Resin, method for producing resin, and curable resin composition

Abstract

The present invention addresses the problem of providing: a cured resin that has a high biomass ratio and is formed even without contact with oxygen; and a curable resin composition that has a high biomass ratio and can be cured even without contact with oxygen. The means for solving the aforementioned problem is a resin comprising: a base reaction product of a polymer of an unsaturated fatty acid; an epoxy resin; and a linking portion that links the base reaction product and the epoxy resin.

Description

Resin, method for producing resin, and curable resin composition

[0001] The present invention relates to a resin, a method for producing a resin, and a curable resin composition, and more particularly to a resin using animal and vegetable oils and fats as raw materials, a method for producing a resin, and a curable resin composition.

[0002] Patent Document 1 describes a bioplastic that is a partial polymer of unsaturated fatty acids or their derivatives, with some of the carboxyl groups neutralized with a basic substance to convert them into carboxylate anion groups. When the unsaturated groups in the bioplastic come into contact with oxygen, an oxidative polymerization reaction occurs, causing the bioplastic to harden and become insolubilized.

[0003] Patent Document 2 describes a crosslinking method (abstract) in which a crosslinking reaction occurs between the vinyl ether group and the anionic group as a result of volatilization of the volatile base (B) from an aqueous resin composition containing a neutralized product of a vinyl-modified epoxy ester (A) having an anionic functional group with a volatile base (B) and a compound (C) having two or more vinyl ether groups. The vinyl-modified epoxy ester (A) having an anionic functional group is a resin obtained by reacting a fatty acid-modified epoxy ester (a) with a vinyl monomer (b). An example of the fatty acid-modified epoxy ester (a) is a resin obtained by addition condensation of soybean oil and a bisphenol A-type epoxy resin.

[0004] The aqueous resin composition of Patent Document 2 is said to have excellent storage stability, be crosslinkable at room temperature after application, and be capable of forming a cured coating film that is excellent in corrosion resistance, water resistance, solvent resistance, etc. on the substrate, and further be capable of imparting sufficient coating film hardness even immediately after application.

[0005] International Publication No. 2023 / 027057 Japanese Patent Application Laid-Open No. 2006-182976

[0006] The bioplastic of Patent Document 1 can be cured by an oxidative polymerization reaction that occurs when the unsaturated groups come into contact with oxygen. Therefore, when the bioplastic is used as a thick material such as a molded product, oxygen must be introduced into the interior to cause curing, which poses a problem of increased effort and cost required to make the interior porous.

[0007] Compounds in which a fatty acid and an epoxy are ester-bonded, including the aqueous resin composition of Patent Document 2, have been known for some time. However, although such ester compounds using fatty acid monomers can provide flexibility, when the ratio of fatty acid, i.e., the ratio of biomass, increases, the strength decreases significantly, making them unsuitable for practical use.

[0008] The present invention solves the above-mentioned problems by increasing strength by using oxidized polymers of fatty acids or oxidized polymers of oils as raw materials instead of fatty acid or oil monomers. Its objective is to provide a cured resin with a high biomass ratio that can be produced without contact with oxygen, and a curable resin composition with a high biomass ratio that can be cured without contact with oxygen. In particular, fatty acid polymers that have become so polymerized that they would normally be difficult to solidify and subject to esterification can be converted into aqueous FADP, which can be solubilized in a polar solvent and esterified with an epoxy. As a result, the biomass ratio can be further increased. The biomass ratio refers to the weight ratio of animal and plant-derived components in the resin components excluding fillers.

[0009] The present invention provides the following aspects: [1] A resin having a portion consisting of a base reaction product of a polymer of an unsaturated fatty acid, a portion consisting of an epoxy resin, and a linking portion connecting the two portions.

[0010] [2] The resin of [1], wherein the linking moiety contains an ester bond.

[0011] [3] The resin according to [1] or [2], wherein the epoxy resin comprises at least one selected from bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, glycidyl amine type epoxy resins, naphthalene type epoxy resins, brominated bisphenol A type epoxy resins, glycidyl ester type epoxy resins, alicyclic epoxy resins, and heterocyclic epoxy resins.

[0012] [4] The resin according to any one of [1] to [3], wherein the base reaction product of the polymer of the unsaturated fatty acid contains a polymer electrolyte in which a portion of the carboxyl groups has been neutralized with a basic substance and converted into a carboxylate anion group.

[0013] [5] The resin according to [4], wherein the base reaction product of the polymer of unsaturated fatty acid includes a product obtained by reacting the polymer electrolyte with an acid to liberate a carboxyl group from the carboxylate of the base reaction product.

[0014] [6] The resin according to any one of [1] to [5], wherein the base comprises a strong base.

[0015] [7] The resin according to any one of [1] to [5], wherein the base comprises an amine.

[0016] [8] The resin according to any one of [1] to [7], wherein the unsaturated fatty acid includes one having 16 to 22 carbon atoms.

[0017] [9] The resin according to any one of [1] to [8], wherein the unsaturated fatty acid comprises a drying oil or a semi-drying oil.

[0018]

[10] The resin according to any one of [1] to [9], wherein the unsaturated fatty acid comprises at least one selected from the group consisting of linoleic acid, linolenic acid, and linseed oil.

[0019]

[11] The resin according to any one of [1] to

[10] , having a biomass ratio of 50% or more.

[0020]

[12] A method for producing the resin according to any one of [1] to

[11] , comprising contacting a base reaction product of a polymer of an unsaturated fatty acid, an epoxy resin, and an amine-based epoxy resin curing agent.

[0021]

[13] The method for producing a resin according to

[12] , wherein the base and the amine-based epoxy resin curing agent contain a primary amine or a secondary amine.

[0022]

[14] A curable resin composition comprising a base reaction product of a polymer of an unsaturated fatty acid, an epoxy resin, and an amine-based epoxy resin curing agent.

[0023]

[15] The curable resin composition according to

[14] , wherein the base and the amine-based epoxy resin curing agent contain a primary amine or a secondary amine.

[0024]

[16] The curable resin composition according to

[14] or

[15] , wherein the epoxy resin comprises at least one selected from bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, glycidyl amine type epoxy resins, naphthalene type epoxy resins, brominated bisphenol A type epoxy resins, glycidyl ester type epoxy resins, alicyclic epoxy resins, and heterocyclic epoxy resins.

[0025]

[17] The curable resin composition of any one of

[14] to

[16] , wherein the amine-based epoxy resin curing agent comprises at least one selected from the group consisting of ethylenediamine, trimethylhexamethylenediamine, diethylenetriamine, 2-hydroxyethyldiethylenetriamine, dipropylenetriamine, triethylenetetraamine, tetraethylenepentamine, dipropylenediamine, diethylaminopropylamine, dimethylaminopropylamine, m-xylylenediamine, N-aminoethylpiperazine, methanediamine, isophoronediamine, and cyclohexylpropylenediamine.

[0026]

[18] The curable resin composition according to any one of

[14] to

[17] , wherein the base reaction product of the polymer of the unsaturated fatty acid contains a polymer electrolyte in which a part of the carboxyl groups has been neutralized with a basic substance and converted into a carboxylate anion group.

[0027]

[19] The curable resin composition according to any one of

[14] to

[18] , wherein the base reaction product of the polymer of the unsaturated fatty acid comprises a product obtained by reacting the polymer electrolyte with an acid to liberate a carboxyl group from a carboxylate of the base reaction product.

[0028]

[20] The curable resin composition according to any one of

[14] to

[19] , wherein the base comprises a strong base.

[0029]

[21] The curable resin composition according to any one of

[14] to

[20] , wherein the unsaturated fatty acid includes one having 16 to 22 carbon atoms.

[0030]

[22] The curable resin composition according to any one of

[14] to

[21] , wherein the unsaturated fatty acid comprises a drying oil or a semi-drying oil.

[0031]

[23] The curable resin composition according to any one of

[14] to

[22] , wherein the unsaturated fatty acid comprises at least one selected from the group consisting of linoleic acid, linolenic acid, and linseed oil.

[0032]

[24] The curable resin composition according to any one of

[14] to

[23] , having a biomass ratio of 50% or more.

[0033] According to the present invention, there are provided a cured resin having a high biomass ratio that can be produced without contact with oxygen, and a curable resin composition having a high biomass ratio that can be cured without contact with oxygen. The cured resin and curable resin composition of the present invention have a high biomass ratio of 50 mass% or more, and therefore have a reduced environmental impact.

[0034] 1 is an infrared absorption spectrum of the sample of Example 1 and a control sample. 2 is a photograph of an epoxy cured resin of electrolytic FADP superimposed on a document. 3 is a photograph of an epoxy cured resin of aqueous FADP superimposed on a document. 4 is a photograph of the rope-shaped prepreg obtained in Example 6 in a wound state. 5 is a graph showing the results of a three-point bending test of the resin of the present invention composited with cellulose and a control sample. 6 is a schematic diagram explaining the mechanism of the self-repair phenomenon exhibited by the resin of the present invention.

[0035] Hereinafter, one embodiment of the present invention will be described in detail, but the scope of the present invention is not limited to the embodiment described here, and various modifications can be made without departing from the spirit of the present invention. Furthermore, when multiple upper and lower limit values ​​are specified for a specific parameter, any upper and lower limit values ​​can be combined to form a suitable numerical range.

[0036] <Base reaction product of unsaturated fatty acid polymer> The resin of the present invention has a portion consisting of a base reaction product of an unsaturated fatty acid polymer. The base reaction product of an unsaturated fatty acid polymer refers to a reaction product obtained by reacting a polymer obtained by polymerizing at least a portion of the unsaturated groups of an unsaturated fatty acid with a base. Hereinafter, the base reaction product of an unsaturated fatty acid polymer may be referred to as FADP (Fatty Acid Derived Polymer).

[0037] As the unsaturated fatty acid, for example, a fatty acid having 16 or more carbon atoms, two or more double bonds, and a carboxyl group is used. By having two or more double bonds, the unsaturated fatty acid can form a crosslinked structure during the polymerization reaction, improving the chemical resistance, heat resistance, or strength of the resulting molded article. The number of double bonds in the unsaturated fatty acid is preferably 2 to 6, more preferably 2 to 4, and even more preferably 2 or 3. Furthermore, from the viewpoint of easy availability, the number of carbon atoms in the unsaturated fatty acid is preferably 16 to 22, more preferably 16 to 20, and even more preferably 18.

[0038] Specific examples of unsaturated fatty acids include oleic acid, linoleic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid, and docosahexaenoic acid. Among these, preferred unsaturated fatty acids are linoleic acid, linolenic acid, and arachidonic acid. From the viewpoint of reducing the environmental load, unsaturated fatty acids are preferably derived from plants, more preferably linoleic acid, α-linolenic acid, and γ-linolenic acid. A single type of unsaturated fatty acid may be used, or multiple types may be mixed and used. When the raw material unsaturated fatty acid is derived from vegetable oils and fats, the FADP can be said to have a biomass ratio of 100%.

[0039] The unsaturated fatty acid referred to in the present invention may be a drying oil or semi-drying oil. The above description of unsaturated fatty acids also applies to the unsaturated fatty acids constituting drying oils or semi-drying oils. Specific examples of drying oils or semi-drying oils include linseed oil, tung oil, perilla oil, sesame oil, poppy oil, walnut oil, safflower oil, fish oil, dehydrated castor oil, rice oil, corn oil, grape seed oil, soybean oil, sunflower oil, peanut oil, rapeseed oil, cottonseed oil, tall oil, almond oil, jojoba oil, kukui nut oil, macadamia nut oil, and persic oil.

[0040] Polymerization of unsaturated fatty acids is carried out by oxidative polymerization of unsaturated groups in the presence of oxygen. The oxidative polymerization can be carried out, for example, by stirring the unsaturated fatty acids in air or by blowing air into the unsaturated fatty acids to bring them into contact with oxygen in the air. The polymerization can be carried out at room temperature.

[0041] To accelerate the oxidative polymerization reaction, heating or a catalyst may be used, if necessary. The oxidative polymerization reaction is preferably carried out until the polymer irreversibly gels, turns into powder, and loses its thermoplasticity. This improves the strength or water resistance of coatings and molded articles formed from FADP.

[0042] When the oxidative polymerization reaction is carried out by heating, the reaction temperature is, for example, 100 to 500° C., preferably 200 to 450° C., and more preferably 300 to 400° C. If the heating temperature is less than 100° C., the oxidative polymerization reaction may not be sufficiently promoted, whereas if it exceeds 500° C., the amount of volatilization of the composition increases, which may reduce the yield of aqueous FADP.

[0043] The catalyst used in the oxidative polymerization reaction may be a conventionally known oxidation catalyst. Specific examples of the catalyst that can be used include metal powders of Co, Mn, Pb, Ca, Zn, Cu, Zr, Ce, Fe, Pd, Pt, Sn, Mo, W, Ti, V, Rh, Ni, Zr, Al, Ag, B, and Cr, which are used in drying oil driers, and oxides, hydroxides, sulfates, nitrates, chlorides, acetates, and naphthenates of these metals, as well as organic oxidizing agents such as anthracene, methyl ethyl ketone peroxide, and benzoyl peroxide.

[0044] The reaction time for the oxidation polymerization reaction varies depending on reaction conditions such as reaction temperature and type of catalyst, but is preferably adjusted appropriately between 3 and 48 hours, and more preferably between 6 and 10 hours.

[0045] The resulting polymer is then reacted with a base to saponify the polymer and convert the carboxyl groups derived from the unsaturated fatty acids into their salts. Specific examples of bases that can be used in the reaction include NaOH, KOH, LiOH, and Ba(OH). ２ , Ca(OH) ２ , NaHCO ３ , Na ２ CO ３ In a preferred embodiment, a strong base is used. Specific examples of preferred bases include NaOH and KOH.

[0046] An amine can also be used as a base to react with the unsaturated fatty acid polymer. For example, the amine may include a primary amine or a secondary amine. In this case, the amine can also be used as an amine-based epoxy resin curing agent, which will be described below.

[0047] Specific examples of the amine include those listed below as amine-based epoxy resin curing agents, and aliphatic polyamines, such as modified alicyclic polyamines, particularly isophoronediamine-based polyamines having isophoronediamine (3-aminomethyl-3,5,5-trimethylcyclohexylamine) in the skeleton, isophoronediamine, or a mixture of isophoronediamine and other auxiliary aliphatic polyamines (e.g., 2,2,4- or 2,4,4-trimethylhexane-1,6-diamine).

[0048] In an embodiment in which an amine is used as a base to react with a polymer of unsaturated fatty acid, the reaction temperature of the oxidative polymerization reaction may be 5 to 400°C, preferably 20 to 180°C, and more preferably 40 to 100°C. Furthermore, in this embodiment, the reaction time of the oxidative polymerization reaction may be 0.5 hours to 12 weeks, preferably 1 hour to 10 weeks, and more preferably 4 hours to 8 weeks. By allowing the polymerization to proceed for a long period of time at low temperatures, cyclization and dehydrogenation of the fatty acid due to side reactions can be suppressed, making it easier to impart self-healing properties and transparency to the resin of the present invention. The self-healing properties of the resin will be described later.

[0049] The polymer can be reacted with a base, for example, by mixing it with an aqueous base solution. The concentration of the base in the aqueous solution is adjusted to 0.1 to 18 normal (N), preferably 1 to 10 N, and more preferably 3 to 6 N, from the viewpoint of improving the hydrophilicity of the aqueous FADP. To promote the reaction, the reaction solution may be heated under pressure as necessary. The heating temperature of the reaction solution is adjusted to, for example, 50 to 200°C, preferably 80 to 180°C, and more preferably 100 to 150°C under pressure.

[0050] The reaction time for the reaction varies depending on reaction conditions such as the concentration of the base and the reaction temperature, but is preferably adjusted appropriately between 1 minute and 3 hours, preferably between 5 and 90 minutes, and more preferably between 10 and 60 minutes. Upon completion of the reaction, the base reactant (FADP) of the polymer becomes a viscous fluid.

[0051] <Electrolyzed FADP> One form of FADP is a polymer electrolyte having carboxylate anion groups (hereinafter, sometimes referred to as "electrolyzed FADP"). The polymer electrolyte is a base reaction product of a polymer of the unsaturated fatty acid, in which some of the carboxyl groups of the unsaturated fatty acid have been neutralized with a basic substance and converted to carboxylate anion groups. Details of the polymer electrolyte are described in Patent Document 1, and the description is incorporated herein by reference.

[0052] In the polymer electrolyte, preferred examples of the fatty acid include oleic acid, linoleic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid, and docosahexaenoic acid. Preferred examples of the basic substance include NaOH, KOH, LiOH, and Ca(OH). ２ , Mg(OH) ２ , Ba(OH) ２ , Zn(OH) ２ , ammonia, monoethanolamine, diethanolamine, triethanolamine, etc.

[0053] <Aqueous FADP> Another form of FADP is an unsaturated fatty acid polymer solubilizing resin (hereinafter, sometimes referred to as "aqueous FADP"). Details of the unsaturated fatty acid polymer solubilizing resin are described in Japanese Patent Application No. 2023-148449, and the description therein is incorporated by reference.

[0054] Polymers of unsaturated fatty acids have an internal structure in which unsaturated groups are bonded to each other and three-dimensionally crosslinked, and are known to be insoluble. For example, when unsaturated fatty acids are thermally polymerized in the atmosphere, particulate insoluble polymers (i.e., insoluble resin masses) are produced, as shown in Example 1 described later.

[0055] When the unsaturated fatty acid polymer is brought into contact with a base and water, the addition of the base converts the unsaturated fatty acid-derived carboxyl groups and a portion thereof into salts, resulting in the unsaturated fatty acid polymer being dissolved in water. In other words, the unsaturated fatty acid polymer is saponified with a strong base and made water-soluble.

[0056] On the other hand, because this aqueous solution is a liquid soap, the dried product does not exhibit water resistance and cannot be used as a resin to form coatings or molded articles. However, when an acid was added to this solution to convert the carboxyl-derived salt into a carboxylic acid, thereby returning the resin to its original state, it was found that a viscous gum-like substance was produced without returning to the insoluble resin mass before saponification. It was also found that by dispersing or dissolving this in a hydrophilic solvent, a liquid resin composition could be obtained. Furthermore, it was found that when the resulting liquid resin composition was dried and the internal water evaporated, it hardened and became a solid with the same strength as the insoluble resin before saponification.

[0057] By adding an acid to a saponified solution of an unsaturated fatty acid polymer, the salts derived from the carboxyl groups are rapidly converted to carboxylic acids, which then aggregate to a certain size through hydrophobic interactions, resulting in a state in which the separated water particles surround the periphery. As a result, the interior of the aqueous FADP is filled with fine hydrophilic solvent channels. This increases the surface area that can contact the resin with hydrophilic solvents such as water and alcohol, allowing the resin to swell, disperse, or dissolve in these solvents. In this specification, "aqueous" refers to a resin that can be dispersed or dissolved in a hydrophilic solvent to form a liquid resin composition. Hydrophilic solvents include water; water-soluble organic solvents such as ethanol, isopropanol, and acetone; aqueous solutions of water-soluble organic solvents; and aqueous solutions of water-soluble bases such as ammonia.

[0058] Furthermore, since cured resins made of polymeric compounds have poor solubility, they are difficult to separate into individual molecules, making it difficult to determine their internal structure using existing analytical methods. The aqueous FADP has an internal structure in which the polymers are three-dimensionally crosslinked, making it impossible to separate into independent polymers without destroying the molecules. In other words, at the time of filing, it was impossible or almost impractical to directly identify the aqueous FADP by its internal structure or properties.

[0059] <Epoxy Resin> The resin of the present invention has a portion made of an epoxy resin. An epoxy resin is a resin having one or more epoxy groups in its molecule. The epoxy group can thermally react with a carboxyl group to form a crosslinked structure within the resin having the carboxyl group.

[0060] Examples of epoxy resins include bixylenol-type epoxy resins, bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, bisphenol S-type epoxy resins, bisphenol AF-type epoxy resins, dicyclopentadiene-type epoxy resins, trisphenol-type epoxy resins, naphthol novolac-type epoxy resins, phenol novolac-type epoxy resins, tert-butyl-catechol-type epoxy resins, naphthalene-type epoxy resins, naphthol-type epoxy resins, anthracene-type epoxy resins, glycidylamine-type epoxy resins, glycidyl ester-type epoxy resins, cresol novolac-type epoxy resins, biphenyl-type epoxy resins, linear aliphatic epoxy resins, epoxy resins having a butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, spiro ring-containing epoxy resins, cyclohexane-type epoxy resins, cyclohexane dimethanol-type epoxy resins, naphthylene ether-type epoxy resins, trimethylol-type epoxy resins, tetraphenylethane-type epoxy resins, and dimers, trimers, and oligomers thereof.

[0061] The epoxy resin may be used alone or in combination of two or more. The epoxy resin preferably contains an epoxy resin having two or more epoxy groups in the molecule.

[0062] <Linking Moiety> The resin of the present invention has a linking moiety that connects the FADP moiety and the epoxy resin moiety. The linking moiety refers to a moiety that includes a covalent bond that connects the two resins. The linking moiety preferably includes an ester bond or an ether bond.

[0063] <Curable Resin Composition> The curable resin composition of the present invention contains FADP, the epoxy resin, and an amine-based epoxy resin curing agent. The curable resin composition of the present invention can also be prepared in an aqueous system. Epoxy resins are cured by a ring-opening polymerization reaction between the primary amine curing agent and the base epoxy resin, forming a network of covalent bonds to secondary and tertiary amines. Meanwhile, tertiary amines not only form ether bonds in epoxy monomers, but also act as catalysts for the esterification reaction of epoxy and carboxylic acid. Therefore, in a mixture of FADP, amines, and epoxies, the epoxy cures to form tertiary amines, which then epoxy esterify the carboxylic acid in the FADP, resulting in a tough resin that is oxygen-independent. The curing reaction of an amine-based epoxy resin curing agent, epoxy resin, and FADP is shown below.

[0064]

[0065] In the formula, R １ is a residue of an amine-based epoxy resin curing agent, and R ２ is a residue of an epoxy resin, and FADP is a residue of a base reaction product of a polymer of unsaturated fatty acids.

[0066] The amine-based epoxy resin curing agent is not particularly limited in terms of molecular weight or structure, as long as it contains a primary amine or a secondary amine capable of forming a covalent bond with an epoxy group in an epoxy resin.

[0067] Examples of such amine-based epoxy resin curing agents include ethylenediamine, trimethylhexamethylenediamine, diethylenetriamine, 2-hydroxyethyldiethylenetriamine, dipropylenetriamine, triethylenetetraamine, tetraethylenepentamine, dipropylenediamine, diethylaminopropylamine, dimethylaminopropylamine, m-xylylenediamine, N-(2-aminoethyl)piperazine, methanediamine, isophoronediamine, and cyclohexylpropylenediamine.

[0068] When reacting an epoxy resin with FADP, the ratio of the two components to be used is not strictly limited, but it is suitable for the equivalent ratio of the epoxy groups in the epoxy resin to the carboxyl groups in FADP to be in the range of 0.1 to 3.0, preferably 0.1 to 0.8.

[0069] The epoxy resin and the amine-based epoxy resin curing agent are preferably blended so that the equivalent ratio (EP) / (H) of the number of epoxy groups (EP) in the total epoxy resin to the number of active hydrogen groups (H) in the total amine-based epoxy resin curing agent is 0.4 to 1.6, and more preferably 0.7 to 1.3.

[0070] In the curable resin composition of the present invention, both the base of FADP and the amine-based epoxy resin curing agent may contain a primary amine or a secondary amine capable of forming a covalent bond with an epoxy group. In this case, there is no need to use a strong base such as NaOH as a base to react with the unsaturated fatty acid polymer. In other words, in one embodiment, the curable resin composition of the present invention contains an unsaturated fatty acid polymer, the epoxy resin, and an amine-based epoxy resin curing agent.

[0071] In this embodiment, the amine-based epoxy resin curing agent of the curable resin composition may be the aliphatic polyamines. In this case, the resin of the present invention obtained by curing the curable resin composition can be prepared into a material having self-repairing properties. Self-repairing properties refer to the ability of a damaged material to repair the damage itself. Figure 6 is a schematic diagram explaining the mechanism of the self-repairing phenomenon exhibited by the resin of the present invention. A preferred specific example of the aliphatic polyamines includes isophoronediamine.

[0072] When preparing a self-repairing resin, the ratio of the epoxy resin to the FADP used when reacting them is not strictly limited, but it is appropriate that the equivalent ratio of the epoxy groups in the epoxy resin to the carboxyl groups in the FADP is in the range of 0.5 to 3.0, preferably 0.6 to 1.1.

[0073] When preparing a self-repairing resin, the epoxy resin and the amine-based epoxy resin curing agent are preferably blended so that the equivalent ratio (EP) / (H) of the number of epoxy groups (EP) in the total epoxy resin to the number of active hydrogen groups (H) in the total amine-based epoxy resin curing agent is 0.4 to 1.6, and more preferably 0.7 to 1.3.

[0074] When the epoxy resin or the amine-based epoxy resin curing agent is not derived from an animal or plant, the amount of the epoxy resin or the amine-based epoxy resin curing agent used in the curable resin composition is adjusted so that the biomass ratio is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more.

[0075] The electrolytic FADP has a carboxylate anion group, which is not consumed in the epoxy esterification reaction. Therefore, FADP and the resin of the present invention exhibit high affinity with hydrophilic materials. FADP also has a fatty chain. Therefore, FADP and the resin of the present invention also exhibit high affinity with hydrophobic materials. The curable resin composition of the present invention has amphiphilicity and can contain both hydrophilic materials such as biomass and hydrophobic materials such as carbon fiber as fillers at high filling rates. Furthermore, the curable resin composition of the present invention can form high-strength composite materials using both hydrophilic materials such as biomass and hydrophobic materials such as carbon fiber as substrates.

[0076] The curable resin composition of the present invention can be cured by contacting FADP, an epoxy resin, and an amine-based epoxy resin curing agent to produce the resin of the present invention. Because curing proceeds through an esterification reaction between the epoxy and carboxylic acid, there is no need to supply oxygen to the FADP. In many combinations, curing proceeds slowly and is completed at room temperature. The curing reaction can also be accelerated by heating, with the heating temperature adjusted to, for example, 50 to 200°C, preferably 60 to 180°C, and more preferably 70 to 160°C. Furthermore, when preparing a self-healing resin, the heating temperature of the curable resin composition may be adjusted to 5 to 160°C, preferably 80 to 140°C.

[0077] The reaction time for the reaction varies depending on reaction conditions such as the concentration of the base and the reaction temperature, but is preferably adjusted appropriately between 1 minute and 3 hours, preferably between 5 and 90 minutes, and more preferably between 10 and 60 minutes during heating. Upon completion of the reaction, the curable resin composition becomes a solid resin material that is non-adhesive, insoluble, and tough.

[0078] The curable resin composition cured by the esterification reaction can be further cured by subjecting the unsaturated groups of FADP to an oxidative polymerization reaction. In this case, the composition is further heated in the presence of oxygen, such as in air, at 100 to 450°C, preferably 140 to 400°C, more preferably 180 to 350°C, for 5 seconds to 4 hours, preferably 10 seconds to 2 hours, more preferably 1 minute to 1 hour. Upon completion of the reaction, a tougher solid resin material is obtained.

[0079] The present invention will be explained in more detail below with reference to examples, but the present invention is not limited to these examples.

[0080] Example 1 Confirmation of Covalent Bond Formation between FADP and Epoxy Resin by FT-IR Measurement (Synthesis of Electrolyzed FADP) 100 mL of linoleic acid was transferred to a 1 L beaker and polymerized at 350°C for approximately 4 hours while stirring and thoroughly mixing with air. A black, starch-syrup-like mixture was obtained, to which NaOH was further added to make the concentration 1% (w / w), and stirring was continued under the same conditions until the NaOH was dissolved, yielding FADP as a viscous liquid.

[0081] (Synthesis of aqueous FADP) 500 mL of linseed oil was poured into a 2 L beaker on a heater, and polymerized at 350°C for approximately 6 hours while stirring and thoroughly mixing with air. Since the liquid linseed oil disintegrated from a gel to a powder, 500 mL of a 5N aqueous solution of NaOH was added and heated at 200°C for approximately 1 hour. This resulted in saponification of the linseed oil polymer, and further H ２ SO ４A 500 mL 6N aqueous solution of FADP was added and stirred at 100°C for approximately 1 hour, yielding a highly viscous polymer. This polymer was separated and placed in a separate beaker. While heating to 300°C, the separated liquid phase was gradually added to generate hot concentrated sulfuric acid, promoting oxidation and finely adjusting the polymer until it became rubbery. To remove any remaining sulfuric acid or salts, the polymer was thoroughly washed with water. An equal weight of ethanol was added to dissolve the resin. The precipitate was centrifuged, and the supernatant was collected. The ethanol was evaporated to obtain the residue, yielding aqueous FADP.

[0082] (Curable Resin Composition and Resin) 7 mL of FADP or 7 mL of aqueous FADP (based on solids), 5 mL of bisphenol A diglycidyl ether (BADGE, manufactured by Sigma-Aldrich), and 2 mL of 5-amino-1,3,3-trimethylcyclohexanemethylamine (isophoronediamine, manufactured by Sigma-Aldrich) were placed in a beaker and thoroughly kneaded at room temperature to obtain a curable resin composition.

[0083] Approximately 1 mL of the curable resin composition was dispensed onto a Teflon (registered trademark) film and allowed to stand at 25°C for 48 hours to cure. The cured resin mass was analyzed using an FT-IR device (Nicolet iS50 (trade name), manufactured by Thermo Fisher Scientific). Figure 1 shows the infrared absorption spectra of the sample of Example 1 and the control sample. In Figure 1, the relationship between the curves and the objects being measured is as follows:

[0084] Curve (1): FADP and epoxy raw material and hardener, Curve (2): Water-based FADP and epoxy raw material and hardener, Curve (3): Epoxy raw material and hardener only, Curve (4): FADP only, Curve (5): FADP and hardener only, Curve (6): FADP and epoxy raw material only.

[0085] The biomass ratio of the curable resin composition was 50 mass %.

[0086] (Discussion) Only curves (1) and (2) show the peaks at 1750-1730 cm －１ The absorption peak at 1000 s was attributed to the ester bond, indicating that the carboxylic acids of FADP and aqueous FADP formed ester bonds with BADG.

[0087] In the curve (4) for FADP alone, the carboxylic acid-derived 1740-1710 cm －１ Therefore, based on the results of curves (1) to (4) alone, it was possible that a peak derived from some ester bond originally contained in FADP was buried within this peak. On the other hand, by including the results of curve (5), in which most of the carboxylic acids form salts with amines and only FADP and amines, it was found that there were almost no peaks corresponding to the ester bonds originally present in FADP, and it became clear that the ester bonds in curves (1) and (2) were newly formed.

[0088] Example 2 Curability Test The thermosetting properties of the curable resin composition of the present invention were tested. First, various FADPs were prepared as control samples.

[0089] 100 mL of linoleic acid was transferred to a 1-L beaker and polymerized at 350°C for approximately 2 hours while stirring and thoroughly mixing with air. The polymerization reaction was continued while sampling with an Ostwald viscometer from time to time, yielding polymers with viscosities of approximately 600 and approximately 2000 mPa·s. FADP was obtained in the same manner as in Example 1, except that the monomer and the resulting polymer were used. Furthermore, aqueous FADP was obtained in the same manner as in Example 1, except that linoleic acid was used instead of linseed oil. Compounds esterified with epoxy resins using linoleic acid or linseed oil as monomers were included in the test as comparative examples with already known oil-modified epoxy resins.

[0090] Next, linseed oil polymerized FADP and aqueous FADP of about 400 and about 2000 mPa·s were obtained in the same manner as above except that linseed oil was used instead of linoleic acid.

[0091] Next, to prepare the samples according to the present invention, 5 mL of BADGE and 2 mL of isophorone diamine were added to 7 mL of each control sample and mixed thoroughly to prepare resin compositions. These resin compositions were transferred to glass petri dishes to a thickness of approximately 3 mm and heated at 120°C for 1 hour to attempt curing of the resin layer. Pencil hardness tests were performed on the cured resin layers.

[0092] The tip of the pencil lead (3B to 6H) used for the hardness test was placed perpendicular to 400-grit abrasive paper and ground to a flat, sharp edge. The sharpened lead was then placed at a 45° angle against each resin surface and pressed down while being pushed forward at a speed of 1 cm / s for a distance of approximately 1 cm to scratch the surface. The tip of the pencil lead was sharpened after each scratch, and the test was repeated five times for each pencil. The hardness of each pencil that resulted in plastic deformation and cohesive failure at least twice in five tests was recorded. The test for that coating was terminated when cohesive failure occurred twice. The test results are shown in Table 1.

[0093] [Rule 26 amendment 09.09.2025]

[0094] From the test results in Table 1, it can be seen that the curable resin composition of the present invention has ２ It was found that even in thick samples where the carboxylic acid could not reach the inside and conventional fatty acid polymers would not harden, sufficient hardening proceeded through covalent bonding with the epoxy resin component. Furthermore, no hardening was observed in linseed oil polymers in which the carboxylic acid was modified in the form of triglycerol, but sufficient hardening was observed in aqueous FADP conversion from which glycerol was removed. This result indicates that the covalent bond in this study is due to a reaction occurring on the carboxylic acid in the fatty acid, and supports the new ester bond formation shown in Example 1.

[0095] Example 3: Acquisition and evaluation of room temperature stability after initial cure. Conventional epoxy resins based on polymerized BADGE rapidly become brittle at around 250°C, and their strength drops significantly even after cooling. In contrast, the resin of the present invention, which contains 20-60% (w / w) FADP, has high heat resistance, reaching peak strength and modulus after heating at around 300°C. Furthermore, heating at 25°C for 24-72 hours or at 80°C for 30-60 minutes results in a flexible, non-tacky material that does not cure further at room temperature.

[0096] Therefore, we performed a three-point bending test to evaluate the degree to which the mechanical properties of this resin, which is stable despite being semi-cured, change over approximately 90 days at room temperature. First, 2 mL of isophorone diamine as a curing agent was added to 5 mL of BADGE, and then 7 mL of aqueous FADP was added, and the mixture was thoroughly mixed in a beaker.

[0097] This resin raw material was transferred onto a Teflon (registered trademark) sheet, and then sandwiched between the Teflon (registered trademark) sheets and heated in a stretched state at 80°C for 30 minutes to obtain a semi-cured resin of the present invention. Furthermore, two sets of test pieces cut into 10 mm x 80 mm were prepared, one immediately after the test and the other left at 25°C in a dark place for 90 days, and a three-point bending test was performed on each of three samples using a precision universal testing machine (AG-20kNXDplus (trade name), manufactured by Shimadzu Corporation) in accordance with JIS K7171.

[0098] The results showed that the maximum stress immediately after cutting was 0.29±0.02 (standard deviation) MPa and the modulus of elasticity was 15±7.07 MPa, while the maximum stress after 90 days was 0.28±0.02 MPa and the modulus of elasticity was 12.67±3.77, showing no clear difference. These results demonstrate that the semi-cured resin of the present invention is stable at room temperature.

[0099] Example 4: Evaluation of the Compatibility of Epoxy Resin and FADP. Blends of polymers often result in a dispersion of the resins, and even with the use of a compatibilizing solvent, they do not completely mix, resulting in opaque results. On the other hand, examples of miscible polymer alloys in which the polymers completely mix are rare, and in such cases, they are characterized by transparency. Because aqueous FADP undergoes heating at approximately 200-400°C during the production process and is colored, it is believed to contain polycyclic aromatics as part of its structure due to partial carbonization. Therefore, it is expected that it will be highly compatible with carbon fiber, which also has a polycyclic aromatic structure, and with epoxy resins made from BADGE, which is also known to be compatible with carbon fiber. Therefore, relatively thick resin samples were prepared and their appearance after mixing was evaluated.

[0100] To 15 mL of BADGE, 6 mL of isophoronediamine was added as a curing agent, followed by 21 mL of aqueous FADP or 1% (w / w) electrolytic FADP. The mixture was thoroughly mixed in a beaker. These resins were transferred to a glass dish to a thickness of approximately 10 mm and cured by heating at 120°C for 1 hour. The cured characteristics were then observed. Figure 2 shows a photograph of the epoxy resin cured with electrolytic FADP layered on top of a document. The resin appears suspended. Figure 3 shows a photograph of the epoxy resin cured with aqueous FADP layered on top of a document. The aqueous FADP exhibited permeability immediately after mixing and heating with the epoxy resin, and remained highly permeable even after curing. These results demonstrate the unique property of aqueous FADP, which exhibits excellent compatibility with epoxy resins.

[0101] Example 5: Evaluation of flexural strength and modulus when used as a base resin for carbon fiber reinforced composite (CFRP) prepreg and cured. Aqueous FADP prepared from linseed oil was heated at 105°C for 1 hour to dehydrate the solid resin, which was then dispensed into a 14g beaker. 10g of epoxy resin raw material (RSF816 base resin, AXSON) and 4g of amine-based curing agent (RSF816 curing agent, AXSON) were added and kneaded. 28mL of water was then added and further kneaded to produce a low-viscosity water-soluble resin solution.

[0102] This resin was transferred to a tray, and approximately 15 g of carbon fiber fabric (Torayca T300B, Toray Industries, Inc.) was immersed for 10 minutes. The fabric, saturated with the resin of the present invention, was then transferred to a Teflon® sheet and heated at 80°C for 15 minutes to volatilize the water and further reduce the viscosity, promoting penetration of the resin of the present invention. The fiber bundle was then separated from the excess resin on the Teflon® sheet and placed on a separate tray. Several 100 mm x 20 mm pieces were cut out, and five of these were stacked on a Teflon®-coated iron plate. A stable CFRP prepreg was produced by heating at 120°C for 10 minutes under 10 kPa pressure in a press. This was then heated to 300°C for 5 minutes on a heater to fully cure. For control purposes, five cut-out carbon fiber fabrics (Torayca T300B (trade name), manufactured by Toray Industries, Inc.) were laminated on a Teflon (registered trademark)-coated iron plate placed inside a bagging film. A bleeding film was placed on top of this, and the bagging film was sealed with sealant tape. Two suction ports were connected to a container containing epoxy resin raw material (RSF816 (trade name) base agent / curing agent, manufactured by AXSON) and a vacuum pump via hoses, and infusion molding was performed. After 48 hours at room temperature and further complete curing at 80°C for 4 hours, the fabric was cut to a size of 100 mm x 20 mm to prepare a control test piece.

[0103] Three-point bending tests were conducted on these test pieces, and the CFRP using the new resin had a bending strength of 580 MPa and a bending modulus of 56 GPa, while the control CFRP had values ​​of 584 MPa and 42 GPa, respectively. These results show that CFRP made from prepregs using the new resin has bending strength equivalent to that made using conventional methods, and that the modulus of elasticity is higher than that made using conventional methods, similar to the results shown for CFRP pretreated with aqueous FADP or FADP (Patent Application Nos. 2023-543923 and 2024-048367).

[0104] Example 6: Processing example (wire winding) using a room-temperature stable low-tack prepreg. Aqueous FADP prepared from linseed oil was heated at 105°C for 1 hour to dehydrate it, and the resulting solid resin was dispensed into a 14g beaker. 10g of epoxy resin raw material (RSF816 base resin, AXSON) and 4g of amine-based curing agent (RSF816 curing agent, AXSON) were added and kneaded. 28mL of water was then added and further kneaded to prepare a low-viscosity water-soluble resin solution.

[0105] This resin was transferred to a tray, and approximately 5 g of unidirectional carbon fiber (Torayca T700SC (trade name), manufactured by Toray Industries, Inc.) was immersed in it for 10 minutes. The carbon fiber bundle saturated with the resin of the present invention was then folded to a width of approximately 8 mm, twisted approximately five times to increase density, and transferred to a Teflon (registered trademark) sheet with both ends secured with weights to form a rope. The bundle was then heated at 80°C for 20 minutes to volatilize the water and further reduce the viscosity, promoting the penetration of the resin of the present invention. The rope was then separated from the excess resin spread on the Teflon (registered trademark) sheet and placed on another tray. It was then heated at 120°C for 10 minutes to produce a stable semi-cured resin.

[0106] This rope is flexible, stable at room temperature despite being semi-cured, and has very little tack, so it can be wound up and stored. Figure 4 is a photograph of the rope-shaped prepreg obtained in Example 6 in a wound state. Because there is no need to apply a separate film to prevent adhesion between the ropes, this material is low-cost and extremely easy to handle at the site of use compared to previous semi-cured fiber bundles, ropes, and wire-like composite materials. In addition, it can be easily fully cured at the site of use using a heat gun, making it suitable for use in a variety of materials, reinforcing materials, etc.

[0107] Example 7: Regarding the resin removal of the present invention, aqueous FADP prepared from linseed oil was dehydrated by heating at 105°C for 1 hour, and the resulting solid resin was collected in a 14 g beaker. 10 g of BADGE and 4 g of isophoronediamine were added thereto and kneaded. 28 mL of water was then added thereto and further kneaded to prepare a low-viscosity water-soluble resin solution.

[0108] This resin was transferred to a tray and heated at 80°C for 60 minutes to produce a stable semi-cured resin. Half of it was cut off and heated with a heat gun at 300°C for 5 minutes to produce a fully cured resin.

[0109] These samples were immersed in ethanol containing 30% aqueous ammonia and stirred with a stirrer at room temperature (25°C) to attempt to remove the resin of the present invention. While the fully cured samples showed no significant change after 24 hours of treatment, the semi-cured resin had softened as dissolution progressed and could be easily broken down by hand. These results demonstrate that the resin of the present invention can be removed at room temperature and at low cost, making it ideal for maintaining fixtures and equipment at manufacturing sites. It can also be applied to recycling, such as recovering fillers from composite materials.

[0110] Example 8: Evaluation of Cellulose Hybridization 8.6 g of BADGE and 3.4 g of isophoronediamine were mixed together, and 14 g of cellulose powder (Fujifilm Wako Pure Chemical Industries, Ltd.) was added to prepare an epoxy resin raw material in multiple beakers. Next, 14 g of (A) epoxy resin raw material (additionally 10 g of BADGE and 2 g of isophoronediamine), (B) linoleic acid polymer, (C) FADP (lysed with 1% (w / w) NaOH relative to the linoleic acid polymer), (D) aqueous FADP (derived from linseed oil), or (E) 14 g of ethanol added to (D) were added to each beaker and mixed thoroughly to obtain clay-like masses.

[0111] Each sample was transferred onto a Teflon (registered trademark) sheet and evenly spread to a thickness of 3 mm. The resulting mixture was then heated at 80°C for 30 minutes and then at 160°C for 5 minutes to obtain a cured product. Each sample was cut with scissors into 100 mm x 20 mm test pieces.

[0112] Since both materials were relatively flexible, a three-point bending test was conducted with a support distance of 40 mm to maximize bending strain, with other conditions conforming to JIS K7171. Figure 5 is a graph showing the results of a three-point bending test of the resin of the present invention composited with cellulose and a control sample. While the control (A) exhibited a reasonably high bending strength, it lacked flexibility, was brittle, and had low durability. Furthermore, the electrolytically modified (C) was more flexible and showed no fractures than the non-electrolytically modified (B), demonstrating its compatibility with cellulose.

[0113] On the other hand, (D), which contained aqueous FADP, achieved both high bending strength and flexibility, even without any additional treatment to convert the carboxylic acid into an electrolyte. This confirmed that cellulose also exhibits the unique property of easily adapting to hydrophilic materials such as aqueous solvents. Furthermore, the aqueous FADP of the present invention, which has a higher degree of polymerization than the FADP used in this study, exhibited high bending strength, suggesting that the higher the degree of polymerization of the fatty acid polymer, the greater the strength of the final composite. (E) was foamed by adding ethanol to the raw material, which volatilized during heat curing, resulting in a soft and lightweight material similar to foamed urethane materials. The test results were consistent with these sensory characteristics. These results demonstrate that using FADP or aqueous FADP as raw materials makes it possible to produce highly durable materials, even with a high bio-based content (approximately 70%).

[0114] Example 9: Evaluation of flexural bond strength using wood as the adherend. 5g of BADGE and 2g of isophoronediamine were mixed and 21g of aqueous FADP derived from linseed oil was added to produce an adhesive that was approximately 75% bio-based. Two 100mm x 20mm x 3mm lauan plywood boards (Standard Test Piece Co., Ltd.) were prepared. One of the boards was coated with approximately 0.3g of the adhesive of the present invention from one edge to a point 12.5mm from the edge. The other lauan plywood board was placed on top of the adhesive, with the edge overlapping the adhesive surface, and lightly secured with a rubber band. After 72 hours at room temperature (25°C), the flexural bond strength was evaluated according to JIS K6856. As a result, when the test force reached 249N, the boards broke almost simultaneously at the top and bottom at the boundary between the bonded and non-bonded areas, and the adhesive surface did not peel off until the end, resulting in adherend failure. This demonstrated that the adhesive of the present invention exhibits high flexural bond strength to wood.

[0115] Example 10: 200 mL of the self-repairing resin linoleic acid was transferred to a 300 x 500 mm tray and allowed to stand at 40°C for two weeks in contact with atmospheric oxygen to allow the polymerization reaction to proceed. 100 mL of the linoleic acid polymer, which had a viscosity similar to that of starch syrup, was taken, and 50 mL of bisphenol A diglycidyl ether (i.e., BADGE, manufactured by Sigma-Aldrich) and 10 mL of 5-amino-1,3,3-trimethylcyclohexanemethylamine (i.e., isophoronediamine, manufactured by Sigma-Aldrich) were added thereto and kneaded.

[0116] In this case, the linoleic acid polymer immediately undergoes a neutralization reaction with isophorone diamine even at room temperature to form a base reaction product of the linoleic acid polymer.The base reaction product and the isophorone diamine in equilibrium then react with BADGE as an amine-based epoxy resin curing agent, resulting in curing and forming a resin material.

[0117] Since the reaction rate of this curable resin composition is slow at room temperature, the reaction was accelerated by heating at 80°C for 1 hour, and a Teflon film was placed on top to cure the composition in a tray to a thickness of 2.3 mm, forming a resin sheet.

[0118] The resin sheet was punched into a dumbbell shape according to JIS K7161, and a tensile strength test was carried out on the resulting dumbbell-shaped sample. The tensile strength was 9.6 MPa, the tensile modulus was 89 MPa, and the elongation at break was 125%.

[0119] It was revealed that the resin has self-repairing properties. That is, when the dumbbell-shaped sample was cut perpendicular to its length with a cutter and the cut surfaces were glued together, the joint immediately repaired and exhibited a tensile strength of 2.4 MPa after about 5 minutes. On the other hand, when the dumbbell-shaped sample was cut perpendicular to its length to a depth of 1.5 mm with a cutter, the resin exhibited a tensile strength of 8.0 MPa after about 5 minutes after the separated surfaces came into contact.

[0120] This suggests that when cutting, even a slight misalignment in the bonding position creates a tearing point and significantly affects strength, while when cutting, there is less misalignment, resulting in relatively ideal post-repair strength. These results indicate that this resin can become a self-healing resin material by adjusting the manufacturing conditions. Furthermore, the fact that repair occurs specifically between damaged or cut surfaces such as cuts, and does not nonspecifically adhere or bond to various materials like adhesives, also indicates that this resin belongs to the category of self-healing resin materials.

[0121] Possible uses for self-healing resin materials include self-healing three-dimensional molded objects such as packing, catheters, needle-pierced medical instruments, and higher-strength composite materials with added fillers such as fibers and reinforcing agents; self-healing paints applied to the surfaces of car bodies, aircraft, robots, ship hulls, containers, materials, and equipment; self-healing anti-rust paints for use underwater or in high humidity; self-healing waterproofing materials; and adhesive materials that can bond divided surfaces together without fixing.

Claims

A resin having a portion consisting of a base reaction product of a polymer of unsaturated fatty acid, a portion consisting of an epoxy resin, and a connecting portion connecting the two portions. 　 The resin of claim 1 , wherein the linking moiety comprises an ester bond.

3. The resin according to claim 1, wherein the epoxy resin comprises at least one selected from the group consisting of bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, glycidyl amine type epoxy resins, naphthalene type epoxy resins, brominated bisphenol A type epoxy resins, glycidyl ester type epoxy resins, alicyclic epoxy resins, and heterocyclic epoxy resins. 　 The resin according to any one of claims 1 to 3, wherein the base reaction product of the polymer of the unsaturated fatty acid comprises a polymer electrolyte in which a portion of the carboxyl groups has been neutralized with a basic substance and converted into a carboxylate anion group. 　 The resin according to claim 4, wherein the base reaction product of the polymer of unsaturated fatty acid comprises a product obtained by reacting the polymer electrolyte with an acid to liberate a carboxyl group from the carboxylate of the base reaction product. 　 The resin of any one of claims 1 to 5, wherein the base comprises a strong base. 　 The resin of any one of claims 1 to 5, wherein the base comprises an amine. 　 The resin of any one of claims 1 to 7, wherein the unsaturated fatty acids include those having 16 to 22 carbon atoms. 　 The resin of any one of claims 1 to 8, wherein the unsaturated fatty acid comprises a drying oil or a semi-drying oil. 　 The resin according to any one of claims 1 to 9, wherein the unsaturated fatty acid comprises at least one selected from the group consisting of linoleic acid, linolenic acid, and linseed oil. The resin according to any one of claims 1 to 10, having a biomass ratio of 50% or more. 　 A method for producing the resin according to any one of claims 1 to 11, comprising contacting a base reaction product of a polymer of unsaturated fatty acid, an epoxy resin, and an amine-based epoxy resin curing agent. 　 The method for producing a resin according to claim 12, wherein the base and the amine-based epoxy resin curing agent comprise a primary amine or a secondary amine. 　 A curable resin composition comprising a base reaction product of a polymer of an unsaturated fatty acid, an epoxy resin, and an amine-based epoxy resin curing agent.

15. The curable resin composition of claim 14, wherein the base and amine-based epoxy resin curing agent comprises a primary amine or a secondary amine. 　 The curable resin composition according to claim 14 or 15, wherein the amine-based epoxy resin curing agent comprises at least one selected from the group consisting of ethylenediamine, trimethylhexamethylenediamine, diethylenetriamine, 2-hydroxyethyldiethylenetriamine, dipropylenetriamine, triethylenetetraamine, tetraethylenepentamine, dipropylenediamine, diethylaminopropylamine, dimethylaminopropylamine, m-xylylenediamine, N-aminoethylpiperazine, methanediamine, isophoronediamine, and cyclohexylpropylenediamine. 　 The curable resin composition according to claim 14 or 15, wherein the base reaction product of the polymer of the unsaturated fatty acid comprises a polymer electrolyte in which a portion of the carboxyl groups has been neutralized with a basic substance and converted into a carboxylate anion group. 　 The curable resin composition according to claim 17, wherein the base reaction product of the polymer of the unsaturated fatty acid comprises a product obtained by reacting the polymer electrolyte with an acid to liberate a carboxyl group from a carboxylate of the base reaction product. The curable resin composition according to any one of claims 14 to 18, having a biomass ratio of 50% or more.

Images