Epoxy resin composition and resin film

Abstract

An epoxy resin composition and a resin film are provided. The epoxy resin composition includes a hardener; and an epoxy resin monomer. The epoxy resin monomer has a structure represented by Formula (I), wherein A is a substituted or unsubstituted C 6‑24 arylene group, C 3‑16 ycloalkylene group, C 3‑16 heteroarylene group, C 3‑16 icyclic alkylene group, or a divalent C 6‑25 alkylaryl group; X 1 and X 2 are independently Y 1 and Y 2 are independently a substituted or unsubstituted C 6‑24 arylene group, and Y 1 and Y 2 are not the same; and R 1 is hydrogen, C 1‑8 alkyl, or C 1‑8 alkoxy, the hardener and the epoxy resin monomer having Formula (I) are in a weight ratio of 1:100 to 1:1.

Description

TECHNICAL FIELD

[0001] The present disclosure relates to an epoxy resin composition and a resin film. BACKGROUND

[0002] Anisotropic conductive adhesive is widely used in connecting printed contacts on an indium tin oxide (ITO) substrate and a driving circuit substrate (e.g., a flexible printed circuit board).

[0003] Due to the excellent mechanical properties, chemical resistance, heat resistance, and insulation of thermosetting resin, the mainstream anisotropic conductive adhesive currently contains thermosetting resin. However, the thermosetting resin material cannot be melted and dissolved after curing, making it difficult to reshape, rework, or recycle, resulting in problems such as difficulty in disassembling devices prepared using anisotropic conductive adhesive and difficulty in removing residual adhesive material. In addition, in the field of electronic materials, semiconductor packaging is gradually developing towards miniaturization, thinning, and complex shapes. Therefore, as the packaging difficulty increases, the industry's demand for semiconductor packaging materials with high flowability and low stress is also increasing. SUMMARY

[0004] According to embodiments of the present disclosure, an epoxy resin composition (e.g., a thermosetting resin composition) is provided. The epoxy resin composition of the present disclosure comprises a hardener; and an epoxy resin monomer. The epoxy resin monomer has a structure represented by Formula (I)

[0005]

[0006] wherein A can be a substituted or unsubstituted C 6-24 arylene group, a substituted or unsubstituted C 3-16 cycloalkylene group, a substituted or unsubstituted C 3-16 heteroarylene group, a substituted or unsubstituted C 3-16 alicyclic alkylene group, or a substituted or unsubstituted divalent C 6-25 alkylaryl group; X 1 and X 2 may be independently Y 1 and Y 2 may be independently a substituted or unsubstituted C 6-24 arylene group, and Y 1 and Y 2 are not the same; and R 1 may be hydrogen, C 1-8alkyl, or C 1-8 alkoxy. According to embodiments of the present disclosure, the weight ratio of the hardener to the epoxy resin monomer can be 1 : 100 to 1 : 1.

[0007] According to embodiments of the present disclosure, the epoxy resin composition can further comprise an epoxy resin. According to embodiments of the present disclosure, the weight ratio of the epoxy resin to the epoxy resin monomer having the structure shown in Formula (I) can be 1 : 100 to 9: 1.

[0008] According to certain embodiments of the present disclosure, a resin film is provided. The resin film can comprise a cured product of the epoxy resin composition of the present disclosure. DETAILED DESCRIPTION

[0009] The following description is directed to certain embodiments of the epoxy resin composition and resin film of the present disclosure. It should be appreciated that the following description provides many different embodiments, or examples, for implementing different aspects, embodiments, ranges, or examples of the present disclosure. Some of these embodiments can be

[0010] The present disclosure provides an epoxy resin composition and a resin film. According to the present disclosure, the resin film can be a film formed by curing the epoxy resin composition. According to the present disclosure, the epoxy resin composition comprises an epoxy resin monomer having a specific structure and a hardener. Due to the imine group introduced by the epoxy resin monomer of the present disclosure, the cured product of the epoxy resin composition of the present disclosure can be easily cracked in an acidic environment at a relatively low temperature (e.g. 80°C or below), solving the problem that thermosetting resins are not easy to crack. In this way, when the epoxy resin composition of the present disclosure is used as an encapsulation adhesive, its cured product can be easily removed under certain conditions, avoiding the problem of residual glue, and making it easy to disassemble and recycle the device encapsulated using the epoxy resin composition. In addition, the epoxy resin monomer of the present disclosure still has an aromatic group in its chemical structure, so the product obtained using the epoxy resin composition of the present disclosure (i.e. the product comprising the cured product of the epoxy resin composition) not only has the characteristic of low-temperature cracking, but also has high heat resistance, high chemical resistance, and dimensional stability. Furthermore, by designing the asymmetric chemical structure of the epoxy resin monomer, the melting point of the epoxy resin monomer of the present disclosure can be greatly reduced (solving the problem of high melting point of traditional aromatic epoxy resins), thereby making the epoxy resin monomer of the present disclosure present in a liquid state at room temperature. In this way, by adding the liquid epoxy resin monomer, the flowability of the epoxy resin composition of the present disclosure can be greatly improved, expanding the application scope of the epoxy resin composition (e.g. encapsulation systems requiring low-temperature operation, or encapsulation requirements with higher complexity). According to the present disclosure, the epoxy resin composition of the present disclosure can be used as an adhesive for anisotropic conductive adhesive, underfill adhesive, or B-stageable bonding film or liquid adhesive.

[0011] The epoxy resin composition of the present disclosure comprises a hardener and an epoxy resin monomer. According to embodiments of the present disclosure, the amount of the hardener added is not particularly limited and can be adjusted according to actual needs by one of ordinary skill in the art. According to embodiments of the present disclosure, the weight ratio of the hardener to the epoxy resin monomer can be about 1:100 to 1:1, such as about 2:100, 3:100, 5:100, 8:100, 10:100, 15:100, 20:100, 25:100, 30:100, 40:100, 50:100, 60:100, 75:100, 80:100, or 90:100. According to embodiments of the present disclosure, the epoxy resin monomer of the present disclosure is suitable for use with various types of hardeners. The type of hardener is not particularly limited and can be selected according to actual needs by one of ordinary skill in the art. According to embodiments of the present disclosure, the hardener of the present disclosure can be an acid anhydride hardener, an amine hardener, a phenolic hardener, an imidazole hardener, or a combination thereof. For example, the acid anhydride hardener can be methyl hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride (MTHPA), maleic anhydride (MA), polystyrene-co-maleic anhydride (SMA), or a combination thereof, but is not limited thereto. According to embodiments of the present disclosure, the amine hardener can be an aliphatic amine hardener, a cyclic aliphatic amine hardener, or an aromatic amine hardener. The amine hardener can be poly(propylene glycol) bis(2-aminopropyl ether) (e.g., Jeffamine® D-230, Huntsman Corporation), poly(propylene glycol) bis(2-aminoethylether) (e.g., Jeffamine® XTJ-501, Huntsman Corporation), or a combination thereof, but is not limited thereto. D-230), cyclohexanediamine, oxydianiline, or stearyl amine ethoxylate (SAA). According to embodiments of the present disclosure, the phenolic hardener can be phenol-formaldehyde novolac (HRJ series), or melamine phenol novolac. According to embodiments of the present disclosure, the imidazole hardener can be 1-methyl imidazole, 2-methyl imidazole, 2-ethyl-4-methyl imidiazole, 2-phenyl-4-methyl imidazole, 2-phenyl-4-methyl-5-hydroxymethyl imidazole, 2-phenyl-4,5-dihydroxymethyl imidazole, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-(2'-undecylimidazolyl)-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4-methyl imidazolyl-(1')]-ethyl-s-triazine, or latent hardeners such as NOVACURE HXA-3932, and the like. The foregoing are merely examples, and the anhydride hardeners, amine hardeners, phenolic hardeners, imidazole hardeners used in the present disclosure are not limited thereto.

[0012] According to embodiments of the present disclosure, the epoxy resin monomer of the present disclosure is an asymmetric epoxy resin monomer having an imine group within the molecule (i.e., the epoxy resin monomer has an asymmetric chemical structure). According to embodiments of the present disclosure, the epoxy resin monomer of the present disclosure can have a structure represented by Formula (I)

[0013]

[0014] wherein A can be a substituted or unsubstituted C 6-24 arylene group, a substituted or unsubstituted C 3-16 cycloalkylene group, a substituted or unsubstituted C 3-16 heteroarylene group, a substituted or unsubstituted C 3-16 alicyclic alkylene group, or a substituted or unsubstituted divalent C 6-25 alkylaryl group; X 1 and X 2 may be independently Y 1 and Y 2substituted or unsubstituted C 6-24 arylene group; and R 1 may be hydrogen, C 1-8 alkyl, or C 1-8 alkoxy. It is noted that since the epoxy monomer of the present disclosure is an asymmetric epoxy monomer, Y 1 is not the same as Y 2 . According to embodiments of the present disclosure, Y 1 is not the same as Y 2 The constituent elements of Y 6-24 and Y 6-24 may be the same, but the chemical structure thereof must be different.

[0015] According to embodiments of the present disclosure, the substituted C 6-24 alkylene group of the present disclosure means that the hydrogen on at least one carbon of the C 6-24 alkylene group is substituted with C 1-8 alkyl, or C 1-8 alkoxy. The substituted C 3-16 cycloalkylene group of the present disclosure means that the hydrogen on at least one carbon of the C 3-16 cycloalkylene group is substituted with C 1-8 alkyl, or C 1-8 alkoxy. The substituted C 3-16 heteroarylene group of the present disclosure means that the hydrogen on at least one carbon of the C 3-16 heteroarylene group is substituted with C 1-8 alkyl, or C 1-8 alkoxy. The substituted C 3-16 alicycloalkylene group of the present disclosure means that the hydrogen on at least one carbon of the C 3-16 alicycloalkylene group is substituted with C 1-8 alkyl, or C 1-8 alkoxy. The substituted divalent C 6-25 alkylaryl group of the present disclosure means that the hydrogen on at least one carbon of the divalent C 6-25 alkylaryl group is substituted with C 1-8 alkyl, or C 1-8 alkoxy.

[0016] According to embodiments of the present disclosure, A can be a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted thienylene group, a substituted or unsubstituted indolylene, a substituted or unsubstituted phenanthrenylene, a substituted or unsubstituted indenylene, a substituted or unsubstituted anthracenylene, or a substituted or unsubstituted fluorenylene, wherein the substituted phenylene group, the substituted biphenylene group, the substituted naphthylene group, the substituted thienylene group, the substituted indolylene, the substituted phenanthrenylene, the substituted indenylene, the substituted anthracenylene, or the substituted fluorenylene means that a hydrogen on at least one carbon of the group is replaced with C 1-8 alkyl or C 1-8 alkoxy.

[0017] According to embodiments of the present disclosure, C 1-8 alkyl can be a linear or branched chain alkyl. For example, C 1-8 alkyl can be a methyl, an ethyl, a propyl, a butyl, a pentyl, a hexyl, a heptyl, an octyl, or an isomer thereof. According to embodiments of the present disclosure, C 1-8 alkyl can be a linear or branched chain alkyl. For example, C 1-8 alkoxy can be a methoxy, an ethoxy, a propoxy, a butoxy, a pentoxy, a hexoxy, a heptoxy, an octoxy, or an isomer thereof.

[0018] According to embodiments of the present disclosure, X 1 may be connected to Y 1 at carbon and connected to A at nitrogen, and X2 is connected to Y 2 and to A by nitrogen. Furthermore, according to embodiments of the present disclosure, X 1 may be connected to Y 1 and to A by carbon, and X 2 may be connected to Y 2 and to A by carbon.

[0019] According to embodiments of the present disclosure, A can be wherein R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , and R 29 may be independently hydrogen, C 1-8 alkyl, or C 1-8 alkoxy. According to embodiments of the present disclosure, R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , and R 29 may be independently hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, methoxy, ethoxy, propoxy, butoxy, pentoxy, hexyloxy, heptyloxy, octyloxy, or isomers thereof.

[0020] According to embodiments of the present disclosure, Y 1 and Y 2 may be independently

[0021] wherein R 30 , R 31 , R 32 , R 33 , R 34 , and R 35 may be independently hydrogen, C 1-8 alkyl, or C 1-8 alkoxy; and a, b, c, d, e, and f can be independently 1, 2, 3, 4, or 5. According to embodiments of the present disclosure, R 30 , R 31 , R 32 , R 33 , R 34 , and R 35 may be independently hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, methoxy, ethoxy, propoxy, butoxy, pentoxy, hexyloxy, heptyloxy, octyloxy, or isomers thereof.

[0022] According to embodiments of the present disclosure, the epoxy monomer can be

[0023]

[0024]

[0025]

[0026] wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R9 10 11 12 13 independently hydrogen, C 1-8 alkyl, or C 1-8 alkoxy; and Y 1 and Y 2 are independently substituted or unsubstituted C 6-24 arylene groups, and Y 1 is not the same as Y 2 .

[0027] According to embodiments of the present disclosure, the epoxy monomer can be

[0028]

[0029]

[0030] wherein R 1 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , and R 29 are independently hydrogen, C 1-8 alkyl, or C 1-8 alkoxy; and Y 1 and Y 2 are independently substituted or unsubstituted C 6-24 arylene groups, and Y 1 is not the same as Y 2 .

[0031] According to embodiments of the present disclosure, the epoxy monomer can be

[0032] wherein A is a substituted or unsubstituted C 6-24 arylene group, C 3-16 cycloalkylene group, C 3-16 heteroarylene group, C​​​​3-16 alicyclic alkylene group, or a divalent C 6-25 alkylaryl group; and, R 1 , R 30 , R 31 , and R 32 are independently hydrogen, C 1-8 alkyl, or C 1-8 alkoxy.

[0033] According to embodiments of the present disclosure, the epoxy equivalent weight (EEW) of the epoxy resin monomer is about 50 g / eq to 1500 g / eq, such as 100 g / eq, 150 g / eq, 200 g / eq, 300 g / eq, 400 g / eq, 500 g / eq, 600 g / eq, 700 g / eq, 800 g / eq, 900 g / eq, 1000 g / eq, 1200 g / eq, or 1400 g / eq. According to embodiments of the present disclosure, when the epoxy equivalent weight of the epoxy resin monomer is higher, the cured product of the epoxy resin composition of the present disclosure has poorer acid environment cracking properties.

[0034] According to embodiments of the present disclosure, the epoxy resin composition of the present disclosure can further comprise an epoxy resin, wherein the weight ratio of the epoxy resin to the epoxy resin monomer is 1:100 to 9:1. When the content of the epoxy resin monomer is too low, the cured product of the epoxy resin composition of the present disclosure has poorer acid environment cracking properties and poorer flowability.

[0035] According to embodiments of the present disclosure, the epoxy resin is a bisphenol A epoxy resin, a bisphenol F epoxy resin, a bisphenol S epoxy resin, a phenol-aldehyde epoxy resin, a naphthyl epoxy resin, an anthryl epoxy resin, a bisphenol A diglycidyl ether epoxy resin, an ethylene glycol diglycidyl ether epoxy resin, a propylene glycol diglycidyl ether epoxy resin, or a 1,4-butanediol diglycidyl ether epoxy resin. According to embodiments of the present disclosure, the weight average molecular weight of the epoxy resin can be about 200 g / mol to 2,000,000 g / mol, such as 8,000 g / mol, 10,000 g / mol, 20,000 g / mol, 50,000 g / mol, 100,000 g / mol, 300,000 g / mol, 500,000 g / mol, 1,000,000 g / mol, 1,500,000 g / mol, or 1,800,000 g / mol. The weight average molecular weight (Mw) of the epoxy resin of the present disclosure can be measured by gel permeation chromatography (GPC) using polystyrene as a standard. The weight average molecular weight of the commercial resin used in the present embodiments is about <1000 or lower.

[0036] Table 1 lists the epoxy monomers according to embodiments of the present disclosure and shows their chemical structures.

[0037] Table 1

[0038]

[0039]

[0040] According to embodiments of the present disclosure, the present disclosure also provides a resin film, wherein the resin film comprises a cured product of the epoxy resin composition according to the present disclosure.

[0041] To further illustrate the preparation method of the epoxy monomers according to the present disclosure, the preparation process of the epoxy monomers according to embodiments 1 and 2 is illustrated as follows.

[0042] Preparation of epoxy monomers

[0043] Embodiment 1

[0044] Into a reaction flask, 4,4'-methylene bis(2-ethylaniline) (MOEA) (0.04 mole), vanillin (0.04 mole), 3-hydroxybenzaldehyde (MHB) (0.04 mole), p-toluenesulfonic acid (TsOH) (0.09 g), and ethanol (EtOH) (50 mL) were added to obtain a mixture. Then, the reaction flask was heated to 70°C under nitrogen atmosphere, and the mixture was stirred for 5 hours. Then, the reaction flask was cooled to room temperature, and the resulting product was concentrated to obtain compound (1). The reaction formula of the above reaction is shown as follows:

[0045]

[0046] Then, compound (1) was analyzed by nuclear magnetic resonance spectroscopy, and the obtained spectral information is as follows: 1 H NMR (acetone-d6; 400 MHz) δ: 8.48 (s, 1H, -CH=N-), 8.37 (s, 1H, -CH=N-), 7.72 (s, 1H, Ar-H), 7.54 (s, 1H, Ar-H), 7.28-7.49 (m, 5H, Ar-H), 7.21-7.03 (m, 6H, Ar-H), 3.95 (s, 2H, -CH 2- ), 3.85 (s, 3H, -OCH3), 2.75 (q, 4H, -C H2CH3-), 1.20 (t, 6H, -CH2C H3 ).

[0047] Next, compound (1) (0.04 mol), epichlorohydrin (ECH) (37 g), tetrabutyl ammonium bromide (TBAB) (1.29 g) were added to a reaction flask to obtain a mixture. Next, the reaction flask was heated to 80°C under nitrogen atmosphere, and the mixture was stirred for 3 hours. Next, the reaction flask was cooled to below 5°C, and an aqueous sodium hydroxide solution (6 g) (solid content: 40 wt%) was added to the reaction flask. Next, the resulting product was concentrated under stirring at below 5°C for 5 hours, and dissolved in ethyl acetate. Next, the resulting solution was washed with deionized water three times. Next, the organic layer was dehydrated with magnesium sulfate, and concentrated and dried to obtain an epoxy resin monomer (I). The reaction formula of the above reaction is as follows:

[0048]

[0049] The epoxy resin monomer (I) was analyzed by nuclear magnetic resonance spectroscopy, and the resulting spectral information is as follows: 1 H NMR (acetone-d6; 400 MHz) δ: 8.51 (s, 1H, -CH=N-), 8.40 (s, 1H, -CH=N-), 7.75 (s, 1H, Ar-H), 7.68 (s, 1H, Ar-H), 7.52 (d, 1H, Ar-H), 7.47 (m, 1H, Ar-H), 7.25-6.81 (9H, Ar-H), 4.42-2.75 (10H, -CH2-; -CH- and -CH2- of oxirane), 3.98 (s, 2H, -CH 2- ), 3.95 (s, 6H, -OCH3), 2.75 (m, 4H, -CH2C H2 CH3-), 1.20 (t, 6H, -CH2C H3 ).

[0050] Example 2

[0051] A reaction vessel was charged with 1,3-bis(aminomethyl)cyclohexane (1,3-BAC) (0.04 mole), vanillin (0.04 mole), 3-hydroxybenzaldehyde (MHB) (0.04 mole), p-toluenesulfonic acid (TsOH) (0.09 g), and ethanol (EtOH) (50 mL) to give a mixture. Then, the reaction vessel was heated to 70°C under nitrogen atmosphere, and the mixture was stirred for 5 hours. Then, the reaction vessel was cooled to room temperature, and the resulting product was concentrated to give compound (2). The reaction scheme of the above reaction is shown below:

[0052]

[0053] Compound (2) was analyzed by nuclear magnetic resonance spectroscopy, and the resulting spectral information is as follows: 1 H NMR (acetone-d6; 400 MHz) δ: 8.21 (S, 1H, -CH=N-), 8.15 (S, 1H, -CH=N-), 7.48 (s, 1H, Ar-H), 7.30 (s, 1H, Ar-H), 7.25-7.09 (m, 3H, Ar-H), 6.89-6.79 (m, 2H, Ar-H), 3.81 (s, 3H, -OCH3), 3.54-3.36 (m, 2H, -CH2-), 1.99-1.22 (m, 6H, -CH2-), 1.0-0.72 (m, 2H, -CH2-).

[0054] Then, a reaction vessel was charged with compound (2) (0.04 mole), epichlorohydrin (ECH) (37 g), and tetrabutyl ammonium bromide (TBAB) (1.29 g) to give a mixture. Then, the reaction vessel was heated to 80°C under nitrogen atmosphere, and the mixture was stirred for 3 hours. Then, the reaction vessel was cooled to below 5°C and aqueous sodium hydroxide solution (6 g) (solid content: 40 wt%) was added to the reaction vessel. Then, the resulting product was concentrated and dissolved in ethyl acetate after stirring for 5 hours at below 5°C. Then, the resulting solution was washed with deionized water three times. Then, the organic layer was dehydrated with magnesium sulfate and concentrated and dried to give epoxy resin monomer (II). The reaction scheme of the above reaction is shown below:

[0055]

[0056] Next, the epoxy resin monomer (II) was analyzed by nuclear magnetic resonance spectroscopy, and the resulting spectral information was as follows: 1 H NMR (acetone-d6; 400 MHz) δ: 8.19 (m, 1H, -CH=N-), 8.14 (m, 1H, -CH=N-), 7.45 (s, 1H, Ar-H), 7.30 (s, 1H, Ar-H), 7.26-7.10 (m, 3H, Ar-H), 6.93-6.84 (m, 2H, Ar-H), 4.42-2.75 (m, 10H, -O-CH2-; -CH- and -CH2- of oxirane), 3.81 (s, 3H, -OCH3), 3.54-3.36 (m, 4H, -CH2-), 1.99-1.22 (m, 6H, -CH2-), 1.0-0.72 (m, 2H, -CH2-).

[0057] Comparative Example 1

[0058] A reaction vessel was charged with 4,4'-methylene bis(2-ethylaniline) (MOEA) (0.04 mole), vanillin (0.08 mole), p-toluenesulfonic acid (TsOH) (0.09 g), and ethanol (EtOH) (50 mL) to provide a mixture. The reaction vessel was then heated to 70°C under a nitrogen atmosphere, and the mixture was stirred for 5 hours. The reaction vessel was then allowed to cool to room temperature, and the resulting product was concentrated to provide compound (3). The reaction scheme for the above reaction is shown below:

[0059]

[0060] Compound (3) was analyzed by nuclear magnetic resonance spectroscopy, and the resulting spectral information was as follows: 1 H NMR (acetone-d6; 400 MHz) δ: 8.47 (s, 2H, -CH=N-), 7.65 (s, 2H, Ar-H), 7.43 (dd, 2H, Ar-H), 7.16 (s, 2H, Ar-H), 7.10 (dd, 2H, Ar-H), 7.04 (dd, 2H, Ar-H), 6.75 (dd, 2H, Ar-H), 4.42 (dd, 2H, -CH2-), 3.90 (s, 6H, -OCH3), 2.75 (m, 4H, -CH2C H2 ). H3

[0061] ​Next, compound (3) (0.04 moles), epichlorohydrin (ECH) (37 grams), tetrabutyl ammonium bromide (TBAB) (1.29 grams) were added to a reaction flask to obtain a mixture. Next, the reaction flask was heated to 80°C under nitrogen atmosphere and the mixture was stirred for 3 hours. Next, the reaction flask was cooled to below 5°C and aqueous sodium hydroxide solution (6 grams) (40 wt% solid content) was added to the reaction flask. Next, after stirring for 5 hours at below 5°C, the resulting product was concentrated and dissolved in ethyl acetate. Next, the resulting solution was washed with deionized water three times. Next, the organic layer was dehydrated with magnesium sulfate and concentrated and dried to obtain epoxy resin monomer (XI). The reaction formula of the above reaction is as follows:

[0062]

[0063] Next, the epoxy resin monomer (XI) was analyzed by nuclear magnetic resonance spectroscopy and the resulting spectral information is as follows: 1 H NMR (acetone-d6; 400 MHz) δ: 8.47 (s, 2H, -CH=N-), 7.70 (s, 2H, Ar-H), 7.42 (dd, 2H, Ar-H), 7.15 (s, 2H, Ar-H), 7.10 (dd, 2H, Ar-H), 7.05 (dd, 2H, Ar-H), 6.85 (dd, 2H, Ar-H), 4.42 (dd, 2H, -CH2-), 3.90 (s, 6H, -OCH3), 3.88 (dd, 2H, -O-CH2-), 3.35 (dt, 2H, -CH- of oxirane), 2.85-2.78 (m, 4H, -CH2- of oxirane), 2.75 (m, 4H, -CH2- of oxirane), 2.70 (m, 4H, -CH2- of oxirane), 2.65 (m, 4H, -CH2- of oxirane), 2.60 (m, 4H, -CH2- of oxirane), 1.15 (t, 6H, -CH2CH3). H2 CH3), 1.15 (t, 6H, -CH2CH3). H3

[0064] The melting point and epoxy equivalent of the epoxy resin monomers (I) and (II) obtained in Examples 1 and 2 and the epoxy resin monomer (XI) obtained in Comparative Example 1 were measured, and the results are shown in Table 2. The melting point of the epoxy resin monomers was evaluated by micro differential scanning calorimetry (DSC), and the epoxy equivalent of the epoxy resin monomers was determined according to the method specified in ASTM D1652.

[0065] Table 2​

[0066] Melting point (°C) Epoxy equivalent weight (g / eq) Epoxy resin monomer (I) <25 378 Epoxy resin monomer (II) <25 285 Epoxy resin monomer (XI) Epoxy resin monomer (XII) 67 326

[0067] As can be seen from Table 2, since the epoxy resin monomer (XI) is a symmetrical epoxy resin (i.e., it has a symmetrical chemical structure), it has a higher crystallinity, thus resulting in the epoxy resin monomer (XI) having a higher melting point (°C) (solid at room temperature). In addition, the epoxy resin monomers (I) and (II) described in the present case are asymmetrical epoxy resins (i.e., they have an asymmetrical chemical structure), so that the epoxy resin monomers (I) and (II) have a lower melting point (°C) and are in a liquid state at room temperature.

[0068] Preparation of the epoxy resin composition

[0069] Example 11

[0070] The epoxy resin monomer (I) was mixed with 2-methyl imidazole (2MI) (as a hardening agent) to obtain an epoxy resin composition (1). Here, the equivalent ratio of the epoxy resin monomer (I) to 2-methyl imidazole was 1:1.

[0071] Example 12

[0072] The epoxy resin monomer (I) was mixed with poly(propylene glycol) bis(2-aminopropyl ether) (molecular weight: 230) (trade name: Jeffamine® D-230) (as a hardening agent) to obtain an epoxy resin composition (2). Here, the equivalent ratio of the epoxy resin monomer (I) to poly(propylene glycol) bis(2-aminopropyl ether) was 1:1. The epoxy resin monomer (I) was mixed with poly(propylene glycol) bis(2-aminopropyl ether) (molecular weight: 230) (trade name: Jeffamine® D-230) (as a hardening agent) to obtain an epoxy resin composition (2). Here, the equivalent ratio of the epoxy resin monomer (I) to poly(propylene glycol) bis(2-aminopropyl ether) was 1:1.

[0073] Example 13

[0074] The epoxy resin monomer (I) was mixed with methyltetrahydrophthalicanhydride (MTHPA) (as a hardening agent), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), and 2-ethylhexanoic acid to obtain an epoxy resin composition (3). Here, the equivalent ratio of the epoxy resin monomer (I) to methyltetrahydrophthalicanhydride was 1:1, the amount of 1,8-diazabicyclo[5.4.0]-1,8-diazabicyclo[5.4.0]undec-7-ene used was 0.25 phr, and the amount of 2-ethylhexanoic acid used was 0.25 phr (based on the epoxy resin monomer (I)).

[0075] Example 14

[0076] Epoxy resin monomer (I), bisphenol F epoxy resin (trade number: EXA-830LVP), methyltetrahydrophthalic anhydride (MTHPA) (as a curing agent), bicyclo[5.4.0]-1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), and 2-ethylhexanoic acid were mixed to obtain an epoxy resin composition (4). Here, the equivalent ratio of epoxy resin monomer (I), bisphenol F epoxy resin, and methyltetrahydrophthalic anhydride was 1:1:2, the amount of bicyclo[5.4.0]-1,8-diazabicyclo[5.4.0]-1,8-diazabicyclo[5.4.0]undec-7-ene was 0.5 phr, and the amount of 2-ethylhexanoic acid was 0.5 phr (based on epoxy resin monomer (I)). Example 15

[0077] Example 15 was carried out in the same manner as in Example 14, except that the equivalent ratio of epoxy resin monomer (I), bisphenol F epoxy resin, and methyltetrahydrophthalic anhydride was adjusted from 1:1:2 to 0.5:1.5:2 to obtain epoxy resin composition (5).

[0078] Example 16

[0079] Example 16 was carried out in the same manner as in Example 11, except that the equivalent ratio of epoxy resin monomer (I) to 2-methylimidazole was adjusted from 1:1 to 10:7 to obtain an epoxy resin composition (6).

[0080] Example 17

[0081] Example 17 was carried out in the same manner as in Example 12, except that the equivalent ratio of epoxy resin monomer (I) to polypropylene glycol bis(2-aminopropyl ether) was adjusted from 1:1 to 10:7 to obtain an epoxy resin composition (7).

[0082] Example 18

[0083] Example 18 was carried out in the same manner as in Example 13, except that the equivalent ratio of epoxy resin monomer (I) to methyltetrahydrophthalic anhydride was adjusted from 1:1 to 10:7 to obtain epoxy resin composition (8).

[0084] Example 19

[0085] Example 19 was carried out in the manner described in Example 11, except that epoxy resin monomer (I) was replaced with epoxy resin monomer (II) to obtain epoxy resin composition (9).

[0086] Example 20

[0087] Example 20 was carried out in accordance with the manner described in Example 12, except that epoxy resin monomer (I) was replaced with epoxy resin monomer (II) to obtain an epoxy resin composition (10).

[0088] Example 21

[0089] Example 21 was carried out in the manner described in Example 13, except that epoxy resin monomer (I) was replaced with epoxy resin monomer (II) to obtain epoxy resin composition (11).

[0090] Example 22

[0091] Example 22 was carried out in the manner described in Example 14, except that epoxy resin monomer (I) was replaced with epoxy resin monomer (II) to obtain epoxy resin composition (12).

[0092] Example 23

[0093] Example 23 was carried out in the manner described in Example 15, except that epoxy resin monomer (I) was replaced with epoxy resin monomer (II) to obtain epoxy resin composition (13).

[0094] Comparative Example 2

[0095] Comparative Example 2 was carried out in accordance with the manner described in Example 14, except that epoxy resin monomer (I) was replaced with epoxy resin monomer (XI) to obtain epoxy resin composition (14).

[0096] Comparative Example 3

[0097] Comparative Example 3 was carried out in accordance with the manner described in Example 15, except that epoxy resin monomer (I) was replaced with epoxy resin monomer (XI) to obtain epoxy resin composition (15).

[0098] Comparative Example 4

[0099] Comparative Example 4 was carried out in accordance with the manner described in Example 11, except that the epoxy resin monomer (I) was bisphenol F epoxy resin (trade number: By substituting EXA-830LVP, an epoxy resin composition (16) was obtained.

[0100] Comparative Example 5

[0101] Comparative Example 5 was carried out in accordance with the manner described in Example 12, except that the epoxy resin monomer (I) was replaced with bisphenol F epoxy resin (trade number: By substituting EXA-830LVP, an epoxy resin composition (17) was obtained.

[0102] Comparative Example 6

[0103] Example 6 was performed in the same manner as described in Example 13, except that epoxy resin monomer (I) was replaced with bisphenol F epoxy resin (trade name: YD-128LVP) to obtain epoxy resin composition (18). EXA-830LVP) to obtain epoxy resin composition (18).

[0104] Flowability Test

[0105] The flowability of epoxy resin compositions (2)-(5) obtained in Examples 12-15 and epoxy resin compositions (14)-(15) obtained in Comparative Examples 2 and 3 was evaluated, and the results are shown in Table 3. In this evaluation, the viscosity of the epoxy resin composition measured at 25°C at a rotation speed of 10 rpm was used as the flowability standard. When the viscosity was less than 55,000 cps, the epoxy resin composition was determined to have good flowability, and was indicated by. When the viscosity was between 55,000 cps and 65,000 cps, the epoxy resin composition was determined to have acceptable flowability, and was indicated by. When the viscosity was greater than 65,000 cps, the epoxy resin composition was determined to have poor flowability or no flowability, and was indicated by X.

[0106] Table 3

[0107]

[0108] Since the epoxy resin monomer of the present disclosure has an asymmetric chemical structure and a low melting point, it can be in a liquid state at room temperature. Therefore, the epoxy resin composition prepared using the epoxy resin monomer of the present disclosure has flowability and is suitable as a packaging material. As compared with epoxy resin composition (4), the flowability of epoxy resin compositions (14) and (15) was observed to be significantly reduced (as shown in Table 3) when epoxy resin monomer (XI) (symmetric epoxy resin monomer) was used instead of epoxy resin monomer (I) (asymmetric epoxy resin monomer), resulting in a decrease in the processability of the epoxy resin composition.

[0109] The epoxy resin composition (1) obtained in Example 11 and the cured product thereof were analyzed by fourier-transform infrared spectroscopy (FT-IR), and it was found that the oxiranyl group (IR characteristic peak at 911 cm -1 ) on the epoxy resin monomer (I) disappeared after the ring-opening crosslinking of the epoxy resin monomer (I).

[0110] The cured products of the epoxy resin compositions (1)-(3) obtained in Examples 11-13 and the epoxy resin compositions (16)-(18) obtained in Comparative Examples 4-6 were subjected to heat resistance evaluation and acid cleavage test, and the results are shown in Table 3. The heat resistance evaluation was performed by measuring the degradation temperature (Td) (temperature at 5% weight loss) of 5 mg of the cured product of the epoxy resin composition using a thermogravimetric analyzer (TGA) under nitrogen. The acid cleavage test included the following steps: first, sulfuric acid was mixed with water and tetrahydrofuran (THF) to obtain a sulfuric acid solution having a concentration of 0.2 M (volume ratio of water to tetrahydrofuran was 2:8). Next, 25 mg of the cured product of the epoxy resin composition was placed in 5 mL of the sulfuric acid solution and stirred at 65°C. Finally, after a certain period of time, it was observed whether the cured product was cleaved or dissolved in the sulfuric acid solution. When the cured product was completely dissolved in the sulfuric acid solution, it was indicated by. When the cured product was completely cleaved into pieces and partially dissolved in the sulfuric acid solution, it was indicated by. When the cured product could not be cleaved or dissolved, it was indicated by X.

[0111] The cured product of the epoxy resin composition (1) and the product thereof after the acid cleavage test were analyzed by fourier-transform infrared spectroscopy (FT-IR), and it was found that the signal intensity of the C=N characteristic peak at 1625 cm -1 of the cured product of the epoxy resin composition (1) was reduced after the acid cleavage test, and a new characteristic peak (C=0) at 1647 cm -1 was generated, which indicated that the imine group of the cured product of the epoxy resin composition of the present disclosure was indeed broken in an acidic environment, and promoted the cleavage of the cured product of the epoxy resin composition (1).

[0112] Table 4

[0113]

[0114] As shown in Table 4, the thermal degradation temperature (Td) of the cured product of the epoxy resin compositions (1)-(3) of the present disclosure was greater than 280°C, indicating that the cured product of the epoxy resin composition of the present disclosure still had good heat resistance. Compared with the epoxy resin compositions (16)-(18), since the epoxy resin compositions (1)-(3) of the present disclosure used the epoxy resin monomer (I) (asymmetric epoxy resin monomer) to replace the conventional bisphenol F epoxy resin (symmetric epoxy resin), it was observed that the cured product of the epoxy resin compositions (1)-(3) of the present disclosure could be cleaved in an acidic environment at 65°C.

[0115] The cured products of epoxy resin compositions (4) and (5) and epoxy resin compositions (12) and (13) obtained from Examples 14, 15, 22 and 23, respectively, were subjected to heat resistance evaluation and acid cleavage test, and the results are shown in Table 5.

[0116] Table 5

[0117]

[0118] As shown in Table 5, the cured products of epoxy resin compositions (4) and (5) and epoxy resin compositions (12) and (13) according to the present disclosure have a cleavage temperature (Td) greater than 300°C, indicating that the cured products of the epoxy resin compositions according to the present disclosure still have good heat resistance. In addition, the cured products of epoxy resin compositions (4) and (5) and epoxy resin compositions (12) and (13) according to the present disclosure can be cleaved in an acidic environment at 65°C.

[0119] The cured products of epoxy resin compositions (6)-(11) obtained from Examples 16-21, respectively, were subjected to heat resistance evaluation and acid cleavage test, and the results are shown in Table 6.

[0120] Table 6

[0121]

[0122] As shown in Table 6, the cured products of epoxy resin compositions (6)-(11) according to the present disclosure have a cleavage temperature (Td) greater than 290°C, indicating that the cured products of the epoxy resin compositions according to the present disclosure still have good heat resistance. In addition, the cured products of epoxy resin compositions (6)-(11) according to the present disclosure can be cleaved in an acidic environment at 65°C.

[0123] In summary, the cured products of the epoxy resin compositions according to the present disclosure can be cleaved in an acidic environment at a relatively low temperature (e.g., 80°C or below), solving the problem that thermosetting resins are not easy to cleave. In addition, the melting point of the epoxy resin monomers according to the present disclosure can be greatly reduced (e.g., below room temperature), greatly improving the flowability of the epoxy resin compositions according to the present disclosure.

[0124] Although the present disclosure has been disclosed with several examples as above, it is not intended to limit the present disclosure, and any person having ordinary knowledge in the art can make any modification and improvement without departing from the spirit and scope of the present disclosure, and therefore the protection scope of the present disclosure shall be subject to the appended claims.

Claims

1. An epoxy resin composition comprising: Hardener; and An epoxy resin monomer having the structure shown in formula (I). Where A is either substituted or unsubstituted C. 6-24 Aryl styrene, substituted or unsubstituted C 3-16 Cycloalkylene, substituted or unsubstituted C 3-16 heteroaryl groups, or substituted or unsubstituted divalent C 6-25 Alkyl aryl; X 1 and X 2 It is independent as Y 1 and Y 2 Is it C that is substituted or unsubstituted? 6-24 Aroma base, and Y 1 With Y 2 Not the same; and, R 1 It is hydrogen, C 1-8 Alkyl, or C 1-8 Alkoxy, wherein the weight ratio of the curing agent to the epoxy resin monomer is 1:100 to 1:

1.

2. The epoxy resin composition of claim 1, wherein X 1 It is carbon and Y 1 Connected with nitrogen and A, and X 2 It is carbon and Y 2 It is connected with nitrogen and A.

3. The epoxy resin composition of claim 1, wherein X 1 It is nitrogen and Y 1 Connected and bonded to A by carbon, and X 2 It is nitrogen and Y 2 It is connected and linked to A by carbon.

4. The epoxy resin composition of claim 1, wherein A is Where R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 R 10 R 11 R 12 R 13 R 14 R 15 R 16 R 17 R 18 R 19 R 20 R 21 R 22 R 23 R 24 R 25 R 26 R 27 R 28 and R 29 It is independent of hydrogen and C. 1-8 Alkyl, or C 1-8 Alkyl group.

5. The epoxy resin composition of claim 1, wherein Y 1 and Y 2 It is independent as R 30 R 31 R 32 R 33 R 34 and R 35 It is independent of hydrogen and C. 1-8 Alkyl, or C 1-8 Alkyl groups; a, b, c, d, e, and f are independently 1, 2, 3, 4, or 5.

6. The epoxy resin composition of claim 1, wherein the epoxy resin monomer is Where R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 R 10 R 11 R 12 and R 13 It is independent of hydrogen and C. 1-8 Alkyl, or C 1-8 Alkoxy; and, Y 1 and Y 2 Is it C that is substituted or unsubstituted? 6-24 Aroma base, and Y 1 With Y 2 They are not the same.

7. The epoxy resin composition of claim 1, wherein the epoxy resin monomer is , where R 1 R 14 R 15 R 16 R 17 R 18 R 19 R 20 R 21 R 22 R 23 R 24 R 25 R 26 R 27 R 28 and R 29 It is independent of hydrogen and C. 1-8 Alkyl, or C 1-8 Alkoxy; and, Y 1 and Y 2 Is it C that is substituted or unsubstituted? 6-24 Aroma base, and Y 1 With Y 2 They are not the same.

8. The epoxy resin composition of claim 1, wherein the epoxy resin monomer is Where A is either substituted or unsubstituted C. 6-24 Aryl styrene, substituted or unsubstituted C 3-16 Cycloalkylene, substituted or unsubstituted C 3-16 heteroaryl groups, or substituted or unsubstituted divalent C 6-25 alkylaryl; and, R 1 R 30 R 31 and R 32 It is independent of hydrogen and C. 1-8 Alkyl, or C 1-8 Alkyl group.

9. The epoxy resin composition of claim 1, wherein the epoxy equivalent weight (EEW) of the epoxy resin monomer is from 50 g / equivalent to 1500 g / equivalent.

10. The epoxy resin composition of claim 1, further comprising: An epoxy resin, wherein the weight ratio of the epoxy resin to the epoxy resin monomer having the structure shown in formula (I) is 1:100 to 9:

1.

11. The epoxy resin composition of claim 10, wherein the epoxy resin is bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenolic epoxy resin, naphthyl epoxy resin, anthracene epoxy resin, ethylene glycol diglycidyl ether epoxy resin, propylene glycol diglycidyl ether epoxy resin, or 1,4-butanediol diglycidyl ether epoxy resin.

12. The epoxy resin composition of claim 10, wherein the epoxy resin is a bisphenol A diglycidyl ether epoxy resin.

13. The epoxy resin composition of claim 1, wherein the curing agent is an acid anhydride curing agent, an amine curing agent, a phenolic curing agent, an imidazole curing agent, or a combination thereof.

14. A resin film comprising a cured product of the epoxy resin composition according to any one of claims 1 to 13.

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