で合成したエポキシ樹脂をプラスチック容器に量り取り、恒温槽に投入して90℃に加温した。ここに硬化剤として3,3’-ジアミノジフェニルスルホン(和光純薬工業株式会社)を、エポキシ樹脂のエポキシ基の当量数に対する硬化剤の活性水素の当量数の比が1:1となるように添加し、1分間スパチュラで撹拌した。次いで、自転・公転ミキサーを用いて、1600回転/分(rpm)の条件で30分間撹拌し、エポキシ樹脂組成物を調製した。3,3’-ジアミノジフェニルスルホンは、予め平均粒径8μmの粉体となるように粉砕する前処理を実施した。
エポキシ樹脂組成物の動的せん断粘度の測定を、粘弾性測定装置を用いて行った。具体的には、粘弾性測定装置(アントンパール社のMCR-301)のパラレルプレートとステージ間のギャップ:0.2mm、周波数:1Hz、歪み:1000%、測定温度:80℃(一定)とし、120分間連続して行った測定において、初期(測定開始直後)の動的せん断粘度η’3(Pa・s)と、測定中の動的せん断粘度の最大値η’4(Pa・s)とを測定した。
調製したエポキシ樹脂組成物をステンレスシャーレに移し、常温(25℃)まで冷却した後にステンレスシャーレからエポキシ樹脂を取り出し、恒温槽にて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2mm×0.5mm×40mmの短冊状に切り出して破壊靱性評価用の試験片を作製し、50mm×5mm×2mmの短冊状に切り出して弾性率評価用の試験片を作製した。
エポキシ樹脂硬化物の弾性率の評価の指標として、曲げ弾性率(GPa)を測定した。具体的には、作製した試験片に対し、ASTM D790に基づいて3点曲げ測定を行って算出した。評価装置には、インストロン5948(インストロン社製)を用いた。支点間距離は32mm、試験速度は1mm/minとした。結果を表1に示す。
エポキシ樹脂硬化物の靭性の評価の指標として、破壊靭性値(MPa・m1/2)を測定した。具体的には、作製した試験片に対し、ASTM D5045に基づいて3点曲げ測定を行って算出した。評価装置には、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。
エポキシ樹脂硬化物中にスメクチック構造が形成されているか否かを確認するために、X線回折測定を行った。具体的には、CuKα線を用い、管電圧40kV、管電流20mA、走査速度0.03°/分、測定角度2θ=2°~30°として測定を行い、2θ=2°~10°の範囲に回折ピークが現れている場合はスメクチック構造が形成されていると判断した。評価装置には、株式会社リガク製のX線回折装置を用いた。結果を表1に示す。
合成したエポキシ樹脂に含まれる分岐を有するエポキシ化合物の割合を、GPCにより算出した。具体的には、測定対象のエポキシ樹脂の280nmの波長における吸光度を検出し、検出された全てのピークの合計面積から下記面積Aと面積Bを算出し、面積Bの面積Aに対する割合(%)を算出した。
各実施例で合成したエポキシ樹脂及び3,3’-ジアミノジフェニルスルホン(和光純薬工業株式会社)を、エポキシ樹脂のエポキシ基の当量数に対する硬化剤の活性水素の当量数の比が1:1となるように量り取り、プラネタリミキサの撹拌容器に投入し、80℃に加温して樹脂が溶融した後、20回転/分(rpm)の条件で60分間撹拌し、エポキシ樹脂組成物を調製した。3,3’-ジアミノジフェニルスルホンは、予め平均粒径8μmの粉体となるように粉砕する前処理を実施した。
A…エポキシ樹脂が流動性を保ち、均一な外観のまま10cm掃引できる。
B…エポキシ樹脂が一定程度流動性を保ち、10cm掃引できるが、一部かすれる。
C…エポキシ樹脂がダマになって均一に掃引できない、又は、粘度が高すぎて10cmを超えて掃引できないか、全く掃引できない。
表1に示されるように、実施例で合成したエポキシ樹脂及びこれと硬化剤とを含むエポキシ樹脂組成物は、せん断応力を付与したときの粘度上昇率が小さく、粘度安定性、プロセス適合性に優れていた。また、実施例で合成したエポキシ樹脂を含むエポキシ樹脂組成物を硬化して得られるエポキシ樹脂硬化物は、硬化物中にスメクチック構造が存在し、優れた破壊靭性を示した。
本明細書に記載された全ての文献、特許出願及び技術規格は、個々の文献、特許出願及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 (11)
- メソゲン構造を有するエポキシ化合物を含み、動的せん断粘度の測定において、初期の動的せん断粘度をη’1(Pa・s)とし、測定中の動的せん断粘度の最大値をη’2(Pa・s)としたとき、η’2/η’1の値が3以下である、エポキシ樹脂。
- 2つ以上のメソゲン構造と1つ以上のフェニレン基とを有するエポキシ化合物Aと、2つ以上のメソゲン構造と1つ以上の2価のビフェニル基とを有するエポキシ化合物Bと、を含む、請求項1に記載のエポキシ樹脂。
- 2価のビフェニル構造を形成する2つの芳香環と、前記2つの芳香環のそれぞれに結合したメソゲン構造とを有し、前記メソゲン構造の少なくとも一方が前記2価のビフェニル構造の分子軸と角度をなして前記芳香環に結合しているエポキシ化合物を含む、請求項1に記載のエポキシ樹脂。
- 初期の動的せん断粘度η’1が200Pa・s以下である、請求項1~請求項4のいずれか1項に記載のエポキシ樹脂。
- 2つのメソゲン構造を含む主鎖と1つの分岐とを有するエポキシ化合物を含み、ゲルパーミエーションクロマトグラフィー(GPC)により得られるチャートにおいて、2つ以上のメソゲン構造を含む主鎖を有するエポキシ化合物に由来するピークの合計面積Aに占める前記エポキシ化合物に由来するピークの面積Bの割合が3%以上である、エポキシ樹脂。
- 請求項1~請求項7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。
- メソゲン構造を有するエポキシ化合物を含むエポキシ樹脂と、硬化剤と、を含み、動的せん断粘度の測定において、初期の動的せん断粘度をη’3(Pa・s)とし、測定中の動的せん断粘度の最大値をη’4(Pa・s)としたとき、η’4/η’3の値が3以下である、エポキシ樹脂組成物。
- 請求項8又は請求項9に記載のエポキシ樹脂組成物を硬化して得られる、エポキシ樹脂硬化物。
- 請求項10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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- 2019-04-09 EP EP19784303.0A patent/EP3686231A4/en active Pending
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- 2019-04-09 JP JP2020513404A patent/JP6835292B2/ja active Active
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CN111212862B (zh) | 2023-11-14 |
JPWO2019198703A1 (ja) | 2020-07-30 |
KR20200143356A (ko) | 2020-12-23 |
EP3686231A4 (en) | 2021-06-30 |
CA3090628A1 (en) | 2019-10-17 |
US20200325398A1 (en) | 2020-10-15 |
US11352562B2 (en) | 2022-06-07 |
CN111212862A (zh) | 2020-05-29 |
EP3686231A1 (en) | 2020-07-29 |
JP6835292B2 (ja) | 2021-02-24 |
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