Epoxy-based composition

Abstract

The present invention provides an epoxy-based composition which is excellent in fluidity, has low heat release at the time of curing, cures in a short time at ordinary temperature, and can obtain a cured product excellent in mechanical strength. The epoxy-based composition of the present invention comprises: 100 parts by weight of an epoxy resin (A) having an aromatic ring and an epoxy group in the molecule; a reactive amine compound (B) having a reaction rate constant k of 0.10 to 0.37 min ‑1 and a catalyst compound (C) having a cumulative heat of 100 J / g or more and a maximum heat flow of 0.08 W / g or more, a temperature at which the maximum heat flow appears being 130°C or lower, and comprising a tertiary amine (C1) and / or a nitrogen-containing aromatic heterocyclic compound (C2), the ratio of the active hydrogen amount of the reactive amine compound (B) to the epoxy amount of the epoxy resin (A) [active hydrogen amount of reactive amine compound (B) / epoxy amount of epoxy resin (A)] being 0.3 to 0.8.

Description

TECHNICAL FIELD

[0001] The present application relates to an epoxy-based composition. BACKGROUND

[0002] The reaction of an epoxy resin with a curing agent is an exothermic reaction, and thus a large amount of heat is emitted. The exothermic heat generated at the time of the reaction is a cause of shrinkage of a cured product obtained by curing the epoxy resin, and causes problems such as a decrease in dimensional accuracy of a molded product or generation of cracks in the molded product.

[0003] In particular, in a large-sized molded product (bulk molding) in which the molding amount at one time of molding is 1 kg to several tens of kg, the shrinkage of the obtained molded product is significantly increased.

[0004] Further, the exothermic heat generated at the time of the reaction of the epoxy resin with the curing agent can cause deterioration of a mold from which the epoxy resin is supplied or other materials embedded in the epoxy resin. For example, in a molding for fixing a hollow fiber in a hollow fiber membrane module, the shell is deformed or the hollow fiber membrane is damaged due to the exothermic heat, and thus the filtration capacity of the hollow fiber membrane itself is significantly decreased.

[0005] Furthermore, in a case where the exothermic heat at the time of the reaction of the epoxy resin with the curing agent is large, the epoxy resin is partially decomposed, and discoloration or deterioration of quality occurs in the epoxy resin. In a case where the exothermic heat is extremely large, carbonization or charring of the epoxy resin occurs, and there is a problem that a fire can occur from the epoxy resin.

[0006] In terms of the exothermic heat in bulk molding (large-sized molding), heat is not effectively released to the outside due to low heat transfer in a large bulk. Therefore, for example, it is necessary to slowly perform the curing reaction of the epoxy resin with the curing agent for a long time to moderate the exothermic heat, to strictly control the reaction temperature and time at the time of the curing reaction, and to perform the molding in multiple stages, and there is a problem that the production efficiency is decreased.

[0007] On the other hand, the exothermic heat at the time of the curing reaction is caused by the reaction of the epoxy resin with the curing agent, and thus the exothermic heat can be decreased by reducing the number of reactions per unit volume.

[0008] However, in order to suppress the exothermic heat at the time of the reaction caused by bulk molding, it is necessary to reduce the number of reactions by a considerable amount. For this reason, it is necessary to use a monofunctional raw material having a small number of functional groups per unit and a raw material having a large molecular weight, and as a result, the crosslinking density of the cured product of the epoxy resin is decreased, and there is a problem that the high mechanical strength, which is an advantage of the cured product of the epoxy resin, is impaired. Further, if an epoxy resin having a large molecular weight is used, there are other problems such as impairment of flowability, difficulty in molding or potting.

[0009] In Patent Literature 1, there is proposed a liquid epoxy resin composition for injection molding which is cured at a low temperature of normal temperature to 60°C and has an exothermic temperature at the time of curing of not more than 100°C, which contains an epoxy resin which is liquid at normal temperature, a polyoxypropylenediamine as a curing agent having an average molecular weight in the range of 270 to 1800, and an inorganic filler at a content rate of 30% by weight or more of the entire composition.

[0010] Prior Art Documents

[0011] Patent Literature

[0012] Patent Literature 1: Japanese Patent Application Laid-Open (JP-A) No. 6-248059 SUMMARY

[0013] PROBLEMS TO BE SOLVED BY THE INVENTION

[0014] However, the liquid epoxy resin composition for injection molding has problems such as high exothermic heat at the time of curing, long time required for curing, and low mechanical strength of the obtained cured product.

[0015] The present application provides an epoxy-based composition which has low heat generation at the time of curing, is cured at normal temperature for a short time, and is capable of obtaining a cured product having excellent mechanical strength.

[0016] TECHNICAL MEANS FOR SOLVING THE PROBLEMS

[0017] The epoxy-based composition of the present application comprises:

[0018] 100 parts by weight of an epoxy resin (A) having an aromatic ring and an epoxy group in the molecule;

[0019] a reactive amine compound (B) having a reaction rate constant k at 100°C of 0.10 to 0.37 min -1 and contains a polyamine (Bl) and / or a polyamidoamine (B2); and

[0020] a catalyst compound (C) having a cumulative heat of 0 to 200°C of 100 J / g or more and a maximum heat flow of 0.08 W / g or more at a temperature rise rate of 5°C / min in a reaction heat at the time of addition of 5 mol% to the epoxy resin (A), a temperature at which the maximum heat flow is exhibited being 130°C or lower, and containing a tertiary amine (Cl) and / or a nitrogen-containing aromatic heterocyclic compound (C2),

[0021] a ratio of the active hydrogen amount of the reactive amine compound (B) to the epoxy amount of the epoxy resin (A) [active hydrogen amount of reactive amine compound (B) / epoxy amount of epoxy resin (A)] is 0.3 to 0.8.

[0022] The epoxy-based composition of the present application comprises:

[0023] 100 parts by weight of an epoxy resin (A) having an aromatic ring and an epoxy group in the molecule;

[0024] a reaction accelerator (D);

[0025] a reactive amine compound (B) having a reaction rate constant k at 100°C of 0.10 to 0.37 min -1 and comprises a polyamine (Bl) and / or a polyamidoamine (B2); and

[0026] 0.1 to 10 parts by weight of a catalyst compound (C) having a cumulative heat of 0 to 200°C of 100 J / g or more and a maximum heat flow of 0.08 W / g or more in a reaction heat at the time of addition of 5 mol% to the epoxy resin (A) as measured by differential scanning calorimetry at a temperature rise rate of 5°C / min, a temperature at which the maximum heat flow is exhibited of 80 to 130°C, and comprising a tertiary amine (Cl) and / or a nitrogen-containing aromatic heterocyclic compound (C2),

[0027] a ratio of the active hydrogen amount of the reactive amine compound (B) to the epoxy amount of the epoxy resin (A) [active hydrogen amount of the reactive amine compound (B) / epoxy amount of the epoxy resin (A)] of 0.3 to 0.8.

[0028] In the epoxy-based composition of the present application, the reactivity of the epoxy resin (A) with the reactive amine compound comprising a polyamine (Bl) and / or a polyamidoamine (B2) is controlled so that the reaction of the epoxy resin (A) with the polyamine (Bl) and / or the polyamidoamine (B2) does not proceed in a short period of time.

[0029] Further, in the epoxy-based composition of the present application, the curing reaction of the epoxy resin is set as two-step reactions: the reaction of the epoxy resin (A) with the reactive amine compound (B) comprising a polyamine (Bl) and / or a polyamidoamine (B2); and the polymerization (self-crosslinking of the epoxy resin) reaction of the epoxy resin with the catalyst compound (C) comprising a tertiary amine and / or a nitrogen-containing aromatic heterocyclic compound as a catalyst.

[0030] That is, in the epoxy-based composition of the present application, the reaction heat generated by the curing reaction of the epoxy resin is dispersed in time without reducing the number of reactions of the curing reaction, as a result of which the exotherm at the time of curing is reduced.

[0031] The epoxy-based composition of the present application does not require the use of an epoxy resin having a large molecular weight, and has excellent fluidity, and the cured product also has excellent mechanical strength.

[0032] The epoxy-based composition of the present application is a two-liquid type containing a main agent and a curing agent, and is used by mixing and curing the main agent and the curing agent.

[0033] [epoxy resin (A)]

[0034] The main agent of the epoxy-based composition contains an epoxy resin (A). The epoxy resin (A) has an aromatic ring and an epoxy group in the molecule. The epoxy resin (A) is preferably liquid at 23°C under 0.10 MPa. Since the epoxy resin (A) has an aromatic ring, a cured product having excellent mechanical strength can be obtained. Note that the epoxy resin refers to a compound containing a plurality of crosslinkable epoxy groups. Liquid refers to a state having a certain volume and having fluidity.

[0035] The epoxy resin (A) having an aromatic ring and an epoxy group in the molecule is not particularly limited, and examples thereof include a bisphenol A-type epoxy resin, a bisphenol F-type epoxy resin, a tetraglycidyl diamino diphenyl methane-type epoxy resin, an amino phenol-type epoxy resin, an aniline-type epoxy resin, a benzylamine-type epoxy resin, a xylene diamine-type epoxy resin, and the like. In terms of the epoxy resin (A), from the viewpoints of excellent storage stability, being liquid at 23°C under 0.10 MPa, and having a low viscosity, a bisphenol A-type epoxy resin and a bisphenol F-type epoxy resin, and the like are preferred. The epoxy resin is generally a product obtained by adding epichlorohydrin to the hydroxyl group of a polyhydric alcohol such as a polyphenol (for example, in the following formula (1), the number of repetitions n = 0), or has a repeating unit generated by ring-opening addition of epichlorohydrin to a polyhydric alcohol (for example, in the following formula (1), the number of repetitions n is a natural number). In addition, the epoxy resin (A) can be used alone or in combination with two or more kinds.

[0036] When the epoxy resin (A) is a bisphenol A-type epoxy resin (for example, a reaction product of bisphenol A and epichlorohydrin), it has the following structural formula. In the formula, the number of repetitions n is 0 or a natural number.

[0037] [Chemical Formula 1]

[0038]

[0039] The epoxy resin (A) is preferably liquid at 23°C under 0.10 MPa. By making the epoxy resin (A) liquid at 23°C under 0.10 MPa, the flowability of the epoxy-based composition can be ensured. In the case where the epoxy resin (A) is a mixture of a plurality of kinds (also in the case of a mixture of epoxy resins having different repeating numbers n of repeating units), whether the epoxy resin (A) is liquid at 23°C under 0.10 MPa is determined as a whole of the mixture. Therefore, even if an epoxy resin that is solid at 23°C under 0.10 MPa is contained, as long as the mixture of the epoxy resins as a whole is liquid at 23°C under 0.10 MPa, the mixture of the epoxy resins as a whole is the epoxy resin (A). Further, as the epoxy resin that is solid at 23°C under 0.10 MPa, for example, a biphenyl-type epoxy resin, a naphthalene-type epoxy resin, a phenol novolac-type epoxy resin, a bisphenol A novolac-type epoxy resin, a trihydroxy methane-type epoxy resin, a tetraphenyl ethane-type epoxy resin, and the like can be given.

[0040] The epoxy-based composition can contain a diluent in order to adjust the viscosity of the main agent, within a range that does not hinder the curing of the effects of the present application. The diluent can have an aromatic ring within the molecule in the case of having only one epoxy group. The diluent preferably does not have an aromatic ring within the molecule in the case of containing a plurality of cross-linkable epoxy groups. The diluent is not related to the presence or absence of reactivity. The diluent is not particularly limited, and, for example, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 2,2',2"-[1,2,3-propanetri(oxy methylene)] trioxane, pentaerythritol polyglycidyl ether, 1,4-bis[(oxiran-2-ylmethoxy)methyl]cyclohexane, phenyl glycidyl ether, 1,3-bis(oxiran-2-ylmethoxy)benzene, benzyl glycidyl ether, 3,4-epoxycyclohexylmethyl (3,4-epoxy)cyclohexane carboxylate, and the like can be given. Note that the diluent can be used alone or two or more kinds can be used in combination.

[0041] [Polyamine (B1) and / or polyamidoamine (B2)]

[0042] The curing agent of the epoxy-based composition contains a reactive amine compound (B) containing a polyamine (B1) and / or a polyamidoamine (B2). The reactive amine compound (B) reacts with a plurality of epoxy groups of the epoxy resin (A), and constitutes a crosslinked structure of a cured product of the epoxy resin (A).

[0043] The reactive amine compound (B) contains a polyamine (B1) and / or a polyamidoamine (B2).

[0044] The reaction rate constant k at 100°C is 0.10 to 0.37 min when the reactive amine compound (B) reacts stoichiometrically with the epoxy group of the epoxy resin (A) -1 .

[0045] The "stoichiometrically equivalent reaction with the epoxy group of the epoxy resin (A)" means that the epoxy group of the epoxy resin (A) is reacted with the reactive amine compound (B) in such a manner that the ratio of the active hydrogen amount of the reactive amine compound (B) to the epoxy amount of the epoxy resin (A) [active hydrogen amount of the reactive amine compound (B) / epoxy amount of the epoxy resin (A)] is 1. Note that in the present application, the ratio of the active hydrogen amount of the reactive amine compound (B) to the epoxy amount of the epoxy resin (A) [active hydrogen amount of the reactive amine compound (B) / epoxy amount of the epoxy resin (A)] is sometimes referred to as "equivalent value".

[0046] The reaction rate constant k at 100°C when the reactive amine compound (B) reacts stoichiometrically with the epoxy group of the epoxy resin (A) (hereinafter, sometimes simply referred to as "reaction rate constant k") is 0.10 min -1 The above is preferably 0.105 min -1 The above is more preferably 0.106 min -1 The above is more preferably 0.11 min -1 The above is more preferably 0.12 min -1 The above.

[0047] The reaction rate constant k at 100°C when the reactive amine compound (B) reacts stoichiometrically with the epoxy group of the epoxy resin (A) (hereinafter, sometimes simply referred to as "reaction rate constant k") is 0.37 min -1 The above is preferably 0.27 min -1 The above is more preferably 0.22 min -1 The above is more preferably 0.20 min -1 The above is more preferably 0.18 min -1 The above.

[0048] The reaction rate constant k at 100°C when the polyamine (Bl) reacts stoichiometrically with the epoxy group of the epoxy resin (A) is preferably 0.10 min -1 The above is more preferably 0.105 min -1 The above is more preferably 0.106 min -1 The above is more preferably 0.11 min -1 The above is more preferably 0.12 min -1 The above.

[0049] In the polyamine (Bl), the reaction rate constant k at 100°C when reacting stoichiometrically with the epoxy group of the epoxy resin (A) is preferably 0.37 min -1 More preferably, it is 0.27 min -1 More preferably, it is 0.22 min -1 More preferably, it is 0.20 min -1 More preferably, it is 0.18 min -1 More preferably, it is 0.18 min

[0050] In the polyamidoamine (B2), the reaction rate constant k at 100°C when reacting stoichiometrically with the epoxy group of the epoxy resin (A) is preferably 0.10 min -1 More preferably, it is 0.105 min -1 More preferably, it is 0.106 min -1 More preferably, it is 0.11 min -1 More preferably, it is 0.12 min -1 More preferably, it is 0.18 min

[0051] In the polyamidoamine (B2), the reaction rate constant k at 100°C when reacting stoichiometrically with the epoxy group of the epoxy resin (A) is preferably 0.37 min -1 More preferably, it is 0.27 min -1 More preferably, it is 0.22 min -1 More preferably, it is 0.20 min -1 More preferably, it is 0.18 min -1 More preferably, it is 0.18 min

[0052] By making the reaction rate constant k at 100°C of the reactive amine compound (B) 0.10 min -1 More preferably, it is 0.18 min, the epoxy-based composition can be cured in a short time (for example, within about 8 hours) at an atmosphere temperature of about 20 to 30°C. The same applies to the polyamine (Bl) and the polyamidoamine (B2).

[0053] By making the reaction rate constant k at 100°C of the reactive amine compound (B) 0.37 min -1 More preferably, it is 0.18 min, the epoxy-based composition can be cured in a short time (for example, within about 8 hours) at an atmosphere temperature of about 20 to 30°C. The same applies to the polyamine (Bl) and the polyamidoamine (B2).

[0054] The reaction rate constant k of the reactive amine compound (B) can be the reaction rate constant k in the presence of the reaction accelerator (D). That is, the reaction rate constant k of the reactive amine compound (B) can also be adjusted by the reaction accelerator (D). When referred to simply as "reaction rate constant k", it means the reaction rate constant k after adjustment by the reaction accelerator (D) in the case where the reaction rate constant k of the reactive amine compound (B) is adjusted by the reaction accelerator (D).

[0055] The reaction rate constant k of the reactive amine compound (B) after adjustment by the reaction accelerator (D) is preferably 0.10 min -1 The above is more preferably 0.105 min -1 The above is more preferably 0.106 min -1 The above is more preferably 0.11 min -1 The above is more preferably 0.12 min -1 The above.

[0056] The reaction rate constant k of the reactive amine compound (B) after adjustment by the reaction accelerator (D) is 0.37 min -1 The above is preferably 0.27 min -1 The above is more preferably 0.22 min -1 The above is more preferably 0.20 min -1 The above is more preferably 0.18 min -1 The above.

[0057] The reaction rate constant k of the polyamine (Bl) after adjustment by the reaction accelerator (D) is preferably 0.10 min -1 The above is more preferably 0.105 min -1 The above is more preferably 0.106 min -1 The above is more preferably 0.11 min -1 The above is more preferably 0.12 min -1 The above.

[0058] The reaction rate constant k of the polyamine (Bl) at 100°C when the reaction rate constant k of the polyamine (Bl) is adjusted by the reaction accelerator (D) and then reacts stoichiometrically with the epoxy group of the epoxy resin (A) is preferably 0.37 min -1 More preferably, 0.27 min -1 More preferably, 0.22 min -1 More preferably, 0.20 min -1 More preferably, 0.18 min -1 More preferably, 0.18 min

[0059] The reaction rate constant k of the polyamine amine (B2) at 100°C when the reaction rate constant k of the polyamine amine (B2) is adjusted by the reaction accelerator (D) and then reacts stoichiometrically with the epoxy group of the epoxy resin (A) is preferably 0.10 min -1 More preferably, 0.105 min -1 More preferably, 0.106 min -1 More preferably, 0.11 min -1 More preferably, 0.12 min -1 More preferably, 0.12 min

[0060] The reaction rate constant k of the polyamine amine (B2) at 100°C when the reaction rate constant k of the polyamine amine (B2) is adjusted by the reaction accelerator (D) and then reacts stoichiometrically with the epoxy group of the epoxy resin (A) is preferably 0.37 min -1 More preferably, 0.27 min -1 More preferably, 0.22 min -1 More preferably, 0.20 min -1 More preferably, 0.18 min -1 More preferably, 0.18 min

[0061] The reaction rate constant k of the reactive amine compound (B) is 0.10 min -1 More preferably, 0.12 min, after adjustment by the reaction accelerator (D), and then the epoxy resin (A) is cured in a short time (for example, within about 8 hours) at an atmosphere temperature of about 20 to 30°C. The same is true for the polyamine (Bl) and the polyamide amine (B2).

[0062] The reaction rate constant k of the reactive amine compound (B) is 0.37 min -1The following, so that the reaction of the epoxy-based composition has a suitable reaction rate, is able to inhibit the curing reaction from concentrating in a short time, is able to disperse the heat generated during the curing reaction, and is able to reduce the heat generated during the curing reaction. The same applies to the case of polyamine (Bl) and polyamidoamine (B2).

[0063] Note that the reaction rate constant k of the reactive amine compound (B) is obtained by isothermal analysis simulation using parameters (activation energy ΔE, reaction order n, frequency factor A) obtained by reaction rate analysis by the Ozawa method using differential scanning calorimetry.

[0064] Specifically, a mixed solution prepared by mixing the epoxy resin (A), the reactive amine compound (B), and the reaction promoter (D) as necessary is prepared. Note that the epoxy resin (A) and the reactive amine compound (B) are mixed in such a manner that the ratio of the active hydrogen amount of the reactive amine compound (B) to the epoxy amount of the epoxy resin (A) [active hydrogen amount of the reactive amine compound (B) / epoxy amount of the epoxy resin (A)] is 1.

[0065] The resulting mixed solution is supplied to an aluminum sample container at 10 ± 3 mg, and a seal cap is placed on the opening of the sample container. Using a differential scanning calorimeter, differential scanning calorimetry is performed at three levels of temperature increase rates of 5°C / min, 10°C / min, or 20°C / min for a temperature range of -15°C to 300°C, and three DSC curves are obtained. Note that when the epoxy resin is mixed with the curing agent, the reaction proceeds, and therefore, a new mixed solution is prepared for each temperature increase rate. Note that the differential scanning calorimeter can be, for example, a measuring device commercially available from Shimadzu Corporation under the trade name "DSC-60".

[0066] The value obtained by calculating the three DSC curves using reaction rate analysis software (trade name "Reaction Analysis (DSC) Program" manufactured by Shimadzu Corporation) is used as the reaction rate constant k. The analysis range is 0°C to 280°C, and the reaction rate constant k is obtained by isothermal analysis simulation using parameters (activation energy ΔE, reaction order n, frequency factor A) obtained by reaction rate analysis by the Ozawa method.

[0067] When the reactive amine compound (B) contains a plurality of polyamines (Bl) and / or polyamidoamines (B2), the reaction rate constant of the reactive amine compound (B) is a value obtained as a mixture of the polyamines (Bl) and / or the polyamidoamines (B2).

[0068] The polyamine (B1) has a plurality of amino groups (-NH2) in the molecule and does not have an amide bond (-NHCO-). Note that the hydrogen atom of the amino group can also be substituted with only one other substituent or atom. As the polyamine (B1), a polyamine whose reaction rate constant k of the reactive amine compound (B) at 100°C when the reactive amine compound (B) and the epoxy group of the epoxy resin (A) are allowed to react in stoichiometric equivalent amounts is 0.10 to 0.37 min -1 There is no particular limitation. Note that the polyamine (B1) can be used alone or in combination with two or more. As the polyamine (B1), a polyamine commercially available from MITSUBISHI GAS CHEMICAL, Co., Ltd. under the trade name "GASKAMINE 240" can be used.

[0069] The polyamine (B1) is only required to have (1) a plurality of amino groups (-NH2) in the molecule and not have an amide bond (-NHCO-). Note that the hydrogen atom of the amino group can also be substituted with only one other substituent or atom. As the polyamine (B1), (2) reacts with a plurality of epoxy groups of the epoxy resin (A) and constitutes a crosslinked structure of the cured product of the epoxy resin (A). The polyamine (B1) can also have a structure in which all of the three hydrogens of ammonia in the molecule are substituted with other substituents or atoms, as long as the above (1) and (2) are satisfied.

[0070] As the polyamine (B1), a polyamine whose reaction rate constant k of the reactive amine compound (B) is determined using differential scanning calorimetry is 0.10 to 0.37 min -1 As the polyamine (B1) whose reaction rate constant k is 0.10 to 0.37 min -1 As the structural feature of the polyamine (B1) whose reaction rate constant k is 0.10 to 0.37 min

[0071] As the polyamine (B1), for example, a reaction adduct of m-xylylenediamine and styrene, a polyether diamine having a polytetramethylene ether glycol structure and a polypropylene glycol structure, 4,4'-methylenebis(cyclohexylamine), and the like can be given. Note that the polyamine (B1) can be used alone or in combination with two or more.

[0072] The polyamidoamine (B2) has an amide bond (-NHCO-) and a plurality of amino groups in the molecule. Note that the hydrogen atom of the amino group can also be substituted with only one other substituent or atom. The polyamidoamine (B2) is a condensation product of a carboxylic acid and a polyamine, and examples thereof include a condensate of a dimer acid (a dibasic acid generated by dimerization of an unsaturated fatty acid) and a polyamine, a condensation product of a mono- or poly-carboxylic acid and a polyalkyleneamine, and the like. Note that the polyamidoamine (B2) can be used alone or in combination with two or more. As the polyamidoamine (B2), an amine commercially available from Tsukishima Kogyo Co., Ltd. under the trade name "VEGECHEM GREEN G235" can be used.

[0073] The polyamidoamine (B2) only needs to have a plurality of amino groups (-NH2) and an amide bond (-NHCO-) in the molecule. Note that the hydrogen atom of the amino group can also be substituted with only one other substituent or atom. In the case of the polyamidoamine (B2), (2) reacts with a plurality of epoxy groups of the epoxy resin (A) to constitute a crosslinked structure of the cured product of the epoxy resin (A). As long as the above (1) and (2) are satisfied, the polyamidoamine (B1) can include a structure in which all of the three hydrogen atoms of the amino group are substituted with other substituents or atoms in the molecule.

[0074] As the polyalkyleneamine, for example, diethylenetriamine (DETA), dipropylenetriamine (DPTA), bis-hexamethylene triamine (BHMT), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), polyethylene polyamine having 5 to 7 ethylene amine units (HEPA), and the like can be given. Note that the polyalkyleneamine can be used alone or in combination with two or more.

[0075] The content of the polyamine (B1) in the reactive amine compound is preferably 27% by mass or more, more preferably 50% by mass or more, and more preferably 70% by mass or more.

[0076] The content of the polyamine (B1) in the reactive amine compound is preferably 100% by mass, more preferably 99.9% by mass or less, and more preferably 99% by mass or less.

[0077] The content of the polyamidoamine (B2) in the reactive amine compound is preferably 27% by mass or more, more preferably 50% by mass or more, and more preferably 70% by mass or more.

[0078] The content of the polyamidoamine (B2) in the reactive amine compound is preferably 100% by mass, more preferably 99.9% by mass or less, and more preferably 99% by mass or less.

[0079] The total content of the polyamine (Bl) and the polyamideamine (B2) in the reactive amine compound is preferably 27% by mass or more, more preferably 50% by mass or more, and more preferably 70% by mass or more.

[0080] The total content of the polyamine (Bl) and the polyamideamine (B2) in the reactive amine compound is preferably 100% by mass, more preferably 99.9% by mass or less, and more preferably 99% by mass or less.

[0081] A reaction accelerator (D) can also be contained in the curing agent. As described above, the reaction accelerator (D) is used to adjust the reaction rate constant k of the reactive amine compound (B). The degree of adjustment of the reaction rate constant k of the reactive amine compound (B) is determined by the amount (mass) of the reaction accelerator (D) used per unit mass of the reactive amine compound (B). As the reaction accelerator (D), there is no particular limitation, and, for example, polyhydric alcohols such as triethanolamine, glycerol, and the like; carboxylic acids such as salicylic acid, benzoic acid, and the like; sulfonic acids such as p-toluenesulfonic acid, and the like can be given, and polyhydric alcohols are preferred. Furthermore, the reaction accelerator (D) can be used alone or two or more kinds can be used in combination.

[0082] In the epoxy-based composition, the ratio of the active hydrogen amount of the reactive amine compound (B) to the epoxy amount of the epoxy resin (A) [active hydrogen amount of the reactive amine compound (B) / epoxy amount of the epoxy resin (A)] is 0.3 or more, preferably 0.31 or more, more preferably 0.32 or more, more preferably 0.33 or more, more preferably 0.34 or more, and more preferably 0.4 or more.

[0083] In the epoxy-based composition, the ratio of the active hydrogen amount of the reactive amine compound (B) to the epoxy amount of the epoxy resin (A) [active hydrogen amount of the reactive amine compound (B) / epoxy amount of the epoxy resin (A)] is 0.8 or less, preferably 0.70 or less, more preferably 0.65 or less, more preferably 0.60 or less, more preferably 0.50 or less, and more preferably 0.45 or less.

[0084] When the ratio of the active hydrogen amount of the reactive amine compound (B) to the epoxy amount of the epoxy resin (A) [active hydrogen amount of the reactive amine compound (B) / epoxy amount of the epoxy resin (A)] is 0.3 or more, a small amount of reaction heat is generated by the curing reaction of the epoxy resin (A) and the reactive amine compound (B), and the curing reaction of the epoxy-based composition is further promoted by the reaction heat. That is, the heat generated by the curing reaction of the epoxy-based composition itself causes the curing reaction to proceed smoothly to form a cured product at an ambient temperature of about 20 to 30°C. Furthermore, by allowing the curing reaction of the epoxy resin (A) and the reactive amine compound (B) to proceed to some extent, the heat energy required for the polymerization (self-crosslinking of the epoxy resin) reaction of the epoxy resin (A) in the presence of the tertiary amine and / or nitrogen-containing aromatic heterocyclic compound described later can be obtained, and the polymerization of the epoxy resin (A) can be made to proceed later than the curing reaction of the epoxy resin (A) and the reactive amine compound (B).

[0085] When the ratio of the active hydrogen amount of the reactive amine compound (B) to the epoxy amount of the epoxy resin (A) [active hydrogen amount of the reactive amine compound (B) / epoxy amount of the epoxy resin (A)] is 0.8 or less, the amount of heat generated during the curing reaction of the epoxy resin (A) and the reactive amine compound (B) can be suppressed, and the heat generation during the curing reaction of the epoxy-based composition can be reduced.

[0086] The epoxy amount of the epoxy resin (A) is calculated based on the following formula.

[0087] Epoxy amount of the epoxy resin (A) = content of the epoxy resin (A) in the epoxy-based composition [g] / epoxy equivalent of the epoxy resin (A) [g / eq]

[0088] Note that the epoxy equivalent of the epoxy resin (A) refers to a value obtained by dividing the molecular weight of the epoxy resin by the number of epoxy groups in one molecule. In the present application, the epoxy equivalent of the epoxy resin refers to a value determined according to JIS K7236.

[0089] The active hydrogen amount of the reactive amine compound (B) is calculated based on the following formula.

[0090] Active hydrogen amount of the reactive amine compound (B) = active hydrogen equivalent of the reactive amine compound (B) [eq / g] x content of the reactive amine compound (B) in the epoxy-based composition [g]

[0091] The active hydrogen equivalent of the reactive amine compound (B) is calculated in the following manner.

[0092] Active hydrogen equivalent of the reactive amine compound (B) [eq / g] = number of active hydrogens of the reactive amine compound (B) / molecular weight of the reactive amine compound (B)

[0093] The number of active hydrogens of the reactive amine compound (B) refers to the total of the number of active hydrogens contained in each of the plurality of amino groups contained in one molecule of the reactive amine compound (B).

[0094] When the reactive amine compound (B) contains a plurality of polyamines (B1) and / or polyamidoamines (B2), the amount of active hydrogens of the reactive amine compound (B) refers to a value calculated based on the following formula.

[0095] When the reactive amine compound (B) contains a total of m kinds of polyamines (B1) and / or polyamidoamines (B2), the amount of active hydrogens of the reactive amine compound (B) is calculated based on the following formula, with the active hydrogen equivalent of the mth reactive amine compound being set as Qm [eq / g], and the content of the mth reactive amine compound being set as Gm (g).

[0096] [Mathematical Formula 1]

[0097]

[0098] When the reaction accelerator (D) is contained in the epoxy-based composition, the content of the reaction accelerator (D) is adjusted in such a manner that the reaction rate constant k of the reactive amine compound (B) at 100°C after adjustment by the reaction accelerator (D) when the epoxy group of the epoxy resin (A) and the reactive amine compound (B) are stoichiometrically equivalent and react is 0.10 to 0.37 min -1 . Specifically, the content of the reaction accelerator (D) is preferably 0.1 parts by mass or more, more preferably 1 parts by mass or more, and still more preferably 3 parts by mass or more, with respect to 100 parts by mass of the epoxy resin (A). The content of the reaction accelerator (D) is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, and still more preferably 5 parts by mass or less, with respect to 100 parts by mass of the epoxy resin (A).

[0099] The epoxy-based composition contains the reactive amine compound (B) containing the polyamine (B1) and / or the polyamidoamine (B2) as a curing agent, and other curing agents can also be contained within a range that does not impair the effects of the present application. As such a curing agent, for example, a thiol compound, a dicyandiamide-based compound, a polysulfide-based compound, a dihydrazide-based compound, and the like can be given.

[0100] [Tertiary amine (C1) and nitrogen-containing aromatic heterocyclic compound (C2)]

[0101] The curing agent of the epoxy-based composition contains the catalyst compound (C) containing the tertiary amine (C1) and / or the nitrogen-containing aromatic heterocyclic compound (C2).

[0102] The polymerization (self-crosslinking of the epoxy resin) of the epoxy resin is performed in the presence of the catalyst compound (C). The catalyst compound (C) does not form a crosslinking structure in the cured product of the epoxy resin (A). The catalyst compound (C) does not form a crosslinking structure with the epoxy resin (A). It does not form a crosslinking structure of the cured product of the epoxy resin (A) by reacting with only one of the epoxy groups in the epoxy resin (A) or the cured product of the epoxy resin (A).

[0103] The polymerization (self-crosslinking of the epoxy resin) of the epoxy resin is performed in the presence of the catalyst compound (C). By the catalyst compound (C), the polymerization reaction of the epoxy resin is enabled to be performed at a low temperature, and the heat generation upon curing of the epoxy-based composition is inhibited to be low.

[0104] The cumulative heat (hereinafter, sometimes referred to simply as "cumulative heat") of 0 to 200°C obtained by differential scanning calorimetry at a temperature increase rate of 5°C / min in the polymerization reaction of the catalyst compound (C) at 5 mol% added to the epoxy resin (A) is 100 J / g or more and the maximum heat flow (hereinafter, sometimes referred to simply as "maximum heat flow") is 0.08 W / g or more, and the temperature at which the maximum heat flow is exhibited is 130°C or lower.

[0105] The cumulative heat is preferably 100 J / g or more, more preferably 120 J / g or more, and even more preferably 150 J / g or more, and even more preferably 200 J / g or more. If the cumulative heat is 100 J / g or more, the polymerization reaction of the epoxy resin (A) in the presence of the catalyst compound (C) is suitably performed by the heat of reaction at the time of the reaction of the epoxy resin (A) with the reactive amine compound (B).

[0106] The cumulative heat is preferably 500 J / g or less, and more preferably 450 J / g or less. If the cumulative heat is 500 J / g or less, the heat generation upon curing of the epoxy resin can be inhibited to be low.

[0107] The maximum heat flow (hereinafter, sometimes referred to simply as "maximum heat flow") at the time of differential scanning calorimetry of 0 to 200°C at a temperature increase rate of 5°C / min in the polymerization reaction of the catalyst compound (C) at 5 mol% added to the epoxy resin (A) is 0.08 W / g or more, and preferably 0.10 W / g or more, and more preferably 0.12 W / g or more. When the maximum heat flow is 0.08 W / g or more, the polymerization reaction of the epoxy resin (A) in the presence of the catalyst compound (C) is suitably performed by the heat of reaction at the time of the reaction of the epoxy resin (A) with the reactive amine compound (B).

[0108] The maximum heat flow (hereinafter, sometimes referred to as "maximum heat flow") in the anionic polymerization reaction of the catalyst compound (C) at 5 mol% added to the epoxy resin (A) is preferably 0.80 W / g or less, preferably 0.70 W / g or less, and preferably 0.60 W / g or less when measured by differential scanning calorimetry at a temperature increase rate of 5°C / min from 0 to 200°C. If the maximum heat flow is 0.80 W / g or less, the heat generation at the time of curing of the epoxy resin can be suppressed to be low.

[0109] The temperature at which the maximum heat flow is exhibited is 130°C or less, preferably 125°C or less, more preferably 120°C or less, and more preferably 110°C or less. When the temperature at which the maximum heat flow is exhibited is 130°C or less, the polymerization of the epoxy resin can be performed by the heat of reaction at the time of the reaction of the epoxy resin (A) with the reactive amine compound (B), and the mechanical strength of the cured product of the epoxy-based composition can be improved even if the equivalent value of the epoxy resin and the reactive amine compound is less than 1.

[0110] The temperature at which the maximum heat flow is exhibited is preferably 80°C or more, more preferably 92°C or more, and more preferably 94°C or more. When the temperature at which the maximum heat flow is exhibited is 80°C or more, the polymerization of the epoxy resin (A) can be performed later than the curing reaction of the epoxy resin (A) with the reactive amine compound (B), and the dispersion of heat based on the two-step reaction can be promoted.

[0111] The cumulative heat, the maximum heat flow, and the temperature at which the maximum heat flow is exhibited of the catalyst compound (C) refer to the temperatures measured according to the following protocol. 5 mol% of the catalyst compound (C) is mixed with respect to the epoxy resin (A) to prepare a sample. Note that, in the case where the catalyst compound (C) is a solid, the catalyst compound (C) is dissolved in a solvent (e.g., tetrahydrofuran or the like) in which the catalyst compound (C) can be dissolved to prepare a catalyst compound solution. After the catalyst compound solution is mixed with the epoxy resin (A), the solvent is removed under vacuum at 25°C to prepare a sample. The differential scanning heat of the polymerization reaction of the epoxy resin (A) catalyzed by the catalyst compound (C) is measured by a differential scanning calorimeter at a temperature increase rate of 5°C / min from -20°C to 220°C. The maximum heat flow is the maximum value of the heat flow in the range of 0 to 200°C [W / g] based on the heat generation at 0°C [W / g]. The temperature at which the maximum value of the heat flow in the range of 0 to 200°C is exhibited is the temperature at which the maximum heat flow is exhibited [°C]. The cumulative heat is the sum of the heat generation in the range of 0 to 200°C [J / g] based on the heat generation at 0°C [W / g].

[0112] The tertiary amine (C1) does not have a nitrogen-containing aromatic heterocycle in the molecule. The tertiary amine refers to a compound having a structure in which all of the three hydrogens of ammonia are substituted with other substituents or atoms in the molecule. In the case of the tertiary amine (C1), (2) does not form a crosslinked structure of the cured product of the epoxy resin (A) (does not react with the plurality of epoxy groups of the epoxy resin (A)). As the tertiary amine (C1), there is no particular limitation as long as the cumulative heat of 0 to 200°C obtained by differential scanning calorimetry at a temperature increase rate of 5°C / min is 100 J / g or more and the maximum heat flow is 0.08 W / g or more in an anionic polymerization reaction at the time of addition of 5 mol% to the epoxy resin (A), and the temperature at which the maximum heat flow is exhibited is 130°C or less.

[0113] In the case of the tertiary amine (C1), (1) does not have a nitrogen-containing aromatic heterocycle in the molecule. In the case of the tertiary amine (C1), (2) has a structure in which all of the three hydrogens of ammonia are substituted with other substituents or atoms in the molecule. In the case of the tertiary amine (C1), (3) does not form a crosslinked structure of the cured product of the epoxy resin (A). The tertiary amine (C1) can also have an amino group and an amide bond in the molecule as long as (1) to (3) described above are satisfied. As the tertiary amine (C1), for example, a benzylamine derivative; an alicyclic amine such as N,N'-dimethylpiperazine, dimethylcyclohexylamine, and the like, and 2,4,6-tris(dimethylaminomethyl)phenol, N,N'-dimethylpiperazine can be given. The tertiary amine (C1) can use an amine commercially available from Tsukishima Kogyo Co., Ltd. under the trade name "TMA EH-30". Note that the tertiary amine (C1) can be used alone or in combination with two or more.

[0114] The benzylamine derivative refers to a tertiary amine having a benzylamino group in the molecular skeleton. Two hydrogen atoms of the benzylamino group are substituted with other substituents or atoms. As the benzylamine derivative, for example, N,N-dimethylbenzylamine, N-ethyl-N-methylbenzylamine, N,N-diethylbenzylamine, 1,3-bis(dimethylaminomethyl)benzene, 2-dimethylaminomethylphenol, 2,4,6-tris(dimethylaminomethyl)phenol, N,N-dimethyl-1-phenylethylamine, 3-[1-(dimethylamino)ethyl]phenol, 2,6-di-tert-butyl-4-dimethylaminomethylphenol, and the like can be given.

[0115] As the nitrogen-containing aromatic heterocyclic compound (C2), there is no particular limitation as long as the cumulative heat of 0 to 200°C obtained by differential scanning calorimetry at a temperature increase rate of 5°C / min is 100 J / g or more and the maximum heat flow is 0.08 W / g or more in a polymerization reaction at the time of addition of 5 mol% to the epoxy resin (A), and the temperature at which the maximum heat flow is exhibited is 130°C or less.

[0116] The nitrogen-containing aromatic heterocyclic compound (C2) is a compound having a structure in which a nitrogen atom is contained in an aromatic ring in addition to carbon atoms. The aromatic ring includes condensed aromatic rings in which a monocyclic aromatic ring is condensed with another monocyclic aromatic ring. As the nitrogen-containing aromatic heterocyclic compound (C2), for example, imidazole compounds such as 2-ethyl-4-methylimidazole, 2-phenylimidazole, and 1-benzyl-2-phenylimidazole are preferable, and 2-phenylimidazole and 1-benzyl-2-phenylimidazole are more preferable. Note that the nitrogen-containing aromatic heterocyclic compound (C2) can be a compound commercially available from Shikoku Chemicals Corporation under the trade names "CUREZOL 2PZ" and "CUREZOL 1B2PZ".

[0117] As the nitrogen-containing aromatic heterocyclic compound (C2), (1) a structure in which a nitrogen atom is contained in an aromatic ring in addition to carbon atoms. As the nitrogen-containing aromatic heterocyclic compound (C2), (2) does not form a crosslinking structure of a cured product of the epoxy resin (A) (does not react with a plurality of epoxy groups of the epoxy resin (A)). The nitrogen-containing aromatic heterocyclic compound (C2) can contain an amino group and an amide bond in the molecule as long as the above (1) and (2) are satisfied.

[0118] The content of the catalyst compound (C) in the epoxy-based composition is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and still more preferably 1.0 parts by mass or more, relative to 100 parts by mass of the epoxy resin (A). The content of the catalyst compound (C) in the epoxy-based composition is preferably 10 parts by mass or less, more preferably 5.0 parts by mass or less, and still more preferably 2.0 parts by mass or less, relative to 100 parts by mass of the epoxy resin (A). When the content of the catalyst compound (C) is 0.1 parts by mass or more, the polymerization reaction of the epoxy resin proceeds smoothly by the heat of reaction of the epoxy resin and the reactive amine compound. When the content of the catalyst compound (C) is 10 parts by mass or less, the polymerization reaction of the epoxy resin proceeds appropriately in such a manner that the reaction does not concentrate in a short period of time, the curing reaction of the epoxy-based composition is dispersed, and thus the heat release is reduced.

[0119] In the epoxy-based composition, an additive can also be contained within a range not to hinder the effects of the epoxy-based composition. As the additive, for example, thermoplastic resins, deodorants, silane coupling agents, titanium coupling agents, and the like, adhesion-improving / bonding-improving agents, hydroquinones, hindered phenols, and the like, antioxidants, benzophenones, benzotriazoles, salicylates, metal complex salts, and the like, ultraviolet absorbers, metal soaps, heavy metals (for example, zinc, tin, lead, cadmium, and the like), inorganic salts, and organic salts, organotin compounds, and the like, stabilizers, phthalic acid esters, phosphate esters, fatty acid esters, castor oil, liquid paraffin, alkyl polycyclic aromatic hydrocarbons, and the like, plasticizers, paraffin wax, microcrystalline paraffin wax, polymeric wax, densified wax, sperm whale wax, low-molecular-weight polyolefins, and the like, non-reactive diluents such as benzyl alcohol, tar, pitch, and the like, filler materials such as calcium carbonate, kaolin, talc, mica, bentonite, clay, sericite, glass fibers, carbon fibers, aramid fibers, nylon fibers, acrylic fibers, glass powder, glass spheres, silica spheres, coal powder, acrylic resin powder, phenol resin powder, metal powder, ceramic powder, zeolite, slate powder, and the like, pigments or dyes such as carbon black, titanium oxide, red iron oxide, p-phenylene diamine, ultramarine, and the like, solvents such as ethyl acetate, toluene, alcohols, ethers, ketones, and the like, dehydrating agents such as monoisocyanate compounds, carbodiimide compounds, and the like, antistatic agents, antibacterial agents, antifungal agents, viscosity adjustors, fragrances, flame retardants, leveling agents, dispersants, shake resistance imparting agents, electric conductivity imparting agents, and the like, can be exemplified.

[0120] The epoxy-based composition is used by mixing and curing a main agent and a curing agent. The temperature of the atmosphere at the time of curing of the epoxy-based composition is preferably 20 to 30°C, more preferably 22 to 28°C, and particularly preferably 23 to 26°C.

[0121] The epoxy-based composition is excellent in flowability, and thus is excellent in injection molding and potting. The epoxy-based composition can be smoothly supplied into a mold, and a cured product having a correct shape can be obtained. Further, the epoxy-based composition is cured at a short curing time at an atmosphere temperature of about 20 to 30°C, and the heat release at the time of curing is also low. Thus, a large injection molded product can be formed without causing degradation and shrinkage of the epoxy resin. Further, the cured product obtained by curing the epoxy-based composition has excellent mechanical strength.

[0122] Thus, according to the epoxy-based composition, the production of a large molded product based on a large amount of injection molding and the production of a large hollow fiber membrane module can be efficiently performed.

[0123] Effects of the Invention

[0124] The epoxy-based composition of the present application is excellent in flowability, and the heat release at the time of curing is low, and a cured product excellent in mechanical strength can be obtained. DETAILED DESCRIPTION

[0125] The present application will be described in more detail below by way of examples, but the present application is not limited to these examples.

[0126] Examples

[0127] [Epoxy Resin (A)]

[0128] • Epoxy Resin 1 (bisphenol A type epoxy resin, having an aromatic ring and an epoxy group, not containing a nitrogen atom in the molecule, product of MITSUBISHI CHEMICAL Co., Ltd., trade name "jER828", epoxy equivalent: 189, liquid at 23°C, 0.10 MPa, viscosity at 25°C: 13500 mPa-s)

[0129] • Epoxy Resin 2 (bisphenol F type epoxy resin, having an aromatic ring and an epoxy group, not containing a nitrogen atom in the molecule, product of MITSUBISHI CHEMICAL Co., Ltd., trade name "jER806", epoxy equivalent: 165, liquid at 23°C, 0.10 MPa, viscosity at 25°C: 2000 mPa-s)

[0130] [Reactive Amine Compound (B)]

[0131] [Polyamine (B1)]

[0132] • Polyamine 1 (reaction addition product of m-xylylenediamine and styrene, having a plurality of amino groups (-NH2), not having an amide bond, not being a tertiary amine, not constituting a crosslinked structure of a cured product of an epoxy resin, product of MITSUBISHI GAS CHEMICAL Co., Ltd., trade name "GASKAMINE 240", molecular weight: 400, active hydrogen equivalent [eq / g]: 9.7 x 10 -3 , amine value: 403, viscosity at 25°C: 66 mPa-s)

[0133] • Polyamine 2 (mixture of 2,2,4-trimethylhexamethylenediamine and 2,4,4-trimethylhexamethylenediamine, having a plurality of amino groups (-NH2), not having an amide bond, not being a tertiary amine, not constituting a crosslinked structure of a cured product of an epoxy resin, product of EVONIK Co., Ltd., trade name "Vestamin TMD", molecular weight: 158, active hydrogen equivalent [eq / g]: 25 x 10 -3 , amine value: 710, viscosity at 25°C: 7 mPa-s)

[0134] • Polyamine 3 (polyether diamine having polytetramethylene ether glycol structure and polypropylene glycol structure, having multiple amino groups (-NH2), not having amide bond, not being tertiary amine, not constituting cross-linking structure of cured product of epoxy resin, not having amide bond, product name "Elastamine THF-100" manufactured by Huntsman Corporation, active hydrogen equivalent [eq / g]: 3.8 x 10 -3 , amine value: 107 to 114, viscosity at 25°C: 300 mPa-s)

[0135] • Polyamine 4 (4,4'-methylenebis(cyclohexylamine), having multiple amino groups (-NH2), not having amide bond, not being tertiary amine, not constituting cross-linking structure of cured product of epoxy resin, product name "Vestamin PACM" manufactured by EVONIK Corporation, active hydrogen equivalent [eq / g]: 19 x 10 -3 , amine value: 535, viscosity at 40°C: 30 mPa-s)

[0136] [Polyamideamine (B2)]

[0137] • Polyamideamine 1 (product name "VEGECHEM GREEN G235" manufactured by Tsukano Food Industry Co., Ltd., having multiple amino groups (-NH2), having amide bond, constituting cross-linking structure of cured product of epoxy resin, active hydrogen equivalent [eq / g]: 10.5 x 10 -3 , amine value: 350 to 400, viscosity at 25°C: 250 mPa-s)

[0138] • Polyamideamine 2 (product name "TOHMIDE TXE-24" manufactured by T&K TOKA Corporation, polymer of dimer of N-(2-aminoethyl)ethane-1,2-diamine and fatty acid (unsaturated fatty acid, number of carbon atoms: 18) and tall oil fatty acid, having multiple amino groups (-NH2), having amide bond, constituting cross-linking structure of cured product of epoxy resin, active hydrogen equivalent [eq / g]: 7.7 x 10 -3 , amine value: 270, viscosity at 25°C: 130 mPa-s)

[0139] [Catalyst compound (C)]

[0140] [Tertiary amine (C1)]

[0141] • Tertiary amine 1 (2,4,6-tris(dimethylaminomethyl)phenol, product name "TMA EH-30" manufactured by Tsukano Food Co., Ltd., not having nitrogen-containing aromatic heterocycle, not constituting cross-linking structure of cured product of epoxy resin

[0142] • Tertiary amine 2 (1,8-diazabicyclo[5.4.0]undec-7-ene, manufactured by SAN-APRO Co., Ltd., trade name "DABCO", does not have a nitrogen-containing aromatic heterocycle, does not constitute a crosslinked structure of a cured product of an epoxy resin)

[0143] • Tertiary amine 3 (1,4-dimethylpiperazine, does not have a nitrogen-containing aromatic heterocycle, does not constitute a crosslinked structure of a cured product of an epoxy resin)

[0144] • Tertiary amine 4 [1-(2-dimethylaminoethyl)-4-methylpiperazine, manufactured by TOSOH Corporation, trade name "TOYOCA TN", does not have a nitrogen-containing aromatic heterocycle, does not constitute a crosslinked structure of a cured product of an epoxy resin]

[0145] [Nitrogen-containing aromatic heterocycle type compound (C2)]

[0146] • Nitrogen-containing aromatic heterocycle type compound 1 (2-phenylimidazole, manufactured by Shikoku Chemicals Corporation, trade name "CUREZOL 2PZ", has a nitrogen-containing aromatic heterocycle, does not constitute a crosslinked structure of a cured product of an epoxy resin)

[0147] • Nitrogen-containing aromatic heterocycle type compound 2 (1-cyanoethyl-2-ethyl-4-methylimidazole, manufactured by Shikoku Chemicals Corporation, trade name "CUREZOL 2E4MZ-CN", has a nitrogen-containing aromatic heterocycle, does not constitute a crosslinked structure of a cured product of an epoxy resin)

[0148] • Nitrogen-containing aromatic heterocycle type compound 3 (2-ethyl-4-methylimidazole, manufactured by Shikoku Chemicals Corporation, trade name "CUREZOL 2E4MZ", has a nitrogen-containing aromatic heterocycle, does not constitute a crosslinked structure of a cured product of an epoxy resin)

[0149] [Reaction accelerator (D)]

[0150] • Reaction accelerator (triethanolamine, manufactured by JAPAN CHEMTECH Corporation, trade name "TEA99")

[0151] (Examples 1 to 24, Comparative Examples 1 to 11)

[0152] The epoxy resin having the amounts shown in Tables 1 to 3 was used as the main agent. The given amounts of the reactive amine compound (B), the reaction promoter (D), and the catalyst compound (C) shown in Tables 1 to 3 were supplied to a impeller type mixing stirrer and uniformly mixed to prepare a curing agent. Note that in the case where the catalyst compound (C) was solid at the time of mixing, the reactive amine compound (B) was heated to 80 to 110°C, and then the catalyst compound (C) was supplied to the reactive amine compound (B) to dissolve, whereby the reactive amine compound (B), the reaction promoter (D), and the catalyst compound (C) were uniformly mixed. A two-liquid type epoxy-based composition containing the main agent and the curing agent produced as described above was manufactured.

[0153] The ratio of the active hydrogen amount of the reactive amine compound (B) to the epoxy amount of the epoxy resin (A) [active hydrogen amount of reactive amine compound (B) / epoxy amount of epoxy resin (A)] is shown in the "equivalent value" column of Tables 1 to 3.

[0154] As for the reactive amine compound (B), the reaction rate constant k at 100°C when the epoxy group of the epoxy resin is stoichiometrically equivalent reacted was measured by the above-mentioned means, and is shown in the "reaction rate constant k" column of Table 4. In the case where the reaction rate constant k of the reactive amine compound (B) is adjusted by the reaction promoter (D), the reaction rate constant k of the reactive amine compound (B) adjusted by the reaction promoter (D) is shown in the "reaction rate constant k" column. The ratio of the active hydrogen amount of the reactive amine compound (B) to the epoxy amount of the epoxy resin (A) [active hydrogen amount of reactive amine compound (B) / epoxy amount of epoxy resin (A)] is shown in the "equivalent value" column. From Table 4, the polyamine 1 to 3 and the polyamide amine 1 when the epoxy group of 100 parts by mass of the epoxy resin used in the examples is stoichiometrically equivalent reacted are 54.5 parts by mass, 21 parts by mass, 137 parts by mass, and 50.0 parts by mass, respectively. Also, in Table 4, for example, when the adjustment is performed using the reaction promoter (D) 1 part by mass, the amount (mass) of the reaction promoter (D) used per unit mass (1 part by mass) of the reactive amine compound (B) [reaction promoter (D) / reactive amine compound (B)] is 0.018 parts by mass. Also, in Example 2 where the amount (mass) of the reaction promoter (D) used per unit mass of the reactive amine compound (B) [reaction promoter (D) / reactive amine compound (B)] is 0.018 parts by mass, the reaction rate constant k of the polyamine 1 at 100°C after the adjustment by the reaction promoter (D) when the epoxy group of the epoxy resin (A) is stoichiometrically equivalent reacted is 0.15 min -1 .

[0155] As for the catalyst compound (C), the cumulative heat, the maximum heat flow, and the temperature at which the maximum heat flow appears, obtained by differential scanning calorimetry at a temperature rising rate of 5°C / min from 0°C to 200°C in the polymerization reaction at the addition of 5 mol% to the epoxy resin (A), were measured by the above-mentioned protocol and are recorded in the "cumulative heat", "maximum heat flow", and "maximum heat flow temperature" columns of Table 5, respectively.

[0156] The reaction rate constant k of the reactive amine compound (B) at 100°C when the epoxy group of the epoxy resin (A) is stoichiometrically equivalent reacted, or the reaction rate constant k of the reactive amine compound (B) at 100°C after the adjustment by the reaction accelerator (D) when the epoxy group of the epoxy resin (A) is stoichiometrically equivalent reacted, in the examples and comparative examples is recorded in the "reaction rate constant k" column of Tables 1 to 3.

[0157] As for the obtained epoxy-based composition, the exotherm at the time of curing, the curing time, and the hardness of the cured product were measured by the following protocol, and the results are shown in Tables 1 to 3.

[0158] (Exotherm at the time of curing and curing time)

[0159] The main agent and the curing agent of the epoxy-based composition having an initial temperature of 23°C were uniformly mixed, and then the epoxy-based composition was cast into a steel tank having a diameter of 140 mm and a height of 160 mm at a casting amount indicated in Tables 1 to 3 under an atmosphere of 23°C. A thermocouple (K The highest temperature at the time of curing of the epoxy-based composition (exotherm at the time of curing) was measured using a data logger (GRAPHTEC Corporation, trade name "GL220") based on JIS C1602) placed at the center of the cast epoxy-based composition. The time required from the mixing of the main agent and the curing agent of the epoxy-based composition to the time at which the epoxy-based composition showed the highest temperature was measured as the curing time.

[0160] (Hardness of cured product)

[0161] The epoxy-based composition was cured in the same protocol as that for measuring the exotherm at the time of curing, and for the cured product after 24 hours from the time at which the epoxy-based composition showed the highest temperature at the time of curing, the hardness was measured using a D-type durometer hardness meter based on the method of JIS K6253 in an atmosphere of 25°C. Note that the measurement time was 30 seconds. Note that in the case where the epoxy-based composition was not cured, "not cured" is recorded.

[0162]

[0163]

[0164]

[0165]

[0166]

[0167] Industrial applicability

[0168] The epoxy-based composition of the present application is excellent in flowability, and the exothermic heat at the time of curing is reduced, and a cured product excellent in mechanical strength can be obtained. The epoxy-based composition of the present application can form a large injection molded product excellent in mechanical strength. The epoxy-based composition of the present application can manufacture a hollow fiber membrane module without damaging the hollow fiber membrane.

[0169] (CROSS-REFERENCE TO RELATED APPLICATIONS)

[0170] This application claims priority based on Japanese Patent Application No. 2021-31505 filed on March 1, 2021, the disclosure of which is incorporated by reference herein in its entirety.

Claims

1. An epoxy-based composition comprising: 100 parts by weight of an epoxy resin (A) having an aromatic ring and an epoxy group in a molecule; a reaction accelerator (D); The reactive amine compound (B) has a reaction rate constant k at 100°C of 0.10 to 0.37 min when it reacts with the epoxy group of the epoxy resin (A) in the presence of the reaction promoter (D) -1 and comprises a polyamine (B1) and / or a polyamidoamine (B2); and 0.1 to 10 parts by weight of a catalyst compound (C) having a cumulative heat of 100 J / g or more and a maximum heat flow of 0.08 W / g or more in the range of 0 to 200°C obtained by differential scanning calorimetry at a temperature increase rate of 5°C / min in the reaction heat at the time of adding 5 mol% to the epoxy resin (A), a temperature at which the maximum heat flow is exhibited is in the range of 80 to 130°C, and contains a tertiary amine (C1) and / or a nitrogen-containing aromatic heterocyclic compound (C2), a ratio of an active hydrogen amount of the reactive amine compound (B) to an epoxy amount of the epoxy resin (A) [active hydrogen amount of the reactive amine compound (B) / epoxy amount of the epoxy resin (A)] is in the range of 0.3 to 0.7, The reaction rate constant k at 100°C of the reactive amine compound (B) when reacting with the epoxy group of the epoxy resin (A) before adjustment with the reaction accelerator (D) is 0.10 to 0.20 min -1 .

2. An epoxy-based composition for a hollow fiber membrane module comprising: the epoxy-based composition according to claim 1.

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