JP7270318B2 - epoxy composition - Google Patents

Description

The present invention relates to epoxy-based compositions.

The reaction between the epoxy resin and the hardener is exothermic and releases a large amount of heat. The heat generated during the reaction causes shrinkage of the cured product obtained by curing the epoxy resin, and causes problems such as deterioration of the dimensional accuracy of the cast product and the occurrence of cracks in the cast product.

In particular, in the case of molding relatively large-sized castings (mass casting) with a single casting amount of 1 kg to several tens of kg, shrinkage of the obtained castings is significantly increased.

Also, the heat generated during the reaction between the epoxy resin and the curing agent causes deterioration of the mold that supplies the epoxy resin and other materials embedded in the epoxy resin. For example, in a casting for fixing the hollow fibers of a hollow fiber membrane module, heat generation causes distortion of the housing and damage to the hollow fiber membranes, resulting in a significant reduction in the inherent filtering ability of the hollow fiber membranes. .

Furthermore, when the heat generated during the reaction between the epoxy resin and the curing agent is large, the epoxy resin is partially decomposed, resulting in discoloration or deterioration of the quality of the epoxy resin. When the heat generation is extremely large, the epoxy resin is carbonized or scorched, and there is a risk that the epoxy resin may ignite.

Heat generation in mass casting (large casting) cannot efficiently dissipate heat to the outside due to poor heat transfer in the bulk matrix. For this reason, for example, the curing reaction between the epoxy resin and the curing agent is carried out slowly over a long period of time to moderate heat generation, the reaction temperature and time during the curing reaction are strictly controlled, and casting is performed in multiple stages. It is necessary to perform a complicated process such as the above, and there is a problem that the production efficiency is lowered.

On the other hand, the heat generated during the curing reaction is due to the reaction between the epoxy resin and the curing agent, so heat generation can be reduced by reducing the number of reactions per unit volume.

However, it is necessary to reduce the number of reactions by a considerable number in order to suppress heat generation during the reaction due to mass casting. For that purpose, it is necessary to use monofunctional raw materials with a small number of functional groups per unit or raw materials with a large molecular weight. Another problem arises that some high mechanical strength is lost. Further, when an epoxy resin having a large molecular weight is used, there arises another problem that fluidity is impaired and casting and potting become difficult.

Patent Document 1 discloses a liquid epoxy resin composition for casting which cures at a low temperature of room temperature to 60°C and does not generate heat at a temperature exceeding 100°C during curing. polyoxypropylene diamine and an inorganic filler, the average molecular weight of the polyoxypropylene diamine is in the range of 270 to 1800, and the content of the inorganic filler is 30% by weight or more of the entire composition. A liquid epoxy resin composition for casting is proposed.

JP-A-6-248059

However, the liquid epoxy resin composition for casting has the problems that it generates a large amount of heat during curing, requires a long time for curing, and the mechanical strength of the resulting cured product is low.

The present invention provides an epoxy composition that generates little heat during curing, cures at room temperature in a short period of time, and provides a cured product with excellent mechanical strength.

The epoxy-based composition of the present invention is
100 parts by weight of an epoxy resin (A) having an aromatic ring and an epoxy group in the molecule;
Reaction with a reaction rate constant k of 0.10 to 0.37 min ^-1 at 100 ° C. when reacted with the epoxy group of the epoxy resin (A) and containing polyamine (B1) and / or polyamidoamine (B2) a reactive amine compound (B);
In the reaction heat when 5 mol% is added to the epoxy resin (A), the accumulated heat amount from 0 to 200 ° C. measured 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, a catalyst compound (C) having a maximum heat flow temperature of 130°C or less, and containing a tertiary amine (C1) and/or a nitrogen-containing aromatic heterocyclic compound (C2); including
The ratio of the amount of active hydrogen in the reactive amine compound (B) to the amount of epoxy in the epoxy resin (A) [the amount of active hydrogen in the reactive amine compound (B)/the amount of epoxy in the epoxy resin (A)] is 0.5. It is characterized by being 3 to 0.8.

The epoxy-based composition of the present invention is
100 parts by weight of an epoxy resin (A) having an aromatic ring and an epoxy group in the molecule;
a reaction accelerator (D);
A polyamine (B1) having a reaction rate constant k at 100° C. of 0.10 to 0.37 min ⁻¹ when reacted with the epoxy group of the epoxy resin (A) in the presence of the reaction accelerator (D) and / or a reactive amine compound (B) containing polyamidoamine (B2),
In the reaction heat when 5 mol% is added to the epoxy resin (A), the accumulated heat amount from 0 to 200 ° C. measured 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, a catalyst compound (C) having a maximum heat flow temperature of 80 to 130° C., and containing a tertiary amine (C1) and/or a nitrogen-containing aromatic heterocyclic compound (C2) 0.1 to 10 parts by weight,
The ratio of the amount of active hydrogen in the reactive amine compound (B) to the amount of epoxy in the epoxy resin (A) [the amount of active hydrogen in the reactive amine compound (B)/the amount of epoxy in the epoxy resin (A)] is 0.5. It is characterized by being 3 to 0.8.

In the epoxy-based composition of the present invention, the epoxy resin (A) is and the reactivity with reactive amine compounds containing polyamine (B1) and/or polyamidoamine (B2).

Furthermore, the epoxy-based composition of the present invention is capable of curing the epoxy resin by reacting the epoxy resin (A) with a reactive amine compound (B) containing polyamine (B1) and/or polyamidoamine (B2), and polymerization of epoxy resin (self-crosslinking of epoxy resin) using a catalyst compound (C) containing a tertiary amine and/or a nitrogen-containing aromatic heterocyclic compound as a catalyst.

That is, the epoxy-based composition of the present invention temporally disperses reaction heat generated by the curing reaction of the epoxy resin without reducing the number of curing reactions, and as a result, heat generation during curing is reduced. ing.

Since the epoxy-based composition of the present invention does not require a reduction in the number of curing reactions, it does not require the use of epoxy resins with a large molecular weight, and has excellent fluidity, and the obtained cured product is also excellent. It has mechanical strength.

The epoxy-based composition of the present invention is a two-component type containing a main agent and a curing agent, and is used by mixing and curing the main agent and a curing agent.

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

The epoxy resin (A) having an aromatic ring and an epoxy group in the molecule is not particularly limited, and examples thereof include bisphenol A type epoxy resin, bisphenol F type epoxy resin, tetraglycidyldiaminodiphenylmethane type epoxy resin, and aminophenol. type epoxy resin, aniline type epoxy resin, benzylamine type epoxy resin, xylenediamine type epoxy resin, and the like. The epoxy resin (A) has excellent storage stability, is liquid at 23° C. and 0.10 MPa, and has a relatively low viscosity. Epoxy resins are preferred. The epoxy resin is generally a product obtained by adding epichlorohydrin to the hydroxyl group of a polyhydric alcohol such as polyhydric phenol (for example, in the following formula (1), the number of repetitions n = 0), or It has repeating units formed by ring-opening addition of epichlorohydrin to a hydric alcohol (for example, in the following formula (1), the repeating number n is a natural number). The epoxy resin (A) may be used alone or in combination of two or more.

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 structural formula shown below. However, the repetition number n is 0 or a natural number.

The epoxy resin (A) is preferably liquid under conditions of 23° C. and 0.10 MPa. When the epoxy resin (A) is liquid under the conditions of 23° C. and 0.10 MPa, the fluidity of the epoxy-based composition can be ensured. When the epoxy resin (A) is a mixture of a plurality of types (including a mixture of epoxy resins having different repeating numbers n of repeating units), the epoxy resin (A) is heated at 23°C and 0.10 MPa. Whether the mixture is liquid or not is judged as a whole mixture. Therefore, even if an epoxy resin that is solid at 23° C. and 0.10 MPa is included, if the entire mixture of epoxy resins is liquid at 23° C. and 0.10 MPa, the epoxy resin Let the whole mixture be an epoxy resin (A). Examples of epoxy resins that are solid under conditions of 23° C. and 0.10 MPa include biphenyl-type epoxy resins, naphthalene-type epoxy resins, phenol novolac-type epoxy resins, bisphenol A novolak-type epoxy resins, A trishydroxymethane type epoxy resin, a tetraphenolethane type epoxy resin, and the like are included.

The epoxy-based composition may contain a diluent for adjusting the viscosity of the main agent within a range that does not hinder the working curing of the present invention. If the diluent has only one epoxy group, it may have an aromatic ring in its molecule. When the diluent contains multiple crosslinkable epoxy groups, it preferably does not have an aromatic ring in the molecule. Diluents can be reactive or not. The diluent is not particularly limited, and examples thereof include 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-propanetriyltri(oxymethylene)]trisoxirane, pentaerythritol polyglycidyl ether, 1,4-bis[(oxiran-2-ylmethoxy)methyl]cyclohexane, phenyl glycidyl ether, 1,3-bis(oxiranylmethoxy)benzene, benzyl glycidyl ether, 3,4-epoxycyclohexylmethyl(3,4-epoxy)cyclohexane carboxylate, etc. The diluent is used alone. or two or more may be used in combination.

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

Reactive amine compounds (B) include polyamines (B1) and/or polyamidoamines (B2).

The reactive amine compound (B) has a reaction rate constant k of 0.10 to 0.37 min ^-1 at 100° C. when reacted with the epoxy group of the epoxy resin (A) in a stoichiometric equivalent manner. .

"React with the epoxy group of the epoxy resin (A) in a stoichiometric equivalent" means that the epoxy group of the epoxy resin (A) and the reactive amine compound (B) are reacted with the reactive amine compound (B) and the epoxy amount of the epoxy resin (A) [the active hydrogen amount of the reactive amine compound (B) / the epoxy amount of the epoxy resin (A)] is 1. . In the present invention, 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 called an “equivalent value”.

In the reactive amine compound (B), the reaction rate constant k at 100 ° C. (hereinafter simply referred to as "reaction rate constant k" when reacting stoichiometrically equivalent with the epoxy group of the epoxy resin (A) is 0.10 min ^-1 or more, preferably 0.105 min ^-1 or more, more preferably 0.106 min ^-1 or more, more preferably 0.11 min ^-1 or more, and 0.12 min ^-1 or more more preferred.

In the reactive amine compound (B), the reaction rate constant k at 100 ° C. (hereinafter simply referred to as "reaction rate constant k" when reacting stoichiometrically equivalent with the epoxy group of the epoxy resin (A) is 0.37 min ^-1 or less, preferably 0.27 min ^-1 or less, more preferably 0.22 min ^-1 or less, more preferably 0.20 min ^-1 or less, and 0.18 min ^-1 or less more preferred.

In the polyamine (B1), the reaction rate constant k at 100 ° C. when reacted with the epoxy group of the epoxy resin (A) at a stoichiometric equivalent is preferably 0.10 min ^-1 or more, and 0.105 min ^{- 1} or more is more preferable, 0.106 min ⁻¹ or more is more preferable, 0.11 min ⁻¹ or more is more preferable, and 0.12 min ⁻¹ or more is more preferable.

In the polyamine (B1), the reaction rate constant k at 100 ° C. when reacted with the epoxy group of the epoxy resin (A) in a stoichiometric equivalent is preferably 0.37 min ^-1 or less, and 0.27 min ^{- 1} or less is more preferable, 0.22 min ^-1 or less is more preferable, 0.20 min ^-1 or less is more preferable, and 0.18 min ^-1 or less is more preferable.

In the polyamidoamine (B2), the reaction rate constant k at 100 ° C. when reacted in a stoichiometric equivalent with the epoxy group of the epoxy resin (A) is preferably 0.10 min ^-1 or more, and 0.105 min. ⁻¹ or more is more preferable, 0.106 min ⁻¹ or more is more preferable, 0.11 min ⁻¹ or more is more preferable, and 0.12 min ⁻¹ or more is more preferable.

In the polyamidoamine (B2), the reaction rate constant k at 100 ° C. when reacted in a stoichiometric equivalent with the epoxy group of the epoxy resin (A) is preferably 0.37 min ^-1 or less, and 0.27 min. ⁻¹ or less is more preferable, 0.22 min ⁻¹ or less is more preferable, 0.20 min ⁻¹ or less is more preferable, and 0.18 min ⁻¹ or less is more preferable.

By setting the reaction rate constant k at 100° C. of the reactive amine compound (B) to 0.10 min ⁻¹ or more, the reaction can be performed at an ambient temperature of about 20 to 30° C. within a short period of time (for example, within about 8 hours). can be cured to The same is true for polyamine (B1) and polyamidoamine (B2).

By setting the reaction rate constant k at 100° C. of the reactive amine compound (B) to 0.37 min ⁻¹ or less, the reaction of the epoxy composition has an appropriate reaction rate, and the curing reaction takes place within a short period of time. can be suppressed, the heat generated during the curing reaction can be dispersed, and the heat generated during the curing reaction can be reduced. The same is true for polyamine (B1) and polyamidoamine (B2).

The reaction rate constant k of the reactive amine compound (B) may 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) may be adjusted with the reaction accelerator (D). When the reaction rate constant k of the reactive amine compound (B) is adjusted by the reaction accelerator (D), the term "reaction rate constant k" simply refers to the reaction after adjustment by the reaction accelerator (D). Refers to the rate constant k.

When the reaction rate constant k of the reactive amine compound (B) is adjusted with the reaction accelerator (D), after adjustment with the reaction accelerator (D), the epoxy group of the epoxy resin (A) and the stoichiometric The reaction rate constant k of the reactive amine compound (B) at 100 ° C. when reacted at the same temperature is 0.10 min ^-1 or more, preferably 0.105 min ^-1 or more, and 0.106 min ^-1 0.11 min ⁻¹ or more is more preferable, and 0.12 min ⁻¹ or more is more preferable.

When the reaction rate constant k of the reactive amine compound (B) is adjusted with the reaction accelerator (D), after adjustment with the reaction accelerator (D), the epoxy group of the epoxy resin (A) and the stoichiometric For the same reason as above, the reaction rate constant k of the reactive amine compound (B) at 100° C. when reacted at an equivalent temperature of 0.37 min ⁻¹ or less is 0.27 min ⁻¹ or less. It is preferably 0.22 min ^-1 or less, more preferably 0.20 min ^-1 or less, and more preferably 0.18 min ^-1 or less.

When the reaction rate constant k of the polyamine (B1) is adjusted with the reaction accelerator (D), it is stoichiometrically equivalent to the epoxy groups of the epoxy resin (A) after adjustment with the reaction accelerator (D). The reaction rate constant k of the polyamine (B1) at 100 ° C. when reacted with is preferably 0.10 min ^-1 or more, more preferably 0.105 min ^-1 or more, more preferably 0.106 min ^-1 or more, It is more preferably 0.11 min ⁻¹ or more, more preferably 0.12 min ⁻¹ or more.

When the reaction rate constant k of the polyamine (B1) is adjusted with the reaction accelerator (D), it is stoichiometrically equivalent to the epoxy groups of the epoxy resin (A) after adjustment with the reaction accelerator (D). The reaction rate constant k of the polyamine (B1) at 100 ° C. when reacted with is preferably 0.37 min ^-1 or less, more preferably 0.27 min ^-1 or less, more preferably 0.22 min ^-1 or less, 0.20 min ⁻¹ or less is more preferable, and 0.18 min ⁻¹ or less is more preferable.

When the reaction rate constant k of the polyamidoamine (B2) is adjusted with the reaction accelerator (D), it is stoichiometrically equivalent to the epoxy groups of the epoxy resin (A) after adjustment with the reaction accelerator (D). The reaction rate constant k of the polyamidoamine (B2) at 100 ° C. when reacted at is preferably 0.10 min ^-1 or more, more preferably 0.105 min ^-1 or more, and more preferably 0.106 min ^-1 or more. It is preferably 0.11 min ⁻¹ or more, more preferably 0.12 min ⁻¹ or more.

When the reaction rate constant k of the polyamidoamine (B2) is adjusted with the reaction accelerator (D), it is stoichiometrically equivalent to the epoxy groups of the epoxy resin (A) after adjustment with the reaction accelerator (D). The reaction rate constant k of the polyamidoamine (B2) at 100 ° C. when reacted at is preferably 0.37 min ^-1 or less, more preferably 0.27 min ^-1 or less, and more preferably 0.22 min ^-1 or less. It is preferably 0.20 min ^-1 or less, more preferably 0.18 min ^-1 or less.

After adjustment with the reaction accelerator (D), the reaction rate constant k of the reactive amine compound (B) is set to 0.10 min ^{−1 or more, so that the reaction rate constant k is set to 0.10 min −1 or} more at an ambient temperature of about 20 to 30 ° C. for a short time ( for example, within about 8 hours). The same is true for polyamine (B1) and polyamidoamine (B2).

By setting the reaction rate constant k of the reactive amine compound (B) to 0.37 min ^-1 or less after adjustment with the reaction accelerator (D), the reaction of the epoxy-based composition has an appropriate reaction rate. In addition, it is possible to suppress the concentration of the curing reaction in a short period of time, disperse the heat generated during the curing reaction, and reduce the heat generated during the curing reaction. The same is true for polyamine (B1) and polyamidoamine (B2).

The reaction rate constant k of the reactive amine compound (B) is determined using the parameters (activation energy ΔE, reaction order n, frequency factor A) obtained by the Ozawa method reaction rate analysis by differential scanning calorimetry. It shall be obtained by a calculated isothermal analysis simulation.

Specifically, a mixed solution is prepared by mixing an epoxy resin (A), a reactive amine compound (B), and, if necessary, a reaction accelerator (D). 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. Epoxy resin (A) and reactive amine compound (B) are mixed so that

10±3 mg of the resulting mixed solution is supplied to an aluminum sample container, and the opening of the sample container is covered with a crimp cover. Differential scanning calorimetry is performed using a differential scanning calorimeter at a temperature range of -15 ° C. to 300 ° C. at three levels of heating rates of 5 ° C./min, 10 ° C./min or 20 ° C./min. We obtain three DSC curves. In addition, when the epoxy resin is mixed with the curing agent, the reaction progresses, so a new mixed liquid is prepared for each heating rate. As the differential scanning calorimeter, for example, a measurement device commercially available from Shimadzu Corporation under the trade name “DSC-60” can be used.

A value calculated from the obtained three DSC curves using reaction rate analysis software (manufactured by Shimadzu Corporation, trade name "Reaction Analysis (DSC) Program") is defined as a reaction rate constant k. The analysis range was 0° C. to 280° C., and was obtained by an isothermal analysis simulation calculated using the parameters (activation energy ΔE, reaction order n, frequency factor A) obtained by reaction rate analysis of the Ozawa method. shall be

When the reactive amine compound (B) contains multiple types of polyamine (B1) and/or polyamidoamine (B2), the reaction rate constant of the reactive amine compound (B) is the polyamine (B1) and/or Or the value measured as a mixture of polyamidoamine (B2).

Polyamine (B1) has a plurality of amino groups (--NH ₂ ) in the molecule and no amide bond (--NHCO--). Incidentally, only one hydrogen atom of the amino group may be substituted with another substituent or atom. As the polyamine (B1), the reaction rate of the reactive amine compound (B) at 100° C. when the reactive amine compound (B) is reacted with the epoxy groups of the epoxy resin (A) in a stoichiometrically equivalent manner. There is no particular limitation as long as the constant k is 0.10 to 0.37 min ⁻¹ . The polyamine (B1) may be used alone or in combination of two or more. As the polyamine (B1), one commercially available from Mitsubishi Gas Chemical Co., Ltd. under the trade name "Gaskamin 240" can be used.

The polyamine (B1) should (1) have a plurality of amino groups (--NH ₂ ) and no amide bond (--NHCO--) in the molecule. Incidentally, only one hydrogen atom of the amino group may be substituted with another substituent or atom. The polyamine (B1) (2) reacts with a plurality of epoxy groups of the epoxy resin (A) to form a crosslinked structure of the cured product of the epoxy resin (A). As long as the polyamine (B1) satisfies the above (1) and (2), the polyamine (B1) may contain a structure in which all three hydrogen atoms of ammonia are substituted with other substituents or atoms in the molecule.

As the polyamine (B1), the reaction rate constant k of the polyamine is measured using differential scanning calorimetry, and a polyamine having a reaction rate constant k of 0.10 to 0.37 min ⁻¹ is selected as a guideline. good. The structural features of the polyamine (B1) having a reaction rate constant k of 0.10 to 0.37 min ⁻¹ include, for example, the carbon atoms bonded to the nitrogen atoms of the primary amino groups are methyl groups, ethyl groups, and the like. Polyamines that are alkyl groups and have steric hindrance, polyamines that have a secondary amino group, cyclic amines, polyamines that have an aromatic ring amino group, and the like. An aromatic ring amino group refers to a functional group in which an amino group is bonded to a substituent containing an aromatic ring such as a phenyl group.

Examples of the polyamine (B1) include a reaction adduct of metaxylylenediamine and styrene, a polyetherdiamine having a polytetramethylene ether glycol structure and a polypropylene glycol structure, 4,4′-methylenebis(cyclohexylamine), and the like. be done. The polyamine (B1) may be used alone or in combination of two or more.

Polyamidoamine (B2) has an amide bond (--NHCO--) and a plurality of amino groups in the molecule. Incidentally, only one hydrogen atom of the amino group may be substituted with another substituent or atom. The polyamidoamine (B2) is a condensation product of a carboxylic acid and a polyamine, for example, a condensation product of a dimer acid (a dibasic acid produced by dimerization of an unsaturated fatty acid) and a polyamine, a monocarboxylic acid or a polycarboxylic acid. Condensation products of acids and polyalkyleneamines and the like can be mentioned. Incidentally, the polyamidoamine (B2) may be used alone or in combination of two or more. As the polyamidoamine (B2), one commercially available from Tsuno Shokuhin Kogyo Co., Ltd. under the trade name of "Vegichem Green G235" can be used.

The polyamidoamine (B2) may (1) have a plurality of amino groups (--NH ₂ ) and an amide bond (--NHCO--) in the molecule. Incidentally, only one hydrogen atom of the amino group may be substituted with another substituent or atom. The polyamidoamine (B2) (2) reacts with a plurality of epoxy groups of the epoxy resin (A) to form a crosslinked structure of the cured product of the epoxy resin (A). As long as the polyamidoamine (B1) satisfies the above (1) and (2), the polyamidoamine (B1) may contain a structure in which all three hydrogen atoms of ammonia are substituted with other substituents or atoms in the molecule.

Examples of polyalkyleneamines include diethylenetriamine (DETA), dipropylenetriamine (DPTA), bis-hexamethylenetriamine (BHMT), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), and pentaethylenehexamine (PEHA). , polyethylene polyamine (HEPA) having 5 to 7 ethyleneamine units, and the like. The polyalkyleneamines may be used alone or in combination of two or more.

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.

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.

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.

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.

The total content of polyamine (B1) and 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.

The total content of polyamine (B1) and 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.

The curing agent may contain a reaction accelerator (D). The reaction accelerator (D) is used to adjust the reaction rate constant k of the reactive amine compound (B), as described above. 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). The reaction accelerator (D) is not particularly limited, and examples thereof include polyols such as triethanolamine and glycerin; carboxylic acids such as salicylic acid and benzoic acid; and sulfonic acids such as paratoluenesulfonic acid. Polyols are preferred. . The reaction accelerator (D) may be used alone or in combination of two or more.

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.

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.

The ratio of the amount of active hydrogen in the reactive amine compound (B) to the amount of epoxy in the epoxy resin (A) [the amount of active hydrogen in the reactive amine compound (B)/the amount of epoxy in the epoxy resin (A)] is 0.3 or more. Then, a small amount of reaction heat is generated by the curing reaction between the epoxy resin (A) and the reactive amine compound (B), and the reaction heat further advances the curing reaction of the epoxy-based composition. That is, the epoxy-based composition smoothly undergoes a curing reaction at an ambient temperature of about 20 to 30° C. due to the heat generated during the curing reaction of itself to form a cured product. Furthermore, the curing reaction between the epoxy resin (A) and the reactive amine compound (B) progresses to some extent, so that the epoxy resin (A ) can obtain the heat energy necessary to advance the polymerization (self-crosslinking of the epoxy resin) reaction, and the polymerization of the epoxy resin (A) can be performed by curing the epoxy resin (A) and the reactive amine compound (B). The reaction can be delayed to proceed.

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

The epoxy content of the epoxy resin (A) is calculated based on the following formula.
Epoxy content of epoxy resin (A) = content of epoxy resin (A) in epoxy-based composition [g]
/ Epoxy equivalent of epoxy resin (A) [g / eq]

The epoxy equivalent of the epoxy resin (A) is a value obtained by dividing the molecular weight of the epoxy resin by the number of epoxy groups in one molecule. In the present invention, the epoxy equivalent of an epoxy resin refers to a value measured according to JIS K7236.

The amount of active hydrogen in the reactive amine compound (B) is calculated based on the following formula.
Active hydrogen amount of reactive amine compound (B) = Active hydrogen equivalent of reactive amine compound (B) [eq/g]
x Content of reactive amine compound (B) in epoxy-based composition [g]

The active hydrogen equivalent of the reactive amine compound (B) is calculated as follows.
Active hydrogen equivalent [eq/g] of reactive amine compound (B)
= number of active hydrogens in reactive amine compound (B)/molecular weight of reactive amine compound (B)

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

When the reactive amine compound (B) contains multiple types of polyamine (B1) and/or polyamidoamine (B2), the amount of active hydrogen in the reactive amine compound (B) is calculated based on the following formula. value.

The reactive amine compound (B) contains a total of m types of polyamine (B1) and/or polyamidoamine (B2), and the active hydrogen equivalent of the m-th reactive amine compound is Qm [eq/g], Let the content of the m-th reactive amine compound be Gm (g), and let the value calculated based on the following formula be the active hydrogen content Q of the reactive amine compound (B).

When the reaction accelerator (D) is contained in the epoxy-based composition, the content of the reaction accelerator (D) is stoichiometric with the epoxy groups of the epoxy resin (A) and the reactive amine compound (B). so that the reaction rate constant k of the reactive amine compound (B) at 100° C. after adjusting with the reaction accelerator (D) is 0.10 to 0.37 min ⁻¹ should be adjusted to Specifically, the content of the reaction accelerator (D) is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, and more preferably 3 parts by mass or more with respect to 100 parts by mass of the epoxy resin (A). preferable. The content of the reaction accelerator (D) is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, and more preferably 5 parts by mass or less with respect to 100 parts by mass of the epoxy resin (A).

The epoxy-based composition contains a reactive amine compound (B) containing polyamine (B1) and/or polyamidoamine (B2) as a curing agent. may contain a curing agent. Examples of such curing agents include thiol compounds, dicyandiamides, polysulfides, dihydrazides and the like.

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

The epoxy resin polymerization (epoxy resin self-crosslinking) reaction proceeds in the presence of the catalyst compound (C). The catalyst compound (C) does not form a crosslinked structure in the cured epoxy resin (A). The catalyst compound (C) does not form a crosslinked structure with the epoxy resin (A). It reacts with only one epoxy group in the epoxy resin (A) or the cured product of the epoxy resin (A) and does not form a crosslinked structure in the cured product of the epoxy resin (A).

The epoxy resin polymerization (epoxy resin self-crosslinking) reaction is carried out in the presence of the catalyst compound (C). The catalyst compound (C) enables the polymerization reaction of the epoxy resin to proceed at a low temperature, thereby suppressing heat generation during curing of the epoxy-based composition.

The catalyst compound (C) is the cumulative heat amount from 0 to 200 ° C. measured by differential scanning calorimetry at a temperature increase rate of 5 ° C./min in the polymerization reaction when 5 mol% is added to the epoxy resin (A) (hereinafter simply “ 100 J/g or more, the maximum heat flow (hereinafter sometimes simply referred to as “maximum heat flow”) is 0.08 W/g or more, and the temperature exhibiting the maximum heat flow is 130° C. or less. be.

The cumulative heat quantity is 100 J/g or more, preferably 120 J/g or more, more preferably 150 J/g or more, and more preferably 200 J/g or more. When the cumulative heat quantity is 100 J/g or more, the heat of reaction between the epoxy resin (A) and the reactive amine compound (B) causes the polymerization reaction of the epoxy resin (A) in the presence of the catalyst compound (C). can be progressed appropriately.

The cumulative heat quantity is preferably 500 J/g or less, more preferably 450 J/g or less. When the accumulated heat quantity is 500 J/g or less, heat generation during curing of the epoxy resin can be suppressed to a low level.

The catalyst compound (C) is the maximum heat flow (hereinafter simply referred to as 0.08 W/g or more, 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 heat of reaction during the reaction between the epoxy resin (A) and the reactive amine compound (B) causes polymerization of the epoxy resin (A) in the presence of the catalyst compound (C). The reaction can proceed moderately.

The catalyst compound (C) is the maximum heat flow (hereinafter referred to as 0.80 W/g or less, preferably 0.70 W/g or less, and preferably 0.60 W/g or less. When the maximum heat flow is 0.80 W/g or less, heat generation during curing of the epoxy resin can be kept low.

The temperature exhibiting maximum heat flow is 130° C. or lower, preferably 125° C. or lower, more preferably 120° C. or lower, and more preferably 110° C. or lower. When the temperature at which the maximum heat flow is exhibited is 130° C. or less, the reaction heat of the reaction between the epoxy resin (A) and the reactive amine compound (B) can promote the polymerization of the epoxy resin and react with the epoxy resin. Even if the equivalent value to the polyamine compound is less than 1, the mechanical strength of the cured epoxy composition can be improved.

The temperature exhibiting the maximum heat flow is preferably 80° C. or higher, more preferably 92° C. or higher, and more preferably 94° C. or higher. When the temperature at which the maximum heat flow is exhibited is 80° C. or higher, the polymerization of the epoxy resin (A) can be delayed to proceed with the curing reaction of the epoxy resin (A) and the reactive amine compound (B), and the two-step It can help dissipate heat from the reaction.

The cumulative amount of heat, the maximum heat flow, and the temperature indicating the maximum heat flow of the catalyst compound (C) refer to temperatures measured in the following manner. 5 mol % of the catalyst compound (C) is mixed with the epoxy resin (A) to prepare a sample. When the catalyst compound (C) is solid, the catalyst compound (C) is dissolved in a solvent capable of dissolving the catalyst compound (C) (eg, tetrahydrofuran) to prepare a catalyst compound solution. After mixing this catalyst compound solution with the epoxy resin (A), the solvent is removed under vacuum conditions at 25° C. to prepare a sample. The sample was heated from −20° C. to 220° C. with a differential scanning calorimeter at a heating rate of 5° C./min, and the differential scanning calorie of the polymerization reaction of the epoxy resin (A) using the catalyst compound (C) as a catalyst was measured. to measure. The maximum heat flow is based on the calorific value [W/g] at 0.degree. The temperature indicating the maximum value of heat flow in the 0 to 200° C. interval is defined as the temperature [° C.] indicating the maximum heat flow. The cumulative amount of heat is based on the calorific value [W/g] at 0°C, and the total calorific value [J/g] at 0 to 200°C.

The tertiary amine (C1) does not have a nitrogen-containing aromatic heterocycle in its molecule. A tertiary amine is a compound having a structure in its molecule in which all three hydrogen atoms of ammonia are replaced with other substituents or atoms. The tertiary amine (C1) (2) does not constitute a crosslinked structure of the cured product of the epoxy resin (A) (does not react with the multiple epoxy groups of the epoxy resin (A)). As the tertiary amine (C1), in the anionic polymerization reaction when 5 mol% is added to the epoxy resin (A), the accumulated heat amount from 0 to 200 ° C. measured by differential scanning calorimetry at a temperature increase rate of 5 ° C./min is 100 J. /g or more, the maximum heat flow is 0.08 W/g or more, and the temperature exhibiting the maximum heat flow is 130°C or less.

The tertiary amine (C1) has (1) no nitrogen-containing aromatic heterocycle in the molecule. The tertiary amine (C1) has (2) a structure in which all three hydrogen atoms of ammonia are substituted with other substituents or atoms. The tertiary amine (C1) does not constitute a crosslinked structure of (3) the cured product of the epoxy resin (A). The tertiary amine (C1) may contain an amino group and an amide bond in the molecule as long as the above (1) to (3) are satisfied. Examples of the tertiary amine (C1) include benzylamine derivatives; N,N'-dimethylpiperazine, alicyclic amines such as dimethylcyclohexylamine, and 2,4,6-tris(dimethylaminomethyl)phenol. , N,N′-dimethylpiperazine is preferred. As the tertiary amine (C1), one commercially available from Tsukuno Shokuhin Co., Ltd. under the trade name “TMA EH-30” can be used. In addition, the tertiary amine (C1) may be used alone or in combination of two or more.

The benzylamine derivative means a tertiary amine having a benzylamino group in its molecular skeleton. Two hydrogen atoms of the benzylamino group have been replaced with other substituents or atoms. Examples of benzylamine derivatives include N,N-dimethylbenzylamine, N-ethyl-N-methylbenzylamine, N,N-diethylbenzylamine, 1,3-bis(dimethylaminomethyl)benzene, 2-dimethylamino methylphenol, 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.

As the nitrogen-containing aromatic heterocyclic compound (C2), in the polymerization reaction when 5 mol% is added to the epoxy resin (A), the differential scanning calorimetry was measured at a temperature increase rate of 5 ° C./min from 0 to 200 ° C. There are no particular limitations as long as the cumulative heat quantity is 100 J/g or more, the 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 less.

The nitrogen-containing aromatic heterocyclic compound (C2) is a compound having a structure in which an aromatic ring contains nitrogen atoms in addition to carbon atoms. The aromatic ring includes not only a monocyclic aromatic ring but also a condensed aromatic ring formed by combining and condensing monocyclic aromatic rings. The nitrogen-containing aromatic heterocyclic compound (C2) is preferably an imidazole compound such as 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-benzyl-2-phenylimidazole, and 2-phenylimidazole. and 1-benzyl-2-phenylimidazole are more preferred. As the nitrogen-containing aromatic heterocyclic compound (C2), those commercially available from Shikoku Kasei Co., Ltd. under the trade names of "Curesol 2PZ" and "Curesol 1B2PZ" can be used.

The nitrogen-containing aromatic heterocyclic compound (C2) has (1) a structure in which an aromatic ring contains nitrogen atoms in addition to carbon atoms. The nitrogen-containing aromatic heterocyclic compound (C2) (2) does not constitute a crosslinked structure of the cured product of the epoxy resin (A) (does not react with the multiple epoxy groups of the epoxy resin (A)). The nitrogen-containing aromatic heterocyclic compound (C2) may contain an amino group and an amide bond in the molecule as long as the above (1) and (2) are satisfied.

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 1.0 parts by mass with respect to 100 parts by mass of the epoxy resin (A). Part or more is more preferable. 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 2.0 parts by mass or less with respect to 100 parts by mass of the epoxy resin (A). is more preferred. When the content of the catalyst compound (C) is 0.1 parts by mass or more, the reaction heat between the epoxy resin and the reactive amine compound allows the polymerization reaction of the epoxy resin to proceed smoothly. When the content of the catalyst compound (C) is 10 parts by mass or less, the polymerization reaction of the epoxy resin proceeds moderately so as not to concentrate in a short period of time, and the curing reaction of the epoxy-based composition is dispersed, thereby reducing heat generation. can be made

The epoxy-based composition may contain additives within a range that does not impair the effects of the epoxy-based composition. Additives include, for example, thermoplastic resins, deodorants, silane coupling agents, adhesion improvers such as titanium coupling agents, antioxidants such as hydroquinones and hindered phenols, benzophenones, UV absorbers such as benzotriazoles, salicylates, and metal complex salts, metal soaps, inorganic and organic salts of heavy metals (such as zinc, tin, lead, and cadmium), stabilizers such as organic tin compounds, and phthalic acid. Esters, phosphate esters, fatty acid esters, castor oil, liquid paraffin, plasticizers such as alkyl polycyclic aromatic hydrocarbons, waxes such as paraffin wax, microcrystalline wax, polymerized wax, beeswax, whale wax, and low-molecular-weight polyolefins , benzyl alcohol, tar, non-reactive diluents such as picumen, calcium carbonate, kaolin, talc, mica, bentonite, clay, sericite, glass fiber, carbon fiber, aramid fiber, nylon fiber, acrylic fiber, glass powder, glass Fillers such as balloons, shirasu balloons, coal powder, acrylic resin powder, phenolic resin powder, metal powder, ceramic powder, zeolite, slate powder, carbon blanks, titanium oxide, red iron oxide, para red, Prussian blue and other pigments or dyes, Solvents such as ethyl acetate, toluene, alcohols, ethers, ketones, foaming agents, dehydrating agents such as monoisocyanate compounds, carbodiimide compounds, antistatic agents, antibacterial agents, antifungal agents, viscosity modifiers, fragrances, flame retardants , leveling agents, dispersants, thixotropic agents, conductivity imparting agents and the like.

The epoxy-based composition is used after being cured by mixing a main agent and a curing agent. The ambient temperature during curing of the epoxy composition is preferably 20 to 30°C, more preferably 22 to 28°C, and particularly preferably 23 to 26°C.

Epoxy-based compositions are excellent in casting and potting due to their excellent fluidity. The epoxy-based composition can be smoothly fed into the mold, and a cured product having a precise shape can be obtained. Furthermore, the epoxy-based composition cures in a relatively short curing time at an ambient temperature of about 20 to 30° C., and generates little heat during curing. Therefore, it is possible to mold a large-sized cast product with almost no deterioration and shrinkage of the epoxy resin. Moreover, the cured product obtained by curing the epoxy-based composition has excellent mechanical strength.

Therefore, according to the epoxy-based composition, it is possible to efficiently manufacture a large-sized molded article by mass casting and manufacture a large-sized hollow fiber membrane module.

INDUSTRIAL APPLICABILITY The epoxy-based composition of the present invention has excellent fluidity, reduces heat generation during curing, and can provide a cured product having excellent mechanical strength.

EXAMPLES The aspects of the present invention will be described in more detail below with reference to Examples, but the present invention is not limited to these Examples.

[Epoxy resin (A)]
・ Epoxy resin 1 (bisphenol A type epoxy resin, having an aromatic ring and an epoxy group, containing no nitrogen atoms in the molecule, trade name “jER828” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 189, 23 ° C. and 0.10 MPa conditions Bottom: liquid, viscosity at 25 ° C: 13500 mPa s)
・ Epoxy resin 2 (bisphenol F type epoxy resin, having an aromatic ring and an epoxy group, containing no nitrogen atoms in the molecule, trade name “jER806” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 165, 23 ° C. and 0.10 MPa conditions Bottom: liquid, viscosity at 25 ° C: 2000 mPa s)

[Reactive amine compound (B)]
[Polyamine (B1)]
・Polyamine 1 (reaction adduct of metaxylylenediamine and styrene, having multiple amino groups (—NH ₂ ), not having an amide bond, not being a tertiary amine, constituting a crosslinked structure of a cured epoxy resin , trade name "Gascamin 240" manufactured by Mitsubishi Gas Chemical Co., Ltd., molecular weight: 400, active hydrogen equivalent [eq/g]: 9.7 × 10 ^-3 , amine value: 403, viscosity at 25 ° C.: 66 mPa s)
・Polyamine 2 (a mixture of 2,2,4-trimethylhexamethylenediamine and 2,4,4-trimethylhexamethylenediamine, a tertiary amine having multiple amino groups (—NH ₂ ) and no amide bond) Constituting the crosslinked structure of the cured epoxy resin, trade name "Vestamin TMD" manufactured by Evonik, molecular weight: 158, active hydrogen equivalent [eq/g]: 25 × 10 ^-3 , amine value: 710, 25°C Viscosity at: 7 mPa s)
・Polyamine 3 (polyether diamine having a polytetramethylene ether glycol structure and a polypropylene glycol structure, a cured product of an epoxy resin that has multiple amino groups (—NH ₂ ), does not have an amide bond, and is not a tertiary amine having no amide bond, manufactured by Huntsman, trade name “Elastamine THF-100”, active hydrogen equivalent [eq/g]: 3.8×10 ⁻³ , amine value: 107 to 114, 25 Viscosity at ℃: 300 mPa s)
-Polyamine 4 (4,4'-methylenebis(cyclohexylamine), having a plurality of amino groups ( _-NH2 ), having no amide bond, not being a tertiary amine, constituting a crosslinked structure of a cured epoxy resin , trade name “Vestamin PACM” manufactured by Evonik, active hydrogen equivalent [eq/g]: 19×10 ⁻³ , amine value: 535, viscosity at 40° C.: 30 mPa s)

[Polyamidoamine (B2)]
Polyamidoamine 1 (trade name “Vegichem Green G235” manufactured by Tsuno Foods Industry Co., Ltd., having multiple amino groups (—NH ₂ ), having an amide bond, constituting a crosslinked structure of a cured epoxy resin, active Hydrogen equivalent [eq/g]: 10.5 × 10 ^-3 , amine value: 350 to 400, viscosity at 25°C: 250 mPa s)
・Polyamidoamine 2 (trade name “Tomide TXE-524” manufactured by T&K TOKA, a dimer of N-(2-aminoethyl)ethane-1,2-diamine and fatty acid (unsaturated fatty acid, carbon number: 18) Polymer with tall oil fatty acid, having a plurality of amino groups (—NH ₂ ), having an amide bond, constituting a crosslinked structure of a cured epoxy resin, active hydrogen equivalent [eq/g]: 7.7× 10 ⁻³ , amine value: 270, viscosity at 25° C.: 130 mPa·s)

[Catalyst compound (C)]
[Tertiary amine (C1)]
・ Tertiary amine 1 (2,4,6-tris (dimethylaminomethyl) phenol, product name “TMA EH-30” manufactured by Tsukuno Foods Co., Ltd., epoxy resin cured product without nitrogen-containing aromatic heterocycle does not form a crosslinked structure)
・ Tertiary amine 2 (1,8-diazabicyclo[5.4.0]undecene-7, product name “DBU” manufactured by San-Apro Co., Ltd., a crosslinked structure of a cured epoxy resin that does not have a nitrogen-containing aromatic heterocycle do not configure)
・Tertiary amine 3 (1,4-dimethylpiperazine, does not have a nitrogen-containing aromatic heterocycle, does not constitute a crosslinked structure of the cured epoxy resin)
・ Tertiary amine 4 [1-(2-dimethylaminoethyl)-4-methylpiperazine, trade name “TOYOCAT NP” manufactured by Tosoh Corporation, does not have a nitrogen-containing aromatic heterocycle, a crosslinked structure of a cured epoxy resin do not configure)

[Nitrogen-containing aromatic heterocyclic compound (C2)]
Nitrogen-containing aromatic heterocyclic compound 1 (2-phenylimidazole, manufactured by Shikoku Kasei Co., Ltd., trade name “Curesol 2PZ”, having a nitrogen-containing aromatic heterocycle, does not form a crosslinked structure of the cured epoxy resin)
・ Nitrogen-containing aromatic heterocyclic compound 2 (1-cyanoethyl-2-ethyl-4-methylimidazole, trade name “Curesol 2E4MZ-CN” manufactured by Shikoku Kasei Co., Ltd., epoxy resin having a nitrogen-containing aromatic heterocycle does not constitute a crosslinked structure of the cured product)
・ Nitrogen-containing aromatic heterocyclic compound 3 (2-ethyl-4-methylimidazole, product name “Curesol 2E4MZ” manufactured by Shikoku Kasei Co., Ltd., having a nitrogen-containing aromatic heterocycle, constituting a crosslinked structure of the cured epoxy resin do not)

[Reaction accelerator (D)]
・ Reaction accelerator (triethanolamine, trade name “TEA99” manufactured by Japan Chemtech)

(Examples 1-8 , Reference Examples 1-16 , Comparative Examples 1-11)
An epoxy resin having the amount shown in Tables 1 to 3 was used as the main agent. Predetermined amounts of reactive amine compound (B), reaction accelerator (D), and catalyst compound (C) shown in Tables 1 to 3 were supplied to an impeller-type mixing stirrer and uniformly mixed to prepare a curing agent. When the catalyst compound (C) is solid when mixed, the reactive amine compound (B) is heated to 80 to 110° C., and then the catalyst compound (C) is supplied to the reactive amine compound (B). By dissolving, the reactive amine compound (B), the reaction accelerator (D) and the catalyst compound (C) were uniformly mixed. A two-component epoxy composition containing the main agent and curing agent produced as described above was produced.

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 shown in Table 1 to 3 "Equivalent value" column.

Regarding the reactive amine compound (B), the reaction rate constant k at 100 ° C. when reacted in a stoichiometrically equivalent manner with the epoxy group of the epoxy resin was measured in the manner described above. k” column. When the reaction rate constant k of the reactive amine compound (B) is adjusted with the reaction accelerator (D), the reaction rate constant of the reactive amine compound (B) after adjustment with the reaction accelerator (D) k was described in the column of "reaction rate constant k". 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 the "equivalent value ” column. From Table 4, 54.5 parts by mass and 21 parts by mass of polyamines 1 to 3 and polyamidoamine 1 when reacting stoichiometrically equivalently with the epoxy group of 100 parts by mass of the epoxy resin used in the example, respectively. , 137 parts by weight and 50.0 parts by weight. Further, in Table 4, for example, when 1 part by mass of the reaction accelerator (D) is used, the amount of the reaction accelerator (D) used per unit mass (1 part by mass) of the reactive amine compound (B) (Mass) [reaction accelerator (D)/reactive amine compound (B)] is 0.018 parts by mass. The amount (mass) of reaction accelerator (D) used per unit mass of reactive amine compound (B) [reaction accelerator (D)/reactive amine compound (B)] is 0.018 part by mass. In Example 1 , the reaction rate constant k of polyamine 1 at 100° C. when reacted in stoichiometric equivalence with the epoxy groups of the epoxy resin (A) and adjusted with the reaction accelerator (D) is 0.15 min ⁻¹ .

Regarding the catalyst compound (C), in the polymerization reaction when 5 mol% is added to the epoxy resin (A), the cumulative heat value when differential scanning calorimetry is measured from 0 ° C. to 200 ° C. at a temperature increase rate of 5 ° C./min, The maximum heat flow and the temperature at which the maximum heat flow was obtained were measured in the manner described above and listed in the columns of "accumulated heat quantity", "maximum heat flow" and "maximum heat flow temperature" in Table 5, respectively.

In the examples and comparative examples, the reaction rate constant k of the reactive amine compound (B) at 100 ° C. when reacted stoichiometrically equivalent with the epoxy group of the epoxy resin (A), or the epoxy resin ( Table 1 shows the reaction rate constant k of the reactive amine compound (B) at 100° C. when reacted with the epoxy groups of A) at stoichiometric equivalence and after adjustment with the reaction accelerator (D). It is described in the column of "reaction rate constant k" of ~3.

The resulting epoxy composition was measured for heat generation during curing, curing time, and hardness of the cured product in the following manner, and the results are shown in Tables 1-3.

(Heat generation during curing and curing time)
After uniformly mixing the main agent and curing agent of the epoxy-based composition at an initial temperature of 23°C, the epoxy-based composition was placed in a steel can having a diameter of 140 mm and a height of 160 mm in an atmosphere of 23°C, as shown in Tables 1 to 3. Only the casting amount was poured. A thermocouple (K φ0.32, compliant with JIS C1602) is placed in the center of the poured epoxy composition, and a data logger (trade name “GL220” manufactured by Graphtec) is used to monitor the curing time of the epoxy composition. The maximum temperature (exotherm during curing) was measured. The time required for the epoxy composition to reach the maximum temperature after mixing the main agent of the epoxy composition and the curing agent was measured, and this time was defined as the curing time.

(Hardness of cured product)
The epoxy composition is cured in the same manner as measuring heat generation during curing, and the cured product after 24 hours from the time when the maximum temperature during curing of the epoxy composition is reached is measured in accordance with JIS K6253. The hardness was measured using a type D durometer durometer in an atmosphere of 25° C. by the method described above. Note that the measurement time was 30 seconds. In addition, when the epoxy-based composition was not cured, it was described as "uncured".

INDUSTRIAL APPLICABILITY The epoxy-based composition of the present invention has excellent fluidity, reduces heat generation during curing, and can provide a cured product having excellent mechanical strength. INDUSTRIAL APPLICABILITY The epoxy-based composition of the present invention can be molded into large-sized castings having excellent mechanical strength. A hollow fiber membrane module can be produced from the epoxy-based composition of the present invention without damaging the hollow fiber membranes.

(Cross reference to related applications)
This application claims priority based on Japanese Patent Application No. 2021-31505 filed on March 1, 2021, the disclosure of which is incorporated herein by reference in its entirety. .

Claims (2)

100 parts by weight of an epoxy resin (A) having an aromatic ring and an epoxy group in the molecule;
0.1 to 10 parts by mass of a reaction accelerator (D) containing a polyol, carboxylic acid or sulfonic acid ,
A polyamine (B1) having a reaction rate constant k at 100° C. of 0.10 to 0.37 min ⁻¹ when reacted with the epoxy group of the epoxy resin (A) in the presence of the reaction accelerator (D) and / or a reactive amine compound (B) containing polyamidoamine (B2),
In the reaction heat when 5 mol% is added to the epoxy resin (A), the accumulated heat amount from 0 to 200 ° C. measured 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, a catalyst compound (C) having a maximum heat flow temperature of 80 to 130° C., and containing a tertiary amine (C1) and/or a nitrogen-containing aromatic heterocyclic compound (C2) 0.1 to 10 parts by weight,
The ratio of the amount of active hydrogen in the reactive amine compound (B) to the amount of epoxy in the epoxy resin (A) [the amount of active hydrogen in the reactive amine compound (B)/the amount of epoxy in the epoxy resin (A)] is 0.5. 3 to 0.8 epoxy composition. An epoxy-based composition for a hollow fiber membrane module, comprising the epoxy-based composition according to claim 1 .