JP2012082251A - Thermosetting resin composition, and cured resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermosetting resin composition that strikes a balance between storage stability and curing speed thereof, and can be homogeneously cured; and to provide a cured resin.SOLUTION: The thermosetting resin composition contains a liquid polymer having an acid anhydride group, and a latent amine curing agent, and is cured by heating. The thermosetting resin composition contains 0.1 to 50 pts.mass of the latent amine curing agent based on 100 pts.mass of the liquid polymer. The latent amine curing agent is used which has a melting point of ≥80°C, and has two or more primary or secondary amino groups in one molecule.

Description

  The present invention relates to a thermosetting resin composition and a cured resin obtained by heat-curing the thermosetting resin composition.

  In the processing and molding of materials, bonding, coating, and shielding processes are important, and various materials are used. In particular, from the viewpoint of workability, materials that can be added or applied at room temperature and then harden by some action have been used for a long time.

  In general, adhesives and paints use a method in which pigments and resins are dissolved in organic solvents and water, applied to the target material in a liquid state, and a cured product is obtained by volatilizing the organic solvent and water. There are many. However, when an organic solvent is used, there are problems such as environmental effects and flammability due to volatile gas, and water has a problem that it takes time to obtain a cured product because of low volatility. Therefore, the following methods (1) to (4) are mainly used as a so-called solventless curable resin composition in which a liquid substance is added and cured after application without using a solvent.

(1) A method of curing by mixing two liquid compounds having low volatility that react with each other, immediately adding and applying them, and advancing the reaction.
(2) A method in which a low-volatile liquid compound is added and applied, and then cured by reaction with moisture in the air (see, for example, Patent Document 1).
(3) A method in which a low volatile liquid compound is added and applied and then heated to initiate a curing reaction and cure.
(4) A method in which a low-volatile liquid compound is added and applied and then irradiated with light or an electron beam to cause a reaction and cure.

  Epoxy group reaction is used in the curing reactions (1) and (3). The above (1) is a system in which a curing agent such as polyamine or polyol is mixed with an epoxy compound such as glycidyl bisphenol A. The above (3) is prepared by mixing a curing agent of (1) in a thermally decomposable microcapsule, a curing agent that generates a Lewis acid that is a reaction catalyst by heat, and the like in an epoxy compound. The method of curing is taken. The reason why epoxy compounds are widely used as described above is that the cured epoxy resin has high mechanical strength and has excellent features in many respects such as electrical characteristics, heat resistance, water resistance, and chemical resistance. It is because it has.

  However, when the workability of the resin is taken into consideration, there is a problem that the two-component system (1) must be used immediately after mixing. Further, those using the thermosetting epoxy curing agent (3) have problems that curing proceeds at room temperature and inferior in storage stability.

  In addition, the alkoxysilane reaction is used for the curing reaction (2) above, and the ester portion is hydrolyzed by water to form polysiloxane. This method has the advantage that it can be cured at room temperature without using a device such as heating or light irradiation in the air containing moisture. However, the curing reaction is very slow and it takes several hours to several tens of hours to cure. Further, the resin before curing needs to be sealed and stored so as not to come into contact with moisture, and there is a problem that it is difficult to store after opening.

  For the curing reaction (4), a radical polymerization reaction of a compound having a double bond in the molecule such as an acrylate derivative is used. That is, it is a system in which a compound that generates radicals by light or electron beam is mixed with an acrylate derivative or the like, and a curing reaction is caused by light or electron beam irradiation. If this method is used, since a radical having high activity is used, curing in a short time is possible. However, the radical species has a high activity, but has a very short life span and is easily deactivated by oxygen or the like. Therefore, there is a problem that the radical species cannot be cured at a place where light and electron beam irradiation cannot reach. . In addition, this method has a problem that the curing reaction stops immediately when the irradiation of the electron beam or the like is stopped.

JP 2006-282777 A

  The present invention is intended to solve the above-mentioned problems, and provides a thermosetting resin composition having excellent balance between storage stability and curing speed of the composition, and capable of uniform curing, and a cured resin product. The task is to do.

  In order to solve the above problems, the thermosetting resin composition of the present invention is a thermosetting resin composition containing a liquid polymer having an acid anhydride group and a latent amine curing agent and cured by heating, The latent amine curing agent is contained in an amount of 0.1 to 50 parts by mass with respect to 100 parts by mass of the liquid polymer, and the latent amine curing agent has a melting point of 80 ° C. or more and 2 molecules per molecule. The gist is to have the above primary or secondary amino group.

  The said thermosetting resin composition WHEREIN: It is preferable that content of the acid anhydride group in the said liquid polymer is 0.01-10 mass%.

  In the thermosetting resin composition, the liquid polymer preferably has a main chain of a diene liquid rubber, and the diene liquid rubber is a polybutadiene, polybutene, polychloroprene, polyisoprene, butadiene-acrylonitrile copolymer. It is preferably any one selected from the group consisting of a polymer and poly 1,3-pentadiene, or two or more.

  The cured resin of the present invention is that the above-mentioned thermosetting resin composition is formed into a predetermined shape and heat-cured, or is coated on the surface of another article and heat-cured. It is a summary.

  The thermosetting resin composition of the present invention contains 0.1 to 50 parts by mass of the latent amine curing agent with respect to 100 parts by mass of the liquid polymer, and the latent amine curing agent has a melting point of 80. The latent amine curing agent is in a solid state when stored at room temperature because it has a temperature of at least ° C and has two or more primary or secondary amino groups in one molecule. The composition does not react with the liquid polymer and has excellent storage stability of the composition. In addition, the latent amine curing agent has no risk of reacting with moisture in the air, and the composition is stable with respect to humidity and moisture in the air.

  Furthermore, in the thermosetting resin composition of the present invention, when heated, the latent amine cured product is activated and can react with the acid anhydride group to cure the liquid polymer. The thermosetting resin composition of the present invention has an excellent balance between storage stability and curing speed. Furthermore, the latent amine curing agent activated by heating can cure the composition uniformly.

  Hereinafter, embodiments of the present invention will be described in detail. The thermosetting resin composition of the present invention is a curable resin composition containing a liquid polymer having an acid anhydride group and a latent amine curing agent, and the liquid polymer is cured and solidified by heating. It will change to. The heating temperature for curing the resin composition is preferably 60 ° C. or higher. Moreover, it is preferable that the thermosetting resin composition of this invention is a solventless type composition which does not contain low volatile components, such as a solvent, substantially. Hereinafter, the liquid polymer and the latent amine curing agent used in the composition of the present invention will be described in detail.

  The liquid polymer having an acid anhydride group used in the present invention is a liquid polymer in which a plurality of acid anhydride groups are introduced into the main chain of a polymer or oligomer and can be cured with an amine curing agent. It is. That is, the liquid polymer having an acid anhydride group is a so-called acid anhydride-modified liquid polymer in which an acid anhydride group is introduced into the liquid polymer. In the present invention, “liquid” of the liquid polymer means that the liquid polymer is not solidified at room temperature and has fluidity. The viscosity of the liquid polymer is preferably in the range of 0.1 mPa · s to 1000 Pa · s from the viewpoint of handleability.

  The liquid polymer preferably has a main chain of diene liquid rubber. When a liquid polymer whose main chain is a diene liquid rubber is used, the cured product exhibits rubber elasticity, and thus has high flexibility, and an acid anhydride group provides high adhesion to various inorganic and organic materials. Further, the diene liquid rubber has the following advantages compared to the epoxy resin. For example, an epoxy resin has insufficient flexibility, so that when it is used as an adhesive, a coating agent, or the like, there is a problem that the peel strength is very low and cracks, peel, and the like are likely to occur. Further, when an epoxy resin is used as a molding material, there is a problem that the molded product is not flexible and is brittle and easily broken by various impacts. On the other hand, the diene-based liquid rubber has sufficient flexibility, and when the thermosetting resin composition is used for an adhesive, a coating agent or the like, the peel strength is high. Cracks and peeling are unlikely to occur. In addition, the thermosetting resin composition using a diene liquid rubber is characterized by excellent flexibility and high impact strength.

  Examples of the diene-based liquid rubber having a main chain of a liquid polymer having an acid anhydride group include polybutadiene, polybutene, polychloroprene, polyisoprene, a butadiene-acrylonitrile copolymer, and poly1,3-pentadiene. The diene liquid rubber may be used alone or in combination of two or more by copolymerization or the like.

  In a liquid polymer having an acid anhydride group, the acid anhydride group refers to a substituent having a structure (R—CO—O—CO—R) obtained by dehydration condensation of two molecules of carboxylic acid. As such a liquid polymer having an acid anhydride group, a carboxylic acid anhydride (for example, phthalic anhydride, maleic anhydride, etc.) is directly or via an organic group in the main chain and / or side chain of the polymer. Can be formed by introducing them. The liquid polymer having an acid anhydride group is preferably a liquid polymer having a maleic anhydride group because of high reactivity with the latent amine curing agent described later.

  In the present invention, the acid anhydride group is formed by introducing phthalic anhydride or maleic anhydride directly or through an organic group into the main chain and / or side chain of the liquid polymer. The introduction method is not particularly limited, and can be introduced by an ene reaction between unsaturated double bonds.

  The number average molecular weight of the liquid polymer used in the present invention is preferably 500 to 100,000, more preferably 600 to 70,000. If the number average molecular weight of the liquid polymer is in the above range, the viscosity before curing of the composition of the present invention containing the liquid polymer is not so high, so that the workability is not adversely affected, and the adherend or the like. This is because wettability can be ensured and good adhesiveness is exhibited.

  When the acid anhydride group introduced into the liquid polymer is mixed with an active diamine, the liquid polymer is cured by causing a crosslinking reaction as shown in the following [Chemical Formula 1] even at room temperature.

  The liquid polymer having an acid anhydride group preferably has an acid anhydride group introduction rate of 0.01 to 10% by mass, more preferably 0.02 to 5% by mass. When the introduction ratio of the acid anhydride group exceeds 10% by mass, the viscosity before curing is increased, the polarity of the cured product is increased, and the water resistance may be deteriorated. On the contrary, when the introduction ratio of the acid anhydride group is less than 0.01% by mass, the crosslinking becomes insufficient and a cured product may not be obtained. The introduction rate of the acid anhydride group is a ratio of the mass of the acid anhydride group to the total amount of the mass of the liquid polymer and the acid anhydride group, and is represented by mass (%).

  In the present invention, a commercially available acid anhydride-modified liquid polymer may be used as the liquid polymer having an acid anhydride group. Specific examples of commercially available acid anhydride-modified liquid polymers include polybutadiene derivatives, manufactured by Degussa Co., Ltd., trade name “PolyvestOC800”, Nippon Cima Co., Ltd., trade name “Cornova MAH-1”, and polyisoprene derivatives. If there is a product name "Polyisoprene-graft-maleic anhydride" manufactured by Aldrich, Kuraray Co., Ltd. Can be mentioned.

  The latent amine curing agent used in the present invention is a liquid polymer thermosetting agent having the above acid anhydride group, having two or more primary or secondary amino groups in one molecule, melting point Is 80 ° C. or higher. The latent amine curing agent preferably has a melting point of 100 to 200 ° C. When the melting point of the latent amine curing agent is 100 ° C. or higher, the storage stability of the thermosetting resin composition is further improved, and it is possible to more reliably prevent thickening or curing during storage. . In addition, since the melting point of the latent amine curing agent is 300 ° C. or higher, there is a possibility that the reaction of the acid anhydride group does not occur. More preferably, it is less than 200 degreeC. When the melting point of the latent amine curing agent is in the range of 100 to 200 ° C., the balance between storage stability and curability is particularly good.

  In addition, the latent amine curing agent can have an appropriate melting point depending on the type of liquid polymer such as liquid rubber, the use environment of the thermosetting resin composition, the curing temperature, and the like.

  The latent amine curing agent is specifically an aromatic amine such as 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, 4,4′-diaminodiphenylether, 3,3′-diaminodiphenylether. 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, dicyandiamide, hydrazide compounds such as carbohydrazide, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, adipic acid dihydrazide, azelaic acid dihydrazide, sebacic acid dihydrazide , Dodecane-2-acid dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide, diglycolic acid dihydrazide, tartaric acid dihydrazide, malic acid dihydrazide, isophthalic acid dihydrazide, terephthalic acid dihydrate Dorazide, dimer acid dihydrazide, glutaric acid dihydrazide, pimelic acid dihydrazide, 4,4'-bisbenzenedihydrazide, 1,4-cyclohexanedihydrazide, iminodiacetic acid dihydrazide, N, N'-hexamethylenebissemicarbazide, itaconic acid dihydrazide, 2, 4-dihydrazino-6-methylamino-sym-triazine, ethylenediaminetetraacetic acid tetrahydrazide, citric acid trihydrazide, 1,2,3-benzenetrihydrazide, 1,4,5,8-naphthoic acid tetrahydrazide, nitriloacetic acid tri Examples thereof include hydrazide, cyclohexanetricarboxylic acid trihydrazide, and pyromellitic acid tetrahydrazide.

  Other than the above compounds, other than the above compounds may be used as curing agents as long as they are solid at room temperature and have a melting point of 80 ° C. or higher and are amine-based compounds used as amine-generating epoxy resin curing agents such as a two-component curing type. I can do things.

  The compounds listed above are solid at room temperature and do not exhibit basicity due to amines, but have the property of exhibiting basicity rapidly from a temperature lower than the melting point when heated. If such a reactive liquid polymer is present as a matrix when basicity is exerted, a crosslinking reaction is immediately caused.

  Also, amine compounds that have a low melting point of less than 80 ° C. and are liquid at room temperature can be reacted with acid anhydrides or acid halides or with carboxylic acid derivatives in the presence of a dehydration condensing agent to increase the melting point. And may be a latent amine curing agent.

  The latent amine curing agent may be used alone or in combination of two or more.

  Moreover, in a thermosetting resin composition, content of the said latent amine hardening | curing agent is the range of 0.1-50 mass parts with respect to 100 mass parts of said liquid polymers, Preferably 0.2-40 Within the range of parts by mass. If the content of the latent amine curing agent is within the above range, the viscosity of the liquid polymer can be kept in a usable range.

  The latent amine curing agent is in a state of being uniformly dispersed in the composition by being finely dispersed or emulsified and dispersed in the liquid polymer.

  The thermosetting resin composition of the present invention can contain various additives as necessary in addition to the above-mentioned various components within a range not impairing the object of the present invention. Examples of additives include fillers, plasticizers, softeners, thixotropic agents, pigments, dyes, anti-aging agents, antioxidants, antistatic agents, flame retardants, adhesion promoters, dispersants, solvents, Antibacterial and antifungal agents are mentioned.

  As the filler, those having various shapes can be used. For example, calcium carbonate, fumed silica, calcined silica, precipitated silica, ground silica, fused silica, diatomaceous earth, iron oxide, zinc oxide, titanium oxide, barium oxide, magnesium oxide, magnesium carbonate, zinc carbonate, wax stone clay, Examples thereof include organic or inorganic fillers such as kaolin clay, calcined clay, and carbon black, these fatty acids, resin acids, fatty acid ester treated products, and fatty acid ester urethane compound treated products.

  Examples of the plasticizer or softener include diisononyl phthalate, dioctyl phthalate, dibutyl phthalate, dioctyl adipate, isodecyl succinate, diethylene glycol dipenzoate, pentaerythritol ester, butyl oleate, methyl acetylricinoleate, Examples include petroleum softeners such as tricresyl phosphate, trioctyl phosphate, propylene glycol adipate polyester, butylene glycol polyester adipate, paraffinic oil, naphthenic oil, and aromatic oil.

  Examples of the thixotropic property-imparting agent include dry silica, white carbon, hydrogenated castor oil, calcium carbonate, and fluororesin.

  Examples of the pigment include inorganic pigments such as titanium dioxide, zinc oxide, ultramarine, bengara, lithopone, lead, cadmium, iron, cobalt, aluminum, hydrochloride, sulfate, and organic pigments such as azo pigments and copper phthalocyanine pigments. Can be mentioned.

  Examples of the anti-aging agent include hindered phenol compounds and hindered amine compounds.

  Examples of the antioxidant include butylhydroxytoluene and butylhydroxyanisole.

  Examples of the antistatic agent include hydrophilic compounds such as quaternary ammonium salts, polyglycols, and ethylene oxide derivatives.

Examples of the flame retardant include chloroalkyl phosphate, dimethyl / methylphosphonate, bromine / phosphorus compound, ammonium polyphosphate, neopentyl bromide
Examples include polyethers and brominated polyethers.

  Examples of the adhesion-imparting agent include terpene resins, phenol resins, terpene-phenol resins, rosin resins, xylene resins, and epoxy resins.

  The above additives can be used in combination as appropriate.

  Although the manufacturing method of the thermosetting resin composition of the present invention containing the above components is not particularly limited, each of the above components is used under a reduced pressure or an inert gas atmosphere such as nitrogen using a stirring device such as a mixing mixer. A method of sufficiently kneading and uniformly dispersing is preferable.

  The thermosetting resin composition of the present invention can be suitably used for molded articles, adhesives, paints and the like. The resin cured product of the present invention is a heat-cured molded product obtained by molding the thermosetting resin composition into a predetermined shape. Moreover, the resin cured product of the present invention is a coating film obtained by coating the thermosetting resin composition on the surface of another article and heat curing.

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples of the present invention. However, the present invention is not limited to these examples.

[Examples 1 to 10, Comparative Examples 1 to 9]
In each component composition (parts by mass) shown in Table 1, mixing and dispersion were performed using a stirrer to obtain curable resin compositions of Examples 1 to 10 of the present invention. As a comparative example, each component composition (part by mass) shown in Table 2 was mixed and dispersed using a stirrer to obtain curable resin compositions of Comparative Examples 1 to 9. In Comparative Examples 1 and 2, the amount of the latent curing agent added is outside the scope of the present invention. In Comparative Example 3, polyisoprene having no acid anhydride group is used as the liquid polymer. Comparative Example 4 uses terminal hydroxy polybutadiene as the liquid polymer. In Comparative Example 5, a moisture-curable silicone resin is used as the liquid polymer. The comparative example 6 uses glycidyl bisphenol A of an epoxy reaction system as a liquid polymer. In Comparative Example 7, a diamine having a melting point of less than 80 ° C. is used as the latent amine curing agent. In Comparative Example 9, 4-phenoxyaniline having only one amino group in one molecule was used as a latent amine curing agent.

  The obtained composition was evaluated for storage stability, curability and flexibility. The evaluation results are shown in Tables 1 and 2. Details, evaluation methods, and evaluations of the components shown in Tables 1 and 2 are as follows.

Acid anhydride-modified polybutadiene: manufactured by Nippon Cima, trade name “Cornova MAH-1”
Acid anhydride-modified polyisoprene: “Polyisoprene-graft-maleic anhydride” manufactured by Aldrich
Polyisoprene: “Polyisoprene, cis” manufactured by Aldrich
Terminal hydroxy polybutadiene: “Polybutadiene, hydroxylated” manufactured by Aldrich
・ Silicone cured resin: “SE9185” manufactured by Toray Dow Corning
・ Glycidyl bisphenol A: “2,2-Bis (4-glycidyloxyphenyl) propane” manufactured by Tokyo Chemical Industry Co., Ltd.
・ 4,4′-diaminodiphenyl ether: “4,4′-Diaminodiphenyl Ether” (mp 192 ° C.) manufactured by Wako Pure Chemical Industries, Ltd.
・ 4,4′-Diaminodiphenylmethane: “4,4′-Diaminodiphenylmethane” (mp 91 ° C.), manufactured by Wako Pure Chemical Industries, Ltd.
Adipic acid dihydrazide: “Adipic acid dihydrazide” (mp 182 ° C.) manufactured by Tokyo Chemical Industry Co., Ltd.
Citric acid trihydrazide: A compound synthesized by the following method was used.
1,10-diaminodecane: 1,10-Diaminodecane (mp 61 ° C.)
Hexamethylenediamine: “Hexamethylenediamine” manufactured by Wako Pure Chemical Industries, Ltd. (mp 42 ° C.)
4-phenoxyaniline: “4-phenoxyaniline” (mp 85 ° C.) manufactured by Tokyo Chemical Industry Co., Ltd.

<Synthesis of citric acid trihydrazide>
200 mL of ethanol was put into a 500 mL three-necked flask equipped with a cooling reflux tube and a thermometer, and 10 g (43 mmol) of trimethyl citrate and 10.7 g (171 mmol) of hydrazine hydrate (51% in H ₂ O) were added thereto. Stir with a stir bar. Heat to reflux temperature with stirring and stir overnight with continued reflux. Thereafter, the mixture is allowed to cool to room temperature, and the precipitated solid is collected by a suction filter. The filtered product was vacuum-dried overnight to obtain 8.5 g of the desired product as a white powder. (Yield 85%)

<Storage stability>
Each of the compositions shown in Table 1 or Table 2 was put in a sample bottle, left in a constant temperature bath at 40 ° C. for 7 days, and the storage stability of the curable resin composition was evaluated by visually checking the change in appearance. As is clear from the results in Table 1, the curable resin compositions of Examples 1 to 9 did not change at all at 40 ° C. for 7 days, and their storage stability was excellent. It turns out that the composition of an Example becomes easy to manage temperature and humidity when it is used for molding and coating applications. On the other hand, as shown in Table 2 as a comparative example, when a silicone cured resin or glycidyl bisphenol A is used as the liquid polymer (Comparative Examples 5 and 6), the latent amine curing agent has a melting point of less than 80 ° C. , 10-diaminodecane and hexamethylene diamine, it can be seen that the curable resin composition (Comparative Examples 7 and 8) is not stable because it is cured and browned under the storage conditions. Further, as shown in Comparative Example 1, when the amount of the latent curing agent added is excessive, it is partially solidified and the storage stability is poor.

<Curing property>
The composition in Table 1 or Table 2 is poured into a mold having a length of 50 mm, a width of 50 mm, and a thickness of 10 mm, and heated in an oven at 120 ° C. for 10 minutes. Thereafter, after cooling to room temperature (25 ° C.), the sample was taken out of the mold and a sample piece for hardness measurement was produced. If it was not cured at this time and could not be removed from the mold, it was evaluated as defective (x). Hardness measurement was performed by pressing a JIS K 6253 type A hardness tester against a sample piece for hardness measurement on a horizontal metal plate at a speed of 1 mm / min until a load of 10 N was applied, and when the load reached 10 N. I read the scale of the hardness tester. Evaluation could be taken out of the mold, but those with a measured value of 2 or less had insufficient curability (Δ), and those with a measured value over 2 had good curability and had a measured value (hardness Value).

  As shown in Table 1, the curable resin compositions of Examples 1 to 10 were sufficiently cured by heating at 120 ° C. for 10 minutes, and a cured product having rubber elasticity was obtained from the hardness value. I understand that On the other hand, as shown in Table 2, Comparative Examples 3 and 4 using a liquid polymer having no acid anhydride modification did not cure even when heated, and one amine was used as a latent amine curing agent in one molecule. It can be seen that Comparative Example 9 using only one has no heat curing. Moreover, the comparative example 2 with a small addition amount of the latent amine curing agent also has insufficient curability.

<Flexibility>
The compositions shown in Tables 1 and 2 were JIS using a press molding machine (Toyo Seiki Seisakusho).
A No. 2 test piece based on K-7113 was produced. It should be noted that this test was not carried out for those with insufficient curing in the above-described curing experiment. Since the composition is liquid, the pressure of 1 MPa or less was initially applied at 40 ° C., the temperature was increased over about 15 minutes, and finally the pressure was maintained at 140 ° C. and 2 MPa for 3 minutes. . Then, it cooled for 10 minutes with the cooling press which applied the pressure of 2 MPa. Using the prepared test piece, elongation at break (%) was measured with a tensile tester (manufactured by Shimadzu Corporation). As a result, as shown in Table 1, it can be seen that the cured products of the curable resin compositions of Examples 1 to 10 exhibit break elongation of 100% or more and have sufficient flexibility for practical use. On the other hand, as shown in Table 2, it can be seen that the cured product using the epoxy liquid polymer of Comparative Example 6 has poor flexibility and is a brittle material.

Claims (5)

  A thermosetting resin composition containing a liquid polymer having an acid anhydride group and a latent amine curing agent and cured by heating, wherein the latent amine curing agent is added to 100 parts by mass of the liquid polymer. 0.1 to 50 parts by mass, and the latent amine curing agent has a melting point of 80 ° C. or higher and has two or more primary or secondary amino groups in one molecule. Resin composition.   The thermosetting resin composition according to claim 1, wherein the content of the acid anhydride group in the liquid polymer is 0.01 to 10% by mass.   The thermosetting resin composition according to claim 1, wherein the liquid polymer has a main chain of diene liquid rubber.   The diene liquid rubber is any one selected from the group consisting of polybutadiene, polybutene, polychloroprene, polyisoprene, butadiene-acrylonitrile copolymer, poly 1,3-pentadiene, or two or more. The thermosetting resin composition according to claim 3.   The thermosetting resin composition according to any one of claims 1 to 4, wherein the thermosetting resin composition is molded into a predetermined shape and heat-cured, or is coated on the surface of another article and heat-cured. A cured resin product characterized by being.