Aliphatic diamines and aliphatic diamine compositions

Abstract

To provide a novel alicyclic diamine which can form a coating film having excellent water resistance when used as an epoxy resin curing agent, in particular. To also provide an alicyclic diamine which can be manufactured using a raw material derived from biomass. Further, to provide an epoxy resin curing agent containing the aforementioned alicyclic diamine, an alicyclic diamine composition containing the aforementioned alicyclic diamine, a reaction product of an epoxy compound and the aforementioned alicyclic diamine, and the like. An alicyclic diamine represented by the following general formula (1). (In formula (1), -CH2NH2is bonded to a or b.)

Description

Technical Field

[0001] It involves alicyclic diamines and alicyclic diamine compositions. Background Technology

[0002] Diamines with cyclic structures composed of saturated hydrocarbons (alicyclic diamines) are used as raw materials for synthetic resins, intermediates in organic synthetic chemistry, and curing agents for epoxy resins.

[0003] For example, in Patent Document 1, diaminomethylnorbornene is listed as an example of a raw material for obtaining a novel diamide compound that becomes a resin with good transparency.

[0004] In addition, diamine compounds are known as epoxy resin curing agents. Epoxy resin compositions using diamine compounds as epoxy resin curing agents are also used in coatings such as anti-corrosion coatings for ships / bridges / land and sea iron structures, lining / reinforcement / repair materials for concrete structures, flooring materials for buildings, linings for water supply and drainage systems, paving materials, adhesives, and other civil engineering / construction applications.

[0005] Among these, for epoxy resin compositions used in coatings, it is important that the resulting coating film has good appearance, water resistance, chemical resistance, and physical properties.

[0006] For example, bis(aminomethyl)cyclohexane is a fast-curing epoxy resin curing agent, and the coating obtained by curing the epoxy resin composition containing this epoxy resin curing agent at room temperature has excellent weather resistance.

[0007] Existing technical documents

[0008] Patent documents

[0009] Patent Document 1: Japanese Patent Application Publication No. 2011-219539 Summary of the Invention

[0010] The problem the invention aims to solve

[0011] It is known that using bis(aminomethyl)cyclohexane or similar materials as epoxy resin curing agents results in a sticky coating surface due to amine brushing, leading to a decrease in water resistance. As a method to improve this decrease in water resistance, modified diamines have been used as epoxy resin curing agents. However, modified diamines typically have high viscosity, and further improvement in the water resistance of the resulting coating is desired. High water resistance is also desired in applications beyond coatings, such as flooring materials and linings, where water comes into contact with the material.

[0012] In addition, in order to address environmental issues in recent years, biomass-derived resins have been developed. Therefore, their raw materials must also be derived from biomass.

[0013] Therefore, the objective of this invention is to provide a novel alicyclic diamine that can form a coating with excellent water resistance, particularly when used as an epoxy resin curing agent. Furthermore, the objective is to provide an alicyclic diamine that can be manufactured using raw materials derived from biomass.

[0014] Solution for solving the problem

[0015] The inventors have discovered that alicyclic diamines and alicyclic diamine compositions having specific structures can solve the aforementioned problems, thus completing the present invention.

[0016] That is, the present invention is as follows.

[0017] [1] The alicyclic diamine represented by the following general formula (1).

[0018]

[0019] (In formula (1), -CH2NH2 is bonded to a or b.)

[0020] [2] The alicyclic diamine described in [1] above has a biomass content of 30% or more.

[0021] [3] An alicyclic diamine composition comprising an alicyclic diamine of formula (2) and an alicyclic diamine of formula (3).

[0022]

[0023] [4] The alicyclic diamine composition according to the above [3] has a biomass content of 30% by mass or more.

[0024] [5] An epoxy resin curing agent comprising at least one of the following groups: the alicyclic diamine described in [1] or [2] above, the alicyclic diamine composition described in [3] or [4] above, a reactant of an epoxy compound having at least one epoxy group with the alicyclic diamine described in [1] or [2] above, and a reactant of an epoxy compound having at least one epoxy group with the alicyclic diamine composition described in [3] or [4] above.

[0025] [6] The epoxy resin curing agent described in [5] above has a biomass content of 30% by mass or more.

[0026] [7] A method for manufacturing an alicyclic diamine, wherein a dinitrile of the following general formula (4) or a dinitrile of the following general formula (5) is hydrogenated to obtain an alicyclic diamine of the following general formula (1).

[0027]

[0028] (In equations (4) and (5), -CN is bonded to a or b.)

[0029] In equation (1), -CH2NH2 is bonded to a or b.

[0030] [8] According to the method for manufacturing alicyclic diamine described above [7], the alicyclic dinitrile represented by the aforementioned general formula (4) or the dinitrile represented by the aforementioned general formula (5) is an alicyclic dinitrile obtained from furfural or furfuryl alcohol as raw materials.

[0031] The effects of the invention

[0032] According to the present invention, a novel alicyclic diamine that can form a coating with excellent water resistance, particularly when used as an epoxy resin curing agent, can be provided. Furthermore, an alicyclic diamine that can be manufactured using raw materials derived from biomass can be provided. Detailed Implementation

[0033] In this specification, “XX~YY” refers to “XX and above and YY and below”.

[0034] [Alicyclic diamines and alicyclic diamine compositions]

[0035] The alicyclic diamine of the present invention is the alicyclic diamine represented by the following general formula (1).

[0036]

[0037] (In formula (1), -CH2NH2 is bonded to a or b.)

[0038] In equation (1), a and b represent the carbon atom of the hydrocarbon ring and the position of that carbon atom.

[0039] In formula (1), -CH2NH2 is bonded to a or b. When -CH2NH2 is bonded to b, the alicyclic diamine shown in formula (1) is the alicyclic diamine shown in formula (2) below. When -CH2NH2 is bonded to a, the alicyclic diamine shown in formula (1) is the alicyclic diamine shown in formula (3) below. Therefore, the alicyclic diamine shown in formula (1) is either the alicyclic diamine shown in formula (2) or the alicyclic diamine shown in formula (3).

[0040] Furthermore, the alicyclic diamines shown in formula (2) and formula (3) each contain two stereoisomers (exo (external type) and endo (internal type)). The alicyclic diamines of the present invention can be any one stereoisomer or a mixture of two stereoisomers. The alicyclic diamine shown in formula (2) is 3-((3-(aminomethyl)-7-oxabicyclo[2.2.1]heptan-1-yl)methoxy)propane-1-amine), and the alicyclic diamine shown in formula (3) is 3-((2-(aminomethyl)-7-oxabicyclo[2.2.1]heptan-1-yl)methoxy)propane-1-amine).

[0041]

[0042] The biomass content of the alicyclic diamine of the present invention is preferably 30% by mass or more, more preferably 50% by mass or more, further preferably 70% by mass or more, and even more preferably 90% by mass or more. There is no upper limit, but it is 100% by mass or less, and even more preferably 100% by mass. As described below, the aforementioned alicyclic diamine can be obtained from furfural or furfuryl alcohol derived from biomass, and the biomass content can be adjusted to the above range by using biomass-derived raw materials including them. It should be noted that the biomass content is the mass ratio of biomass raw materials in the raw materials that contribute to the structure of the obtained alicyclic diamine.

[0043] The alicyclic diamine composition of the present invention is an alicyclic diamine composition containing the alicyclic diamine shown in formula (2) and the alicyclic diamine shown in formula (3). That is, the alicyclic diamine composition of the present invention can also be said to be a mixture of the alicyclic diamine shown in formula (2) and the alicyclic diamine shown in formula (3) that belong to the aforementioned alicyclic diamines.

[0044] Furthermore, the alicyclic diamines shown in formula (2) and formula (3) each contain two stereoisomers (exo, endo). The alicyclic diamines shown in formula (2) and formula (3) contained in the alicyclic diamine composition of the present invention can be any one stereoisomer or a mixture of two stereoisomers. The alicyclic diamine shown in formula (2) is 3-((3-(aminomethyl)-7-oxabicyclo[2.2.1]heptan-1-yl)methoxy)propane-1-amine), and the alicyclic diamine shown in formula (3) is 3-((2-(aminomethyl)-7-oxabicyclo[2.2.1]heptan-1-yl)methoxy)propane-1-amine).

[0045]

[0046] The biomass content of the alicyclic diamine composition of the present invention is preferably 30% by mass or more, more preferably 50% by mass or more, further preferably 70% by mass or more, and even more preferably 90% by mass or more. There is no upper limit, but it is 100% by mass or less, and even more preferably 100% by mass. As described below, the aforementioned alicyclic diamine composition can be obtained from furfural or furfuryl alcohol derived from biomass, and the biomass content can be adjusted to the above range by using biomass-derived raw materials including them. It should be noted that the biomass content is the mass ratio of the biomass raw material in the raw materials that contribute to the structure of the obtained alicyclic diamine.

[0047] In the alicyclic diamine composition of the present invention, the mass ratio of the alicyclic diamine shown in formula (2) to the alicyclic diamine shown in formula (3) [(2) / (3)] is preferably 10 / 90 to 90 / 10, more preferably 10 / 90 to 70 / 30, even more preferably 20 / 80 to 50 / 50, even more preferably 20 / 80 to 45 / 55, and even more preferably 25 / 75 to 40 / 60.

[0048] [Method for manufacturing alicyclic diamines]

[0049] There are no limitations on the method for manufacturing the alicyclic diamine of the present invention, but it is preferred to obtain it by the manufacturing method shown below.

[0050] That is, the preferred method for manufacturing alicyclic diamine is to hydrogenate the dinitrile shown in general formula (4) or the dinitrile shown in general formula (5) to obtain the alicyclic diamine shown in general formula (1).

[0051] Typically, only the dinitrile shown in formula (4) or only the dinitrile shown in formula (5) is used as the raw material for this manufacturing method, but a mixture of them may also be used as the raw material.

[0052]

[0053] (In equations (4) and (5), -CN is bonded to a or b.)

[0054] In equation (1), -CH2NH2 is bonded to a or b.

[0055] <Hydrogenation process of dionitrile>

[0056] This process involves hydrogenating the dinitrile shown in formula (4) or the dinitrile shown in formula (5) to obtain the alicyclic diamine shown in general formula (1).

[0057] The reaction in this process is shown in the following formula.

[0058]

[0059] (In equations (4) and (5), -CN is bonded to a or b.)

[0060] In equation (1), -CH2NH2 is bonded to a or b.

[0061] The reaction in this process will be explained in more detail below.

[0062] In equation (4), a and b represent the carbon atoms and their positions in the hydrocarbon ring.

[0063] In formula (4), -CN is bonded to a or b. When -CN is bonded to b, the dinitrile shown in formula (4) is the dinitrile shown in formula (4b) below. When -CN is bonded to a, the dinitrile shown in formula (4) is the dinitrile shown in formula (4a) below. Therefore, the dinitrile shown in formula (4) is the dinitrile shown in formula (4b) or the dinitrile shown in formula (4a).

[0064] Furthermore, the dinitrile shown in formula (4b) and the dinitrile shown in formula (4a) each contain two stereoisomers (exo, endo). The aforementioned dinitrile can be any one stereoisomer or a mixture of two stereoisomers. The dinitrile shown in formula (4b) is 4-((2-cyanoethoxy)methyl)-7-oxabicyclo[2.2.1]heptane-2-carboxynitrile, and the dinitrile shown in formula (4a) is 1-((2-cyanoethoxy)methyl)-7-oxabicyclo[2.2.1]heptane-2-carboxynitrile.

[0065]

[0066] As mentioned above, in this process, the dinitrile shown in formula (4b) can be hydrogenated to obtain the alicyclic diamine shown in formula (2), and the dinitrile shown in formula (4a) can be hydrogenated to obtain the alicyclic diamine shown in formula (3).

[0067] In the case of obtaining the aforementioned alicyclic diamine composition containing the alicyclic diamine shown in formula (2) and the alicyclic diamine shown in formula (3), the alicyclic diamine shown in formula (2) and the alicyclic diamine shown in formula (3) can be synthesized separately by the above reaction, and then mixed in a target ratio to obtain the alicyclic diamine composition. Alternatively, a mixture of dionitriles containing the dionitriles shown in formula (4b) and the dionitriles shown in formula (4a) can be used as a raw material, and the alicyclic diamine shown in formula (2) and the alicyclic diamine shown in formula (3) can be obtained by the above reaction. From the viewpoint of efficiently obtaining the alicyclic diamine composition by one reaction, it is preferable to use a mixture of dionitriles containing the dionitriles shown in formula (4b) and the dionitriles shown in formula (4a) as a raw material, and obtain the alicyclic diamine shown in formula (2) and the alicyclic diamine shown in formula (3) by the above reaction.

[0068] In equation (5), a and b represent the carbon atoms and their positions in the hydrocarbon ring.

[0069] In formula (5), -CN is bonded to a or b. When -CN is bonded to b, the dinitrile shown in formula (5) is the dinitrile shown in formula (5b) below. When -CN is bonded to a, the dinitrile shown in formula (5) is the dinitrile shown in formula (5a) below. Therefore, the dinitrile shown in formula (5) is the dinitrile shown in formula (5b) or the dinitrile shown in formula (5a).

[0070] Furthermore, the dinitrile shown in formula (5b) and the dinitrile shown in formula (5a) each contain two stereoisomers (exo, endo). The aforementioned dinitrile can be any one stereoisomer or a mixture of two stereoisomers. The dinitrile shown in formula (5b) is 4-((2-cyanoethoxy)methyl)-7-oxabicyclo[2.2.1]hept-5-ene-2-carboxynitrile, and the dinitrile shown in formula (5a) is 1-((2-cyanoethoxy)methyl)-7-oxabicyclo[2.2.1]hept-5-ene-2-carboxynitrile.

[0071]

[0072] As mentioned above, in this process, the dinitrile shown in formula (5b) can be hydrogenated to obtain the alicyclic diamine shown in formula (2), and the dinitrile shown in formula (5a) can be hydrogenated to obtain the alicyclic diamine shown in formula (3).

[0073] In the case of obtaining the aforementioned alicyclic diamine composition containing the alicyclic diamine shown in formula (2) and the alicyclic diamine shown in formula (3), the alicyclic diamine shown in formula (2) and the alicyclic diamine shown in formula (3) can be synthesized separately by the above reaction, and then mixed in a target ratio to obtain the alicyclic diamine composition. Alternatively, a mixture of dionitriles containing the dionitriles shown in formula (5b) and the dionitriles shown in formula (5a) can be used as a starting material, and the alicyclic diamine shown in formula (2) and the alicyclic diamine shown in formula (3) can be obtained by the above reaction. From the viewpoint of efficiently obtaining the alicyclic diamine composition by one reaction, it is preferable to use a mixture of dionitriles containing the dionitriles shown in formula (5b) and the dionitriles shown in formula (5a) as a starting material, and obtain the alicyclic diamine shown in formula (2) and the alicyclic diamine shown in formula (3) by the above reaction.

[0074] There are no particular restrictions on the form of hydrogenation reaction in this process; it can be any method, such as batch, semi-continuous, or continuous.

[0075] The preferred reaction temperature for the hydrogenation reaction is 80 to 180°C, more preferably 100 to 140°C from the viewpoint of reaction rate, and even more preferably 110 to 130°C from the viewpoint of selectivity and reaction rate.

[0076] The pressure during the hydrogenation reaction is preferably 1~20 MPa, more preferably 5~10 MPa.

[0077] Hydrogenation can be carried out in a solvent-free environment or with a solvent.

[0078] Examples of solvents that can be used in hydrogenation reactions include water; aromatic compounds such as benzene, o-dichlorobenzene, toluene, and xylene; hydrocarbons such as hexane, heptane, and cyclohexane; alcohols such as methanol, ethanol, isopropanol, tert-butanol, ethylene glycol, and diethylene glycol; ethers such as dioxane, tetrahydrofuran, dimethoxyethane, and diethylene glycol dimethyl ether; or mixtures thereof.

[0079] The amount of solvent used in the hydrogenation reaction is preferably 0 to 30 times the mass of the dinitrile shown in formula (4) or formula (5), more preferably 0 to 20 times the mass of the dinitrile shown in formula (5).

[0080] The catalyst used in the hydrogenation reaction is not particularly limited as long as it is a catalyst commonly used in the hydrogenation of nitrile compounds, but preferably contains at least one catalyst selected from metals in groups 8 to 11 of the periodic table.

[0081] Specifically, examples include hydrogenation catalysts containing at least one of iron, cobalt, nickel, copper, ruthenium, rhodium, palladium, silver, osmium, iridium, platinum, and gold.

[0082] Hydrogenation catalysts can be solid catalysts or homogeneous catalysts. From the viewpoint of separation from reactants, solid catalysts are preferred. Examples of solid catalysts include unsupported metal catalysts and supported metal catalysts.

[0083] As unsupported metal catalysts, sponge metal catalysts such as sponge nickel, sponge cobalt, and sponge copper are preferred, or oxide and colloidal catalysts such as platinum, palladium, rhodium, and ruthenium are preferred.

[0084] Examples of supported metal catalysts include catalysts formed by supporting at least one of iron, cobalt, nickel, copper, ruthenium, rhodium, palladium, silver, osmium, iridium, platinum, and gold on supports such as magnesium oxide, zirconium oxide, cerium oxide, diatomite, activated carbon, alumina, silica, zeolite, or titanium dioxide. Preferred catalysts include copper-chromium catalysts (Adkins catalysts), copper-zinc catalysts, or copper-iron catalysts, platinum catalysts supported by Pt / C or Pt / alumina, palladium catalysts supported by Pd / C or Pd / alumina, ruthenium catalysts supported by Ru / C or Ru / alumina, or rhodium catalysts supported by Rh / C or Rh / alumina.

[0085] From the viewpoint of reactivity, a catalyst containing at least one of nickel, cobalt, and ruthenium is preferred.

[0086] The amount of hydrogenation catalyst can be adjusted appropriately according to the type of catalyst. It is preferably 0.1 to 100% by mass relative to the total amount of dinitrile shown in formula (4) and dinitrile shown in formula (5) as raw materials, and more preferably 1 to 20% by mass.

[0087] The alicyclic diamine obtained in this way is preferably purified by distillation. The distillation conditions can be adjusted appropriately according to the pressure and temperature during distillation.

[0088] <Manufacturing method using furfural or furfural alcohol as raw materials>

[0089] A further preferred method for manufacturing alicyclic diamines is a method for manufacturing alicyclic diamines of dinitrile represented by the aforementioned general formula (4) or dinitrile represented by the aforementioned general formula (5) obtained from furfural or furfuryl alcohol. Using the dinitrile obtained here as an intermediate raw material, the target alicyclic diamine can be obtained through the aforementioned hydrogenation process. Using furfural or furfuryl alcohol as a raw material can improve the biomass content of the obtained alicyclic diamine, and is therefore preferred.

[0090] When the obtained dinitrile is the dinitrile shown in formula (4), this manufacturing method is a method for manufacturing an alicyclic diamine of the dinitrile shown in formula (4) obtained from furfural or furfuryl alcohol.

[0091] In the case where the obtained dinitrile is the dinitrile shown in formula (5), this manufacturing method is a method for manufacturing an alicyclic diamine of the dinitrile shown in formula (5) obtained from furfural or furfuryl alcohol.

[0092] Furthermore, in the aforementioned hydrogenation process, when using the dinitrile shown in formula (4) and the dinitrile shown in formula (5) as raw materials, it is preferable that the dinitrile shown in formula (4) and the dinitrile shown in formula (5) are both a method for manufacturing alicyclic diamines of dinitrile obtained from furfural or furfuryl alcohol as raw materials.

[0093] There are no restrictions on the method for obtaining the dinitrile shown in formula (4) or formula (5) from furfural or furfuryl alcohol as raw materials, as long as the method ultimately yields the dinitrile shown in formula (4) or formula (5). Among them, the preferred method is shown in detail below.

[0094] When using furfural, a biomass-derived raw material, as the starting material for this manufacturing method, it is first hydrogenated to obtain furfuryl alcohol.

[0095] Next, furfuryl alcohol and acrylonitrile are used to carry out a Diels-Alder reaction as shown in the following formula, thereby obtaining the nitrile shown in the following formula (6) (Diels-Alder reaction step).

[0096] Next, the olefin portion of the nitrile shown in formula (6) is hydrogenated as shown in the following formula to obtain the nitrile shown in formula (7) (hydrogenation process of the olefin portion).

[0097] Next, as shown in the following formula, acrylonitrile is added to the nitrile shown in formula (7) to obtain the dinitrile shown in formula (4) (acrylonitrile addition process).

[0098]

[0099] (In equations (4), (6) and (7), -CN is bonded to either a or b.)

[0100] When using furfural, a biomass-derived raw material, as the starting material for this manufacturing method, it is first hydrogenated to obtain furfuryl alcohol.

[0101] Next, furfuryl alcohol and acrylonitrile are used to carry out a Diels-Alder reaction as shown in the following formula, thereby obtaining the nitrile shown in the following formula (6) (Diels-Alder reaction step).

[0102] Next, acrylonitrile is added to the nitrile shown in formula (6) to obtain the alicyclic nitrile shown in formula (5) (acrylonitrile addition process).

[0103]

[0104] (In equations (5) and (6), -CN is bonded to either a or b.)

[0105] Next, the above-mentioned processes will be explained.

[0106] (Diels-Alder reaction process)

[0107] In this process, a nitrile as shown in formula (6) is obtained by using furfuryl alcohol and acrylonitrile to carry out a Diels-Alder reaction.

[0108] There are no particular restrictions on the form of the Diels-Alder reaction; it can be any method, such as batch, semi-continuous, or continuous.

[0109] The preferred reaction temperature for the Diels-Alder reaction is 20–120 °C, more preferably 40–80 °C. The reaction pressure is not particularly limited as long as it allows the reaction to proceed suitably, but is preferably 0–5 MPa, more preferably 0–1 MPa. The molar ratio of furfuryl alcohol to acrylonitrile (furfuryl alcohol:acrylonitrile) is preferably 1:1–1:20, more preferably 1:3–1:10.

[0110] The Diels-Alder reaction is preferably carried out in a solvent-free environment, but solvents can also be used. Examples of solvents that can be used in the Diels-Alder reaction include: water; aromatic compounds such as benzene, o-dichlorobenzene, toluene, and xylene; hydrocarbons such as hexane, heptane, and cyclohexane; alcohols such as methanol, ethanol, isopropanol, tert-butanol, ethylene glycol, and diethylene glycol; ethers such as dioxane, tetrahydrofuran, dimethoxyethane, and diethylene glycol dimethyl ether; or mixtures thereof.

[0111] The Diels-Alder reaction is preferably carried out without a catalyst, but a catalyst can also be used.

[0112] Examples of Lewis acids used as catalysts include silica gel, zeolites, and alumina. Specific examples of Lewis acids used as catalysts include ZnCl2, ZnI2, AlCl3, and FeCl3.

[0113] The amount of catalyst relative to furfuryl alcohol is preferably 0.001 to 1 molar, more preferably 0.01 to 0.2 molar.

[0114] In equation (6), a and b represent the carbon atoms and their positions in the hydrocarbon ring.

[0115] In formula (6), -CN is bonded to a or b. When -CN is bonded to b, the nitrile shown in formula (6) is 4-(hydroxymethyl)-7-oxabicyclo[2.2.1]hept-5-en-2-carboxynitrile. When -CN is bonded to a, the nitrile shown in formula (6) is 1-(hydroxymethyl)-7-oxabicyclo[2.2.1]hept-5-en-2-carboxynitrile. In addition, each of the aforementioned nitriles contains two stereoisomers (exo, endo). The aforementioned nitrile can be any one stereoisomer or a mixture of two stereoisomers.

[0116] It should be noted that, typically, the aforementioned Diels-Alder reaction yields two nitrile compounds: a nitrile with -CN (cyano) bonded to a and a nitrile with -CN (cyano) bonded to b. However, this mixture can also be used directly as a raw material for the next step. By using the mixture, an alicyclic diamine composition containing the alicyclic diamine shown in formula (2) and the alicyclic diamine shown in formula (3) can be obtained. However, when the alicyclic diamine composition is the target product, for simplicity, it is preferable to use the aforementioned mixture as a raw material for the next step. The two nitrile compounds can be separated and used individually as raw materials for the next step, or the ratio of the two nitrile compounds can be adjusted for use as raw materials for the next step.

[0117] (Hydrogenation process of olefins)

[0118] In this process, the olefin portion of the nitrile shown in formula (6) is hydrogenated to obtain the nitrile shown in formula (7).

[0119] There are no particular restrictions on the form of hydrogenation reaction of olefin moiety; it can be any method, such as batch, semi-continuous, or continuous.

[0120] The preferred reaction temperature for hydrogenation is 0–100°C, more preferably 20–60°C. The preferred reaction pressure for hydrogenation is 0.1–20 MPa, more preferably 0.5–3 MPa. The hydrogenation reaction can be carried out without a solvent or with a solvent.

[0121] Solvents that can be used in hydrogenation reactions include: water; aromatic compounds such as benzene, o-dichlorobenzene, toluene, and xylene; hydrocarbons such as hexane, heptane, and cyclohexane; alcohols such as methanol, ethanol, isopropanol, tert-butanol, ethylene glycol, and diethylene glycol; ethers such as dioxane, tetrahydrofuran, dimethoxyethane, and diethylene glycol dimethyl ether; or mixtures thereof.

[0122] The amount of solvent used in the hydrogenation reaction is preferably 0 to 30 times by mass relative to the nitrile shown in formula (6) that is used as a raw material in this process, more preferably 0 to 20 times by mass.

[0123] The catalyst used in the hydrogenation reaction is not particularly limited as long as it is a common catalyst used in the hydrogenation of olefins, but preferably contains at least one metal selected from Groups 8 to 11 of the periodic table.

[0124] Specifically, examples include hydrogenation catalysts containing at least one of iron, cobalt, nickel, copper, ruthenium, rhodium, palladium, silver, osmium, iridium, platinum, and gold.

[0125] Hydrogenation catalysts can be solid catalysts or homogeneous catalysts. From the viewpoint of separation from reactants, solid catalysts are preferred. Examples of solid catalysts include unsupported metal catalysts and supported metal catalysts.

[0126] As unsupported metal catalysts, sponge metal catalysts such as sponge nickel, sponge cobalt, and sponge copper are preferred, or oxide and colloidal catalysts such as platinum, palladium, rhodium, and ruthenium are preferred.

[0127] Examples of supported metal catalysts include catalysts formed by supporting at least one of iron, cobalt, nickel, copper, ruthenium, rhodium, palladium, silver, osmium, iridium, platinum, and gold on supports such as magnesium oxide, zirconium oxide, cerium oxide, diatomite, activated carbon, alumina, silica, zeolite, or titanium dioxide. Preferred catalysts include copper-chromium catalysts (Adkins catalysts), copper-zinc catalysts, or copper-iron catalysts, platinum catalysts supported by Pt / C or Pt / alumina, palladium catalysts supported by Pd / C or Pd / alumina, ruthenium catalysts supported by Ru / C or Ru / alumina, or rhodium catalysts supported by Rh / C or Rh / alumina.

[0128] From the viewpoint of reactivity, a catalyst containing at least one of palladium and nickel is preferred.

[0129] The amount of hydrogenation catalyst used varies depending on the type of catalyst, and is preferably 0.1 to 100% by mass relative to the nitrile shown in formula (7) that is used as a raw material in this process, more preferably 0.1 to 5% by mass.

[0130] In equation (7), a and b represent the carbon atoms and their positions in the hydrocarbon ring.

[0131] In formula (7), -CN is bonded to a or b. When -CN is bonded to b, the nitrile shown in formula (7) is 4-(hydroxymethyl)-7-oxabicyclo[2.2.1]heptane-2-carboxynitrile. When -CN is bonded to a, the nitrile shown in formula (7) is 1-(hydroxymethyl)-7-oxabicyclo[2.2.1]heptane-2-carboxynitrile. In addition, each of the aforementioned nitriles contains two stereoisomers (exo, endo). The aforementioned nitrile can be any one stereoisomer or a mixture of two stereoisomers.

[0132] It should be noted that the nitrile shown in formula (6) is used as the raw material in this process. When using a mixture of two nitriles, one with -CN (cyano) bonded to a and the other with -CN (cyano) bonded to b, a mixture of the two nitriles shown in formula (7) is obtained in this process. However, this mixture can also be used directly as the raw material in the next process. By using the mixture, an alicyclic diamine composition containing the alicyclic diamine shown in formula (2) and the alicyclic diamine shown in formula (3) can be obtained. However, when the alicyclic diamine composition is used as the target product, it is preferable to use the aforementioned mixture as the raw material in the next process for simplicity. The two nitriles can be separated and used individually as the raw material in the next process, or the ratio of the two nitriles can be adjusted as the raw material in the next process.

[0133] (Acrylonitrile addition process)

[0134] In this process, acrylonitrile is added to the nitrile shown in formula (7) or the nitrile shown in formula (6) to obtain the dinitrile shown in formula (4) or the dinitrile shown in formula (5).

[0135] There are no particular restrictions on the form of acrylonitrile addition reaction; it can be any method, such as batch, semi-continuous, or continuous.

[0136] The preferred reaction temperature for the acrylonitrile addition reaction is 0°C to 100°C, more preferably 10°C to 40°C. The reaction pressure for the acrylonitrile addition reaction is not limited as long as the reaction proceeds appropriately, but is preferably 0 to 5 MPa, more preferably 0 to 1 MPa.

[0137] The base catalyst used in the acrylonitrile addition reaction is preferably an inorganic base or an organic base, more preferably an inorganic base.

[0138] The aforementioned inorganic base is preferably selected from at least one of the following groups: LiOH, NaOH, KOH, LiHCO3, NaHO3, KHO3, Li2CO3, Na2CO3, K2CO3, Cs2CO3, Mg(OH)2, Ca(OH)2, Li3PO4, Na3PO4, K3PO4, t-BuONa, t-BuOK, and NaH; more preferably, it is selected from at least one of the following groups: NaOH and KOH.

[0139] The amount of alkaline catalyst is preferably 0.01 to 1 molar multiple relative to the nitriles shown in formula (7) or formula (6), more preferably 0.01 to 0.1 molar multiple. Alkaline catalyst may also be used in greater than 1 molar multiple of the matrix, but the amount of alkali as waste increases, so it is not preferred.

[0140] The acrylonitrile addition process can be carried out in a solvent-free environment or with a solvent. Examples of solvents include aromatic compounds such as water, benzene, o-dichlorobenzene, toluene, and xylene; hydrocarbons such as hexane, heptane, and cyclohexane; alcohols such as methanol, ethanol, isopropanol, tert-butanol, ethylene glycol, and diethylene glycol; ethers such as dioxane, tetrahydrofuran, dimethoxyethane, and diethylene glycol dimethyl ether; or mixtures thereof.

[0141] The amount of solvent used in the acrylonitrile addition process is preferably 0 to 30 times by mass relative to the nitrile shown in formula (6) as the raw material of this process, and more preferably 0 to 10 times by mass.

[0142] The amount of acrylonitrile used in the acrylonitrile addition process is preferably 1 to 20, more preferably 1 to 2, relative to the molar ratio of the nitrile shown in formula (7) or formula (6) as the raw material of this process [acrylonitrile / ((7) or (6))].

[0143] In equation (4), a and b represent the carbon atoms and their positions in the hydrocarbon ring.

[0144] In formula (4), -CN is bonded to a or b. When -CN is bonded to b, the dinitrile shown in formula (4) is 4-((2-cyanoethoxy)methyl)-7-oxabicyclo[2.2.1]heptane-2-carboxynitrile. When -CN is bonded to a, the nitrile shown in formula (6) is 1-((2-cyanoethoxy)methyl)-7-oxabicyclo[2.2.1]heptane-2-carboxynitrile. In addition, each of the aforementioned nitriles contains two stereoisomers (exo, endo). The aforementioned nitrile can be any one stereoisomer or a mixture of two stereoisomers.

[0145] It should be noted that, when using a mixture of two nitriles—the nitrile represented by formula (7) and the nitrile represented by -CN (cyano) bonded to a and the nitrile represented by b—as the raw material for this process, a mixture of the two dinitriles represented by formula (4) is obtained in this process. However, this mixture can also be used directly as the raw material for the next process. By using the mixture, an alicyclic diamine composition containing the alicyclic diamine represented by formula (2) and the alicyclic diamine represented by formula (3) can be obtained. However, when the alicyclic diamine composition is used as the target product, for simplicity, it is preferable to use the aforementioned mixture as the raw material for the next process. The two nitriles can be separated and used individually as the raw material for the next process, or the ratio of the two nitriles can be adjusted for use as the raw material for the next process.

[0146] In equation (5), a and b represent the carbon atoms and their positions in the hydrocarbon ring.

[0147] In formula (5), -CN is bonded to either a or b. When -CN is bonded to b, the dinitrile shown in formula (5) is 4-((2-cyanoethoxy)methyl)-7-oxabicyclo[2.2.1]hept-5-ene-2-carboxynitrile. When -CN is bonded to a, the nitrile shown in formula (5) is 1-((2-cyanoethoxy)methyl)-7-oxabicyclo[2.2.1]hept-5-ene-2-carboxynitrile. In addition, each of the aforementioned nitriles contains two stereoisomers (exo, endo). The aforementioned nitrile can be any one stereoisomer or a mixture of two stereoisomers.

[0148] It should be noted that, when using a mixture of two nitriles—the nitrile represented by formula (6) and the nitrile represented by -CN (cyano) bonded to a and the nitrile represented by b—as the raw material for this process, a mixture of the two dinitriles represented by formula (5) is obtained in this process. However, this mixture can also be used directly as the raw material for the next process. By using the mixture, an alicyclic diamine composition containing the alicyclic diamine represented by formula (2) and the alicyclic diamine represented by formula (3) can be obtained. However, when the alicyclic diamine composition is used as the target product, for simplicity, it is preferable to use the aforementioned mixture as the raw material for the next process. The two nitriles can be separated and used individually as the raw material for the next process, or the ratio of the two nitriles can be adjusted for use as the raw material for the next process.

[0149] <Other methods for manufacturing alicyclic diamines>

[0150] In addition to the above-described method for manufacturing alicyclic diamines, it is preferable to manufacture the alicyclic diamine shown in formula (1) by the following method. That is, as a method for manufacturing the alicyclic diamine shown in formula (1), the methods shown in (A) and (B) below are also preferred.

[0151] Method (A) involves an acrylonitrile addition reaction of furfuryl alcohol and acrylonitrile to obtain an acrylonitrile adduct of furfuryl alcohol. Next, the aforementioned adduct and acrylonitrile are subjected to a Diels-Alder reaction to obtain a dinitrile as shown in formula (5). Then, the olefinic moiety is hydrogenated to obtain a dinitrile as shown in formula (4). Finally, as described above, the dinitrile as shown in formula (4) is hydrogenated to obtain an alicyclic diamine as shown in formula (1).

[0152]

[0153] (In equations (5) and (4), -CN is bonded to either a or b.)

[0154] Method (B) involves an acrylonitrile addition reaction of furfuryl alcohol and acrylonitrile to obtain an acrylonitrile adduct of furfuryl alcohol. Then, the aforementioned adduct is reacted with acrylonitrile in a Diels-Alder reaction to obtain a dinitrile as shown in formula (5). Finally, as described above, an alicyclic diamine as shown in formula (1) is obtained.

[0155]

[0156] (In equation (5), -CN is bonded to a or b.)

[0157] [Epoxy Resin Curing Agent]

[0158] The aforementioned alicyclic diamine and alicyclic diamine composition are suitable for use as epoxy resin curing agents. When used as epoxy resin curing agents, they can produce epoxy resin compositions with excellent water resistance.

[0159] In addition, the reactant obtained by reacting the aforementioned alicyclic diamine or alicyclic diamine composition with an epoxy compound can also be used as an epoxy resin curing agent. When used as an epoxy resin curing agent, the resulting epoxy resin composition coating can have excellent water resistance.

[0160] Furthermore, the modified compounds obtained by the Mannich reaction of the aforementioned alicyclic diamine or alicyclic diamine composition with phenolic compounds and aldehyde compounds, the modified compounds obtained by the reaction of the aforementioned alicyclic diamine or alicyclic diamine composition with compounds having carboxyl groups, and the modified compounds obtained by the Michael reaction of the aforementioned alicyclic diamine or alicyclic diamine composition with acrylic compounds can also be suitable for use as epoxy resin curing agents. When used as epoxy resin curing agents, the resulting epoxy resin composition coating can exhibit excellent water resistance.

[0161] Therefore, the epoxy resin curing agent of the present invention preferably contains a reaction product selected from the aforementioned alicyclic diamine, the aforementioned alicyclic diamine composition, an epoxy compound having at least one epoxy group reacting with the aforementioned alicyclic diamine, an epoxy compound having at least one epoxy group reacting with the aforementioned alicyclic diamine composition, a modified product obtained by the Mannich reaction of the aforementioned alicyclic diamine with phenolic compounds and aldehyde compounds, a modified product obtained by the reaction of the aforementioned alicyclic diamine with a compound having a carboxyl group, a modified product obtained by the Michael reaction of the aforementioned alicyclic diamine with an acrylic compound, or a modified product obtained by the reaction of the aforementioned alicyclic diamine composition with a phenolic compound. An epoxy resin curing agent comprising at least one of the following groups: a modified product obtained by the Mannich reaction of an aldehyde compound and a modified product obtained by the reaction of the aforementioned alicyclic diamine composition with a carboxyl-containing compound, and a modified product obtained by the Michael reaction of the aforementioned alicyclic diamine composition with an acrylic compound; more preferably, an epoxy resin curing agent comprising at least one of the following groups: the aforementioned alicyclic diamine, the aforementioned alicyclic diamine composition, a reaction product of an epoxy compound having at least one epoxy group with the aforementioned alicyclic diamine, and a reaction product of an epoxy compound having at least one epoxy group with the aforementioned alicyclic diamine composition.

[0162] Typically, the epoxy resin curing agent of the present invention contains any one of the following: the aforementioned alicyclic diamine, the aforementioned alicyclic diamine composition, the reaction product of the aforementioned epoxy compound and the aforementioned alicyclic diamine, the reaction product of the aforementioned epoxy compound and the aforementioned alicyclic diamine composition, a modified product obtained by the Mannich reaction of the aforementioned alicyclic diamine with phenolic compounds and aldehyde compounds, a modified product obtained by the reaction of the aforementioned alicyclic diamine with a compound having a carboxyl group, a modified product obtained by the Michael reaction of the aforementioned alicyclic diamine with an acrylic compound, a modified product obtained by the Mannich reaction of the aforementioned alicyclic diamine composition with phenolic compounds and aldehyde compounds, a modified product obtained by the reaction of the aforementioned alicyclic diamine composition with a compound having a carboxyl group, and a modified product obtained by the Michael reaction of the aforementioned alicyclic diamine composition with an acrylic compound, and may also contain two or more of the following.

[0163] In the epoxy resin curing agent of the present invention, known non-reactive diluents may be further mixed in without impairing the effects of the present invention.

[0164] Examples of non-reactive diluents include benzyl alcohol, furfuryl alcohol, tetrafurfuryl alcohol, and aromatic hydrocarbon formaldehyde resins; one or more of these can be used.

[0165] Aromatic hydrocarbon formaldehyde resin is a resin obtained by reacting aromatic hydrocarbons with formaldehyde. Examples include toluene-formaldehyde resin obtained by reacting toluene with formaldehyde, xylene-formaldehyde resin obtained by reacting xylene with formaldehyde, mesitylene-formaldehyde resin obtained by reacting mesitylene with formaldehyde, and pseudocumene-formaldehyde resin obtained by reacting pseudocumene with formaldehyde.

[0166] Commercially available aromatic hydrocarbon formaldehyde resins include, for example, xylene formaldehyde resins manufactured by Fudow Co., Ltd., such as “NIKANOL Y-50”, “NIKANOL Y-100”, “NIKANOL Y-300”, “NIKANOL Y-1000”, “NIKANOL L”, “NIKANOL LL”, “NIKANOL LLL”, “NIKANOL G”, “NIKANOL H”, and “NIKANOL H-80”.

[0167] Of the above, preferably at least one is selected from the group consisting of benzyl alcohol and aromatic hydrocarbon formaldehyde resin, more preferably at least one is selected from the group consisting of benzyl alcohol and xylene formaldehyde resin, further preferably containing benzyl alcohol, and even more preferably benzyl alcohol.

[0168] The content of the non-reactive diluent relative to the total amount of epoxy resin curing agent is preferably 1 to 99% by mass, more preferably 10 to 90% by mass, even more preferably 20 to 70% by mass, even more preferably 30 to 60% by mass, and even more preferably 35 to 50% by mass.

[0169] The total content of the aforementioned alicyclic diamine, the aforementioned alicyclic diamine composition, the reaction product of the aforementioned epoxy compound and the aforementioned alicyclic diamine, and the reaction product of the aforementioned epoxy compound and the aforementioned alicyclic diamine composition used in the epoxy resin curing agent of the present invention is not particularly limited as long as the upper limit is 100% by mass or less. Relative to the total amount of epoxy resin curing agent, it is preferably 1 to 99% by mass, more preferably 10 to 90% by mass, even more preferably 30 to 80% by mass, even more preferably 40 to 70% by mass, and even more preferably 50 to 65% by mass.

[0170] There are no particular limitations on the preparation method of the epoxy resin curing agent of the present invention, and appropriate selections can be made according to the form of use, the device of use, the type of compounding components, and the mixing ratio. For example, it can be prepared by mixing and blending the aforementioned alicyclic diamine, the aforementioned alicyclic diamine composition, the reaction product of the aforementioned epoxy compound and the aforementioned alicyclic diamine, or the reaction product of the aforementioned epoxy compound and the aforementioned alicyclic diamine composition, with other curing agent components used as needed, non-reactive diluents, etc. In addition, when preparing the epoxy resin composition, each component contained in the epoxy resin curing agent can also be mixed with the epoxy resin simultaneously.

[0171] When the epoxy resin curing agent of the present invention contains a reaction product of an epoxy compound having at least one epoxy group and the aforementioned alicyclic diamine, or a reaction product of an epoxy compound having at least one epoxy group and the aforementioned alicyclic diamine composition, the aforementioned "epoxy compound having at least one epoxy group" can be any compound having at least one epoxy group, and more preferably a compound having two or more epoxy groups.

[0172] Specific examples of epoxy compounds include epichlorohydrin, butyl diglycidyl ether, neopentyl glycol diglycidyl ether, 1,3-propanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, biphenol diglycidyl ether, dihydroxynaphthalene diglycidyl ether, dihydroxyanthracene diglycidyl ether, triglycidyl isocyanurate, tetraglycidyl glycidyl urea, multifunctional epoxy resins having a glycidyl amino group derived from m-phenylenediamine, and multifunctional epoxy resins having a glycidyl amino group derived from 1,3-bis(aminomethyl)cyclohexane. Epoxy resins, multifunctional epoxy resins having glycidyl amino groups derived from diaminodiphenylmethane, multifunctional epoxy resins having glycidyl amino groups derived from p-aminophenol, multifunctional epoxy resins having glycidyloxy groups derived from p-aminophenol, multifunctional epoxy resins having glycidyloxy groups derived from bisphenol A, multifunctional epoxy resins having glycidyloxy groups derived from bisphenol F, multifunctional epoxy resins having glycidyloxy groups derived from phenolic varnishes, and multifunctional epoxy resins having two or more glycidyloxy groups derived from resorcinol, etc. They can be used alone or in combination of two or more.

[0173] From the viewpoint of forming epoxy resin cured products with excellent chemical resistance and from the viewpoint of curability, as an epoxy compound, compounds containing aromatic rings or alicyclic structures in the molecule are more preferred, compounds containing aromatic rings in the molecule are even more preferred, and multifunctional epoxy resins having glycidyloxy groups derived from bisphenol A are even more preferred.

[0174] The reactant of the aforementioned epoxy compound with an alicyclic diamine or a combination of alicyclic diamines can be obtained by a ring-opening addition reaction using known methods. For example, a method can be described as follows: an alicyclic diamine or a combination of alicyclic diamines is introduced into a reactor, and an epoxy compound is simultaneously added or added dropwise in batches, followed by heating to allow the reaction to proceed. This addition reaction is preferably carried out under an inert atmosphere such as nitrogen.

[0175] The amount of alicyclic diamine or alicyclic diamine composition to epoxy compound is not particularly limited as long as the ratio of the resulting reactant to an amino group having active hydrogen is present. From the viewpoint that the resulting reactant exhibits the function of an epoxy resin curing agent, it is preferable to use an alicyclic diamine or alicyclic diamine composition in excess of the epoxy equivalent relative to the epoxy compound in this addition reaction. Specifically, it is preferable to use the alicyclic diamine or alicyclic diamine composition and epoxy compound in such a manner that [D] / [G] = 50 / 1 to 4 / 1, more preferably in a manner that [D] / [G] = 20 / 1 to 8 / 1 (here, [D] represents the number of active hydrogens in the alicyclic diamine or alicyclic diamine composition, and [G] represents the number of epoxy groups in the epoxy compound).

[0176] The temperature and reaction time during the addition reaction can be appropriately selected. From the viewpoints of reaction rate and productivity, as well as preventing the decomposition of raw materials, the temperature during the addition reaction is preferably 50~150°C, more preferably 70~120°C. In addition, the reaction time from the end of the addition of the epoxide compound is preferably 0.5~12 hours, more preferably 1~6 hours.

[0177] The biomass content of the epoxy resin curing agent of the present invention is preferably 30% by mass or more, more preferably 50% by mass or more, further preferably 70% by mass or more, and even more preferably 90% by mass or more. There is no upper limit, but it is 100% by mass or less, and even more preferably 100% by mass. The alicyclic diamine and alicyclic diamine composition contained in the aforementioned epoxy resin curing agent, as described above, can be obtained from furfural or furfuryl alcohol derived from biomass. By using biomass-derived raw materials including them, the biomass content can be adjusted to the above-mentioned range. It should be noted that the biomass content is the mass ratio of the biomass raw material in the raw material that contributes to the structure of the obtained alicyclic diamine.

[0178] There are no particular limitations on the preparation method of the epoxy resin curing agent of the present invention, and it can be appropriately selected according to the form of use, the device of use, the type of compounding components, and the mixing ratio. For example, it can be prepared by mixing the aforementioned alicyclic diamine or alicyclic diamine composition with other curing agent components, non-reactive diluents, etc., as needed. Alternatively, when preparing the epoxy resin composition, each component contained in the epoxy resin curing agent can be mixed with the epoxy resin simultaneously.

[0179] Examples of modified products obtained through the Mannich reaction of the aforementioned alicyclic diamine with phenolic and aldehyde compounds include the reaction products of the aforementioned alicyclic diamine with phenolic and aldehyde compounds. Examples of phenolic compounds used in the above modification include phenol, cresol, butylphenol, and nonylphenol. Examples of aldehyde compounds include formaldehyde, acetaldehyde, and benzaldehyde; aqueous formaldehyde solution is typically used. The reaction ratio of the aforementioned alicyclic diamine with the phenolic and aldehyde compounds during modification is not particularly limited, as long as it avoids gelation and the resulting reaction product contains an amino group with active hydrogen.

[0180] Examples of modified alicyclic diamines and compounds containing carboxyl groups include the reaction products of the aforementioned alicyclic diamines and compounds containing carboxyl groups. Examples of carboxyl-containing compounds used for modification include polymeric fatty acids commonly referred to as dimer acids, dicarboxylic acids such as adipic acid and sebacic acid, tall oil fatty acids, oleic acid, stearic acid, and other monocarboxylic acids. The reaction ratio of the aforementioned alicyclic diamine to the carboxyl-containing compound during modification is not particularly limited, as long as it avoids gelation and the resulting reaction product contains an amino group with an active hydrogen atom.

[0181] The modified products obtained by the Michael reaction of the aforementioned alicyclic diamine with acrylic compounds can be exemplified by the reaction products of the aforementioned alicyclic diamine with compounds having carbon-carbon double bonds adjacent to a nitrile or carbonyl group. Examples of acrylic compounds specifically used for modification include acrylonitrile and methyl methacrylate. The reaction ratio of the aforementioned alicyclic diamine to the acrylic compound during modification is not particularly limited, as long as it avoids gelation and the resulting reaction product contains an amino group with active hydrogen.

[0182] Examples of modified products obtained by the Mannich reaction of the aforementioned alicyclic diamine composition with phenolic and aldehyde compounds include the reaction products of the aforementioned alicyclic diamine composition with phenolic and aldehyde compounds. Examples of phenolic compounds used in the above modification include phenol, cresol, butylphenol, and nonylphenol. Examples of aldehyde compounds include formaldehyde, acetaldehyde, and benzaldehyde; aqueous formaldehyde solution is typically used. The reaction ratio of the aforementioned alicyclic diamine composition with the phenolic and aldehyde compounds during modification is not particularly limited, as long as it avoids gelation and the resulting reaction product contains an amino group with active hydrogen.

[0183] Examples of modified alicyclic diamine compositions and carboxyl-containing compounds include the reaction products of the aforementioned alicyclic diamine compositions and carboxyl-containing compounds. Examples of carboxyl-containing compounds used for modification include dicarboxylic acids such as polymeric fatty acids (commonly referred to as dimers), adipic acid, sebacic acid, and monocarboxylic acids such as tall oil fatty acids, oleic acid, and stearic acid. The reaction ratio of the aforementioned alicyclic diamine composition to the carboxyl-containing compound during modification is not particularly limited, as long as it avoids gelation and results in a reaction product containing an amino group with an active hydrogen atom.

[0184] The modified product obtained by the Michael reaction of the aforementioned alicyclic diamine composition with an acrylic compound can be the reaction product of the aforementioned alicyclic diamine composition with a compound having a carbon-carbon double bond adjacent to a nitrile or carbonyl group. Examples of acrylic compounds specifically used for modification include acrylonitrile and methyl methacrylate. The reaction ratio of the aforementioned alicyclic diamine composition to the acrylic compound during modification is not particularly limited, as long as it avoids gelation and the resulting reaction product contains an amino group with active hydrogen.

[0185] The epoxy resin curing agent of the present invention can be mixed with epoxy resin to obtain an epoxy resin composition that becomes a raw material for curing.

[0186] The aforementioned epoxy resin can be any of the following: saturated or unsaturated aliphatic compounds, alicyclic compounds, aromatic compounds, or heterocyclic compounds. From the viewpoint of obtaining a cured product with a high Tg, epoxy resins containing aromatic rings or alicyclic structures within the molecule are preferred.

[0187] Specific examples of this epoxy resin include at least one resin selected from the following: epoxy resin having a glycidylamino group derived from m-phenylenediamine; epoxy resin having a glycidylamino group derived from p-phenylenediamine; epoxy resin having a glycidylamino group derived from 1,3-bis(aminomethyl)cyclohexane; epoxy resin having a glycidylamino group derived from 1,4-bis(aminomethyl)cyclohexane; epoxy resin having a glycidylamino group derived from diaminodiphenylmethane; epoxy resin having a glycidylamino group and / or a glycidyloxy group derived from p-aminophenol; epoxy resin having a glycidyloxy group derived from bisphenol A; epoxy resin having a glycidyloxy group derived from bisphenol F; epoxy resin having a glycidyloxy group derived from phenolic varnish; and epoxy resin having a glycidyloxy group derived from resorcinol. Two or more of the above epoxy resins may also be used in combination.

[0188] From the viewpoint of obtaining a cured product with high Tg, the epoxy resin preferably uses at least one of the following as the main component: an epoxy resin having a glycidyl amino group derived from m-phenylenediamine, an epoxy resin having a glycidyl amino group derived from p-phenylenediamine, an epoxy resin having a glycidyloxy group derived from bisphenol A, and an epoxy resin having a glycidyloxy group derived from bisphenol F. From the viewpoint of obtaining a cured product with high Tg, availability, and economy, the epoxy resin having a glycidyloxy group derived from bisphenol A is more preferably used as the main component.

[0189] It should be noted that the term "main component" here refers to the inclusion of other components without departing from the spirit of the present invention. Preferably, it refers to 50-100% by mass of the whole, more preferably 70-100% by mass of the whole, and even more preferably 90-100% by mass of the whole.

[0190] The content of epoxy resin curing agent in the aforementioned epoxy resin composition is preferably 1 / 0.5 to 1 / 2, more preferably 1 / 0.75 to 1 / 1.5, and even more preferably 1 / 0.8 to 1 / 1.2, which is the ratio of the number of active hydrogen atoms in the epoxy resin curing agent to the number of epoxy groups in the epoxy resin (number of active hydrogen atoms in the epoxy resin curing agent / number of epoxy groups in the epoxy resin).

[0191] The aforementioned epoxy resin composition may also contain other components such as fillers, plasticizers and other modifying components, thixotropic agents and other flow modifiers, pigments, leveling agents, tackifiers, and elastomer microparticles, depending on the intended use.

[0192] The total amount of epoxy resin and epoxy resin curing agent in the epoxy resin composition is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and even more preferably 90% by mass or more. Furthermore, the upper limit is 100% by mass.

[0193] There are no particular limitations on the preparation method of the aforementioned epoxy resin composition. Known methods and apparatus can be used to mix the epoxy resin, epoxy resin curing agent, and other components as needed. There are also no particular limitations on the mixing order of the components in the epoxy resin composition. The epoxy resin curing agent can be prepared first and then mixed with the epoxy resin, or the components constituting the epoxy resin curing agent can be mixed simultaneously with the epoxy resin.

[0194] Cured epoxy resin products can be obtained by curing the aforementioned epoxy resin composition using known methods. The curing conditions of the epoxy resin composition are appropriately selected according to the application and form.

[0195] The cured product obtained as described above exhibits excellent water resistance, making it particularly suitable for coating applications. Furthermore, it is also suitable for applications involving contact with water, such as flooring materials and linings, in fields other than coatings. In addition, the aforementioned epoxy resin composition exhibits excellent drying properties, resulting in a superior appearance of the cured product.

[0196] [Uses of alicyclic diamines and alicyclic diamine compositions]

[0197] The aforementioned alicyclic diamines and alicyclic diamine compositions are novel alicyclic diamines and novel alicyclic diamine compositions, characterized by excellent solvent solubility, and therefore can be used for various applications. Furthermore, it is believed that when used as a raw material for resins, it can impart weather resistance and transparency to the resulting resins.

[0198] For example, it can be used as a raw material for polyamides, polyimides, polyurethanes, polyureas, and as a ligand. The specific applications will then be explained in detail.

[0199] <Uses as a raw material for polyamides>

[0200] The aforementioned alicyclic diamines and alicyclic diamine compositions are novel alicyclic diamines and novel alicyclic diamine compositions, characterized by excellent solvent solubility, and therefore suitable for use as raw materials for polyamides. Furthermore, it is believed that the aforementioned alicyclic diamines and alicyclic diamine compositions can impart weather resistance and transparency to the obtained polyamides.

[0201] Polyamides can be obtained by introducing a diamine and a dicarboxylic acid containing the aforementioned alicyclic diamine or alicyclic diamine composition into a reaction system and carrying out a polycondensation reaction.

[0202] There are no particular limitations on dicarboxylic acids, but they are preferably selected from at least one of aliphatic dicarboxylic acids, terephthalic acid and isophthalic acid with 4 to 20 carbon atoms, more preferably aliphatic dicarboxylic acids with 4 to 20 carbon atoms, and even more preferably aliphatic dicarboxylic acids with 4 to 12 carbon atoms.

[0203] Examples of aliphatic dicarboxylic acids with 4 to 20 carbon atoms include succinic acid, glutaric acid, adipic acid, pimelic acid, octanoic acid, azelaic acid, sebacic acid, 1,10-decanedicarboxylic acid, 1,11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,16-hexadecanedicarboxylic acid, and 1,18-octadecanedicarboxylic acid. Among these, from the viewpoint of crystallinity and high elasticity, at least one of succinic acid and sebacic acid is preferred. These dicarboxylic acids can be used in one form or in combination of two or more.

[0204] Other dicarboxylic acids include aliphatic dicarboxylic acids with 3 or fewer carbon atoms, such as oxalic acid and malonic acid; and aromatic dicarboxylic acids other than terephthalic acid and isophthalic acid, such as 2,6-naphthalenedicarboxylic acid.

[0205] The molar ratio of diamine to dicarboxylic acid (diamine / dicarboxylic acid) is preferably in the range of 0.9 to 1.1, more preferably in the range of 0.93 to 1.07, even more preferably in the range of 0.95 to 1.05, and even more preferably in the range of 0.97 to 1.02. If the molar ratio is within the above range, increasing the molecular weight becomes easier.

[0206] <Uses as a raw material for polyimide>

[0207] The aforementioned alicyclic diamines and alicyclic diamine compositions are novel alicyclic diamines and novel alicyclic diamine compositions, characterized by excellent solvent solubility, and therefore suitable for use as raw materials for polyimides. Furthermore, it is believed that the aforementioned alicyclic diamines and alicyclic diamine compositions can impart weather resistance and transparency to the resulting polyimides.

[0208] Polyimide can be obtained by introducing a diamine containing the aforementioned alicyclic diamine or alicyclic diamine composition and a tetracarboxylic dianhydride into a reaction system, followed by ring-opening addition polymerization to obtain polyamic acid, and then further imidization. Alternatively, the ring-opening addition polymerization and imidization can be carried out in a single step.

[0209] There are no particular limitations on tetracarboxylic dianhydrides; examples include aromatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, and aliphatic tetracarboxylic dianhydrides.

[0210] Examples of aromatic tetracarboxylic dianhydrides include biphenyl tetracarboxylic dianhydride (BPDA), 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride (BPAF), pyromellitic dianhydride, 3,3',4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, and 2,2',3,3'-benzophenone tetracarboxylic dianhydride.

[0211] Examples of alicyclic tetracarboxylic dianhydrides that provide structural units derived from alicyclic tetracarboxylic dianhydrides include 1,2,4,5-cyclohexanetetracarboxylic dianhydrides, 1,2,3,4-cyclobutanetetracarboxylic dianhydrides, norbornane-2-spiro-α-cyclopentanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydrides, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydrides, dicyclohexyltetracarboxylic dianhydrides, 5,5'-bis-2-norbornene-5,5',6,6'-tetracarboxylic-5,5',6,6'-dianhydrides, or their positional isomers.

[0212] Examples of aliphatic tetracarboxylic dianhydrides that provide structural units derived from aliphatic tetracarboxylic dianhydrides include 1,2,3,4-butanetetracarboxylic dianhydrides. These tetracarboxylic dianhydrides can be used in one form or in combination of two or more.

[0213] <Uses as a raw material for polyurethane>

[0214] The aforementioned alicyclic diamines and alicyclic diamine compositions are novel alicyclic diamines and novel alicyclic diamine compositions, characterized by excellent solvent solubility, and therefore suitable for use as raw materials for polyurethanes. Furthermore, it is believed that the aforementioned alicyclic diamines and alicyclic diamine compositions can impart weather resistance and transparency to the resulting polyurethanes.

[0215] The aforementioned alicyclic diamine and alicyclic diamine composition are first reacted with phosgene to obtain the corresponding isocyanate. The obtained isocyanate is then reacted with a polyol to obtain a polyurethane.

[0216] As a polyol, there are no particular limitations; examples include polyester polyols, polyether polyols, polycarbonate polyols, and polylactone polyols.

[0217] Examples of polyester polyols include condensation-based polyester polyols such as polyethylene adipate diol, polybutylene adipate diol, polyhexane adipate diol, and polyethylene glycol butylene adipate diol.

[0218] Examples of polyether polyols include aliphatic polyether polyols such as polybutanediol, polyethylene glycol, and polypropylene glycol.

[0219] Examples of polycarbonate-based polyols include those obtained by the dealcoholization reaction of low-molecular-weight polyols such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, octanediol, nonanediol, and 1,4-cyclohexanediethanol with carbonate compounds such as diethylene carbonate, dipropylene carbonate, and diphenyl carbonate.

[0220] Examples of polylactone-based polyols include polylactone diols, polycaprolactone diols, and polymethylpentyllactone diols, which are obtained by ring-opening polymerization of lactones using the aforementioned low-molecular-weight polyols as initiators.

[0221] Polyols can be used alone or in combination of two or more.

[0222] <Uses as a raw material for polyurea>

[0223] The aforementioned alicyclic diamines and alicyclic diamine compositions are novel alicyclic diamines and novel alicyclic diamine compositions, characterized by excellent solvent solubility, and therefore suitable for use as raw materials for polyurea. Furthermore, it is believed that the aforementioned alicyclic diamines and alicyclic diamine compositions can impart weather resistance and transparency to the resulting polyurea.

[0224] Polyurea can be obtained by reacting the aforementioned alicyclic diamine and alicyclic diamine composition with a polyisocyanate.

[0225] There are no particular limitations on polyisocyanates as long as they contain compounds having two or more isocyanate groups. Polyisocyanates are preferably diisocyanates having two or more isocyanate groups.

[0226] Examples of diisocyanates having two isocyanate groups include aliphatic isocyanate compounds such as 1,6-hexamethylene diisocyanate (HDI), 2,2,4-trimethylhexamethylene diisocyanate, methylene diisocyanate, isopropylidene diisocyanate, lysine diisocyanate, methyl lysine diisocyanate, and 1,5-octylene diisocyanate; 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate (IPDI), norbornene diisocyanate, hydrogenated toluene diisocyanate, and methylcyclohexane diisocyanate. Alicyclic isocyanate compounds such as esters, isopropylidene bis(4-cyclohexyl isocyanate), and dimer acid diisocyanate; aromatic isocyanate compounds such as 2,4- or 2,6-toluene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), 1,5-naphthalene diisocyanate, p- or m-phenylenediamine diisocyanate (XDI), bitoluidine diisocyanate, p-phenylenediamine diisocyanate, diphenyl ether diisocyanate, diphenyl sulfone diisocyanate, bianisidine diisocyanate, and tetramethyl-m-phenylenediamine diisocyanate.

[0227] Examples of polyisocyanates having three or more isocyanate groups include triphenylmethane triisocyanate, triisocyanate-based phenyl thiophosphate, polymethylene polyphenyl polyisocyanate (polymeric MDI), isocyanurate modified forms of trimers of HDI and TDI, and biuret modified forms.

[0228] Polyisocyanates can be used alone or in combination of two or more.

[0229] <Uses as a ligand>

[0230] The aforementioned alicyclic diamines and alicyclic diamine compositions are novel alicyclic diamines and novel alicyclic diamine compositions, characterized by excellent solvent solubility, and therefore suitable for use as ligands. It is believed that by using the aforementioned alicyclic diamines and alicyclic diamine compositions as ligands, they can be used in metal catalysts, etc., and also as chelating agents for the removal and separation of metal ions.

[0231] The metals used as the aforementioned metals or as metal ions are preferably elements from groups 3 to 11, more preferably transition metals, and even more preferably noble metals.

[0232] <Other uses>

[0233] The alicyclic diamine and alicyclic diamine composition of the present invention, as well as the above-mentioned polyamide resin, polyimide resin, polyurethane resin, polyurea resin, etc. using the alicyclic diamine or alicyclic diamine composition of the present invention, can be used in a variety of applications, including various molded bodies, various housings, coatings, adhesives, composite materials, insulating materials, sealing materials, molding powders, gaskets, various coatings, water treatment agents, fiber treatment agents, dispersants, surfactants, bleaching agents, preservatives, paper strength enhancers, connectors, CO2 absorbents, dielectric materials, various films, electronic substrate materials, fiber materials, switches, etc.

[0234] However, the uses of the alicyclic diamine and the alicyclic diamine composition of the present invention are not limited to the above-described uses.

[0235] Example

[0236] The present invention will be described in detail below with examples and comparative examples, but the present invention is not limited to the following examples. It should be noted that the analysis and evaluation of the alicyclic diamine composition were performed by the following methods.

[0237] Gas chromatography

[0238] Equipment used: Gas chromatograph 8860GC (manufactured by Agilent Technologies, Inc.)

[0239] Column: DB-1 (length 30m, inner diameter 530μm, film thickness 1.5μm)

[0240] Detector: FID (H2 40 mL / min, air 450 mL / min)

[0241] Carrier gas: He

[0242] Flow split ratio: 5:1

[0243] Inlet temperature: 250℃

[0244] Detector temperature: 250℃

[0245] Injection volume: 1.0 μL

[0246] Oven temperature: Hold at 60℃ for 6 minutes, then increase the temperature from 60℃ to 280℃ at a rate of 7℃ / minute. Once the temperature reaches 280℃, hold for 20 minutes.

[0247] <gc-ms>

[0248] (GC side)

[0249] Equipment used: Gas chromatograph GC2010 Plus (manufactured by Shimadzu Corporation)

[0250] Column: DB-1MS (length 30m, inner diameter 0.25mm, film thickness 0.25μm)

[0251] Carrier gas: He

[0252] Flow split ratio: 5:1

[0253] Vaporization chamber temperature: 250℃

[0254] Injection volume: 1 μL

[0255] Oven temperature: Hold at 60℃ for 6 minutes, then increase the temperature from 60℃ to 280℃ at a rate of 7℃ / minute. Once the temperature reaches 280℃, hold for 20 minutes.

[0256] (MS side)

[0257] Equipment used: GCMS-QP2010 Ultra (manufactured by Shimadzu Corporation)

[0258] Fragmentation method: EI

[0259] Ion source temperature: 200℃

[0260] Interface temperature: 250℃

[0261] <Determination of Total Amine Value>

[0262] The total amine value of the alicyclic diamine composition was determined using an automatic potentiometric titration apparatus "AT-710S" manufactured by Kyoto Electronics Industries, Ltd., according to JIS-K-7237:1995, by potentiometric titration. The sample solvent was changed from o-nitrotoluene / acetic acid solution as described in JIS to acetic acid.

[0263] <Determination of Active Hydrogen Equivalent (AHEW)>

[0264] The AHEW of the alicyclic diamine composition and epoxy resin curing agent was determined using an automatic potentiometric titration apparatus "AT-710S" manufactured by Kyoto Electronics Industry Co., Ltd., and the AHEW was calculated from the result. The total amine value was determined using a 0.1 mol / L perchloric acid / acetic acid solution (manufactured by Kanto Chemical Co., Ltd.).

[0265] The structural identification of each component in the alicyclic diamine composition obtained in the examples was performed by NMR analysis under the following conditions.

[0266] (NMR analysis)

[0267] Equipment used: Bruker Japan AVANCE NEO 400 NMR device

[0268] Resonant frequency: 400MHz

[0269] Mode: Proton ( 1 H), carbon ( 13 C), HSQC ( 1 H- 13 C)

[0270] Measurement temperature: room temperature

[0271] Solvent: CDCl3 (deuterated chloroform)

[0272] Chemical shift reference material: Tetramethylsilane

[0273] <Evaluation of drying properties (touch drying)>

[0274] Zinc phosphate treated steel sheet (manufactured by PALTEK CORPORATION; SPCC-SD PB-N1440.8mm×70mm×150mm) was used as the substrate. An epoxy resin composition was applied to the substrate using a squeegee at 23°C and 50%RH to form a coating film (film thickness immediately after application: 200μm). The coating film was stored at 23°C and 50%RH and evaluated by touch after 1 day and 7 days according to the following criteria.

[0275] Example: Excellent (no stickiness from the coating or fingerprint residue when pressing the thumb with approximately 50N of force)

[0276] G: Good (No sticky coating when pressing the thumb with a force of about 50N, but fingerprints remain after touching)

[0277] F: Pass (When you press your thumb with a force of about 50N, there is a sticky coating)

[0278] P: Poor (a sticky coating is felt when pressing the thumb with approximately 5N of force)

[0279] <Evaluation of water resistance (water stain test)>

[0280] An epoxy resin composition was applied to a substrate (zinc phosphate treated steel sheet) using the same method described above to form a coating (200 μm thickness immediately after coating). The coating was stored at 23°C and 50% RH. After 1 day and 7 days, 2-3 drops of pure water were added to the coating surface using a dropper, and the area was capped with a 50 mL spiral tube. After 24 hours, the water was wiped off, and the appearance was visually observed and evaluated according to the following criteria. The results are shown in Table 1.

[0281] Example: Excellent (no change in appearance)

[0282] G: Good (no cloudiness or roughness, but reduced gloss is noticeable)

[0283] F: Pass (slightly cloudy or rough surface)

[0284] P: Poor (significant cloudiness or rough surface)

[0285] <Appearance>

[0286] An epoxy resin composition was applied to a substrate (zinc phosphate treated steel sheet) using the same method as described above to form a coating (thickness immediately after application: 200 μm). The appearance of the resulting coating was visually observed after one day, and its transparency and gloss were evaluated according to the following criteria.

[0287] (Transparency)

[0288] Example: Excellent (no white discharge)

[0289] G: Good (slightly cloudy, but no problems with use)

[0290] F: Possible (slightly cloudy)

[0291] P: Unhealthy (cloudy)

[0292] (luster)

[0293] Example: Excellent (glossy)

[0294] G: Good (slightly less glossy, but no problems with use)

[0295] F: Pass (low gloss)

[0296] P: Poor quality (dull)

[0297] Example 1

[0298] (Preparation of alicyclic diamine compositions)

[0299] (1) Diels-Alder reaction process

[0300]

[0301] (In equation (6), -CN is bonded to a or b.)

[0302] 150 g (1.53 mol) of furfuryl alcohol and 405 g (7.63 mol) of acrylonitrile were added to a 1000 mL two-necked flask equipped with a condenser. The mixture was heated to 60 °C in an oil bath under a nitrogen atmosphere and stirred to prepare a homogeneous solution. The reaction was carried out at 60 °C for 48 hours with stirring.

[0303] After cooling, acrylonitrile is removed in an evaporator to obtain 210g of a concentrated solution containing the nitrile composition shown in the aforementioned formula (6) (containing nitrile with -CN bonded to a and nitrile with -CN bonded to b).

[0304] (2) Hydrogenation process of olefins

[0305]

[0306] (In equation (6), -CN is bonded to a or b. In equation (7), -CN is bonded to a or b.)

[0307] Next, 210g of the aforementioned concentrated solution, 1.2g of 5% Pd / C catalyst (56.7% water content, 0.52g dry weight) and 27g of ethyl acetate were added into a 500mL autoclave. After purging the reactor with nitrogen and hydrogen, hydrogen was introduced at a pressure of 2.0MPa, and the reaction was carried out at a reaction temperature of 60°C for 2 hours while stirring.

[0308] Then, the mixture was cooled and the furfuryl alcohol and ethyl acetate were removed by simple distillation to obtain 160g of a concentrated solution containing the nitrile composition shown in the aforementioned formula (7) (containing nitrile with -CN bonded to a and nitrile with -CN bonded to b).

[0309] (3) Acrylonitrile addition process

[0310]

[0311] (In equation (7), -CN is bonded to a or b. In equation (4), -CN is bonded to a or b.)

[0312] Next, 160g of the aforementioned concentrated solution, 160g of tetrahydrofuran, 4.5g of 50% sodium hydroxide aqueous solution, and 77g of acrylonitrile were added to a 1000mL two-necked flask equipped with a condenser. The solution was heated to 25°C in a water bath and stirred to form a homogeneous solution. The reaction was carried out at a reaction temperature of 25°C for 6 hours while stirring. After the reaction was completed, the solution was neutralized with 1mol / L hydrochloric acid, and the tetrahydrofuran was removed in an evaporator. Then, 100mL of water was added, and the solution was extracted with a mixture of ethyl acetate / methanol (127mL / 5mL). The extract was washed with a saturated sodium carbonate aqueous solution, dehydrated with magnesium sulfate, and the solvent was removed in an evaporator to obtain 180g of concentrated solution containing the dinitrile composition shown in the aforementioned formula (4) (containing dinitrile with -CN bonded to a and dinitrile with -CN bonded to b).

[0313] (4) Hydrogenation process of dinitrile

[0314]

[0315] (In equation (4), -CN is bonded to a or b. In equation (1), -CH2NH2 is bonded to a or b.)

[0316] Next, 150g of the aforementioned concentrated solution containing the dinitrile composition shown in formula (4), 15g of sponge cobalt catalyst (RANEY2724, manufactured by WRGrace) (40.0% water content, 9g dry weight) and 150g of tetrahydrofuran were added into a 500mL high-pressure reactor. After purging the reactor with nitrogen and hydrogen, hydrogen was introduced at a hydrogen pressure of 8.0MPa, and the reaction was carried out for 2 hours at a reaction temperature of 120°C while stirring.

[0317] After cooling, the resulting reaction mixture was filtered to remove the sponge cobalt catalyst, and tetrahydrofuran was removed from the filtrate in an evaporator to obtain 150 g of concentrate. The concentrate was simply distilled to obtain the alicyclic diamine composition shown in formula (1). The combined purity of 3-((3-(aminomethyl)-7-oxabicyclo[2.2.1]heptane-1-yl)methoxy)propane-1-amine (the alicyclic diamine shown in formula (2)) and 3-((2-(aminomethyl)-7-oxabicyclo[2.2.1]heptane-1-yl)methoxy)propane-1-amine (the alicyclic diamine shown in formula (3)) was 99.9% based on the peak area in gas chromatography.

[0318] In the obtained alicyclic diamine composition, the molar ratio ((2) / (3)) of the alicyclic diamine shown in formula (2) to that shown in formula (3) is 35 / 65. The total amine value of the aforementioned alicyclic diamine composition is 522 mg KOH / g. The theoretical total amine value is 523.6 mg KOH / g, which is approximately the same. In addition, the AHEW of the aforementioned alicyclic diamine composition is 54 g / equivalent.

[0319] The NMR analysis results of the obtained alicyclic diamine composition are shown. It should be noted that the NMR results were obtained using HSQC (…). 1 H- 13 C), confirm in 1 The peaks observed in the H-NMR spectrum are determined to be signals from protons of hydrogen atoms bonded to a specific carbon atom or from protons of hydrogen atoms bonded to nitrogen atom. This requires confirmation within the H-NMR spectrum. 13 The peaks observed in the C-NMR spectrum represent the signals of which carbon atom.

[0320]

[0321] 1 ¹H-NMR chemical shifts: δ: 1.12 (s, 4H, [b]), 0.97–2.29 (m, 9H, [a]), 1.85–2.85 (m, 4H, [c]), 3.54–3.80 (m, 4H, [d]), 4.33–4.52 (m, 1H, [e])

[0322]

[0323] 13 C-NMR chemical shifts: δ: 24.97, 26.40, 30.51, 30.95, 31.26, 31.28, 32.03, 33.30, 33.53, 33.57, 36.85, 36.94, 37.07, 37.42, 39.60, 39.62, 39.63, 39.69, 44.17 ,44.31,44.61,45.97,46.29,47.74,47.77,69.84,69.91,70.01,70.71,71.75,71.85,72.01,76.44,76.65,78.94,79.00,85.91,85.98,86.37,87.44

[0324] 24.97~37.42 carbon atoms from [A]. 39.60~44.61 carbon atoms from [B]. 45.97~47.77 carbon atoms from [C]. 69.84~72.01 carbon atoms from [D]. 76.44~79.00 carbon atoms from [E]. 85.91~87.44 carbon atoms from [F].

[0325] In addition, the GC-MS analysis results of the obtained alicyclic diamine composition, corresponding to the molecular weight of each alicyclic diamine constituting the alicyclic diamine composition of 214, show 214.

[0326] Example 2

[0327] (Preparation of epoxy resin curing agent)

[0328] For the aforementioned alicyclic diamine composition, benzyl alcohol, as a non-reactive diluent, was added as a 40% by weight amount to dilute the composition, resulting in an epoxy resin curing agent with a concentration of 60% by weight of the aforementioned alicyclic diamine composition. The active hydrogen equivalent (AHEW) derived from the amino group of the epoxy resin curing agent (containing the total amount of benzyl alcohol) was 90 g / equivalent.

[0329] (Preparation and evaluation of epoxy resin compositions)

[0330] The epoxy resin used as the main component is a liquid epoxy resin (manufactured by Mitsubishi Chemical Corporation, "jER828", epoxy equivalent 186 g / equivalent) having a glycidyl group derived from bisphenol A.

[0331] The epoxy resin and the aforementioned epoxy resin curing agent were mixed in the proportions shown in Table 1, and stirred and mixed at 23°C to prepare an epoxy resin composition. The ratio of the number of active hydrogen atoms in the epoxy resin curing agent to the number of epoxy groups in the main epoxy resin (number of active hydrogen atoms in the epoxy resin curing agent / number of epoxy groups in the main epoxy resin) was set to 1 / 1.

[0332] The obtained epoxy resin composition was used to evaluate its drying properties, water resistance, and appearance using the aforementioned method. The results are shown in Table 1.

[0333] Comparison of Examples 1 and 2

[0334] (Preparation and evaluation of epoxy resin compositions)

[0335] In Example 1, 1,3-BAC (1,3-bis(aminomethyl)cyclohexane) and IPDA (isophorone diamine) were used instead of the aforementioned alicyclic diamine composition. Otherwise, the epoxy resin composition was prepared and evaluated using the same method as in Example 1. The results are shown in Table 1.

[0336] Example 3

[0337] (Preparation of epoxy resin curing agent)

[0338] In a detachable flask with a volume of 300 ml, equipped with a stirrer, thermometer, nitrogen inlet tube, dropping funnel, and condenser, 29 g of the alicyclic diamine composition obtained in Example 1 was added. Under a nitrogen flow, while stirring, 10 g of a multifunctional epoxy resin (Mitsubishi Chemical Corporation "jER828", epoxy equivalent: 186 g / equivalent) with glycidyl group derived from bisphenol A was added dropwise over 2 hours (to achieve an amount where the number of active hydrogens in the aforementioned alicyclic diamine composition / the number of epoxy groups in the epoxy compound = 10 / 1). After the addition was completed, the temperature was raised to 80°C and the reaction was carried out for 2 hours to obtain the reactant of the epoxy compound and the alicyclic diamine composition. Benzyl alcohol was added as a non-reactive diluent to make it 40% by mass of the total amount, and the mixture was diluted to obtain an epoxy resin curing agent with a concentration of 60% by mass. The active hydrogen equivalent (AHEW) of the epoxy resin curing agent (containing the total amount of benzyl alcohol) is 134 g / equivalent.

[0339] (Preparation and evaluation of epoxy resin compositions)

[0340] The epoxy resin used as the main component is a liquid epoxy resin (manufactured by Mitsubishi Chemical Corporation, "jER828", epoxy equivalent 186 g / equivalent) having a glycidyl group derived from bisphenol A.

[0341] Epoxy resin and epoxy resin curing agent were mixed in the proportions shown in Table 1, and stirred and mixed at 23°C to prepare an epoxy resin composition. The ratio of the number of active hydrogen atoms in the epoxy resin curing agent to the number of epoxy groups in the main epoxy resin (number of active hydrogen atoms in the epoxy resin curing agent / number of epoxy groups in the main epoxy resin) was set to 1 / 1.

[0342] The obtained epoxy resin composition was used to evaluate its drying properties, water resistance, and appearance using the aforementioned method. The results are shown in Table 1.

[0343] Compare Examples 3 and 4

[0344] (Preparation and evaluation of epoxy resin compositions)

[0345] In Example 3, 1,3-BAC (1,3-bis(aminomethyl)cyclohexane) and IPDA (isophorone diamine) were used instead of the aforementioned alicyclic diamine composition. Otherwise, the epoxy resin composition was prepared and evaluated using the same method as in Example 3. The results are shown in Table 1.

[0346] [Table 1]

[0347]

[0348] As shown in Table 1, the epoxy resin composition using the epoxy resin curing agent containing the alicyclic diamine of the present invention exhibits excellent water resistance. Furthermore, the epoxy resin composition using the epoxy resin curing agent containing the alicyclic diamine of the present invention demonstrates excellent drying properties, and the resulting cured product also exhibits excellent appearance. Therefore, the alicyclic diamine and alicyclic diamine composition of the present invention are particularly useful as epoxy resin curing agents.

[0349] Therefore, the alicyclic diamines and alicyclic diamine compositions of the present invention, the epoxy resin curing agents using them, and the epoxy resin compositions thereof are suitable for use in coatings. Furthermore, in fields other than coatings, they are also suitable for use in flooring materials, linings, and other applications that come into contact with water.

Claims

1. The alicyclic diamine represented by the following general formula (1), In equation (1), -CH2NH2 is bonded to a or b.

2. The alicyclic diamine according to claim 1, wherein the biomass content is 30% by mass or more.

3. An alicyclic diamine composition comprising an alicyclic diamine of formula (2) and an alicyclic diamine of formula (3). 。 4. The alicyclic diamine composition according to claim 3, wherein the biomass content is 30% by mass or more.

5. An epoxy resin curing agent comprising at least one selected from the group consisting of an alicyclic diamine of claim 1 or 2, an alicyclic diamine composition of claim 3 or 4, a reactant of an epoxy compound having at least one epoxy group with an alicyclic diamine of claim 1 or 2, and a reactant of an epoxy compound having at least one epoxy group with an alicyclic diamine composition of claim 3 or 4.

6. The epoxy resin curing agent according to claim 5, wherein the biomass content is 30% by mass or more.

7. A method for producing an alicyclic diamine, wherein, Hydrogenation of the dinitrile represented by general formula (4) or the dinitrile represented by general formula (5) yields the alicyclic diamine represented by general formula (1). In equations (4) and (5), -CN is bonded to a or b. In equation (1), -CH2NH2 is bonded to a or b.

8. The method for producing an alicyclic diamine according to claim 7, wherein, The dinitrile represented by general formula (4) or the dinitrile represented by general formula (5) is a dinitrile obtained from furfural or furfural alcohol.

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