WO2021020109A1 - Epoxy resin composition, cured product thereof, and diamine curing agent composition used therein - Google Patents
Epoxy resin composition, cured product thereof, and diamine curing agent composition used therein Download PDFInfo
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- WO2021020109A1 WO2021020109A1 PCT/JP2020/027367 JP2020027367W WO2021020109A1 WO 2021020109 A1 WO2021020109 A1 WO 2021020109A1 JP 2020027367 W JP2020027367 W JP 2020027367W WO 2021020109 A1 WO2021020109 A1 WO 2021020109A1
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- WIPO (PCT)
- Prior art keywords
- curing agent
- epoxy resin
- diamine curing
- resin composition
- general formula
- Prior art date
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- 0 *C(*)(c(cc1)ccc1N)c(cc1)ccc1N Chemical compound *C(*)(c(cc1)ccc1N)c(cc1)ccc1N 0.000 description 1
- KIFDSGGWDIVQGN-UHFFFAOYSA-N Nc1ccc(C2(c3ccccc3-c3c2cccc3)c(cc2)ccc2N)cc1 Chemical compound Nc1ccc(C2(c3ccccc3-c3c2cccc3)c(cc2)ccc2N)cc1 KIFDSGGWDIVQGN-UHFFFAOYSA-N 0.000 description 1
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N Nc1cccc(S(c2cc(N)ccc2)(=O)=O)c1 Chemical compound Nc1cccc(S(c2cc(N)ccc2)(=O)=O)c1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
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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
- C08G59/40—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
- C08G59/56—Amines together with other curing agents
Definitions
- the present invention relates to an epoxy resin composition, a cured product thereof, and a diamine curing agent composition used therein.
- Fiber-reinforced composite materials consisting of reinforcing fibers and matrix resins can be designed to take advantage of the advantages of reinforcing fibers and matrix resins, so their applications are expanding to the aerospace field, sports field, and general industrial fields. ..
- the reinforcing fiber glass fiber, aramid fiber, carbon fiber, boron fiber and the like are used. Further, as the matrix resin, both a thermosetting resin and a thermoplastic resin are used, but a thermosetting resin that can be easily impregnated into the reinforcing fibers is often used.
- the thermosetting resin an epoxy resin, an unsaturated polyester resin, a vinyl ester resin, a phenol resin, a bismaleimide resin, a cyanate resin and the like are used.
- a method for forming a fiber-reinforced composite material a method such as a prepreg method, a hand layup method, a filament winding method, a plutrusion method, or an RTM (Resin Transfer Molding) method is applied.
- the prepreg method is a method of obtaining a molded product by laminating a prepreg in which reinforcing fibers are impregnated with an epoxy resin composition into a desired shape and heating the prepreg.
- this epoxy resin composition or prepreg is stored at room temperature for a long period of time, an unintended curing reaction proceeds, so that there is a problem in storage stability.
- Patent Document 1 an epoxy resin composition (Patent Document 1) in which a fluorene type curing agent is dispersed in a solid state has been proposed. Further, an epoxy resin composition (Patent Document 2) in which a fluorene type curing agent and a naphthalene type epoxy resin are used in combination has been proposed. Further, Patent Document 3 proposes an epoxy resin composition using an amine curing agent which makes it easy to be compatible with an epoxy resin as a glassy solid by melting a high melting point crystalline amine once and then quenching it. There is.
- Patent Document 1 the epoxy resin composition described in Patent Document 1 has not been able to achieve high storage stability, and there is still room for improvement.
- the epoxy resin composition described in Patent Document 2 has not been able to achieve high storage stability. Further, since the dissolution temperature of the fluorene type curing agent in the epoxy resin is high, there are restrictions on the use and molding method, and the strength of the fiber-reinforced composite material obtained from the epoxy resin composition is also insufficient.
- the epoxy resin composition described in Patent Document 3 is a material in which unevenness is likely to occur when the fiber-reinforced base material is impregnated because the viscosity of the glassy solid amine curing agent gradually decreases when the temperature is raised and heated.
- Epoxy resin compositions that have such high storage stability and high solubility in epoxy resins, and which can provide highly heat-resistant and high-strength fiber-reinforced composite materials required for structural material applications such as airplanes and automobiles, are available. It didn't exist before.
- an object of the present invention is to improve the drawbacks of the prior art, to obtain an epoxy resin composition having high storage stability, a highly heat-resistant and high-strength epoxy resin cured product using the same, and an epoxy resin.
- An object of the present invention is to provide a diamine curing agent having high solubility.
- the present invention for solving the above problems has the following configurations.
- An epoxy resin composition containing at least the following main agent (A) and curing agent composition (B), wherein the curing agent composition is based on 100 parts by mass of the epoxy resin component in the epoxy resin composition.
- A Bifunctional or higher functional epoxy resin curing agent composition
- B Diamine curing agent represented by the following general formula [1], diamine curing agent represented by the following general formula [2], the following formula [ A diamine curing agent composition containing at least two selected from the group consisting of the diamine curing agent represented by 3] and the diamine curing agent represented by the following formula [4] and having a single melting point (provided that the diamine curing agent composition has a single melting point.
- R 1 and R 2 are independently aromatic hydrocarbon groups having 6 to 16 carbon atoms, and these may be bonded to each other to form a ring.
- R 3 and R 4 are carbon atoms. It is at least one selected from the group consisting of aliphatic hydrocarbon groups of numbers 1 to 4 and halogen atoms, and R 3 and R 4 are different groups.
- the diamine curing agent represented by the general formula [1] is the diamine curing agent represented by the following general formula [5], and / or the diamine curing agent represented by the general formula [2] is described below.
- R 1 and R 2 are independently aromatic hydrocarbon groups having 6 to 16 carbon atoms, and these may be bonded to each other to form a ring.
- R 3 and R 4 are , At least one selected from the group consisting of an aliphatic hydrocarbon group having 1 to 4 carbon atoms and a halogen atom, and R 3 and R 4 are different groups.
- the diamine curing agent represented by the general formula [1] is the diamine curing agent represented by the following general formula [5], and / or the diamine curing agent represented by the general formula [2] is described below.
- an epoxy resin composition having high storage stability, a cured epoxy resin having high heat resistance and high strength using the same, and a diamine curing agent having high solubility in an epoxy resin are provided. It becomes possible to do.
- the epoxy resin means a compound containing one or more epoxy groups in the molecule. Moreover, the epoxy resin in the present invention may contain two or more kinds of such compounds.
- the epoxy resin composition of the present invention is an epoxy resin composition containing at least the following main agent (A) and curing agent composition (B), and is based on 100 parts by mass of the epoxy resin component in the epoxy resin composition.
- the curing agent composition (B) is contained in an amount of 20 parts by mass or more and 100 parts by mass or less.
- R 1 and R 2 are independently aromatic hydrocarbon groups having 6 to 16 carbon atoms, and these may be bonded to each other to form a ring.
- R 3 and R 4 are at least one selected from the group consisting of an aliphatic hydrocarbon group having 1 to 4 carbon atoms and a halogen atom, and R 3 and R 4 are different groups.
- the main agent (A), which is a component of the epoxy resin composition of the present invention, is a bifunctional or higher functional epoxy resin.
- Specific examples of the main agent (A) are not particularly limited, but are bisphenol type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, hydroquinone type epoxy resin, thioether type epoxy resin, and phenylene. Examples thereof include ether type epoxy resin, trishydroxyphenylmethane type epoxy resin, terephthalic acid type epoxy resin, isocyanuric acid type epoxy resin, phthalimide type epoxy resin, and tetraphenylethane type epoxy resin.
- the curing agent composition (B), which is a component of the epoxy resin composition of the present invention, or the diamine curing agent composition of the present invention is a diamine curing agent represented by the above general formula [1], the above general formula [2]. ], At least two selected from the group consisting of the diamine curing agent represented by the above formula [3], and the diamine curing agent represented by the above formula [4], and simply. It is a diamine curing agent composition having one melting point.
- Such a curing agent composition is excellent in solubility in an epoxy resin. Further, by using such a curing agent composition, it becomes easy to obtain an epoxy resin composition having excellent storage stability and a cured epoxy resin composition having high strength and high heat resistance. Further, since such a curing agent composition is often excellent in curability, the epoxy resin composition can be easily cured at a high speed.
- having a single melting point means that the crystalline component is heated in a nitrogen atmosphere by differential scanning calorimetry (DSC) according to JIS K 7121: 2012, and the endothermic peak in the obtained DSC curve. Indicates that is not separated into two or more.
- the fact that the endothermic peak is not separated into two means that both ends of the endothermic peak do not drop to the baseline and become a continuous endothermic peak, and even if it has two or more peaks, it does not drop to the baseline.
- R 1 and R 2 in the general formula [1] and the general formula [2] are independently aromatic hydrocarbon groups having 6 to 16 carbon atoms.
- R 1 and R 2 include a phenyl group, a fluorene group, an anthracene group and the like.
- R 1 and R 2 may be combined with each other to form a ring.
- the diamine curing agent represented by the general formula [1] is the diamine curing agent represented by the general formula [5], and / or the general formula [2].
- the diamine curing agent represented is preferably the diamine curing agent represented by the above general formula [6].
- R 3 and R 4 in the general formula [1] and the general formula [2] are at least one selected from the group consisting of an aliphatic hydrocarbon group having 1 to 4 carbon atoms and a halogen atom, and are R. 3 and R 4 are different groups. Specific examples of R 3 and R 4 include a methyl group, an ethyl group, a propyl group, a butyl group and the like. Above all, from the viewpoint of further improving the storage stability of the epoxy resin composition, it is preferable that either or both of R 3 and R 4 are methyl groups or ethyl groups.
- the epoxy resin composition of the present invention contains 20 parts by mass or more and 100 parts by mass or less of the curing agent composition (B) with respect to 100 parts by mass of the epoxy resin component in the epoxy resin composition, preferably 30 parts by mass or more and 100 parts by mass. It is less than a part by mass.
- the content of the curing agent composition (B) with respect to the epoxy resin component within the above range, the strength of the epoxy resin cured product obtained by curing the epoxy resin composition is improved, and the heat resistance is improved. ..
- Such an epoxy resin component is a component in which all the epoxy resins in the epoxy resin composition are combined.
- the epoxy resin composition of the present invention has a diamine curing agent represented by the general formula [1], a diamine curing agent represented by the general formula [2], a diamine curing agent represented by the formula [3], and a formula [4]. ],
- Each of at least two diamine curing agents selected from the group consisting of diamine curing agents is contained in an amount of 10 parts by mass or more and 80 parts by mass or less with respect to 100 parts by mass of the epoxy resin component in the epoxy resin composition. It is more preferable to contain 15 parts by mass or more and 75 parts by mass or less, and 25 parts by mass or more and 50 parts by mass or less is particularly preferable.
- the total content of each of the two diamine curing agents is 20 parts by mass or more and 100 parts by mass or less, which is within the range of the content of the curing agent composition (B).
- the total content of the main agent (A) and the curing agent composition (B) is preferably 75% by mass or more, more preferably 80% by mass or more in 100% by mass of the epoxy resin composition.
- 85% by mass or more is further preferable, 90% by mass or more is further preferable, and 95% by mass or more is particularly preferable.
- the epoxy resin other than the main agent (A) may be contained in the epoxy resin composition as long as it is 20 parts by mass or less with respect to 100 parts by mass of the main agent (A). Further, in the present invention, if the curing agent other than the curing agent composition (B) is 20 parts by mass or less with respect to 100 parts by mass of the main agent (A), it may be contained in the epoxy resin composition.
- the epoxy resin composition of the present invention further comprises a Lewis acid such as aluminum chloride, aluminum bromide, boron trifluoride, antimony pentafluoride, phosphorus pentafluoride, and titanium tetrafluoride, and a tertiary of aliphatic or aromatic. It may contain amines, imidazoles, alcohols and phenols. By including such a component, the reaction is easily promoted.
- a Lewis acid such as aluminum chloride, aluminum bromide, boron trifluoride, antimony pentafluoride, phosphorus pentafluoride, and titanium tetrafluoride, and a tertiary of aliphatic or aromatic. It may contain amines, imidazoles, alcohols and phenols. By including such a component, the reaction is easily promoted.
- the contents of all the curing agents including the curing agent composition (B) are the total number of active hydrogens (H) of the curing agent and the total number of epoxy groups (E) in all the epoxy resin components. Can be indicated by the ratio of, so-called H / E.
- the content of all the curing agents is preferably a content that satisfies the range of H / E of 0.80 or more and 1.10 or less, and preferably a content that satisfies the range of 0.85 or more and 1.05 or less. Is more preferable.
- H / E is 0.80 or more, the reaction rate of the cured epoxy resin product tends to be sufficiently high, and the heat resistance and material strength tend to be improved. Further, when the H / E is 1.10 or less, the plastic deformation ability tends to be improved, and the impact resistance of the fiber-reinforced composite material tends to be sufficient.
- the content of the curing agent composition (B) is the ratio of the number of active hydrogens derived from the curing agent composition (B) to the total number of active hydrogens (H) of the curing agent in the epoxy resin composition, that is, the so-called curing agent composition ( It can be indicated by the active hydrogen ratio of B).
- the active hydrogen ratio of the curing agent composition (B) is preferably 20% or more and 100% or less.
- the diamine curing agent having a single melting point constituting the curing agent composition (B) preferably has crystallinity.
- Crystallinity is a component that has a melting point at room temperature or higher and is solid at room temperature.
- the melting point can be determined by differential scanning calorimetry (DSC) according to JIS K 7121: 2012.
- DSC differential scanning calorimetry
- the temperature of the crystalline component can be measured by raising the temperature in a nitrogen atmosphere, and the peak temperature of the endothermic peak in the obtained DSC curve can be obtained as the melting point.
- the normal temperature means 25 ° C.
- the melting point is higher than the melting point of a single compound having crystalline property.
- the method of co-crystallization includes, for example, a diamine curing agent represented by the general formula [1], a diamine curing agent represented by the general formula [2], a diamine curing agent represented by the formula [3], and a formula [ A method in which at least two selected from the group consisting of the diamine curing agent represented by 4] are once melted, uniformly mixed, and then slowly cooled to near the crystallization temperature to crystallize, represented by the general formula [1]. At least 2 selected from the group consisting of a diamine curing agent, a diamine curing agent represented by the general formula [2], a diamine curing agent represented by the formula [3], and a diamine curing agent represented by the formula [4].
- the curing agent composition (B) is irreversible (that is, the obtained crystal mixture is subjected to physical operations such as heating and mixing to obtain a diamine curing agent represented by the general formula [1], generally. It does not return to at least two states selected from the group consisting of the diamine curing agent represented by the formula [2], the diamine curing agent represented by the formula [3], and the diamine curing agent represented by the formula [4]. ) Is the curing agent composition (B) containing at least two diamine curing agents including such a crystal mixture in the present invention.
- the epoxy resin composition of the present invention has excellent storage stability and solubility in an epoxy resin, it is used together with a reinforcing fiber base material to obtain a fiber-reinforced composite material. Therefore, a cured epoxy resin (cured epoxy resin composition) is used. It is suitable for
- Main agent (A) -"Araldite (registered trademark)" MY721 manufactured by Huntsman Advanced Materials
- TGDDM Tetraglycidyldiaminodiphenylmethane
- TGD-128 bisphenol A type epoxy resin manufactured by Toto Kasei Co., Ltd.
- the temperature of the liquid was raised to 90 to 110 ° C., and water and toluene in the system were azeotropically heated.
- 14.4 g (1 mass times / 9-fluorenone) of toluene is further added, and the liquid temperature is raised to 130 to 140 ° C. while azeotropically boiling the water and toluene in the system again.
- the condensation reaction was carried out by aging with stirring for 22 hours.
- reaction solution was cooled, and 56.4 g of 17% by mass caustic soda water was added at 50 ° C. to neutralize the reaction solution.
- the aqueous phase was discharged from the lower layer, and 21.6 g of 2-propanol and 10.8 g of water were added to the obtained oil phase to crystallize 9,9-bis (3-methyl-4-aminophenyl) fluorene.
- the obtained slurry was cooled to room temperature and solid-liquid separation was performed. The obtained cake was rinsed with 21.6 g of 2-propanol to obtain crude 9,9-bis (3-methyl-4-aminophenyl) fluorene.
- the temperature of the liquid was raised to 90 to 110 ° C., and water and toluene in the system were azeotropically heated.
- 14.4 g (1 mass times / 9-fluorenone) of toluene is further added, and the liquid temperature is raised to 130 to 140 ° C. while azeotropically boiling the water and toluene in the system again.
- the condensation reaction was carried out by aging with stirring for 66 hours.
- reaction solution was cooled, and 56.4 g of 17% by mass caustic soda water was added at 50 ° C. to neutralize the reaction solution.
- the aqueous phase was discharged from the lower layer, and 21.6 g of 2-propanol and 10.8 g of water were added to the obtained oil phase to crystallize 9,9-bis (3-ethyl-4-aminophenyl) fluorene.
- the obtained slurry was cooled to room temperature and solid-liquid separation was performed. The obtained cake was rinsed with 21.6 g of 2-propanol to obtain crude 9,9-bis (3-ethyl-4-aminophenyl) fluorene.
- the curing agent composition (B) was collected in an aluminum sample pan and measured at a heating rate of 10 ° C./min in a nitrogen atmosphere. In the obtained DSC curve, the temperature at the apex of the endothermic peak due to melting of the components was measured as the melting point. If both ends of the endothermic peak do not drop to the baseline but become continuous endothermic peaks and do not drop to the baseline even if they have two or more peak vertices, the endothermic peak with a high intensity is the melting point. And said.
- the hardener composition (B) described is recrystallized near the crystallization temperature after the two types of hardeners shown in Table 1 are once melted and uniformly mixed. Prepared by crystallization.
- the prepared epoxy resin composition was measured by differential scanning calorimetry (DSC).
- DSC differential scanning calorimetry
- Pyris1 DSC manufactured by Perkin Elmer
- the sample was collected in an aluminum sample pan and measured at a heating rate of 10 ° C./min in a nitrogen atmosphere.
- the temperature at which the exothermic reaction started was measured as the exothermic start temperature.
- the hardener composition (B) described is recrystallized near the crystallization temperature after the two types of hardeners shown in Table 1 are once melted and uniformly mixed. Prepared by crystallization.
- the prepared epoxy resin composition was measured by differential scanning calorimetry (DSC).
- DSC differential scanning calorimetry
- Pyris1 DSC manufactured by Perkin Elmer
- the sample was collected in an aluminum sample pan and measured at a heating rate of 10 ° C./min in a nitrogen atmosphere.
- the temperature at the peak of the exothermic reaction was measured as the exothermic peak temperature.
- the hardener composition (B) described is recrystallized near the crystallization temperature after the two types of hardeners shown in Table 1 are once melted and uniformly mixed. Prepared by crystallization.
- the epoxy resin composition prepared above was defoamed at 80 ° C. and 0.2 kPa, and then injected into a mold set to have a thickness of 2 mm by using a 2 mm thick “Teflon®” spacer. It was cured at a temperature of 180 ° C. for 2 hours to obtain a resin cured plate having a thickness of 2 mm.
- Tg glass transition temperature
- the epoxy resin composition of the present invention is excellent in storage stability, it is possible to provide a fiber-reinforced composite material having high heat resistance and high strength by a prepreg method or the like. As a result, the application of fiber-reinforced composite materials to aircraft and automobile applications will progress, and it is expected that further weight reduction will contribute to improved fuel efficiency and reduction of global warming gas emissions.
- the epoxy resin composition of the present invention makes it possible to obtain a cured epoxy resin having high heat resistance and high strength, which can be suitably used for electronic materials such as semiconductor encapsulants.
- the diamine curing agent of the present invention as a diamine raw material for, for example, aromatic polyamide and polyimide, it can be expected that a film or fiber having high heat resistance and high strength can be obtained.
Abstract
The purpose of the present invention is to provide an epoxy resin composition endowed with high storage stability, an epoxy resin cured product having high heat resistance and high strength obtained by using the epoxy resin composition, and a diamine curing agent endowed with high solubility in epoxy resins. To achieve the aforementioned purpose, the present invention has the following configuration. Specifically, an epoxy resin composition comprising at least a main agent (A) and a curing agent composition (B), wherein the epoxy resin composition includes 20-100 parts by mass (inclusive) of the curing agent composition (B) per 100 parts by mass of epoxy resin components in the epoxy resin composition. Main agent (A): bifunctional or higher epoxy resin.
Curing agent composition (B): diamine curing agent composition that has a single melting point and includes at least two selected from the group consisting of four diamine curing agents represented by specific chemical formulas.
Description
本発明は、エポキシ樹脂組成物およびその硬化物、ならびにそれに用いられるジアミン硬化剤組成物に関する。
The present invention relates to an epoxy resin composition, a cured product thereof, and a diamine curing agent composition used therein.
強化繊維とマトリックス樹脂とからなる繊維強化複合材料は、強化繊維とマトリックス樹脂の利点を生かした材料設計ができるため、航空宇宙分野を始め、スポーツ分野および一般産業分野などに用途が拡大されている。
Fiber-reinforced composite materials consisting of reinforcing fibers and matrix resins can be designed to take advantage of the advantages of reinforcing fibers and matrix resins, so their applications are expanding to the aerospace field, sports field, and general industrial fields. ..
強化繊維としては、ガラス繊維、アラミド繊維、炭素繊維およびボロン繊維などが用いられる。また、マトリックス樹脂としては、熱硬化性樹脂および熱可塑性樹脂のいずれも用いられるが、強化繊維への含浸が容易な熱硬化性樹脂が用いられることが多い。熱硬化性樹脂としては、エポキシ樹脂、不飽和ポリエステル樹脂、ビニルエステル樹脂、フェノール樹脂、ビスマレイミド樹脂およびシアネート樹脂などが用いられる。
As the reinforcing fiber, glass fiber, aramid fiber, carbon fiber, boron fiber and the like are used. Further, as the matrix resin, both a thermosetting resin and a thermoplastic resin are used, but a thermosetting resin that can be easily impregnated into the reinforcing fibers is often used. As the thermosetting resin, an epoxy resin, an unsaturated polyester resin, a vinyl ester resin, a phenol resin, a bismaleimide resin, a cyanate resin and the like are used.
一般的に繊維強化複合材料の成形方法としては、プリプレグ法、ハンドレイアップ法、フィラメントワインディング法、プルトルージョン法、ＲＴＭ（Ｒｅｓｉｎ Ｔｒａｎｓｆｅｒ Ｍｏｌｄｉｎｇ）法等の方法が適用される。プリプレグ法は、強化繊維にエポキシ樹脂組成物を含浸したプリプレグを所望の形状に積層し、加熱することによって成形物を得る方法である。しかし、このエポキシ樹脂組成物、あるいはプリプレグを室温で長期間に渡り保存しておくと、意図しない硬化反応が進行するため、貯蔵安定性に問題があった。これまでにこの貯蔵安定性を確保する手段としてジシアンジアミド、ＢＦ３－アミン錯体、アミン塩、変性イミダゾール化合物等の潜在性硬化剤を、エポキシ樹脂に配合したものが知られている。しかし、これらのエポキシ樹脂組成物は、貯蔵安定性に優れているものは硬化性に劣る傾向となり、硬化性に優れるものは貯蔵安定性に劣る傾向となる。
Generally, as a method for forming a fiber-reinforced composite material, a method such as a prepreg method, a hand layup method, a filament winding method, a plutrusion method, or an RTM (Resin Transfer Molding) method is applied. The prepreg method is a method of obtaining a molded product by laminating a prepreg in which reinforcing fibers are impregnated with an epoxy resin composition into a desired shape and heating the prepreg. However, when this epoxy resin composition or prepreg is stored at room temperature for a long period of time, an unintended curing reaction proceeds, so that there is a problem in storage stability. Previously dicyandiamide as a means of ensuring the storage stability, BF 3 - amine complex, amine salt, a latent curing agent and modified imidazole compounds, those obtained by blending the epoxy resins. However, those epoxy resin compositions having excellent storage stability tend to be inferior in curability, and those having excellent curability tend to be inferior in storage stability.
このような事情のもと、フルオレン型硬化剤を固体状で分散させたエポキシ樹脂組成物（特許文献１）が提案されている。また、フルオレン型硬化剤とナフタレン型エポキシ樹脂を併用したエポキシ樹脂組成物（特許文献２）が提案されている。また、特許文献３には、高融点の結晶性アミンを一旦溶融後、急冷することによりガラス状固体として、エポキシ樹脂に相溶させやすくしたアミン硬化剤を用いたエポキシ樹脂組成物が提案されている。
Under such circumstances, an epoxy resin composition (Patent Document 1) in which a fluorene type curing agent is dispersed in a solid state has been proposed. Further, an epoxy resin composition (Patent Document 2) in which a fluorene type curing agent and a naphthalene type epoxy resin are used in combination has been proposed. Further, Patent Document 3 proposes an epoxy resin composition using an amine curing agent which makes it easy to be compatible with an epoxy resin as a glassy solid by melting a high melting point crystalline amine once and then quenching it. There is.
しかしながら、特許文献１に記載のエポキシ樹脂組成物は、高い貯蔵安定性を実現することはできておらず、未だ改善の余地がある。
However, the epoxy resin composition described in Patent Document 1 has not been able to achieve high storage stability, and there is still room for improvement.
また、特許文献２に記載のエポキシ樹脂組成物も、高い貯蔵安定性を実現することはできていない。また、フルオレン型硬化剤のエポキシ樹脂への溶解温度が高いため用途や成形法に制限があり、そのエポキシ樹脂組成物から得られる繊維強化複合材料の強度も不十分なものであった。
Also, the epoxy resin composition described in Patent Document 2 has not been able to achieve high storage stability. Further, since the dissolution temperature of the fluorene type curing agent in the epoxy resin is high, there are restrictions on the use and molding method, and the strength of the fiber-reinforced composite material obtained from the epoxy resin composition is also insufficient.
特許文献３に記載のエポキシ樹脂組成物は、ガラス状固体としたアミン硬化剤が昇温加熱時に徐々に粘度低下するため、繊維強化基材への含浸時にムラが発生しやすい材料であった。
The epoxy resin composition described in Patent Document 3 is a material in which unevenness is likely to occur when the fiber-reinforced base material is impregnated because the viscosity of the glassy solid amine curing agent gradually decreases when the temperature is raised and heated.
このように高い貯蔵安定性およびエポキシ樹脂への高溶解性を兼ね備え、さらに飛行機や自動車等の構造材用途で要求される高耐熱かつ高強度な繊維強化複合材料が得られるエポキシ樹脂組成物は、これまで存在しなかった。
Epoxy resin compositions that have such high storage stability and high solubility in epoxy resins, and which can provide highly heat-resistant and high-strength fiber-reinforced composite materials required for structural material applications such as airplanes and automobiles, are available. It didn't exist before.
そこで、本発明の目的は、かかる従来技術の欠点を改良し、高い貯蔵安定性を備えたエポキシ樹脂組成物、それを用いてなる高耐熱かつ高強度なエポキシ樹脂硬化物、およびエポキシ樹脂への高溶解性を備えたジアミン硬化剤を提供することにある。
Therefore, an object of the present invention is to improve the drawbacks of the prior art, to obtain an epoxy resin composition having high storage stability, a highly heat-resistant and high-strength epoxy resin cured product using the same, and an epoxy resin. An object of the present invention is to provide a diamine curing agent having high solubility.
上記課題を解決するための本発明は以下の構成からなる。
（１）少なくとも次の主剤（Ａ）および硬化剤組成物（Ｂ）を含んでなるエポキシ樹脂組成物であって、エポキシ樹脂組成物中のエポキシ樹脂成分１００質量部に対して、硬化剤組成物（Ｂ）を２０質量部以上１００質量部以下含むエポキシ樹脂組成物。 The present invention for solving the above problems has the following configurations.
(1) An epoxy resin composition containing at least the following main agent (A) and curing agent composition (B), wherein the curing agent composition is based on 100 parts by mass of the epoxy resin component in the epoxy resin composition. An epoxy resin composition containing 20 parts by mass or more and 100 parts by mass or less of (B).
（１）少なくとも次の主剤（Ａ）および硬化剤組成物（Ｂ）を含んでなるエポキシ樹脂組成物であって、エポキシ樹脂組成物中のエポキシ樹脂成分１００質量部に対して、硬化剤組成物（Ｂ）を２０質量部以上１００質量部以下含むエポキシ樹脂組成物。 The present invention for solving the above problems has the following configurations.
(1) An epoxy resin composition containing at least the following main agent (A) and curing agent composition (B), wherein the curing agent composition is based on 100 parts by mass of the epoxy resin component in the epoxy resin composition. An epoxy resin composition containing 20 parts by mass or more and 100 parts by mass or less of (B).
主剤（Ａ）：２官能以上のエポキシ樹脂
硬化剤組成物（Ｂ）：下記一般式［１］で表されるジアミン硬化剤、下記一般式［２］で表されるジアミン硬化剤、下記式［３］で表されるジアミン硬化剤、および下記式［４］で表されるジアミン硬化剤からなる群から選ばれた少なくとも２つを含み、かつ単一の融点を有するジアミン硬化剤組成物
（ただし、式中、Ｒ１，Ｒ２は、それぞれ独立に炭素数６～１６の芳香族炭化水素基であり、これらが互いに結合して環を形成してもよい。Ｒ３，Ｒ４は、炭素数１～４の脂肪族炭化水素基、およびハロゲン原子からなる群から選ばれた少なくとも１つであり、Ｒ３とＲ４は異なる基である。） Main agent (A): Bifunctional or higher functional epoxy resin curing agent composition (B): Diamine curing agent represented by the following general formula [1], diamine curing agent represented by the following general formula [2], the following formula [ A diamine curing agent composition containing at least two selected from the group consisting of the diamine curing agent represented by 3] and the diamine curing agent represented by the following formula [4] and having a single melting point (provided that the diamine curing agent composition has a single melting point. , In the formula, R 1 and R 2 are independently aromatic hydrocarbon groups having 6 to 16 carbon atoms, and these may be bonded to each other to form a ring. R 3 and R 4 are carbon atoms. It is at least one selected from the group consisting of aliphatic hydrocarbon groups of numbers 1 to 4 and halogen atoms, and R 3 and R 4 are different groups.)
硬化剤組成物（Ｂ）：下記一般式［１］で表されるジアミン硬化剤、下記一般式［２］で表されるジアミン硬化剤、下記式［３］で表されるジアミン硬化剤、および下記式［４］で表されるジアミン硬化剤からなる群から選ばれた少なくとも２つを含み、かつ単一の融点を有するジアミン硬化剤組成物
（ただし、式中、Ｒ１，Ｒ２は、それぞれ独立に炭素数６～１６の芳香族炭化水素基であり、これらが互いに結合して環を形成してもよい。Ｒ３，Ｒ４は、炭素数１～４の脂肪族炭化水素基、およびハロゲン原子からなる群から選ばれた少なくとも１つであり、Ｒ３とＲ４は異なる基である。） Main agent (A): Bifunctional or higher functional epoxy resin curing agent composition (B): Diamine curing agent represented by the following general formula [1], diamine curing agent represented by the following general formula [2], the following formula [ A diamine curing agent composition containing at least two selected from the group consisting of the diamine curing agent represented by 3] and the diamine curing agent represented by the following formula [4] and having a single melting point (provided that the diamine curing agent composition has a single melting point. , In the formula, R 1 and R 2 are independently aromatic hydrocarbon groups having 6 to 16 carbon atoms, and these may be bonded to each other to form a ring. R 3 and R 4 are carbon atoms. It is at least one selected from the group consisting of aliphatic hydrocarbon groups of numbers 1 to 4 and halogen atoms, and R 3 and R 4 are different groups.)
（２）一般式［１］で表されるジアミン硬化剤が下記一般式［５］で表されるジアミン硬化剤である、および／または、一般式［２］で表されるジアミン硬化剤が下記一般式［６］で表されるジアミン硬化剤である、上記（１）記載のエポキシ樹脂組成物。
(2) The diamine curing agent represented by the general formula [1] is the diamine curing agent represented by the following general formula [5], and / or the diamine curing agent represented by the general formula [2] is described below. The epoxy resin composition according to (1) above, which is a diamine curing agent represented by the general formula [6].
（３）Ｒ３，Ｒ４のいずれか一方または両方がメチル基またはエチル基のいずれかである、上記（１）または（２）記載のエポキシ樹脂組成物。
（４）一般式［１］で表されるジアミン硬化剤、一般式［２］で表されるジアミン硬化剤、式［３］で表されるジアミン硬化剤および式［４］で表されるジアミン硬化剤からなる群から選ばれた少なくとも２つの各ジアミン硬化剤を、エポキシ樹脂組成物中のエポキシ樹脂成分１００質量部に対して、それぞれ１０質量部以上８０質量部以下含む、上記（１）～（３）のいずれか記載のエポキシ樹脂組成物。
（５）上記（１）～（４）のいずれか記載のエポキシ樹脂組成物を硬化してなるエポキシ樹脂硬化物。
（６）下記一般式［１］で表されるジアミン硬化剤、下記一般式［２］で表されるジアミン硬化剤、下記式［３］で表されるジアミン硬化剤および下記式［４］で表されるジアミン硬化剤からなる群から選ばれた少なくとも２つを含み、かつ単一の融点を有するジアミン硬化剤組成物。
（ただし、式中、Ｒ１，Ｒ２は、それぞれ独立に炭素数６～１６の芳香族炭化水素基であり、これらが互いに結合して環を形成してもよい。Ｒ３，Ｒ４は、炭素数１～４の脂肪族炭化水素基、およびハロゲン原子からなる群から選ばれた少なくとも１つであり、Ｒ３とＲ４は異なる基である。） (3) The epoxy resin composition according to (1) or (2) above, wherein either or both of R 3 and R 4 are either a methyl group or an ethyl group.
(4) Diamine curing agent represented by the general formula [1], diamine curing agent represented by the general formula [2], diamine curing agent represented by the formula [3], and diamine represented by the formula [4]. The above (1) to 80 parts by mass, respectively, containing at least two diamine curing agents selected from the group consisting of curing agents with respect to 100 parts by mass of the epoxy resin component in the epoxy resin composition. The epoxy resin composition according to any one of (3).
(5) An epoxy resin cured product obtained by curing the epoxy resin composition according to any one of (1) to (4) above.
(6) The diamine curing agent represented by the following general formula [1], the diamine curing agent represented by the following general formula [2], the diamine curing agent represented by the following formula [3], and the following formula [4]. A diamine curing agent composition containing at least two selected from the group consisting of the represented diamine curing agents and having a single melting point.
(However, in the formula, R 1 and R 2 are independently aromatic hydrocarbon groups having 6 to 16 carbon atoms, and these may be bonded to each other to form a ring. R 3 and R 4 are , At least one selected from the group consisting of an aliphatic hydrocarbon group having 1 to 4 carbon atoms and a halogen atom, and R 3 and R 4 are different groups.)
（４）一般式［１］で表されるジアミン硬化剤、一般式［２］で表されるジアミン硬化剤、式［３］で表されるジアミン硬化剤および式［４］で表されるジアミン硬化剤からなる群から選ばれた少なくとも２つの各ジアミン硬化剤を、エポキシ樹脂組成物中のエポキシ樹脂成分１００質量部に対して、それぞれ１０質量部以上８０質量部以下含む、上記（１）～（３）のいずれか記載のエポキシ樹脂組成物。
（５）上記（１）～（４）のいずれか記載のエポキシ樹脂組成物を硬化してなるエポキシ樹脂硬化物。
（６）下記一般式［１］で表されるジアミン硬化剤、下記一般式［２］で表されるジアミン硬化剤、下記式［３］で表されるジアミン硬化剤および下記式［４］で表されるジアミン硬化剤からなる群から選ばれた少なくとも２つを含み、かつ単一の融点を有するジアミン硬化剤組成物。
（ただし、式中、Ｒ１，Ｒ２は、それぞれ独立に炭素数６～１６の芳香族炭化水素基であり、これらが互いに結合して環を形成してもよい。Ｒ３，Ｒ４は、炭素数１～４の脂肪族炭化水素基、およびハロゲン原子からなる群から選ばれた少なくとも１つであり、Ｒ３とＲ４は異なる基である。） (3) The epoxy resin composition according to (1) or (2) above, wherein either or both of R 3 and R 4 are either a methyl group or an ethyl group.
(4) Diamine curing agent represented by the general formula [1], diamine curing agent represented by the general formula [2], diamine curing agent represented by the formula [3], and diamine represented by the formula [4]. The above (1) to 80 parts by mass, respectively, containing at least two diamine curing agents selected from the group consisting of curing agents with respect to 100 parts by mass of the epoxy resin component in the epoxy resin composition. The epoxy resin composition according to any one of (3).
(5) An epoxy resin cured product obtained by curing the epoxy resin composition according to any one of (1) to (4) above.
(6) The diamine curing agent represented by the following general formula [1], the diamine curing agent represented by the following general formula [2], the diamine curing agent represented by the following formula [3], and the following formula [4]. A diamine curing agent composition containing at least two selected from the group consisting of the represented diamine curing agents and having a single melting point.
(However, in the formula, R 1 and R 2 are independently aromatic hydrocarbon groups having 6 to 16 carbon atoms, and these may be bonded to each other to form a ring. R 3 and R 4 are , At least one selected from the group consisting of an aliphatic hydrocarbon group having 1 to 4 carbon atoms and a halogen atom, and R 3 and R 4 are different groups.)
（７）一般式［１］で表されるジアミン硬化剤が下記一般式［５］で表されるジアミン硬化剤である、および／または、一般式［２］で表されるジアミン硬化剤が下記一般式［６］で表されるジアミン硬化剤である、上記（６）記載のジアミン硬化剤組成物。
(7) The diamine curing agent represented by the general formula [1] is the diamine curing agent represented by the following general formula [5], and / or the diamine curing agent represented by the general formula [2] is described below. The diamine curing agent composition according to (6) above, which is a diamine curing agent represented by the general formula [6].
（８）Ｒ３，Ｒ４のいずれか一方または両方がメチル基またはエチル基のいずれかである、上記（６）または（７）記載のジアミン硬化剤組成物。
(8) The diamine curing agent composition according to (6) or (7) above, wherein either or both of R 3 and R 4 are either a methyl group or an ethyl group.
本発明によれば、高い貯蔵安定性を備えたエポキシ樹脂組成物、それを用いてなる高耐熱かつ高強度なエポキシ樹脂硬化物、およびエポキシ樹脂への高溶解性を備えたジアミン硬化剤を提供することが可能になる。
According to the present invention, an epoxy resin composition having high storage stability, a cured epoxy resin having high heat resistance and high strength using the same, and a diamine curing agent having high solubility in an epoxy resin are provided. It becomes possible to do.
以下に、本発明の望ましい実施の形態について説明する。
The preferred embodiment of the present invention will be described below.
本発明において、エポキシ樹脂とは、分子内にエポキシ基を１つ以上含む化合物を意味する。また、本発明におけるエポキシ樹脂は、そのような化合物を２種類以上含んでいてもよい。
In the present invention, the epoxy resin means a compound containing one or more epoxy groups in the molecule. Moreover, the epoxy resin in the present invention may contain two or more kinds of such compounds.
本発明のエポキシ樹脂組成物は、少なくとも次の主剤（Ａ）および硬化剤組成物（Ｂ）を含んでなるエポキシ樹脂組成物であって、エポキシ樹脂組成物中のエポキシ樹脂成分１００質量部に対して、硬化剤組成物（Ｂ）を２０質量部以上１００質量部以下含む。
The epoxy resin composition of the present invention is an epoxy resin composition containing at least the following main agent (A) and curing agent composition (B), and is based on 100 parts by mass of the epoxy resin component in the epoxy resin composition. The curing agent composition (B) is contained in an amount of 20 parts by mass or more and 100 parts by mass or less.
主剤（Ａ）：２官能以上のエポキシ樹脂
硬化剤組成物（Ｂ）：上記一般式［１］で表されるジアミン硬化剤、上記一般式［２］で表されるジアミン硬化剤、上記式［３］で表されるジアミン硬化剤、および上記式［４］で表されるジアミン硬化剤からなる群から選ばれた少なくとも２つを含み、かつ単一の融点を有するジアミン硬化剤組成物。 Main agent (A): Bifunctional or higher functional epoxy resin curing agent composition (B): Diamine curing agent represented by the general formula [1], diamine curing agent represented by the general formula [2], the above formula [ A diamine curing agent composition containing at least two selected from the group consisting of the diamine curing agent represented by 3] and the diamine curing agent represented by the above formula [4] and having a single melting point.
硬化剤組成物（Ｂ）：上記一般式［１］で表されるジアミン硬化剤、上記一般式［２］で表されるジアミン硬化剤、上記式［３］で表されるジアミン硬化剤、および上記式［４］で表されるジアミン硬化剤からなる群から選ばれた少なくとも２つを含み、かつ単一の融点を有するジアミン硬化剤組成物。 Main agent (A): Bifunctional or higher functional epoxy resin curing agent composition (B): Diamine curing agent represented by the general formula [1], diamine curing agent represented by the general formula [2], the above formula [ A diamine curing agent composition containing at least two selected from the group consisting of the diamine curing agent represented by 3] and the diamine curing agent represented by the above formula [4] and having a single melting point.
ただし、式中、Ｒ１，Ｒ２は、それぞれ独立に炭素数６～１６の芳香族炭化水素基であり、これらが互いに結合して環を形成してもよい。Ｒ３，Ｒ４は、炭素数１～４の脂肪族炭化水素基、およびハロゲン原子からなる群から選ばれた少なくとも１つであり、Ｒ３とＲ４は異なる基である。
However, in the formula, R 1 and R 2 are independently aromatic hydrocarbon groups having 6 to 16 carbon atoms, and these may be bonded to each other to form a ring. R 3 and R 4 are at least one selected from the group consisting of an aliphatic hydrocarbon group having 1 to 4 carbon atoms and a halogen atom, and R 3 and R 4 are different groups.
本発明のエポキシ樹脂組成物の構成要素である主剤（Ａ）は、２官能以上のエポキシ樹脂である。主剤（Ａ）の具体例としては、特に限定されるものではないが、ビスフェノール型エポキシ樹脂、ビフェニル型エポキシ樹脂、ナフタレン型エポキシ樹脂、アントラセン型エポキシ樹脂、ハイドロキノン型エポキシ樹脂、チオエーテル型エポキシ樹脂、フェニレンエーテル型エポキシ樹脂、トリスヒドロキシフェニルメタン型エポキシ樹脂、テレフタル酸型エポキシ樹脂、イソシアヌル酸型エポキシ樹脂、フタルイミド型エポキシ樹脂、テトラフェニルエタン型エポキシ樹脂などが挙げられる。
The main agent (A), which is a component of the epoxy resin composition of the present invention, is a bifunctional or higher functional epoxy resin. Specific examples of the main agent (A) are not particularly limited, but are bisphenol type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, hydroquinone type epoxy resin, thioether type epoxy resin, and phenylene. Examples thereof include ether type epoxy resin, trishydroxyphenylmethane type epoxy resin, terephthalic acid type epoxy resin, isocyanuric acid type epoxy resin, phthalimide type epoxy resin, and tetraphenylethane type epoxy resin.
本発明のエポキシ樹脂組成物の構成要素である硬化剤組成物（Ｂ）、または本発明のジアミン硬化剤組成物は、上記一般式［１］で表されるジアミン硬化剤、上記一般式［２］で表されるジアミン硬化剤、上記式［３］で表されるジアミン硬化剤、および上記式［４］で表されるジアミン硬化剤からなる群から選ばれた少なくとも２つを含み、かつ単一の融点を有するジアミン硬化剤組成物である。かかる硬化剤組成物は、エポキシ樹脂への溶解性に優れる。また、かかる硬化剤組成物を用いることにより、貯蔵安定性に優れたエポキシ樹脂組成物や、高強度、高耐熱のエポキシ樹脂硬化物が得られやすくなる。さらに、かかる硬化剤組成物は硬化性に優れることが多いため、エポキシ樹脂組成物を高速で硬化しやすい。
The curing agent composition (B), which is a component of the epoxy resin composition of the present invention, or the diamine curing agent composition of the present invention is a diamine curing agent represented by the above general formula [1], the above general formula [2]. ], At least two selected from the group consisting of the diamine curing agent represented by the above formula [3], and the diamine curing agent represented by the above formula [4], and simply. It is a diamine curing agent composition having one melting point. Such a curing agent composition is excellent in solubility in an epoxy resin. Further, by using such a curing agent composition, it becomes easy to obtain an epoxy resin composition having excellent storage stability and a cured epoxy resin composition having high strength and high heat resistance. Further, since such a curing agent composition is often excellent in curability, the epoxy resin composition can be easily cured at a high speed.
本発明において、単一の融点を有するとは、ＪＩＳ Ｋ ７１２１：２０１２に従って、示差走査熱量測定（ＤＳＣ）により結晶性成分を窒素雰囲気下において昇温測定を行い、得られたＤＳＣ曲線における吸熱ピークが２つ以上に分離しないことを指す。吸熱ピークが２つに分離しないとは、吸熱ピークの両端がベースラインまで落ち込まず連続的な吸熱ピークとなることを指し、２つ以上のピークの頂点を有してもベースラインまで落ち込まない場合は単一の融点を有するとする。
In the present invention, having a single melting point means that the crystalline component is heated in a nitrogen atmosphere by differential scanning calorimetry (DSC) according to JIS K 7121: 2012, and the endothermic peak in the obtained DSC curve. Indicates that is not separated into two or more. The fact that the endothermic peak is not separated into two means that both ends of the endothermic peak do not drop to the baseline and become a continuous endothermic peak, and even if it has two or more peaks, it does not drop to the baseline. Has a single melting point.
上記一般式［１］、一般式［２］中のＲ１、Ｒ２は、それぞれ独立に炭素数６～１６の芳香族炭化水素基である。Ｒ１、Ｒ２の具体例としては、フェニル基、フルオレン基、アントラセン基などが挙げられる。Ｒ１、Ｒ２は、互いに結合して環を形成してもよい。中でも、硬化物の耐熱性の観点より、一般式［１］で表されるジアミン硬化剤が上記一般式［５］で表されるジアミン硬化剤である、および／または、一般式［２］で表されるジアミン硬化剤が上記一般式［６］で表されるジアミン硬化剤であることが好ましい。
R 1 and R 2 in the general formula [1] and the general formula [2] are independently aromatic hydrocarbon groups having 6 to 16 carbon atoms. Specific examples of R 1 and R 2 include a phenyl group, a fluorene group, an anthracene group and the like. R 1 and R 2 may be combined with each other to form a ring. Among them, from the viewpoint of heat resistance of the cured product, the diamine curing agent represented by the general formula [1] is the diamine curing agent represented by the general formula [5], and / or the general formula [2]. The diamine curing agent represented is preferably the diamine curing agent represented by the above general formula [6].
上記一般式［１］、一般式［２］中のＲ３，Ｒ４は、炭素数１～４の脂肪族炭化水素基、およびハロゲン原子からなる群から選ばれた少なくとも１つであり、Ｒ３とＲ４は異なる基である。Ｒ３、Ｒ４の具体例としては、メチル基、エチル基、プロピル基、ブチル基などが挙げられる。中でも、エポキシ樹脂組成物の貯蔵安定性をより向上させる観点より、Ｒ３、Ｒ４のいずれか一方または両方がメチル基またはエチル基であることが好ましい。
R 3 and R 4 in the general formula [1] and the general formula [2] are at least one selected from the group consisting of an aliphatic hydrocarbon group having 1 to 4 carbon atoms and a halogen atom, and are R. 3 and R 4 are different groups. Specific examples of R 3 and R 4 include a methyl group, an ethyl group, a propyl group, a butyl group and the like. Above all, from the viewpoint of further improving the storage stability of the epoxy resin composition, it is preferable that either or both of R 3 and R 4 are methyl groups or ethyl groups.
本発明のエポキシ樹脂組成物は、エポキシ樹脂組成物中のエポキシ樹脂成分１００質量部に対して、硬化剤組成物（Ｂ）を２０質量部以上１００質量部以下含み、好ましくは３０質量部以上１００質量部以下である。エポキシ樹脂成分に対する硬化剤組成物（Ｂ）の含有量を前記した範囲内とすることで、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の強度が向上し、耐熱性が良好になる。かかるエポキシ樹脂成分とは、エポキシ樹脂組成物中の全てのエポキシ樹脂を併せた成分である。
The epoxy resin composition of the present invention contains 20 parts by mass or more and 100 parts by mass or less of the curing agent composition (B) with respect to 100 parts by mass of the epoxy resin component in the epoxy resin composition, preferably 30 parts by mass or more and 100 parts by mass. It is less than a part by mass. By setting the content of the curing agent composition (B) with respect to the epoxy resin component within the above range, the strength of the epoxy resin cured product obtained by curing the epoxy resin composition is improved, and the heat resistance is improved. .. Such an epoxy resin component is a component in which all the epoxy resins in the epoxy resin composition are combined.
本発明のエポキシ樹脂組成物は、一般式［１］で表されるジアミン硬化剤、一般式［２］で表されるジアミン硬化剤、式［３］で表されるジアミン硬化剤および式［４］で表されるジアミン硬化剤からなる群から選ばれた少なくとも２つの各ジアミン硬化剤を、エポキシ樹脂組成物中のエポキシ樹脂成分１００質量部に対して、それぞれ１０質量部以上８０質量部以下含むことが好ましく、１５質量部以上７５質量部以下含むことがより好ましく、２５質量部以上５０質量部以下含むことが特に好ましい。前記の各成分それぞれを前記した範囲内とすることで、エポキシ樹脂組成物の貯蔵安定性を向上し、さらにエポキシ樹脂への溶解温度を低下させることができる。なお、前記２つの各ジアミン硬化剤の合計含有量は、硬化剤組成物（Ｂ）の含有量の範囲である２０質量部以上１００質量部以下である。
The epoxy resin composition of the present invention has a diamine curing agent represented by the general formula [1], a diamine curing agent represented by the general formula [2], a diamine curing agent represented by the formula [3], and a formula [4]. ], Each of at least two diamine curing agents selected from the group consisting of diamine curing agents is contained in an amount of 10 parts by mass or more and 80 parts by mass or less with respect to 100 parts by mass of the epoxy resin component in the epoxy resin composition. It is more preferable to contain 15 parts by mass or more and 75 parts by mass or less, and 25 parts by mass or more and 50 parts by mass or less is particularly preferable. By setting each of the above components within the above range, the storage stability of the epoxy resin composition can be improved, and the dissolution temperature in the epoxy resin can be lowered. The total content of each of the two diamine curing agents is 20 parts by mass or more and 100 parts by mass or less, which is within the range of the content of the curing agent composition (B).
本発明において、主剤（Ａ）と硬化剤組成物（Ｂ）との合計の含有量は、エポキシ樹脂組成物１００質量％中に、７５質量％以上であることが好ましく、８０質量％以上がより好ましく、８５質量％以上がさらに好ましく、９０質量％以上が一層好ましく、９５質量％以上が特に好ましい。
In the present invention, the total content of the main agent (A) and the curing agent composition (B) is preferably 75% by mass or more, more preferably 80% by mass or more in 100% by mass of the epoxy resin composition. Preferably, 85% by mass or more is further preferable, 90% by mass or more is further preferable, and 95% by mass or more is particularly preferable.
本発明において、主剤（Ａ）以外のエポキシ樹脂が、主剤（Ａ）１００質量部に対して２０質量部以下であれば、エポキシ樹脂組成物に含まれていても良い。また、本発明において、硬化剤組成物（Ｂ）以外の硬化剤が、主剤（Ａ）１００質量部に対して２０質量部以下であれば、エポキシ樹脂組成物に含まれていても良い。
In the present invention, the epoxy resin other than the main agent (A) may be contained in the epoxy resin composition as long as it is 20 parts by mass or less with respect to 100 parts by mass of the main agent (A). Further, in the present invention, if the curing agent other than the curing agent composition (B) is 20 parts by mass or less with respect to 100 parts by mass of the main agent (A), it may be contained in the epoxy resin composition.
本発明のエポキシ樹脂組成物は、さらにアルミニウム塩化物、アルミニウム臭化物、三フッ化ホウ素、五フッ化アンチモン、五フッ化リン、四フッ化チタン等のルイス酸、脂肪族あるいは芳香族の第三級アミン、イミダゾール類、アルコール類、フェノール類を含んでいても良い。かかる成分を含むことにより、反応が促進されやすくなる。
The epoxy resin composition of the present invention further comprises a Lewis acid such as aluminum chloride, aluminum bromide, boron trifluoride, antimony pentafluoride, phosphorus pentafluoride, and titanium tetrafluoride, and a tertiary of aliphatic or aromatic. It may contain amines, imidazoles, alcohols and phenols. By including such a component, the reaction is easily promoted.
エポキシ樹脂組成物において、硬化剤組成物（Ｂ）を含む全ての硬化剤の含有量は、硬化剤の全活性水素数（Ｈ）と、全てのエポキシ樹脂成分中のエポキシ基総数(Ｅ)との比、いわゆるＨ／Ｅで示すことができる。全ての硬化剤の含有量は、Ｈ／Ｅが０．８０以上１．１０以下の範囲を満たす含有量であることが好ましく、０．８５以上１．０５以下の範囲を満たす含有量であることがより好ましい。Ｈ／Ｅが０．８０以上であると、エポキシ樹脂硬化物の反応率が十分高くなりやすく、耐熱性や材料強度が向上しやすい。また、Ｈ／Ｅが１．１０以下であると、塑性変形能力が向上しやすくなり、繊維強化複合材料の耐衝撃性が十分なものとなりやすい。
In the epoxy resin composition, the contents of all the curing agents including the curing agent composition (B) are the total number of active hydrogens (H) of the curing agent and the total number of epoxy groups (E) in all the epoxy resin components. Can be indicated by the ratio of, so-called H / E. The content of all the curing agents is preferably a content that satisfies the range of H / E of 0.80 or more and 1.10 or less, and preferably a content that satisfies the range of 0.85 or more and 1.05 or less. Is more preferable. When the H / E is 0.80 or more, the reaction rate of the cured epoxy resin product tends to be sufficiently high, and the heat resistance and material strength tend to be improved. Further, when the H / E is 1.10 or less, the plastic deformation ability tends to be improved, and the impact resistance of the fiber-reinforced composite material tends to be sufficient.
硬化剤組成物（Ｂ）の含有量は、エポキシ樹脂組成物中の硬化剤の全活性水素数（Ｈ）に対する硬化剤組成物（Ｂ）由来の活性水素数の割合、いわゆる硬化剤組成物（Ｂ）の活性水素割合で示すことができる。本発明において、硬化剤組成物（Ｂ）の活性水素割合は２０％以上１００％以下であることが好ましい。硬化剤組成物（Ｂ）の活性水素割合をかかる範囲とすることにより、硬化剤組成物（Ｂ）が有するエポキシ樹脂組成物の貯蔵安定性やエポキシ樹脂硬化物の耐熱性を高める効果が十分に発揮されやすい。
The content of the curing agent composition (B) is the ratio of the number of active hydrogens derived from the curing agent composition (B) to the total number of active hydrogens (H) of the curing agent in the epoxy resin composition, that is, the so-called curing agent composition ( It can be indicated by the active hydrogen ratio of B). In the present invention, the active hydrogen ratio of the curing agent composition (B) is preferably 20% or more and 100% or less. By setting the active hydrogen ratio of the curing agent composition (B) to such a range, the effect of enhancing the storage stability of the epoxy resin composition and the heat resistance of the epoxy resin cured product of the curing agent composition (B) is sufficient. Easy to demonstrate.
硬化剤組成物（Ｂ）を構成する単一の融点を有するジアミン硬化剤は、結晶性を有することが好ましい。結晶性を有するとは、常温以上の温度に融点を有し、常温で固体の成分のことである。融点は、ＪＩＳ Ｋ ７１２１：２０１２に従って、示差走査熱量測定（ＤＳＣ）により求めることができる。結晶性成分を窒素雰囲気下において昇温測定を行い、得られたＤＳＣ曲線における吸熱ピークの頂点温度を融点として得ることができる。なお、常温とは２５℃を指す。
The diamine curing agent having a single melting point constituting the curing agent composition (B) preferably has crystallinity. Crystallinity is a component that has a melting point at room temperature or higher and is solid at room temperature. The melting point can be determined by differential scanning calorimetry (DSC) according to JIS K 7121: 2012. The temperature of the crystalline component can be measured by raising the temperature in a nitrogen atmosphere, and the peak temperature of the endothermic peak in the obtained DSC curve can be obtained as the melting point. The normal temperature means 25 ° C.
ジアミン硬化剤が結晶性を有する化合物である場合であって、当該結晶性を有する化合物２種類以上が混ざり合った結晶混合物（共晶）では、その融点が結晶性を有する化合物単一の融点よりも低下する融点降下の現象が見られる場合がある。融点降下の現象を利用して、結晶性成分の融点を制御することにより、樹脂組成物とした時の融解挙動を制御でき、強化繊維基材への含浸性を向上させやすくなる。
In the case where the diamine curing agent is a crystalline compound, and in a crystal mixture (eutectic) in which two or more kinds of the crystalline compound are mixed, the melting point is higher than the melting point of a single compound having crystalline property. There may be a phenomenon of melting point drop that also decreases. By controlling the melting point of the crystalline component by utilizing the phenomenon of melting point drop, the melting behavior of the resin composition can be controlled, and the impregnation property into the reinforcing fiber base material can be easily improved.
共晶化の方法は、例えば、一般式［１］で表されるジアミン硬化剤、一般式［２］で表されるジアミン硬化剤、式［３］で表されるジアミン硬化剤、および式［４］で表されるジアミン硬化剤からなる群から選ばれた少なくとも２つを一旦融解して均一混合後にゆっくりと結晶化温度付近に冷却し結晶化させる方法、一般式［１］で表されるジアミン硬化剤、一般式［２］で表されるジアミン硬化剤、式［３］で表されるジアミン硬化剤、および式［４］で表されるジアミン硬化剤からなる群から選ばれた少なくとも２つを溶媒に溶解後に温度低下や貧溶媒滴下などにより結晶析出させる方法などで調製することができる。共晶の均一性の点から、一般式［１］で表されるジアミン硬化剤、一般式［２］で表されるジアミン硬化剤、式［３］で表されるジアミン硬化剤、および式［４］で表されるジアミン硬化剤からなる群から選ばれた少なくとも２つを一旦融解して均一混合後にゆっくりと結晶化温度付近に冷却し結晶化させることが好ましい。このとき、硬化剤組成物（Ｂ）は不可逆的である（すなわち、得られた結晶混合物は、加熱、混合などの物理的な操作によって、一般式［１］で表されるジアミン硬化剤、一般式［２］で表されるジアミン硬化剤、式［３］で表されるジアミン硬化剤、および式［４］で表されるジアミン硬化剤からなる群から選ばれた少なくとも２つの状態に戻らない）が、本発明では、かかる結晶混合物を含めて少なくとも２つのジアミン硬化剤を含む硬化剤組成物（Ｂ）であるとする。
The method of co-crystallization includes, for example, a diamine curing agent represented by the general formula [1], a diamine curing agent represented by the general formula [2], a diamine curing agent represented by the formula [3], and a formula [ A method in which at least two selected from the group consisting of the diamine curing agent represented by 4] are once melted, uniformly mixed, and then slowly cooled to near the crystallization temperature to crystallize, represented by the general formula [1]. At least 2 selected from the group consisting of a diamine curing agent, a diamine curing agent represented by the general formula [2], a diamine curing agent represented by the formula [3], and a diamine curing agent represented by the formula [4]. It can be prepared by a method such as dissolving one in a solvent and then precipitating crystals by lowering the temperature or dropping a poor solvent. From the viewpoint of eutectic uniformity, the diamine curing agent represented by the general formula [1], the diamine curing agent represented by the general formula [2], the diamine curing agent represented by the formula [3], and the formula [ It is preferable that at least two selected from the group consisting of the diamine curing agent represented by 4] are once melted, uniformly mixed, and then slowly cooled to near the crystallization temperature for crystallization. At this time, the curing agent composition (B) is irreversible (that is, the obtained crystal mixture is subjected to physical operations such as heating and mixing to obtain a diamine curing agent represented by the general formula [1], generally. It does not return to at least two states selected from the group consisting of the diamine curing agent represented by the formula [2], the diamine curing agent represented by the formula [3], and the diamine curing agent represented by the formula [4]. ) Is the curing agent composition (B) containing at least two diamine curing agents including such a crystal mixture in the present invention.
本発明のエポキシ樹脂組成物は、貯蔵安定性およびエポキシ樹脂への溶解性に優れるため、繊維強化複合材料を得るために強化繊維基材とともに用いられる、エポキシ樹脂硬化物（エポキシ樹脂組成物を硬化してなるもの）に好適である。
Since the epoxy resin composition of the present invention has excellent storage stability and solubility in an epoxy resin, it is used together with a reinforcing fiber base material to obtain a fiber-reinforced composite material. Therefore, a cured epoxy resin (cured epoxy resin composition) is used. It is suitable for
以下、実施例により、本発明についてさらに詳細に説明するが、本発明はこれらの実施例に限定されない。
Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
（樹脂原料）
各実施例の樹脂組成物を得るために、以下の樹脂原料を用いた。なお、表１中の樹脂組成物の含有割合の単位は、特に断らない限り「質量部」を意味する。 (Resin raw material)
The following resin raw materials were used to obtain the resin compositions of each example. The unit of the content ratio of the resin composition in Table 1 means "part by mass" unless otherwise specified.
各実施例の樹脂組成物を得るために、以下の樹脂原料を用いた。なお、表１中の樹脂組成物の含有割合の単位は、特に断らない限り「質量部」を意味する。 (Resin raw material)
The following resin raw materials were used to obtain the resin compositions of each example. The unit of the content ratio of the resin composition in Table 1 means "part by mass" unless otherwise specified.
１．主剤（Ａ）
・“アラルダイト（登録商標）”ＭＹ７２１（ハンツマン・アドバンスド・マテリアルズ社製）：テトラグリシジルジアミノジフェニルメタン（ＴＧＤＤＭ）
・ＹＤ－１２８（東都化成（株）製、ビスフェノールＡ型エポキシ樹脂）。 1. 1. Main agent (A)
-"Araldite (registered trademark)" MY721 (manufactured by Huntsman Advanced Materials): Tetraglycidyldiaminodiphenylmethane (TGDDM)
-YD-128 (bisphenol A type epoxy resin manufactured by Toto Kasei Co., Ltd.).
・“アラルダイト（登録商標）”ＭＹ７２１（ハンツマン・アドバンスド・マテリアルズ社製）：テトラグリシジルジアミノジフェニルメタン（ＴＧＤＤＭ）
・ＹＤ－１２８（東都化成（株）製、ビスフェノールＡ型エポキシ樹脂）。 1. 1. Main agent (A)
-"Araldite (registered trademark)" MY721 (manufactured by Huntsman Advanced Materials): Tetraglycidyldiaminodiphenylmethane (TGDDM)
-YD-128 (bisphenol A type epoxy resin manufactured by Toto Kasei Co., Ltd.).
２．硬化剤組成物（Ｂ）
・ＦＭＭＡ：９，９－ビス（３－メチル―４－アミノフェニル）フルオレン
以下に記載の方法で合成した。 2. 2. Hardener composition (B)
-FMMA: 9,9-bis (3-methyl-4-aminophenyl) fluorene Synthesized by the method described below.
・ＦＭＭＡ：９，９－ビス（３－メチル―４－アミノフェニル）フルオレン
以下に記載の方法で合成した。 2. 2. Hardener composition (B)
-FMMA: 9,9-bis (3-methyl-4-aminophenyl) fluorene Synthesized by the method described below.
温度計、滴下漏斗、冷却管および攪拌機を取り付けた四つ口フラスコに、９－フルオレノン（東京化成工業（株）製） １４．４ｇ（０．０８モル）、オルト－トルイジン（東京化成工業（株）製） １１２．１ｇ（１．０５モル）およびトルエン ５７．６ｇ（４質量倍／９－フルオレノン）を仕込んだ。窒素パージ攪拌下、溶液を１５℃以下に冷却し、３５％塩酸 ２５．０ｇ（０．２４モル）を滴下した。発熱が収まった後、液温９０～１１０℃に昇温し、系中の水とトルエンを共沸させた。留出が収まった後、さらにトルエン １４．４ｇ（１質量倍／９－フルオレノン）を投入し、再度系中の水とトルエンを共沸させながら、液温を１３０～１４０℃まで昇温し、２２時間撹拌しながら熟成することにより縮合反応を行った。
9-Fluorenone (manufactured by Tokyo Chemical Industry Co., Ltd.) 14.4 g (0.08 mol), ortho-toluidine (Tokyo Chemical Industry Co., Ltd.) in a four-necked flask equipped with a thermometer, a dropping funnel, a condenser and a stirrer )) 112.1 g (1.05 mol) and 57.6 g of toluene (4 mass times / 9-fluorenone) were charged. The solution was cooled to 15 ° C. or lower under stirring with a nitrogen purge, and 25.0 g (0.24 mol) of 35% hydrochloric acid was added dropwise. After the heat generation had subsided, the temperature of the liquid was raised to 90 to 110 ° C., and water and toluene in the system were azeotropically heated. After the distillation has subsided, 14.4 g (1 mass times / 9-fluorenone) of toluene is further added, and the liquid temperature is raised to 130 to 140 ° C. while azeotropically boiling the water and toluene in the system again. The condensation reaction was carried out by aging with stirring for 22 hours.
縮合反応後、反応液を冷却し、５０℃で１７質量％苛性ソーダ水 ５６．４ｇを投入し、反応液を中和した。下層から水相を払出し、取得した油相に２－プロパノール ２１，６ｇと水 １０．８ｇを投入し、９，９－ビス（３－メチル－４－アミノフェニル）フルオレンを晶析させた。得られたスラリーを室温まで冷却し、固液分離を行った。得られたケークに２－プロパノール ２１．６ｇでリンスし、粗９，９－ビス（３－メチル－４－アミノフェニル）フルオレンを得た。これをトルエン ４３．２ｇでリフラックス下、１時間、リスラリーを行い、室温に冷却後、ろ過し、得られたケークにトルエン ７．２ｇでリンスを行った。これを温度６０℃、減圧度０．０１ｋＰａ以下で一晩真空乾燥した。９，９－ビス（３－メチル－４－アミノフェニル）フルオレン ２８．０ｇ（収率 ９３％／９－フルオレノン）を取得した。液体クロマトグラフィー分析による化学純度は、９８．８％であった。
After the condensation reaction, the reaction solution was cooled, and 56.4 g of 17% by mass caustic soda water was added at 50 ° C. to neutralize the reaction solution. The aqueous phase was discharged from the lower layer, and 21.6 g of 2-propanol and 10.8 g of water were added to the obtained oil phase to crystallize 9,9-bis (3-methyl-4-aminophenyl) fluorene. The obtained slurry was cooled to room temperature and solid-liquid separation was performed. The obtained cake was rinsed with 21.6 g of 2-propanol to obtain crude 9,9-bis (3-methyl-4-aminophenyl) fluorene. This was reslurried with 43.2 g of toluene for 1 hour, cooled to room temperature, filtered, and the obtained cake was rinsed with 7.2 g of toluene. This was vacuum dried overnight at a temperature of 60 ° C. and a reduced pressure of 0.01 kPa or less. 28.0 g (yield 93% / 9-fluorenone) of 9,9-bis (3-methyl-4-aminophenyl) fluorene was obtained. The chemical purity by liquid chromatography analysis was 98.8%.
・ＦＭＥＡ：９，９－ビス（３－エチル－４－アミノフェニル）フルオレン
以下に記載の方法で合成した。 -FMEA: 9,9-bis (3-ethyl-4-aminophenyl) fluorene Synthesized by the method described below.
以下に記載の方法で合成した。 -FMEA: 9,9-bis (3-ethyl-4-aminophenyl) fluorene Synthesized by the method described below.
温度計、滴下漏斗、冷却管および攪拌機を取り付けた四つ口フラスコに、９－フルオレノン（東京化成工業（株）製） １４．４ｇ（０．０８モル）、２－エチルアニリン（東京化成工業（株）製） １１５．６ｇ（１．０５モル）およびトルエン ５７．６ｇ（４質量倍／９－フルオレノン）を仕込んだ。窒素パージ攪拌下、溶液を１５℃以下に冷却し、３５％塩酸 ２５．０ｇ（０．２４モル）を滴下した。発熱が収まった後、液温９０～１１０℃に昇温し、系中の水とトルエンを共沸させた。留出が収まった後、さらにトルエン １４．４ｇ（１質量倍／９－フルオレノン）を投入し、再度系中の水とトルエンを共沸させながら、液温を１３０～１４０℃まで昇温し、６６時間撹拌しながら熟成することにより縮合反応を行った。
9-Fluorenone (manufactured by Tokyo Chemical Industry Co., Ltd.) 14.4 g (0.08 mol), 2-ethylaniline (Tokyo Chemical Industry Co., Ltd.) in a four-necked flask equipped with a thermometer, dropping funnel, condenser and stirrer. (Manufactured by Co., Ltd.) 115.6 g (1.05 mol) and 57.6 g of toluene (4 mass times / 9-fluorenone) were charged. The solution was cooled to 15 ° C. or lower under stirring with a nitrogen purge, and 25.0 g (0.24 mol) of 35% hydrochloric acid was added dropwise. After the heat generation had subsided, the temperature of the liquid was raised to 90 to 110 ° C., and water and toluene in the system were azeotropically heated. After the distillation has subsided, 14.4 g (1 mass times / 9-fluorenone) of toluene is further added, and the liquid temperature is raised to 130 to 140 ° C. while azeotropically boiling the water and toluene in the system again. The condensation reaction was carried out by aging with stirring for 66 hours.
縮合反応後、反応液を冷却し、５０℃で１７質量％苛性ソーダ水 ５６．４ｇを投入し、反応液を中和した。下層から水相を払出し、取得した油相に２－プロパノール ２１，６ｇと水 １０．８ｇを投入し、９，９－ビス（３－エチル－４－アミノフェニル）フルオレンを晶析させた。得られたスラリーを室温まで冷却し、固液分離を行った。得られたケークに２－プロパノール ２１．６ｇでリンスし、粗９，９－ビス（３－エチル－４－アミノフェニル）フルオレンを得た。これをトルエン ４３．２ｇでリフラックス下、１時間、リスラリーを行い、室温に冷却後、ろ過し、得られたケークにトルエン ７．２ｇでリンスを行った。これを温度６０℃、減圧度０．０１ｋＰａ以下で一晩真空乾燥した。９，９－ビス（３－エチル－４－アミノフェニル）フルオレン ２５．４ｇ（収率 ７８％／９－フルオレノン）を取得した。液体クロマトグラフィー分析による化学純度は、９９．２％であった。
After the condensation reaction, the reaction solution was cooled, and 56.4 g of 17% by mass caustic soda water was added at 50 ° C. to neutralize the reaction solution. The aqueous phase was discharged from the lower layer, and 21.6 g of 2-propanol and 10.8 g of water were added to the obtained oil phase to crystallize 9,9-bis (3-ethyl-4-aminophenyl) fluorene. The obtained slurry was cooled to room temperature and solid-liquid separation was performed. The obtained cake was rinsed with 21.6 g of 2-propanol to obtain crude 9,9-bis (3-ethyl-4-aminophenyl) fluorene. This was reslurried with 43.2 g of toluene for 1 hour, cooled to room temperature, filtered, and the obtained cake was rinsed with 7.2 g of toluene. This was vacuum dried overnight at a temperature of 60 ° C. and a reduced pressure of 0.01 kPa or less. 25.4 g (yield 78% / 9-fluorenone) of 9,9-bis (3-ethyl-4-aminophenyl) fluorene was obtained. The chemical purity by liquid chromatography analysis was 99.2%.
・セイカキュアＳ（和歌山精化工業（株）製）：４，４’－ジアミノジフェニルスルホン
・３，３’－ＤＡＳ（小西化学工業（株）製）：３，３’－ジアミノジフェニルスルホン
（硬化剤組成物（Ｂ）の融点の測定）
ＪＩＳ Ｋ ７１２１：２０１２に従って、示差走査熱量測定（ＤＳＣ）により測定した。測定装置としてはＰｙｒｉｓ１ ＤＳＣ（Ｐｅｒｋｉｎ Ｅｌｍｅｒ社製）を使用した。硬化剤組成物（Ｂ）をアルミサンプルパンに採取し、窒素雰囲気下において、１０℃／ｍｉｎの昇温速度で測定を行った。得られたＤＳＣ曲線において、成分の融解による吸熱ピークの頂点の温度を融点として測定した。また、吸熱ピークの両端がベースラインまで落ち込まず連続的な吸熱ピークとなり、２つ以上のピークの頂点を有してもベースラインまで落ち込まない場合は、吸熱ピークの頂点の強度が大きいものを融点とした。なお、表１に記載の共晶化処理：有りの記載の硬化剤組成物（Ｂ）は、表１に記載の２種類の硬化剤を一旦融解して均一混合後に結晶化温度付近で再結晶化して調製した。 ・ Seika Cure S (manufactured by Wakayama Seika Kogyo Co., Ltd.): 4,4'-diaminodiphenyl sulfone ・ 3,3'-DAS (manufactured by Konishi Chemical Industry Co., Ltd.): 3,3'-diaminodiphenyl sulfone (curing agent) Measurement of melting point of composition (B))
Measured by differential scanning calorimetry (DSC) according to JIS K 7121: 2012. As a measuring device, Pyris1 DSC (manufactured by Perkin Elmer) was used. The curing agent composition (B) was collected in an aluminum sample pan and measured at a heating rate of 10 ° C./min in a nitrogen atmosphere. In the obtained DSC curve, the temperature at the apex of the endothermic peak due to melting of the components was measured as the melting point. If both ends of the endothermic peak do not drop to the baseline but become continuous endothermic peaks and do not drop to the baseline even if they have two or more peak vertices, the endothermic peak with a high intensity is the melting point. And said. The eutectic treatment shown in Table 1: Yes The hardener composition (B) described is recrystallized near the crystallization temperature after the two types of hardeners shown in Table 1 are once melted and uniformly mixed. Prepared by crystallization.
・３，３’－ＤＡＳ（小西化学工業（株）製）：３，３’－ジアミノジフェニルスルホン
（硬化剤組成物（Ｂ）の融点の測定）
ＪＩＳ Ｋ ７１２１：２０１２に従って、示差走査熱量測定（ＤＳＣ）により測定した。測定装置としてはＰｙｒｉｓ１ ＤＳＣ（Ｐｅｒｋｉｎ Ｅｌｍｅｒ社製）を使用した。硬化剤組成物（Ｂ）をアルミサンプルパンに採取し、窒素雰囲気下において、１０℃／ｍｉｎの昇温速度で測定を行った。得られたＤＳＣ曲線において、成分の融解による吸熱ピークの頂点の温度を融点として測定した。また、吸熱ピークの両端がベースラインまで落ち込まず連続的な吸熱ピークとなり、２つ以上のピークの頂点を有してもベースラインまで落ち込まない場合は、吸熱ピークの頂点の強度が大きいものを融点とした。なお、表１に記載の共晶化処理：有りの記載の硬化剤組成物（Ｂ）は、表１に記載の２種類の硬化剤を一旦融解して均一混合後に結晶化温度付近で再結晶化して調製した。 ・ Seika Cure S (manufactured by Wakayama Seika Kogyo Co., Ltd.): 4,4'-diaminodiphenyl sulfone ・ 3,3'-DAS (manufactured by Konishi Chemical Industry Co., Ltd.): 3,3'-diaminodiphenyl sulfone (curing agent) Measurement of melting point of composition (B))
Measured by differential scanning calorimetry (DSC) according to JIS K 7121: 2012. As a measuring device, Pyris1 DSC (manufactured by Perkin Elmer) was used. The curing agent composition (B) was collected in an aluminum sample pan and measured at a heating rate of 10 ° C./min in a nitrogen atmosphere. In the obtained DSC curve, the temperature at the apex of the endothermic peak due to melting of the components was measured as the melting point. If both ends of the endothermic peak do not drop to the baseline but become continuous endothermic peaks and do not drop to the baseline even if they have two or more peak vertices, the endothermic peak with a high intensity is the melting point. And said. The eutectic treatment shown in Table 1: Yes The hardener composition (B) described is recrystallized near the crystallization temperature after the two types of hardeners shown in Table 1 are once melted and uniformly mixed. Prepared by crystallization.
（エポキシ樹脂組成物の調製）
主剤（Ａ）、硬化剤組成物（Ｂ）を表１に記載した含有比で混合し、エポキシ樹脂組成物を調製した。 (Preparation of epoxy resin composition)
The main agent (A) and the curing agent composition (B) were mixed at the content ratios shown in Table 1 to prepare an epoxy resin composition.
主剤（Ａ）、硬化剤組成物（Ｂ）を表１に記載した含有比で混合し、エポキシ樹脂組成物を調製した。 (Preparation of epoxy resin composition)
The main agent (A) and the curing agent composition (B) were mixed at the content ratios shown in Table 1 to prepare an epoxy resin composition.
（発熱開始温度の測定）
調製したエポキシ樹脂組成物を、示差走査熱量測定（ＤＳＣ）により測定した。測定装置としてはＰｙｒｉｓ１ ＤＳＣ（Ｐｅｒｋｉｎ Ｅｌｍｅｒ社製）を使用した。アルミサンプルパンに採取し、窒素雰囲気下において、１０℃／ｍｉｎの昇温速度で測定を行った。得られたＤＳＣ曲線において、発熱反応が開始した温度を発熱開始温度として測定した。なお、表１に記載の共晶化処理：有りの記載の硬化剤組成物（Ｂ）は、表１に記載の２種類の硬化剤を一旦融解して均一混合後に結晶化温度付近で再結晶化して調製した。 (Measurement of heat generation start temperature)
The prepared epoxy resin composition was measured by differential scanning calorimetry (DSC). As a measuring device, Pyris1 DSC (manufactured by Perkin Elmer) was used. The sample was collected in an aluminum sample pan and measured at a heating rate of 10 ° C./min in a nitrogen atmosphere. In the obtained DSC curve, the temperature at which the exothermic reaction started was measured as the exothermic start temperature. The eutectic treatment shown in Table 1: Yes The hardener composition (B) described is recrystallized near the crystallization temperature after the two types of hardeners shown in Table 1 are once melted and uniformly mixed. Prepared by crystallization.
調製したエポキシ樹脂組成物を、示差走査熱量測定（ＤＳＣ）により測定した。測定装置としてはＰｙｒｉｓ１ ＤＳＣ（Ｐｅｒｋｉｎ Ｅｌｍｅｒ社製）を使用した。アルミサンプルパンに採取し、窒素雰囲気下において、１０℃／ｍｉｎの昇温速度で測定を行った。得られたＤＳＣ曲線において、発熱反応が開始した温度を発熱開始温度として測定した。なお、表１に記載の共晶化処理：有りの記載の硬化剤組成物（Ｂ）は、表１に記載の２種類の硬化剤を一旦融解して均一混合後に結晶化温度付近で再結晶化して調製した。 (Measurement of heat generation start temperature)
The prepared epoxy resin composition was measured by differential scanning calorimetry (DSC). As a measuring device, Pyris1 DSC (manufactured by Perkin Elmer) was used. The sample was collected in an aluminum sample pan and measured at a heating rate of 10 ° C./min in a nitrogen atmosphere. In the obtained DSC curve, the temperature at which the exothermic reaction started was measured as the exothermic start temperature. The eutectic treatment shown in Table 1: Yes The hardener composition (B) described is recrystallized near the crystallization temperature after the two types of hardeners shown in Table 1 are once melted and uniformly mixed. Prepared by crystallization.
（発熱ピーク温度の測定）
調製したエポキシ樹脂組成物を、示差走査熱量測定（ＤＳＣ）により測定した。測定装置としてはＰｙｒｉｓ１ ＤＳＣ（Ｐｅｒｋｉｎ Ｅｌｍｅｒ社製）を使用した。アルミサンプルパンに採取し、窒素雰囲気下において、１０℃／ｍｉｎの昇温速度で測定を行った。得られたＤＳＣ曲線において、発熱反応のピークの頂点の温度を発熱ピーク温度として測定した。なお、表１に記載の共晶化処理：有りの記載の硬化剤組成物（Ｂ）は、表１に記載の２種類の硬化剤を一旦融解して均一混合後に結晶化温度付近で再結晶化して調製した。 (Measurement of exothermic peak temperature)
The prepared epoxy resin composition was measured by differential scanning calorimetry (DSC). As a measuring device, Pyris1 DSC (manufactured by Perkin Elmer) was used. The sample was collected in an aluminum sample pan and measured at a heating rate of 10 ° C./min in a nitrogen atmosphere. In the obtained DSC curve, the temperature at the peak of the exothermic reaction was measured as the exothermic peak temperature. The eutectic treatment shown in Table 1: Yes The hardener composition (B) described is recrystallized near the crystallization temperature after the two types of hardeners shown in Table 1 are once melted and uniformly mixed. Prepared by crystallization.
調製したエポキシ樹脂組成物を、示差走査熱量測定（ＤＳＣ）により測定した。測定装置としてはＰｙｒｉｓ１ ＤＳＣ（Ｐｅｒｋｉｎ Ｅｌｍｅｒ社製）を使用した。アルミサンプルパンに採取し、窒素雰囲気下において、１０℃／ｍｉｎの昇温速度で測定を行った。得られたＤＳＣ曲線において、発熱反応のピークの頂点の温度を発熱ピーク温度として測定した。なお、表１に記載の共晶化処理：有りの記載の硬化剤組成物（Ｂ）は、表１に記載の２種類の硬化剤を一旦融解して均一混合後に結晶化温度付近で再結晶化して調製した。 (Measurement of exothermic peak temperature)
The prepared epoxy resin composition was measured by differential scanning calorimetry (DSC). As a measuring device, Pyris1 DSC (manufactured by Perkin Elmer) was used. The sample was collected in an aluminum sample pan and measured at a heating rate of 10 ° C./min in a nitrogen atmosphere. In the obtained DSC curve, the temperature at the peak of the exothermic reaction was measured as the exothermic peak temperature. The eutectic treatment shown in Table 1: Yes The hardener composition (B) described is recrystallized near the crystallization temperature after the two types of hardeners shown in Table 1 are once melted and uniformly mixed. Prepared by crystallization.
（エポキシ樹脂への溶解温度の測定）
調製したエポキシ樹脂組成物を１０ｇ、バイアルに採取し、ホットプレート上で加熱しホットプレートの設定温度に到達してから１０分間静置した。ホットプレートの設定温度を１０℃ずつ変えて確認し、固体状の硬化剤がエポキシ樹脂に溶解し透明化した温度をエポキシ樹脂への溶解温度とした。なお、表１に記載の共晶化処理：有りの記載の硬化剤組成物（Ｂ）は、表１に記載の２種類の硬化剤を一旦融解して均一混合後に結晶化温度付近で再結晶化して調製した。 (Measurement of dissolution temperature in epoxy resin)
10 g of the prepared epoxy resin composition was collected in a vial, heated on a hot plate, and allowed to stand for 10 minutes after reaching the set temperature of the hot plate. The set temperature of the hot plate was changed by 10 ° C. for confirmation, and the temperature at which the solid curing agent was dissolved in the epoxy resin and made transparent was defined as the dissolution temperature in the epoxy resin. The eutectic treatment shown in Table 1: Yes The hardener composition (B) described is recrystallized near the crystallization temperature after the two types of hardeners shown in Table 1 are once melted and uniformly mixed. Prepared by crystallization.
調製したエポキシ樹脂組成物を１０ｇ、バイアルに採取し、ホットプレート上で加熱しホットプレートの設定温度に到達してから１０分間静置した。ホットプレートの設定温度を１０℃ずつ変えて確認し、固体状の硬化剤がエポキシ樹脂に溶解し透明化した温度をエポキシ樹脂への溶解温度とした。なお、表１に記載の共晶化処理：有りの記載の硬化剤組成物（Ｂ）は、表１に記載の２種類の硬化剤を一旦融解して均一混合後に結晶化温度付近で再結晶化して調製した。 (Measurement of dissolution temperature in epoxy resin)
10 g of the prepared epoxy resin composition was collected in a vial, heated on a hot plate, and allowed to stand for 10 minutes after reaching the set temperature of the hot plate. The set temperature of the hot plate was changed by 10 ° C. for confirmation, and the temperature at which the solid curing agent was dissolved in the epoxy resin and made transparent was defined as the dissolution temperature in the epoxy resin. The eutectic treatment shown in Table 1: Yes The hardener composition (B) described is recrystallized near the crystallization temperature after the two types of hardeners shown in Table 1 are once melted and uniformly mixed. Prepared by crystallization.
（樹脂硬化板の作製）
上記で調製したエポキシ樹脂組成物を８０℃、０．２ｋＰａの条件で脱泡した後、２ｍｍ厚の“テフロン（登録商標）”製スペーサーにより厚み２ｍｍになるように設定したモールド中に注入した。１８０℃の温度で２時間硬化させ、厚さ２ｍｍの樹脂硬化板を得た。 (Making a resin cured plate)
The epoxy resin composition prepared above was defoamed at 80 ° C. and 0.2 kPa, and then injected into a mold set to have a thickness of 2 mm by using a 2 mm thick “Teflon®” spacer. It was cured at a temperature of 180 ° C. for 2 hours to obtain a resin cured plate having a thickness of 2 mm.
上記で調製したエポキシ樹脂組成物を８０℃、０．２ｋＰａの条件で脱泡した後、２ｍｍ厚の“テフロン（登録商標）”製スペーサーにより厚み２ｍｍになるように設定したモールド中に注入した。１８０℃の温度で２時間硬化させ、厚さ２ｍｍの樹脂硬化板を得た。 (Making a resin cured plate)
The epoxy resin composition prepared above was defoamed at 80 ° C. and 0.2 kPa, and then injected into a mold set to have a thickness of 2 mm by using a 2 mm thick “Teflon®” spacer. It was cured at a temperature of 180 ° C. for 2 hours to obtain a resin cured plate having a thickness of 2 mm.
（エポキシ樹脂硬化物の曲げ弾性率測定）
樹脂硬化板の中央付近から幅１０ｍｍ、長さ６０ｍｍの試験片を３枚切り出し、それぞれの試験片について、スパン間３２ｍｍの３点曲げを測定し、ＪＩＳ Ｋ７１７１－１９９４に従い、３枚の試験片の平均値から曲げ弾性率を求めた。 (Measurement of flexural modulus of cured epoxy resin)
Three test pieces with a width of 10 mm and a length of 60 mm were cut out from the vicinity of the center of the resin cured plate, and for each test piece, a three-point bending with a span of 32 mm was measured, and according to JIS K7171-1994, the three test pieces The flexural modulus was calculated from the average value.
樹脂硬化板の中央付近から幅１０ｍｍ、長さ６０ｍｍの試験片を３枚切り出し、それぞれの試験片について、スパン間３２ｍｍの３点曲げを測定し、ＪＩＳ Ｋ７１７１－１９９４に従い、３枚の試験片の平均値から曲げ弾性率を求めた。 (Measurement of flexural modulus of cured epoxy resin)
Three test pieces with a width of 10 mm and a length of 60 mm were cut out from the vicinity of the center of the resin cured plate, and for each test piece, a three-point bending with a span of 32 mm was measured, and according to JIS K7171-1994, the three test pieces The flexural modulus was calculated from the average value.
（エポキシ樹脂硬化物のガラス転移温度（Ｔｇ）測定）
樹脂硬化板の中央付近から幅１２．７ｍｍ、長さ４０ｍｍの試験片を切り出し、ＤＭＡ（ＴＡインスツルメンツ社製、ＡＲＥＳ）を用いてガラス転移温度（Ｔｇ）測定を行った。測定条件は、昇温速度５℃／分である。測定で得られた貯蔵弾性率Ｇ’の変曲点での温度をガラス転移温度（Ｔｇ）とした。 (Measurement of glass transition temperature (Tg) of cured epoxy resin)
A test piece having a width of 12.7 mm and a length of 40 mm was cut out from the vicinity of the center of the resin cured plate, and the glass transition temperature (Tg) was measured using DMA (ARES manufactured by TA Instruments). The measurement conditions are a heating rate of 5 ° C./min. The temperature at the inflection point of the storage elastic modulus G'obtained by the measurement was defined as the glass transition temperature (Tg).
樹脂硬化板の中央付近から幅１２．７ｍｍ、長さ４０ｍｍの試験片を切り出し、ＤＭＡ（ＴＡインスツルメンツ社製、ＡＲＥＳ）を用いてガラス転移温度（Ｔｇ）測定を行った。測定条件は、昇温速度５℃／分である。測定で得られた貯蔵弾性率Ｇ’の変曲点での温度をガラス転移温度（Ｔｇ）とした。 (Measurement of glass transition temperature (Tg) of cured epoxy resin)
A test piece having a width of 12.7 mm and a length of 40 mm was cut out from the vicinity of the center of the resin cured plate, and the glass transition temperature (Tg) was measured using DMA (ARES manufactured by TA Instruments). The measurement conditions are a heating rate of 5 ° C./min. The temperature at the inflection point of the storage elastic modulus G'obtained by the measurement was defined as the glass transition temperature (Tg).
本発明のエポキシ樹脂組成物は、貯蔵安定性に優れるため、プリプレグ法等によって高耐熱かつ高強度な繊維強化複合材料を提供可能となる。これにより、特に航空機、自動車用途への繊維強化複合材料の適用が進み、更なる軽量化による燃費向上、地球温暖化ガス排出削減への貢献が期待できる。また、本発明のエポキシ樹脂組成物は、半導体封止剤等の電子材料用途に好適に用いることができる、高耐熱かつ高強度なエポキシ樹脂硬化物を得ることが可能となる。
Since the epoxy resin composition of the present invention is excellent in storage stability, it is possible to provide a fiber-reinforced composite material having high heat resistance and high strength by a prepreg method or the like. As a result, the application of fiber-reinforced composite materials to aircraft and automobile applications will progress, and it is expected that further weight reduction will contribute to improved fuel efficiency and reduction of global warming gas emissions. In addition, the epoxy resin composition of the present invention makes it possible to obtain a cured epoxy resin having high heat resistance and high strength, which can be suitably used for electronic materials such as semiconductor encapsulants.
本発明のジアミン硬化剤は、例えば芳香族ポリアミドおよびポリイミド等のジアミン原料として用いることで、高耐熱かつ高強度なフィルムや繊維等を得ることが期待できる。
By using the diamine curing agent of the present invention as a diamine raw material for, for example, aromatic polyamide and polyimide, it can be expected that a film or fiber having high heat resistance and high strength can be obtained.
Claims (8)
- 少なくとも次の主剤（Ａ）および硬化剤組成物（Ｂ）を含んでなるエポキシ樹脂組成物であって、エポキシ樹脂組成物中のエポキシ樹脂成分１００質量部に対して、硬化剤組成物（Ｂ）を２０質量部以上１００質量部以下含むエポキシ樹脂組成物。
主剤（Ａ）：２官能以上のエポキシ樹脂
硬化剤組成物（Ｂ）：下記一般式［１］で表されるジアミン硬化剤、下記一般式［２］で表されるジアミン硬化剤、下記式［３］で表されるジアミン硬化剤、および下記式［４］で表されるジアミン硬化剤からなる群から選ばれた少なくとも２つを含み、かつ単一の融点を有するジアミン硬化剤組成物
（ただし、式中、Ｒ１，Ｒ２は、それぞれ独立に炭素数６～１６の芳香族炭化水素基であり、これらが互いに結合して環を形成してもよい。Ｒ３，Ｒ４は、炭素数１～４の脂肪族炭化水素基、およびハロゲン原子からなる群から選ばれた少なくとも１つであり、Ｒ３とＲ４は異なる基である。）
Main agent (A): Bifunctional or higher functional epoxy resin curing agent composition (B): Diamine curing agent represented by the following general formula [1], diamine curing agent represented by the following general formula [2], the following formula [ A diamine curing agent composition containing at least two selected from the group consisting of the diamine curing agent represented by 3] and the diamine curing agent represented by the following formula [4] and having a single melting point (provided that the diamine curing agent composition has a single melting point. , In the formula, R 1 and R 2 are independently aromatic hydrocarbon groups having 6 to 16 carbon atoms, and these may be bonded to each other to form a ring. R 3 and R 4 are carbon atoms. It is at least one selected from the group consisting of aliphatic hydrocarbon groups of numbers 1 to 4 and halogen atoms, and R 3 and R 4 are different groups.)
- 一般式［１］で表されるジアミン硬化剤が下記一般式［５］で表されるジアミン硬化剤である、および／または、一般式［２］で表されるジアミン硬化剤が下記一般式［６］で表されるジアミン硬化剤である、請求項１記載のエポキシ樹脂組成物。
- Ｒ３，Ｒ４のいずれか一方または両方がメチル基またはエチル基のいずれかである、請求項１または２記載のエポキシ樹脂組成物。 The epoxy resin composition according to claim 1 or 2, wherein either or both of R 3 and R 4 are either a methyl group or an ethyl group.
- 一般式［１］で表されるジアミン硬化剤、一般式［２］で表されるジアミン硬化剤、式［３］で表されるジアミン硬化剤および式［４］で表されるジアミン硬化剤からなる群から選ばれた少なくとも２つの各ジアミン硬化剤を、エポキシ樹脂組成物中のエポキシ樹脂成分１００質量部に対して、それぞれ１０質量部以上８０質量部以下含む、請求項１～３のいずれか記載のエポキシ樹脂組成物。 From the diamine curing agent represented by the general formula [1], the diamine curing agent represented by the general formula [2], the diamine curing agent represented by the formula [3], and the diamine curing agent represented by the formula [4]. Any of claims 1 to 3, wherein at least two diamine curing agents selected from the above group are contained in an amount of 10 parts by mass or more and 80 parts by mass or less with respect to 100 parts by mass of the epoxy resin component in the epoxy resin composition. The epoxy resin composition described.
- 請求項１～４のいずれか記載のエポキシ樹脂組成物を硬化してなるエポキシ樹脂硬化物。 An epoxy resin cured product obtained by curing the epoxy resin composition according to any one of claims 1 to 4.
- 下記一般式［１］で表されるジアミン硬化剤、下記一般式［２］で表されるジアミン硬化剤、下記式［３］で表されるジアミン硬化剤および下記式［４］で表されるジアミン硬化剤からなる群から選ばれた少なくとも２つを含み、かつ単一の融点を有するジアミン硬化剤組成物。
（ただし、式中、Ｒ１，Ｒ２は、それぞれ独立に炭素数６～１６の芳香族炭化水素基であり、これらが互いに結合して環を形成してもよい。Ｒ３，Ｒ４は、炭素数１～４の脂肪族炭化水素基、およびハロゲン原子からなる群から選ばれた少なくとも１つであり、Ｒ３とＲ４は異なる基である。）
(However, in the formula, R 1 and R 2 are independently aromatic hydrocarbon groups having 6 to 16 carbon atoms, and these may be bonded to each other to form a ring. R 3 and R 4 are , At least one selected from the group consisting of an aliphatic hydrocarbon group having 1 to 4 carbon atoms and a halogen atom, and R 3 and R 4 are different groups.)
- 一般式［１］で表されるジアミン硬化剤が下記一般式［５］で表されるジアミン硬化剤である、および／または、一般式［２］で表されるジアミン硬化剤が下記一般式［６］で表されるジアミン硬化剤である、請求項６記載のジアミン硬化剤組成物。
- Ｒ３，Ｒ４のいずれか一方または両方がメチル基またはエチル基のいずれかである、請求項６または７記載のジアミン硬化剤組成物。 The diamine curing agent composition according to claim 6 or 7, wherein either or both of R 3 and R 4 are either a methyl group or an ethyl group.
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| JP2016147925A (en) * | 2015-02-10 | 2016-08-18 | 東レ株式会社 | Prepreg and fiber-reinforced composite material |
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