Isosorbide epoxy derivative compound, method for preparing same, epoxy resin composition, and cured product thereof

Abstract

The present invention relates to an isosorbide epoxy derivative compound comprising at least one amine substituent, a method for preparing same, an epoxy resin composition, and a cured product thereof.

Description

Isosorbide epoxy derivative compound and method for preparing the same, epoxy resin composition and cured product thereof

[0001] The present invention relates to an isosorbide epoxy derivative compound and a method for manufacturing the same, an epoxy resin composition and a cured product thereof.

[0002]

[0003] Epoxy resin is a representative thermosetting resin that began to be commercially produced in the 1940s due to its high mechanical properties, excellent thermal stability, chemical resistance, and corrosion resistance, and is the most widely used in various applications for high-performance composites, electrical / electronic insulators, adhesives, and coatings. Epoxy resin is rarely used alone; instead, it exhibits excellent performance by being cross-linked three-dimensionally using a curing agent.

[0004] Curing agents that can be used with epoxy resins can be broadly classified into amine-based curing agents, amide-based curing agents, and acid anhydride-based curing agents, among which amine-based curing agents are the most widely used. Depending on their chemical structure, amine-based curing agents can be applied in a wide variety of physical properties and fields of application.

[0005] The backbone of amine-based curing agents consists of petrochemical raw materials such as bisphenol A (BPA). However, BPA is an endocrine disruptor with a structure similar to the female hormone estrogen, and as it is recognized as a highly toxic substance, there is a global trend to ban its use in applications involving contact with the human body. In particular, not only developed countries, led by the EU, but also Korea is restricting its use in household goods.

[0006] Therefore, there is a need to develop amine-based curing agents that can achieve physical properties equivalent to or better than those of BPA, while being eco-friendly and capable of solving environmental problems.

[0007]

[0008] The object of the present invention is to provide an isosorbide epoxy derivative compound having an amine terminal structure and a method for preparing the same.

[0009] In addition, the object of the present invention is to provide an epoxy resin composition comprising the isosorbide epoxy derivative compound and a cured product thereof.

[0010]

[0011] The problems that the present invention aims to solve are not limited to the problem(s) mentioned above, and other unmentioned problems will be clearly understood by those skilled in the art from the description below.

[0012]

[0013] To achieve the above objective, the present invention provides an isosorbide epoxy derivative compound comprising at least one amine substituent.

[0014] The above isosorbide epoxy derivative compound may have a viscosity of 50 cps or more and 40,000 cps or less at 25 ℃.

[0015] The above isosorbide epoxy derivative compound may have an epoxy active hydrogen equivalent (AHEW) of 50 g / eq or more and 500 g / eq or less.

[0016] The above amine substituent may be derived from at least one of an aliphatic amine, alicyclic amine, aromatic aliphatic amine, and aromatic amine.

[0017] The above isosorbide epoxy derivative compound may have a biocarbon content of 30% or more and 70% or less.

[0018]

[0019] In addition, the present invention provides a method for preparing an isosorbide epoxy derivative compound, comprising the steps of: preparing an isosorbide epoxy compound; and reacting an amine compound containing one or more diamine compounds with the isosorbide epoxy compound at a temperature of 25°C or higher and 150°C or lower for a time of 30 minutes or more and 6 hours or less.

[0020] The molar ratio of the above isosorbide epoxy compound and the above amine compound may be 1:0.1 to 1:5.

[0021]

[0022] In addition, the present invention provides an epoxy resin composition comprising the isosorbide epoxy derivative compound; and an epoxy resin.

[0023] The above epoxy resin composition may further include a diluent.

[0024] The content of the above isosorbide epoxy derivative compound may be 40 parts by weight or more and 160 parts by weight or less per 100 parts by weight of the epoxy resin.

[0025] The above epoxy resin composition may be a water-dispersible epoxy resin composition.

[0026] The above epoxy resin composition may have a color change (△Eab) of less than 10 as measured by ASTM G154 standard after 20 days of curing.

[0027]

[0028] In addition, the present invention provides a cured product formed by curing the epoxy resin composition.

[0029] The biocarbon content of the above cured product may be 10% or more and 90% or less.

[0030]

[0031] The epoxy resin containing the isosorbide epoxy derivative compound of the present invention can exhibit a high biocarbon content.

[0032] In addition, the isosorbide epoxy derivative compound of the present invention can be used not only as a curing agent for non-aqueous epoxy but also as a curing agent for aqueous epoxy.

[0033] In addition, the isosorbide epoxy derivative compound of the present invention exhibits lower viscosity than bisphenol A-based curing agents and has excellent adhesion and anti-yellowing properties.

[0034]

[0035] The effects of the present invention are not limited to the effects described above, and should be understood to include all effects that can be inferred from the configuration of the invention described in the detailed description of the invention or the claims.

[0036]

[0037] Hereinafter, embodiments of the present invention will be described in detail. However, these are presented as examples and are not intended to limit the present invention, and the present invention is defined only by the scope of the claims set forth below.

[0038]

[0039] In one embodiment of the present invention, an isosorbide epoxy derivative compound comprising at least one amine substituent is provided.

[0040] In one embodiment, the amine substituent may be derived from at least one of an aliphatic amine, alicyclic amine, aromatic aliphatic amine, and aromatic amine.

[0041] In one embodiment, the at least one amine substituent may comprise at least one of the following formulas 2-1 to 2-20:

[0042] [Chemical Formula 2-1] [Chemical Formula 2-2]

[0043]

[0044] [Chemical Formula 2-3] [Chemical Formula 2-4]

[0045]

[0046] [Chemical Formula 2-5]

[0047]

[0048] [Chemical Formula 2-6]

[0049]

[0050] [Chemical Formula 2-7]

[0051]

[0052] [Chemical Formula 2-8] [Chemical Formula 2-9]

[0053]

[0054] [Chemical Formula 2-10] [Chemical Formula 2-11]

[0055]

[0056] [Chemical Formula 2-12]

[0057]

[0058] [Chemical Formula 2-13] [Chemical Formula 2-14]

[0059]

[0060] [Chemical Formula 2-15] [Chemical Formula 2-16]

[0061]

[0062] [Chemical Formula 2-17] [Chemical Formula 2-18]

[0063]

[0064] [Chemical Formula 2-19] [Chemical Formula 2-20]

[0065]

[0066]

[0067] In the above chemical formulas 2-1 to 2-14 and the above chemical formulas 2-18 to 2-20,

[0068] Either X1 or X2 is NH2, and the other is And,

[0069] In the above chemical formulas 2-15 and 2-17,

[0070] X3 is And,

[0071] In the above chemical formulas 2-1 to 2-20,

[0072] is a position connected to the above isosorbide epoxy derivative compound, and

[0073] In the above chemical formula 2-1,

[0074] R1 to R5 are each independently hydrogen, or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and n1 is an integer from 0 to 10, and

[0075] In the above chemical formulas 2-12 to 2-13,

[0076] n2 to n5 are integers from 1 to 10, and

[0077] In the above chemical formulas 2-14 to 2-15,

[0078] R6 to R8 are each independently substituted or unsubstituted alkylene groups having 1 to 10 carbon atoms, and

[0079] In the above chemical formula 2-16,

[0080] n6 is an integer from 0 to 10.

[0081]

[0082] In one embodiment, the isosorbide epoxy derivative compound may include two of the formulas 2-1 to 2-20.

[0083] In one embodiment, the isosorbide epoxy derivative compound may be represented by the following chemical formula 1.

[0084] [Chemical Formula 1]

[0085]

[0086] In the above Chemical Formula 1, R9 and R 10 Each is independently the aforementioned amine substituent, and n is an integer from 0 to 100. Specifically, R9 and R 10 Each can be independently represented by any one of the following chemical formulas 2-1 to 2-20.

[0087] [Chemical Formula 2-1] [Chemical Formula 2-2]

[0088]

[0089] [Chemical Formula 2-3] [Chemical Formula 2-4]

[0090]

[0091] [Chemical Formula 2-5]

[0092]

[0093] [Chemical Formula 2-6]

[0094]

[0095] [Chemical Formula 2-7]

[0096]

[0097] [Chemical Formula 2-8] [Chemical Formula 2-9]

[0098]

[0099] [Chemical Formula 2-10] [Chemical Formula 2-11]

[0100]

[0101] [Chemical Formula 2-12]

[0102]

[0103] [Chemical Formula 2-13] [Chemical Formula 2-14]

[0104]

[0105] [Chemical Formula 2-15] [Chemical Formula 2-16]

[0106]

[0107] [Chemical Formula 2-17] [Chemical Formula 2-18]

[0108]

[0109] [Chemical Formula 2-19] [Chemical Formula 2-20]

[0110]

[0111] In the above chemical formulas 2-1 to 2-14 and the above chemical formulas 2-18 to 2-20,

[0112] Either X1 or X2 is NH2, and the other is And,

[0113] In the above chemical formulas 2-15 and 2-17,

[0114] X3 is is,

[0115] In the above chemical formulas 2-1 to 2-20,

[0116] is a position connected to the above-mentioned isosorbide epoxy compound derivative, and

[0117] In the above chemical formula 2-1,

[0118] R1 to R5 are each independently hydrogen, or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and n1 is an integer from 0 to 10, and

[0119] In the above chemical formulas 2-12 to 2-13,

[0120] n2 to n5 are integers from 1 to 10, and

[0121] In the above chemical formulas 2-14 to 2-15,

[0122] R6 to R8 are each independently substituted or unsubstituted alkylene groups having 1 to 10 carbon atoms, and

[0123] In the above chemical formula 2-16,

[0124] n6 is an integer from 0 to 10.

[0125]

[0126] In one embodiment, the viscosity of the isosorbide epoxy derivative compound at 25°C may be 50 cps or more and 40,000 cps or less, 50 cps or more and 35,000 cps or less, 50 cps or more and 30,000 cps or less, 50 cps or more and 25,000 cps or less, 50 cps or more and 20,000 cps or less, 50 cps or more and 17,000 cps or less, or 80 cps or more and 16,400 cps or less. When the viscosity of the isosorbide epoxy derivative compound satisfies the above range, it can be quickly mixed with the epoxy resin, thereby increasing efficiency in the manufacturing process.

[0127] In one embodiment, the isosorbide epoxy derivative compound may have an active hydrogen equivalent (AHEW) of 50 g / eq or more and 500 g / eq or less. When the active hydrogen equivalent of the isosorbide epoxy derivative compound satisfies the above range, it can be used smoothly with epoxy resin, thereby increasing efficiency in coating operations. In addition, it may have excellent physical properties as an epoxy curing agent.

[0128] In one embodiment, the isosorbide epoxy derivative compound may have a biocarbon content of 30% or more and 70% or less, or 30% or more and 60% or less.

[0129] In one embodiment, the isosorbide epoxy derivative compound can be used as a curing agent for epoxy resin.

[0130]

[0131] In one embodiment of the present invention, a method for preparing the aforementioned isosorbide epoxy derivative compound is provided, comprising the steps of: preparing an isosorbide epoxy compound; and reacting an amine compound comprising one or more diamine compounds with the isosorbide epoxy compound at a temperature of 25°C or higher and 150°C or lower for a time of 30 minutes or more and 6 hours or less.

[0132] The above-described isosorbide epoxy derivative compound can be prepared according to the method for preparing the above-described isosorbide epoxy derivative compound.

[0133] In one embodiment, the method for preparing the isosorbide epoxy derivative compound may be a method for preparing a curing agent for an epoxy resin.

[0134] In one embodiment, the isosorbide epoxy compound may be represented by the following chemical formula 1-A.

[0135] [Chemical Formula 1-A]

[0136]

[0137] In the above chemical formula 1-A,

[0138] x is an integer from 0 to 100.

[0139]

[0140] In one embodiment, the amine compound may comprise at least one of the following chemical formulas 2-1 to 2-20. Specifically, it may comprise one or more diamine compounds among the following chemical formulas 2-1 to 2-20.

[0141] [Chemical Formula 2-1] [Chemical Formula 2-2]

[0142]

[0143] [Chemical Formula 2-3] [Chemical Formula 2-4]

[0144]

[0145] [Chemical Formula 2-5]

[0146]

[0147] [Chemical Formula 2-6]

[0148]

[0149] [Chemical Formula 2-7]

[0150]

[0151] [Chemical Formula 2-8] [Chemical Formula 2-9]

[0152]

[0153] [Chemical Formula 2-10] [Chemical Formula 2-11]

[0154]

[0155] [Chemical Formula 2-12]

[0156]

[0157] [Chemical Formula 2-13] [Chemical Formula 2-14]

[0158]

[0159] [Chemical Formula 2-15] [Chemical Formula 2-16]

[0160]

[0161] [Chemical Formula 2-17] [Chemical Formula 2-18]

[0162]

[0163] [Chemical Formula 2-19] [Chemical Formula 2-20]

[0164]

[0165] In the above chemical formulas 2-1 to 2-14 and the above chemical formulas 2-18 to 2-20,

[0166] Either X1 or X2 is NH2, and the other is And,

[0167] In the above chemical formulas 2-15 and 2-17,

[0168] X3 is is,

[0169] In the above chemical formulas 2-1 to 2-20,

[0170] is a position connected to the above-mentioned isosorbide epoxy compound derivative, and

[0171] In the above chemical formula 2-1,

[0172] R1 to R5 are each independently hydrogen, or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and n1 is an integer from 0 to 10, and

[0173] In the above chemical formulas 2-12 to 2-13,

[0174] n2 to n5 are integers from 1 to 10, and

[0175] In the above chemical formulas 2-14 to 2-15,

[0176] R6 to R8 are each independently substituted or unsubstituted alkylene groups having 1 to 10 carbon atoms, and

[0177] In the above chemical formula 2-16,

[0178] n6 is an integer from 0 to 10.

[0179]

[0180] In one embodiment, the amine compound and the isosorbide epoxy compound can be reacted in a temperature range of 25°C or higher and 150°C or lower, 25°C or higher and 145°C or lower, 35°C or higher and 140°C or lower, 45°C or higher and 135°C or lower, 55°C or higher and 130°C or lower, 65°C or higher and 125°C or lower, 75°C or higher and 120°C or lower, 80°C or higher and 110°C or lower, or 80°C or higher and 100°C.

[0181] In one embodiment, by reacting for a time of 30 minutes or more and 6 hours or less, 30 minutes or more and 5 hours or less, 30 minutes or more and 4 hours or less, 30 minutes or more and 3 hours or less, 30 minutes or more and 2 hours or less, or 30 minutes or more and 1 hour or less in the above temperature range, an isosorbide epoxy derivative compound used as a curing agent for epoxy resin can be safely stored without problems such as thickening during storage.

[0182] In one embodiment, the molar ratio of the isosorbide epoxy compound and the amine compound may be 1:0.1 to 1:5. When the above-described molar ratio is satisfied, an isosorbide epoxy derivative compound having a viscosity of 8 cps or more and 40,000 cps or less as described above can be prepared at 25°C.

[0183] In one embodiment, the number of moles of the amine compound may be the sum of the total number of moles of one or more diamine compounds.

[0184] In one embodiment, the method for preparing the isosorbide epoxy derivative compound involves reacting an amine compound with the isosorbide epoxy-based compound, so that an unreacted amine compound may remain as a reaction product in addition to the isosorbide epoxy derivative compound.

[0185] In one embodiment, the reaction product may be mixed with a diluent. The diluent may be mixed to lower the viscosity of the reaction product produced by reacting an amine compound with an isosorbide epoxy compound.

[0186] In one embodiment, the diluent can be reacted with the isosorbide epoxy compound after uniformly mixing the amine compound and the diluent to lower the viscosity of the amine compound and facilitate mixing with the isosorbide epoxy compound.

[0187] In one embodiment, the diluent may be at least one selected from the group consisting of deionized water, n-butanol, xylene, benzyl alcohol, propylene glycol monoethyl ether (PGME), methanol, ethanol, propanol, propylene glycol, cetyl alcohol, lauryl alcohol, ethylene glycol, and combinations thereof.

[0188]

[0189] In one embodiment of the present invention, an epoxy resin composition comprising an isosorbide epoxy derivative compound; and an epoxy resin is provided.

[0190] The above-mentioned isosorbide epoxy derivative compound is identical to the isosorbide epoxy derivative compound described above and can be used as an epoxy resin curing agent; the above-mentioned parts and repeated descriptions are briefly explained or omitted.

[0191] In one embodiment, the content of the isosorbide epoxy derivative compound may be 40 parts by weight or more and 160 parts by weight or less per 100 parts by weight of the epoxy resin. When the content of the isosorbide epoxy derivative compound satisfies the range described above, it may have a biocarbon content and excellent adhesion.

[0192] In one embodiment, a diluent may be further included in the epoxy resin or isosorbide epoxy derivative compound to cure the epoxy resin composition. The content of the diluent may be 5 parts by weight or more and 90 parts by weight or less per 100 parts by weight of the epoxy resin. When the content of the diluent satisfies the above-described range, viscosity control may be easy.

[0193] In one embodiment, the diluent may be at least one selected from the group consisting of deionized water, n-butanol, xylene, benzyl alcohol, propylene glycol monoethyl ether (PGME), methanol, ethanol, propanol, propylene glycol, cetyl alcohol, lauryl alcohol, ethylene glycol, and combinations thereof.

[0194] In one embodiment, the epoxy resin composition may be a water-dispersible epoxy resin composition.

[0195] In one embodiment, the epoxy resin composition may have a color change (△Eab) of less than 10 as measured by ASTM G154 at 20 days after curing. If the color change is less than 10, the problem of discoloration over time after applying the epoxy-based paint can be prevented.

[0196]

[0197] In one embodiment of the present invention, a cured product formed by curing the above-described epoxy resin composition is provided.

[0198] The biocarbon content of the above cured product may be 10% or more and 90% or less.

[0199]

[0200] The above description explains the technical concept of the present invention using one embodiment, and those skilled in the art to which the present invention pertains will be able to make various modifications and variations within the scope of the essential characteristics of the present invention. Accordingly, the embodiments described in this invention are intended to explain, not limit, the technical concept of the present invention, and the scope of the technical concept of the present invention is not limited by such embodiments. The scope of protection of the present invention shall be interpreted by the claims, and all technical concepts within an equivalent scope shall be interpreted as being included within the scope of rights of the present invention.

[0201]

[0202] <Example>

[0203] Example 1

[0204] JEFFAMINE D-230 (240g, 1mol) and Wanamine-2300 (125g, 0.5mol) were added to a 2,000 mL reaction vessel and heated to 80°C while stirring. Subsequently, KDBM-1010 (320g, 1mol, epoxy equivalent (EEW)=160g / eq, BRC>99%), an isosorbide (ISB)-based isosorbide epoxy (ISBE) from Kookdo Chemical, was slowly added and reacted at 100°C for 1 hour to produce a product represented by Chemical Formula 1 below. The product was cooled to 90°C and 456g of deionized water was slowly added to produce an isosorbide epoxy derivative compound (curing agent) represented by Chemical Formula 1-1 below as the main product.

[0205] [Chemical Formula 1-1]

[0206]

[0207] In the above chemical formula 1-1, n21 is about 2.5 (state average value) and n22 is about 0.3 (state average value).

[0208]

[0209] Examples 2 to 10

[0210] A curing agent composition comprising an isosorbide epoxy derivative compound represented by the following chemical formulas 1-2, 1-4 to 1-5, and 1-7 to 1-12 as the main product was prepared by the same method and conditions as in Example 1, except that instead of the amine compounds used in Example 1, JEFFAMINE D230 (240 g, 1 mol) and Wanamine-2300 (125 g, 0.5 mol), JEFFAMINE D230, Wanamine-2300, IPDA, MXDA, PACM, TEPA, N-AEP, or DMAPAPA were used as amine compounds in the amounts shown in Tables 1 and 2 below, and instead of 456 g of deionized water, a diluent was used in the amounts shown in Tables 1 and 2 below.

[0211] Example 2: [Chemical Formula 1-2]

[0212]

[0213] In the above chemical formula 1-2, n21 is about 2.5 (state average value) and n22 is about 0.3 (state average value).

[0214]

[0215] Example 3: [Chemical Formula 1-4]

[0216]

[0217] In the above chemical formula 1-4, n22 is approximately 0.3 (average value stated).

[0218]

[0219] Example 4: [Chemical Formula 1-5]

[0220]

[0221] In the above chemical formula 1-5, n22 is approximately 0.3 (average value stated).

[0222]

[0223] Example 5: [Chemical Formula 1-7]

[0224]

[0225] In the above chemical formula 1-7, n22 is approximately 0.3 (average value stated).

[0226]

[0227] Example 6: [Chemical Formula 1-8]

[0228]

[0229] In the above chemical formula 1-8, n22 is approximately 0.3 (average value stated).

[0230]

[0231] Example 7: [Chemical Formula 1-9]

[0232]

[0233] In the above chemical formula 1-9, n22 is approximately 0.3 (average value stated).

[0234]

[0235] Example 8: [Chemical Formula 1-10]

[0236]

[0237] In the above chemical formula 1-10, n22 is approximately 0.3 (average value stated).

[0238]

[0239] Example 9: [Chemical Formula 1-11]

[0240]

[0241] In the above chemical formula 1-11, n22 is approximately 0.3 (average value stated).

[0242]

[0243] Example 10: [Chemical Formula 1-12]

[0244]

[0245] In the above chemical formula 1-12, n22 is approximately 0.3 (average value stated).

[0246]

[0247] Reference Example 1

[0248] 610g of KMH-101 from Kukdo Chemical was added to a 2,000mL reaction vessel, followed by the addition of 200g of Xylene and 100g of n-BuOH, and the mixture was stirred to be uniformly mixed. The temperature of the uniformly mixed reaction mixture was raised to 80℃, and KDBM-1010 (90g, 0.28mol, EEW=160g / mol, BRC>99%), an ISB-based ISBE from Kukdo Chemical, was slowly added. The mixture was reacted at 100℃ for 1 hour to prepare an isosorbide epoxy derivative compound (curing agent).

[0249]

[0250] Reference Example 2

[0251] 650g of Kukdo Chemical’s G-5022 was added to a 2,000mL reaction vessel, followed by the addition of 200g of Xylene and 100g of n-BuOH, and the mixture was stirred to be uniformly mixed. The temperature of the uniformly mixed reaction mixture was raised to 80℃, and Kukdo Chemical’s ISB-based ISBE, KDBM-1010 (50g, 0.16mol, EEW=160g / mol, BRC>99%), was slowly added. The mixture was reacted at 100℃ for 1 hour to prepare an isosorbide epoxy derivative compound (curing agent).

[0252]

[0253] Raw Material Example 1 Example 2 Example 3 Example 4 Example 5 W-2300(g) 125250---IPDA(g)--340-255MXDA(g)---272-PACM(g)-----JEFFAMINE D230(g) 240240---KDBM-1010(g) 320320320320320Water(g) 456540440394382 * W-2300: Kukdo Chemical's Wanamine-2300* IPDA: Isophorone diamine* MXDA: m-Xylylenediamine* PACM: 4,4'-Diaminodicyclohexylmethane* JEFFAMINE D230: Kukdo Chemical's JEFFAMINE D230

[0254]

[0255] Raw Material Example 6 Example 7 Example 8 Example 9 Example 10 Reference Example 1 Reference Example 2 TEPA(g)-378-----IPDA(g)170---170--MXDA(g)----136--N-AEP(g)--320---DMAPAPA(g)--260---JEFFAMINE D230(g)120------KMH-101(g)-----610-G-5022(g)------650KDBM-1010(g)3203203203203209050Water(g)406465425388417--Xylene(g)-----200200n-BuOH(g)-----100100* TEPA: Tetraethylenepentamine* IPDA: Isophorone diamine* MXDA: m-Xylylenediamine* N-AEP: N-Aminoethylpiperazine* DMAPAPA: N,N-Dimethyldipropylene triamine* JEFFAMINE D230: Kukdo Chemical's JEFFAMINE D230* KMH-101: Kukdo Chemical's KMH-101* G-5022: Kukdo Chemical's G-5022

[0256]

[0257] <Comparative Example>

[0258] Comparative Example 1

[0259] JEFFAMINE D-230 (480g, 2mol) and Wanamine-2300 (250g, 1mol) were added to a 2,000mL reaction vessel, and 735g of benzyl alcohol was added and heated to 80℃. Afterwards, YD-128 (374g, 1mol, EEW=187g / mol), a Liquid Epoxy Resin (LER) from Kookdo Chemical, was slowly added and reacted at 100℃ for 1 hour to prepare a product (curing agent).

[0260]

[0261] Comparative Example 2

[0262] A product (curing agent) was prepared using the same method and conditions as in Comparative Example 1, except that IPDA (680g, 4mol) was used instead of JEFFAMINE D-230 (480g, 2mol) and Wanamine-2300 (250g, 1mol) in Comparative Example 1, and 700g was used instead of 735g of benzyl alcohol.

[0263]

[0264] Comparative Example 3

[0265] JEFFAMINE D-230 (480g, 1mol) and Wanamine-2300 (250g, 0.5mol) were added to a 2,000mL reaction vessel, and 493g of benzyl alcohol was added and heated to 80℃. Afterwards, Kookdo Chemical's LER YD-128 (374g, 1mol, EEW=187g / mol) was slowly added and reacted at 100℃ for 1 hour to produce a product (curing agent).

[0266]

[0267] Raw Material Comparative Example 1 Comparative Example 2 Comparative Example 3 IPDA(g)-680 -W-2300(g)250-125 JEFFAMINE D230(g)480-240 YD-128(g)374374374 Benzyl alcohol(g)735700493* IPDA: Isophorone diamine* W-2300: Wanamine-2300* YD-128: Kukdo Chemical's YD-128

[0268]

[0269] <Experimental Example>

[0270] Experimental Example 1. Confirmation of physical properties of the curing agent (isosorbide epoxy derivative compound)

[0271] The appearance, viscosity, amine value, active hydrogen equivalent (AHEW), amine / epoxy molar ratio, theoretical solid content, and biocarbon content (Solid BRC) of the curing agents prepared according to the above examples, comparative examples, and reference examples were determined and are shown in Table 4 below.

[0272]

[0273] appearance

[0274] The appearance of the compounds prepared according to the examples, comparative examples, and reference examples was visually inspected, and cases were evaluated as transparent, opaque, and crystallinity as becoming transparent when the temperature increased.

[0275]

[0276] viscosity

[0277] Viscosity was measured using a Brookfield viscometer at a temperature of 25°C with a torque of 30% or more, by ensuring that the marked part at the pointed end of the spindle was submerged in the Thermosel containing the sample.

[0278]

[0279] amine

[0280] The method for measuring the amine value (mgKOH / g) involved placing approximately 0.2g of the product (sample) prepared according to the examples, comparative examples, and reference examples into a flask, dissolving it in neutralized acetic acid, cooling the solution, and titrating it with 0.1N HClO4 using a crystal violet indicator until the color changed from purple to blue-green. The formula for calculating the amine value (mgKOH / g) is as follows.

[0281] [Equation 1]

[0282] Amine value (mgKOH / g) = mol 0.1N HClO₄X 100 X 5.61 / sample weight

[0283]

[0284] Active hydrogen equivalent

[0285] The active hydrogen equivalent was calculated according to Equation 2 below.

[0286] [Equation 2]

[0287] Active Hydrogen Equivalent (AHEW) = Molecular Weight / Number of Active Hydrogens (H atoms bonded to nitrogen atoms)

[0288]

[0289] Biocarbon content (Solid BRC: Bio Renewable Carbon content, Calculated value)

[0290] 1. Biocarbon content (%) = Biocarbon weight 1) / Carbon weight 2) X 100

[0291] 1) Biocarbon weight = Number of biocarbons x 12 (atomic weight of carbon)

[0292]

[0293] 2) Weight of carbon = Number of carbon atoms x 12 (atomic weight of carbon)

[0294] Here, biocarbon refers to the number of carbon atoms in bio-derived materials containing C14. C14 is generated in the upper atmosphere through nuclear reactions when cosmic rays from space or the sun irradiate nitrogen-14 contained in the air. A certain amount of C14 exists in the atmosphere, which is incorporated into carbon dioxide and fixed to the carbon in bio-derived materials through photosynthesis. On the other hand, carbon derived from fossil resources is buried underground for millions of years and does not contain C14. By analyzing the presence of C14, it is possible to determine whether the carbon is derived from biomass or fossil resources. The aforementioned number of biocarbons refers to the number of carbon atoms in the chemical structure of biomass-derived materials (materials containing C14), and the number of carbons refers to the total number of carbons, including both biocarbon and carbon derived from petroleum resources.

[0295] 2. Biocarbon content (%) of the mixture (A+B)

[0296] = ((A weight ratio XA carbon content 3) XA Biocarbon Content) + (B Weight Ratio XB Carbon Content) 3) XB Biocarbon Content)) / ((A Weight Ratio XA Carbon Content 3) ) + (B weight ratio XB carbon content 3) ))

[0297] 3) Carbon content = Carbon weight 2) / Molecular weight

[0298] In the method for calculating the biocarbon content of a mixture, A represents component A and B represents component B in the calculation of the mixture of A and B.

[0299]

[0300] Appearance Viscosity (cps @ 25℃) Amine value (mg KOH / g) Theoretical solid (%) AHEW (g / eq) Amine / Epoxy (Molar ratio) Solid BRC (%) Example 1 Transparent 16,400 152 60 270 1.54 1.6 Example 2 Opaque 5,700 167 60 209 23 2.7 Example 3 Transparent 1,200 204 60 184 24 1.2 Example 4 Transparent 400 226 60 164 24 6.7 Example 5 Transparent 5,700 181 60 240 1.54 8.3 Example 6 Transparent 2,900 160 60 255 1.54 7.9 Example 7 Transparent 804 1960 103 24 6.7 Example 8 Transparent 300 29 160 176 246.5 Example 9 Transparent 200 269 60 239 253.7 Example 10 Transparent 880 215 60 174 243.8 Reference Example 1 Transparent 600 170 70 180 -6 4.6 Reference Example 2 Transparent 1,500 165 70 300 -70.8 Comparative Example 1 Transparent 2,100 188 60 175 30 Comparative Example 2 Transparent 2,400 255 60 125 40 Comparative Example 3 Transparent 50,000 136 60 291 1.50

[0301]

[0302] Experimental Example 2. Confirmation of physical properties of water-based epoxy resin composition

[0303] Based on the g / eq (equivalent weight) of the curing agent prepared according to the examples and comparative examples, an epoxy resin composition was prepared by mixing 285 g / eq (equivalent weight) of KEM-128-70, a 70% LER water-based epoxy from Kukdo Chemical, and the physical properties of the epoxy resin composition were measured as follows, and the results are shown in Tables 5 and 6.

[0304]

[0305] Sample preparation

[0306] An epoxy resin composition was poured onto glass specimens and iron specimens to achieve a film thickness of 200 μm, dried at room temperature (25 ℃), and the drying time was checked.

[0307]

[0308] Biocarbon content (Solid BRC: Bio Renewable Carbon content, Calculated value)

[0309] It was calculated by excluding water using the aforementioned "2. Biocarbon content (%) of mixture (A+B)".

[0310]

[0311] appearance

[0312] An epoxy resin composition was poured onto a glass specimen and dried at room temperature (25 ℃) for 24 hours, after which the appearance of the coating film was evaluated by visual inspection and touch. When the coating film was visually inspected, it was evaluated as transparent (t: transparent) if the film was transparent enough to be seen through the glass specimen to the back, opaque (h: hazy) if the film was hazy and the back could not be seen through the glass specimen, smooth (s: smooth) if the surface was formed smoothly and the reflective surface was smooth, and rough and amine brushed (r: rough) if the surface was not smooth and reflected light showed diffuse reflection. In addition, when the coating film was lightly touched with a finger, it was evaluated as Hard if there was no adhesion and Tacky if there was adhesion.

[0313]

[0314] Pencil hardness

[0315] The hardness of the coating film formed on the glass specimen according to the curing time was evaluated with a 750 g load in accordance with JIS 5600-5-4. Mitsubishi pencils were used, and the test was performed 5 times per pencil hardness; if two or more scratches occurred, it was judged as defective.

[0316] Pencil Hardness: 9B~3B → 2B → 1B → HB → F → H → 2H → 3H~9H

[0317]

[0318] Content

[0319] The solvent resistance was evaluated by relatively comparing the degree of appearance abnormalities, such as swelling of the film, which were checked by removing the film formed on the iron specimen after immersion in xylene every day and determining that the later the problem occurred, the better and the sooner it occurred, with the degree ranging from 5 (good) to 1 (bad).

[0320]

[0321] acid resistance

[0322] Acid resistance was evaluated by relatively comparing the degree of appearance, with the coating formed on the iron specimen being immersed in a 5% sulfuric acid solution and then removed daily to check the appearance, with the order in which external abnormalities such as swelling occurred, such as the later the problem occurred, the better, and the earlier it occurred, the worse. The degree was rated from 5 (good) to 1 (bad).

[0323]

[0324] alkali resistance

[0325] Basic resistance was evaluated by relatively comparing the degree from 5 (good) to 1 (bad) based on the order in which external abnormalities, such as swelling of the film, occurred when the film formed on the iron specimen was immersed in a 5% NaOH solution and removed daily to check the appearance. The later the problem occurred, the better, and the sooner it occurred, the worse.

[0326]

[0327] Audience

[0328] The corrosion resistance was evaluated by relatively comparing the degree of appearance abnormalities, such as swelling of the film, that occurred in order of how quickly the problem occurred, with the later the problem occurred and the earlier the problem occurred, ranging from 5 (good) to 1 (bad), after the film formed on the iron specimen was immersed in a 5% NaCl solution and taken out daily to check the appearance.

[0329]

[0330] adhesive power

[0331] The adhesion strength of the coating formed on the iron specimen was evaluated by relatively comparing the degree of goodness and poorness according to the ASTM D3359 method, with 5 (good) to 1 (poor).

[0332]

[0333] Weather resistance

[0334] The coating formed on the iron specimen was evaluated for Delta E (color change, △Eab) at the 20-day evaluation point according to the ASTM G154 method.

[0335]

[0336] KEM-128-70 SoliddB.RC(%) Appearance Tackiness Evaluation 1 Day Drying Time (25℃) Hardness 3 Day Hardness 7 Day Example 1 16.4h, sHard23B2B Example 2 11.5h, sHard2.5BHB Example 3 13.1t, rTacky16--Example 4 13.6h, rTacky12--Example 5 18.1t, rTacky4--Example 6 18t, rTacky18--Example 78.4h, rTacky3 Example 8 13.5h, rTacky4--Example 9 18.5h, rTacky2--Example 10 13.3t, sHard84B3B Comparative Example 1 Compatibility with KEM-128-70 Dropping Comparison Example 2 Comparison Example 3

[0337]

[0338] KEM-128-70 Solvent Resistance Acid Resistance Base Resistance Rust Prevention Adhesion Impact Resistance Weather Resistance Delta E Example 1 5544558 Example 2 5555558 Example 3 2233138 Example 4 3331238 Example 5 3333228 Example 6 2233338 Example 7 2232339 Example 8 2121228 Example 9 2122328 Example 10 3333338 Comparative Example 1 Poor compatibility with water-soluble epoxy Comparative Example 2 Comparative Example 3

[0339]

[0340] Experimental Example 3. Confirmation of Physical Properties of Non-Aqueous Epoxy Resin Composition

[0341] An epoxy resin composition was prepared by mixing 187 g / eq (equivalent) of YD-128, a Bisphenol A type LER epoxy from Kookdo Chemical, based on 1 g / eq (equivalent) of the curing agent prepared according to the examples and comparative examples, and the physical properties of the epoxy resin composition were measured as follows, and the results are shown in Tables 7 and 8.

[0342]

[0343] Sample preparation

[0344] An epoxy resin composition was poured onto glass specimens and iron specimens to achieve a film thickness of 200 μm, dried at room temperature (25 ℃), and the drying time was checked.

[0345]

[0346] Biocarbon content (Solid BRC: Bio Renewable Carbon content, Calculated value)

[0347] It was calculated by excluding water using the aforementioned "2. Biocarbon content (%) of mixture (A+B)".

[0348]

[0349] appearance

[0350] An epoxy resin composition was poured onto a glass specimen and dried at room temperature (25 ℃) for 24 hours, after which the appearance of the coating film was evaluated by visual inspection and touch. When the coating film was visually inspected, it was evaluated as transparent (t: transparent) if the film was transparent enough to be seen through the glass specimen to the back, opaque (h: hazy) if the film was hazy and the back could not be seen through the glass specimen, smooth (s: smooth) if the surface was formed smoothly and the reflective surface was smooth, and rough and amine brushed (r: rough) if the surface was not smooth and reflected light showed diffuse reflection. In addition, when the coating film was lightly touched with a finger, it was evaluated as Hard if there was no adhesion and Tacky if there was adhesion.

[0351]

[0352] Pencil hardness

[0353] The hardness of the coating film formed on the glass specimen according to the curing time was evaluated with a 750 g load in accordance with JIS 5600-5-4. Mitsubishi pencils were used, and the test was performed 5 times per pencil hardness; if two or more scratches occurred, it was judged as defective.

[0354] Pencil Hardness: 9B~3B → 2B → 1B → HB → F → H → 2H → 3H~9H

[0355]

[0356] Content

[0357] The solvent resistance was evaluated by relatively comparing the degree of appearance abnormalities, such as swelling of the film, which were checked by removing the film formed on the iron specimen after immersion in xylene every day and determining that the later the problem occurred, the better and the sooner it occurred, with the degree ranging from 5 (good) to 1 (bad).

[0358]

[0359] acid resistance

[0360] Acid resistance was evaluated by relatively comparing the degree of appearance, with the coating formed on the iron specimen being immersed in a 5% sulfuric acid solution and then removed daily to check the appearance, with the order in which external abnormalities such as swelling occurred, such as the later the problem occurred, the better, and the earlier it occurred, the worse. The degree was rated from 5 (good) to 1 (bad).

[0361]

[0362] alkali resistance

[0363] Basic resistance was evaluated by relatively comparing the degree from 5 (good) to 1 (bad) based on the order in which external abnormalities, such as swelling of the film, occurred when the film formed on the iron specimen was immersed in a 5% NaOH solution and removed daily to check the appearance. The later the problem occurred, the better, and the sooner it occurred, the worse.

[0364]

[0365] Audience

[0366] The corrosion resistance was evaluated by relatively comparing the degree of appearance abnormalities, such as swelling of the film, that occurred in order of how quickly the problem occurred, with the later the problem occurred and the earlier the problem occurred, ranging from 5 (good) to 1 (bad), after the film formed on the iron specimen was immersed in a 5% NaCl solution and taken out daily to check the appearance.

[0367]

[0368] adhesive power

[0369] The adhesion strength of the coating formed on the iron specimen was evaluated by relatively comparing the degree of goodness and poorness according to the ASTM D3359 method, with 5 (good) to 1 (poor).

[0370]

[0371] Weather resistance

[0372] The coating formed on the iron specimen was evaluated for Delta E (color change, △Eab) at the 20-day evaluation point according to the ASTM G154 method.

[0373]

[0374] YD-128 SoliddB.RC(%) Appearance Tackiness Evaluation 1-day Drying Time (25°C) Hardness 3-day Hardness 7-day Example 1 15.4t, sHard 4HBH Example 2 10.8t, sHard 4.5HBH Example 3 11.9t, sHard 7HBH Comparative Example 10t, sHard 6HBH Comparative Example 20t, sHard 7HBH Comparative Example 30t, sHard 5HBH

[0375]

[0376] YD-128 Solvent Resistance Acid Resistance Base Resistance Rust Prevention Adhesion Impact Resistance Color Change Delta E Example 1 4544448 Example 2 4554548 Example 3 4445448 Comparative Example 1 4554449 Comparative Example 2 5555339 Comparative Example 3 4554449

[0377]

[0378] Experimental Example 4. Confirmation of cured material properties

[0379] Hardener (Hardener) and KDBM-1010 were mixed in the amounts shown in Table 9 below, and a cured product was formed on the coating film after 30 minutes.

[0380] -Hardener(g)KDBM-1010(g)SolidB.RC *1 (%) Example 1 168.8 10068.9 Example 2 130.6 10067.3 Example 3 115 10073.7 Example 4 102.5 10077.8 Example 5 150 10073.7 Example 6 159.4 10073.4 Example 7 64.8 10082.3 Example 8 110.2 10077.8 Example 9 149.2 10077.8 Example 10 108.8 10075.7 Reference Example 1 112.9 10087.8 Reference Example 2 189.5 10085.9 Comparative Example 1 109.8 10054 Comparative Example 2 78.5 10060.8 Comparative Example 3181.910041

[0381]

[0382] Although the present invention has been described above with reference to embodiments, the present invention is not limited by the embodiments disclosed in this specification, and it is obvious that various modifications can be made by a person skilled in the art within the scope of the technical concept of the present invention. Furthermore, even if the effects of the configuration of the present invention were not explicitly described while describing the embodiments of the present invention above, it is natural to acknowledge that the effects predictable by said configuration should also be recognized.

Claims

1. An isosorbide epoxy derivative compound comprising at least one amine substituent.

2. In Paragraph 1, The above isosorbide epoxy derivative compound is an isosorbide epoxy derivative compound having a viscosity of 50 cps or more and 40,000 cps or less at 25 ℃.

3. In Paragraph 1, The above isosorbide epoxy derivative compound is an isosorbide epoxy derivative compound having an active hydrogen equivalent (AHEW) of 50 g / eq or more and 500 g / eq or less.

4. In Paragraph 1, The above amine substituent is an isosorbide epoxy derivative compound derived from at least one of an aliphatic amine, alicyclic amine, aromatic aliphatic amine, and aromatic amine.

5. In Paragraph 1, The above isosorbide epoxy derivative compound is an isosorbide epoxy derivative compound having a biocarbon content of 30% or more and 70% or less.

6. Step of preparing an isosorbide epoxy-based compound; and A method for preparing an isosorbide epoxy derivative compound according to claim 1, comprising the step of reacting an amine compound containing one or more diamine-based compounds with the isosorbide epoxy-based compound at a temperature of 25°C or higher and 150°C or lower for a time of 30 minutes or more and 6 hours or less.

7. In Paragraph 6, A method for preparing an isosorbide epoxy derivative compound, wherein the molar ratio of the isosorbide epoxy compound to the amine compound is 1:0.1 to 1:

5.

8. An isosorbide epoxy derivative compound according to claim 1; and Epoxy resin composition comprising epoxy resin.

9. In Paragraph 8, Epoxy resin composition further comprising a diluent.

10. In Paragraph 8, An epoxy resin composition in which the content of the isosorbide epoxy derivative compound is 40 parts by weight or more and 160 parts by weight or less per 100 parts by weight of the epoxy resin.

11. In Paragraph 8, The above epoxy resin composition is a water-dispersible epoxy resin composition.

12. In Paragraph 8, The above epoxy resin composition is an epoxy resin composition having a color change (△Eab) of less than 10 as measured by ASTM G154 standard at 20 days after curing.

13. A cured product formed by curing the epoxy resin composition according to paragraph 8.

14. In Paragraph 13, A cured product having a biocarbon content of 10% or more and 90% or less.

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