TW202020003A - Resin composition and cured resin composition - Google Patents

Abstract

A resin composition is provided, which includes an oligomer formed by reacting bisphenol epoxy resin monomer, aliphatic diglycidyl ether, anhydride compound, and catalyst, wherein the molar ratio of epoxy groups of the bisphenol epoxy resin monomer and aliphatic diglycidyl ether to anhydride groups of the anhydride compound is between 3.5:1 and 8.8:1. The bisphenol epoxy resin monomer and aliphatic diglycidyl ether have a molar ratio of 0.3:1 to 1.3:1, and the resin composition has a viscosity of 20Pa．s to 80Pa．s at 25℃.

Description

Resin composition and hardened resin composition

This disclosure relates to the resin composition, and more particularly to the molar ratio of the epoxy group of the bisphenol-type epoxy resin monomer and the aliphatic diglycidyl ether to the acid anhydride group of the acid anhydride compound.

Epoxy resins have excellent electrical characteristics, adhesion, weather resistance and other characteristics, and are widely used in electronic applications such as electrical insulation, laminates, and electronic semiconductor packaging. However, the curing of epoxy resin requires high ultraviolet (UV) energy, so it cannot avoid the disadvantage of its slow light curing rate. In addition, high-viscosity bisphenol-based epoxy resins must use aliphatic diglycidyl ether as a reactive diluent to reduce viscosity, but the hardening speed of this composition will become slower. Although the hydrogenated bisphenol-based epoxy resin has a high photo-hardening rate, the problem of hardening the surface film layer but not hardening the inner portion occurs when thick-film coating.

In summary, there is an urgent need for a new epoxy resin composition to solve the above problems.

The resin composition provided by an embodiment of the present invention includes: a bisphenol-type epoxy resin monomer, an aliphatic diglycidyl ether, an acid anhydride compound, and an oligomer formed by reacting with a catalyst, wherein the bisphenol-type epoxy resin monomer The molar ratio of the epoxy group of the body and the aliphatic diglycidyl ether to the anhydride group of the acid anhydride compound is between 3.5:1 and 8.8:1, in which the bisphenol epoxy resin monomer and the aliphatic diglycidyl ether The molar ratio of ether is between 0.3:1 and 1.3:1; and the viscosity of the resin composition at 25°C is between 20Pa. s to 80Pa. between s.

In some embodiments, the resin composition includes unreacted bisphenol-type epoxy resin monomer and aliphatic diglycidyl ether.

In some embodiments, the bisphenol-type epoxy resin monomers include bisphenol A epoxy resin monomers, hydrogenated bisphenol A epoxy resin monomers, bisphenol F epoxy resin monomers, hydrogenated bisphenol F epoxy resin monomers Monomer, or a combination of the above.

In some embodiments, the aliphatic diglycidyl ether includes ethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1 , 6-hexanediol diglycidyl ether, 1,4-cyclohexyl dimethanol diglycidyl ether, polypropylene glycol diglycidyl ether, or a combination thereof.

In some embodiments, the anhydride compound includes 4-methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methylnadic anhydride, 1,2,4-benzenetricarboxylic anhydride, dodecenylsuccinic anhydride, phthalic anhydride, Tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, or a combination thereof.

In some embodiments, the catalyst includes triethanolamine, dimethylbenzylamine, triphenylphosphine, or a combination of the foregoing.

In some embodiments, the resin composition further includes a hardener.

In some embodiments, the hardener includes a cationic initiator or an anionic initiator.

In some embodiments, the resin composition further includes an acrylate oligomer and a radical initiator.

In some embodiments, the resin composition further includes fillers, defoamers, leveling agents, or a combination thereof.

An embodiment of the present invention provides a hardened resin composition, wherein the resin composition includes: a bisphenol-type epoxy resin monomer, an aliphatic diglycidyl ether, an acid anhydride compound, an oligomer reacted with a catalyst; and a hardener ; Among them, the molar ratio of the epoxy group of the bisphenol epoxy resin monomer and the aliphatic diglycidyl ether to the anhydride group of the acid anhydride compound is between 3.5:1 and 8.8:1, of which the bisphenol epoxy resin The molar ratio of the resin monomer to the aliphatic diglycidyl ether is between 0.3:1 and 1.3:1; the viscosity of the resin composition at 25°C is between 20 Pa. s to 80Pa. s; and where the hardened resin composition has a first glass transition temperature below room temperature and a second glass transition temperature above room temperature.

In some embodiments, the resin composition includes unreacted bisphenol-type epoxy resin monomer and aliphatic diglycidyl ether.

In some embodiments, the bisphenol-type epoxy resin monomers include bisphenol A epoxy resin monomers, hydrogenated bisphenol A epoxy resin monomers, bisphenol F epoxy resin monomers, hydrogenated bisphenol F epoxy resin monomers Monomer, or a combination of the above.

In some embodiments, the aliphatic diglycidyl ether includes ethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1 , 6-hexanediol diglycidyl ether, 1,4-cyclohexyl dimethanol diglycidyl ether, polypropylene glycol diglycidyl ether, or a combination thereof.

In some embodiments, the anhydride compound includes 4-methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methylnadic anhydride, 1,2,4-benzenetricarboxylic anhydride, dodecenylsuccinic anhydride, phthalic anhydride, Tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, or a combination thereof.

In some embodiments, the catalyst includes triethanolamine, dimethylbenzylamine, triphenylphosphine, or a combination of the foregoing.

In some embodiments, the hardener includes a cationic initiator or an anionic initiator.

In some embodiments, the resin composition further includes an acrylate oligomer and a radical initiator.

In some embodiments, the resin composition further includes fillers, defoamers, leveling agents, or a combination thereof.

The resin composition provided by an embodiment of the present invention includes: a bisphenol epoxy resin monomer, an aliphatic diglycidyl ether, an acid anhydride compound, and an oligomer formed by reacting with a catalyst. The oligomer has multiple epoxy groups, which can be opened in the subsequent hardening step. In addition, the oligomer has a hard segment derived from a bisphenol-type epoxy resin monomer, and a soft segment of aliphatic diglycidyl ether. Therefore, in addition to being flexible, oligomers have excellent adhesion to soft substrates, especially heterogeneous substrates (such as PET to TAC, PET to PEN, PET to PI, PEN to PI, and PEN to TAC). Excellent adhesion. In one embodiment, the molar ratio of the epoxy group of the bisphenol epoxy resin and the aliphatic diglycidyl ether to the anhydride group of the acid anhydride compound is between 3.5:1 and 8.8:1. If the proportion of epoxy groups is too high, there will be too much unreacted bisphenol epoxy resin monomer or aliphatic diglycidyl ether, resulting in insufficient esterification reaction of the resin. If the proportion of epoxy groups is too low, it is easy to cause the resin reaction viscosity to be too high and not easy to control, or even gel. The molar ratio of the bisphenol epoxy resin monomer to the aliphatic diglycidyl ether is between 0.3:1 and 1.3:1. If the proportion of bisphenol-type epoxy resin monomer is too high, the resin will be relatively rigid and the adhesion to the soft substrate will be poor. If the proportion of bisphenol epoxy resin monomer is too low, the resin is too soft, the cohesion between the molecular chains is not good, and the adhesion to the heterogeneous substrate is reduced. The viscosity of the oligomer-containing resin composition at 25 ℃ is between 20Pa. s to 80Pa. between s. If the viscosity of the resin composition is too low, it will result in poor film-forming properties on the flexible substrate. If the viscosity of the resin composition is too high, it is difficult to apply and use.

The temperature of the above-mentioned bisphenol epoxy resin monomer, aliphatic diglycidyl ether, acid anhydride compound, and reaction with the catalyst to form an oligomer is between 100°C and 130°C, and lasts between 0.5 and 3 hours. If the reaction temperature is lower, the reaction time is longer, and vice versa. If the reaction temperature is too high and/or the reaction time is too long, gelation is likely to occur. If the reaction temperature is too low and/or the reaction time is too short, the bisphenol epoxy resin monomer and the epoxy group of the aliphatic diglycidyl ether cannot ring-open to form a hydroxyl group, which is formed by reacting with other epoxy groups and acid anhydride compounds Prepolymer.

In some embodiments, the resin composition includes an unreacted bisphenol-type epoxy resin monomer and an aliphatic diglycidyl ether whose epoxy group can undergo a ring-opening reaction in a subsequent hardening step to crosslink the oligomer. In addition, the more unreacted bisphenol epoxy resin monomer and aliphatic diglycidyl ether, the lower the viscosity of the resin composition, and vice versa.

In some embodiments, the bisphenol-type epoxy resin monomers include bisphenol A epoxy resin monomers, hydrogenated bisphenol A epoxy resin monomers, bisphenol F epoxy resin monomers, hydrogenated bisphenol F epoxy resin monomers Monomer, or a combination of the above.

In some embodiments, the aliphatic diglycidyl ether includes ethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1 , 6-hexanediol diglycidyl ether, 1,4-cyclohexyl dimethanol diglycidyl ether, polypropylene glycol diglycidyl ether, or a combination thereof.

In some embodiments, the anhydride compound includes 4-methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methylnadic anhydride, 1,2,4-benzenetricarboxylic anhydride, dodecenylsuccinic anhydride, phthalic anhydride, Tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, or a combination thereof.

In some embodiments, the catalyst includes triethanolamine, dimethylbenzylamine, triphenylphosphine, or a combination of the foregoing.

In some embodiments, the resin composition further includes a hardener, such as a cationic initiator or an anionic initiator. The above-mentioned hardening agent helps to make the ring-opening reaction of the epoxy group and hardens the oligomer cross-link. The cationic initiator can be further subdivided into UV-type cationic initiator or thermal-type cationic initiator depending on the type of applied energy. For example, the UV-type cationic initiator may be a diaryl iodide compound or a triaryl sulfur compound. The thermal cationic initiator may be an aromatic salt salt compound such as [4-[(methoxycarbonyl)oxy]phenyl]methyl (phenylmethyl) succinate: (OC-6-11)-hexafluoro Antimonate (1-), (4-hydroxyphenyl)methyl (1-naphthylmethyl) agar: (OC-6-11)-hexafluoroantimonate (1-), (4-hydroxybenzene Yl)methyl[(2-methylphenyl)methyl]methyl: (OC-6-11)-hexafluoroantimonate (1-), (4-hydroxyphenyl)methyl (phenylmethyl ) 鋶: (OC-6-11)-hexafluoroantimonate (1-), [4-(acetoxy) phenyl] dimethyl amide: (OC-6-11)-hexafluoroantimonate Salt (1-), (4-hydroxyphenyl)methyl (phenylmethyl) alkane: hexafluorophosphate (1-), or a combination of the above. In an embodiment, the anionic starter may be a thermal anionic starter, such as (4-hydroxyphenyl)methyl (phenylmethyl) alkane: tetra(2,3,4,5,6-penta Fluorophenyl) borate (1-) (1:1), (4-hydroxyphenyl) dimethyl alkane: tetrakis(2,3,4,5,6-pentafluorophenyl) borate (1- ) (1:1), [4-(acetoxy)phenyl] dimethyl alkane: tetrakis(2,3,4,5,6-pentafluorophenyl) borate (1-) (1: 1), or a combination of the above.

In some embodiments, the resin composition further includes an acrylate oligomer and a radical initiator. For example, the acrylate oligomer may be a polyester acrylate, such as the commercially available DM623 (purchased from Double Bond Chemical). The free radical initiator may be a UV-type free radical initiator, which includes benzoin series (such as benzoin methyl ether, benzoin ethyl ether, or benzoin n-butyl ether), and acetophenone series (such as dialkoxyacetophenone, chlorine Acetophenone, or 2-hydroxy-2-methyl-1-acetone), or a combination thereof. Acrylic oligomers can be used to adjust the viscosity of the resin composition. The radical initiator can be used to harden the acrylate oligomer in the resin composition in the step of hardening the resin composition.

In some embodiments, the resin composition further includes a filler, an antifoaming agent, a leveling agent, or a combination thereof to adjust the properties or appearance of the resin composition after hardening. For example, the filler can improve the mechanical strength of the resin composition after hardening, and it includes silica, talc, alumina, clay, the like, or a combination thereof. The leveling agent can make the thickness of the coating uniform, which may include Doxflow 6057, Doxflow 6345 of Doxa Chemical, SPL-90 and SPL-460 of Gonglong Chemical, or a combination thereof. The defoamer can exert an excellent defoaming effect, and it can include Chongyue KF-96 and KS-7708, DOXA Chemical's 68 and F22, or a combination of the foregoing.

An embodiment of the present invention provides a hardened resin composition, wherein the resin composition includes: a bisphenol-type epoxy resin monomer, an aliphatic diglycidyl ether, an acid anhydride compound, an oligomer reacted with a catalyst; and a hardener . The curing temperature of the above resin composition is between 80°C and 120°C, and the curing time is between 30 and 60 minutes. If the hardening temperature is lower, the hardening time is longer, and vice versa. If the curing temperature is too high and/or the curing time is too long, it will easily cause deformation or yellowing of the soft substrate. If the curing temperature is too low and/or the curing time is too short, the resin composition cannot be cured or the curing is incomplete.

In one embodiment, the molar ratio of the epoxy group of the bisphenol epoxy resin and the aliphatic diglycidyl ether to the anhydride group of the acid anhydride compound is between 3.5:1 and 8.8:1. The molar ratio of bisphenol epoxy resin monomer to aliphatic diglycidyl ether is between 0.3:1 and 1.3:1. The viscosity of the resin composition at 25 ℃ is between 20Pa. s to 80Pa. between s.

In one embodiment, the hardened resin composition has a first glass transition temperature below room temperature and a second glass transition temperature above room temperature. The resin segment of the second glass transition temperature above room temperature has rigid characteristics; the resin segment of the first glass transition temperature below room temperature has flexible characteristics, and the soft and hard characteristics of different segments increase for different flexible substrates Surface affinity, this interaction enhances the ability to adhere to heterogeneous substrates. It is worth noting that the general epoxy resin composition only has a single glass transition temperature after hardening, so it does not have the above-mentioned effects.

In some embodiments, the resin composition includes unreacted bisphenol-type epoxy resin monomer and aliphatic diglycidyl ether. In some embodiments, the hardener includes a cationic initiator or an anionic initiator. In some embodiments, the resin composition further includes an acrylate oligomer and a radical initiator. In some embodiments, the resin composition further includes fillers, defoamers, leveling agents, or a combination thereof. The details of the above-mentioned composition are similar to the foregoing and will not be repeated here.

In order to make the above-mentioned and other purposes, features, and advantages of the present disclosure more obvious and understandable, a few examples are specifically described below as follows: Examples

Synthesis Example 1-1 (CH-BA-H1 resin) Take 48 parts by weight of 1,4-cyclohexane dimethanol diglycidyl ether (0.310 equivalent moles, 1,4-bis (glycidyloxymethyl) cyclohexane, CHGE, purchased From CVC Thermoset Specialties), 32 parts by weight of bisphenol A epoxy resin monomer (0.171 equivalent molar, BE-188L, purchased from Changchun resin), and 20 parts by weight of 4-methylhexahydrophthalic anhydride (0.119 equivalent molar Ear, 4-Methylhexahydrophthalic anhydride) mixed. The molar ratio between the above epoxy groups of CHGE and BE-188L and the anhydride groups of 4-methylhexahydrophthalic anhydride is 4.04:1. Using 0.08 parts by weight of triethanolamine (Triethanolamine) as a catalyst, the mixture was added and placed in an oil bath at 120°C for 60 minutes to form a CH-BA-H1 resin composition. The room temperature viscosity measured by BROOKFIELD DV-III ULTRA viscosity is about 54Pa•s.

Synthesis Example 1-2 (CH-BF-H1 resin composition) 48 parts by weight of 1,4-cyclohexane dimethanol diglycidyl ether (0.310 equivalent moles, CHGE) and 32 parts by weight of bisphenol F ring Oxygen resin monomer (0.187 equivalent moles, 830S, purchased from DIC) was mixed with 20 parts by weight of 4-methylhexahydrophthalic anhydride (0.119 equivalent moles). The molar ratio between the above epoxy groups of CHGE and 830S and the anhydride groups of 4-methylhexahydrophthalic anhydride is 4.09:1. Using 0.08 parts by weight of triethanolamine (Triethanolamine) as a catalyst, the mixture was added and placed in an oil bath at 120°C for 60 minutes to form a CH-BF-H1 resin composition. The room temperature viscosity measured by BROOKFIELD DV-III ULTRA viscosity is about 51Pa•s.

Synthesis Example 1-3 (BD-BF-H1 resin composition) 50 parts by weight of 1,4-butanediol diglycidyl ether (0.4 equivalent moles, 1,4-Butanediol diglycidyl ether, BDGE, purchased from CVC Thermoset Specialties), 38 parts by weight of bisphenol F epoxy resin monomer (0.222 equivalent moles, 830S), mixed with 12 parts by weight of 4-methylhexahydrophthalic anhydride (0.071 equivalents moles). The molar ratio between the epoxy groups of BDGE and 830S and the acid anhydride groups of 4-methylhexahydrophthalic anhydride is 8.76:1. 0.088 parts by weight of triethanolamine (Triethanolamine) was used as a catalyst, and after adding the above mixture, it was placed in an oil bath at 120°C for 60 minutes to form a BD-BF-H1 resin composition. The room temperature viscosity measured by BROOKFIELD DV-III ULTRA viscosity is about 39Pa•s.

Synthesis Example 1-4 (BD-BA-H2 resin composition) 30 parts by weight of 1,4-butanediol diglycidyl ether (0.24 equivalent moles, BDGE) and 52 parts by weight of bisphenol A epoxy resin The monomer (0.278 equivalent moles, BE-188L) was mixed with 18 parts by weight of hexahydrophthalic anhydride (0.117 equivalent moles). The molar ratio between the epoxy groups of BDGE and BE-188L and the anhydride groups of hexahydrophthalic anhydride is 4.43:1. Using 0.082 parts by weight of triethanolamine (Triethanolamine) as a catalyst, the mixture was added and placed in an oil bath at 120°C for 60 minutes to form a BD-BA-H2 resin composition. The room temperature viscosity measured by BROOKFIELD DV-III ULTRA viscosity is about 57Pa•s.

Synthesis Example 1-5 (BD-HY-H2 resin composition) Take 32 parts by weight of 1,4-butanediol diglycidyl ether (0.256 equivalent moles, BDGE), 48 parts by weight of hydrogenated bisphenol A epoxy The resin monomer (0.218 equivalent moles, EPALLOY ^™ 5000, available from CVC Thermoset Specialties) was mixed with 20 parts by weight of hexahydrophthalic anhydride (0.130 equivalent moles). The molar ratio between the epoxy groups of BDGE and EPALLOY ^™ 5000 and the anhydride groups of hexahydrophthalic anhydride is 3.63:1. Using 0.08 parts by weight of triethanolamine (Triethanolamine) as a catalyst, after adding the above mixture, it was placed in an oil bath at 120°C for 60 minutes to form a BD-HY-H2 resin composition. The room temperature viscosity measured by BROOKFIELD DV-III ULTRA viscosity is about 34Pa•s.

Synthesis Example 1-6 (HD-BA-H1 resin composition) 32 parts by weight of 1,6-hexanediol diglycidyl ether (0.214 equivalent moles, 1,6-Hexanediol diglycidyl ether, HDGE, purchased from CVC Thermoset Specialties), 50 parts by weight of bisphenol A epoxy resin monomer (0.267 equivalent mole, BE-188L), and 18 parts by weight of 4-methylhexahydrophthalic anhydride (0.107 equivalent mole). The molar ratio between the epoxy group of the above HDGE and BE-188L and the anhydride group of 4-methylhexahydrophthalic anhydride is 4.50:1. Using 0.082 parts by weight of triethanolamine (Triethanolamine) as a catalyst, the mixture was added and placed in an oil bath at 120°C for 60 minutes to form an HD-BA-H1 resin composition. The room temperature viscosity measured by BROOKFIELD DV-III ULTRA viscosity is about 55Pa•s.

Synthesis Example 1-7 (HD-BF-H2 resin composition) 32 parts by weight of 1,6-hexanediol diglycidyl ether (0.256 equivalent moles, HDGE), 48 parts by weight of bisphenol F epoxy resin The monomer (0.281 equivalent molar, 830S) was mixed with 20 parts by weight of hexahydrophthalic anhydride (0.122 equivalent molar). The molar ratio between the epoxy group of the above HDGE and 830S and the anhydride group of hexahydrophthalic anhydride is 4.40:1. 0.08 parts by weight of triethanolamine (Triethanolamine) was used as a catalyst, and after adding the above mixture, it was placed in an oil bath at 120°C for 60 minutes to form an HD-BF-H2 resin composition. The room temperature viscosity measured by BROOKFIELD DV-III ULTRA viscosity is about 58Pa•s.

Synthesis Example 1-8 (ND-HY-H1 resin composition) 50 parts by weight of neopentyl glycol diglycidyl ether (0.382 equivalent moles, Neopentyl glycol diglycidyl ether, NDGE, purchased from CVC Thermoset Specialties), 32 parts by weight One part of hydrogenated bisphenol A epoxy resin monomer (0.145 equivalent moles, EPALLOY ^™ 5000) was mixed with 18 parts by weight of 4-methylhexahydrophthalic anhydride (0.107 equivalent moles). The molar ratio between the epoxy group of the aforementioned NDGE and EPALLOY ^™ 5000 and the anhydride group of 4-methylhexahydrophthalic anhydride is 4.93:1. Using 0.082 parts by weight of triethanolamine (Triethanolamine) as a catalyst, after adding the above mixture, it was placed in an oil bath at 120°C for 60 minutes to form an ND-HY-H1 resin composition. The room temperature viscosity measured by BROOKFIELD DV-III ULTRA viscosity is about 25Pa•s.

Synthesis Example 1-9 (ND-BA-H2 resin composition) Take 32 parts by weight of neopentyl glycol diglycidyl ether (0.244 equivalent moles, NDGE), 32 parts by weight of bisphenol A epoxy resin monomer ( 0.171 equivalent molar, BE-188L), mixed with 20 parts by weight of hexahydrophthalic anhydride (0.12 equivalent molar). The molar ratio between the epoxy group of NDGE and BE-188L and the anhydride group of hexahydrophthalic anhydride is 3.46:1. Using 0.064 parts by weight of triethanolamine (Triethanolamine) as a catalyst, the mixture was added and placed in an oil bath at 120°C for 60 minutes to form an ND-BA-H2 resin composition. The room temperature viscosity measured by BROOKFIELD DV-III ULTRA viscosity is about 72Pa•s.

Example 1 100g of CH-BA-H1 resin composition, 1g of fumed silica R974 (Fumed Silica) as a filler, 6g of UV-type cationic initiator Chivacure 1176 (50% dissolved in propylene carbonate, (Purchased from Qitai) as a hardener and mixed at room temperature, and mixed and defoamed using a Thinky agitated deaerator. Next, the above resin composition was coated on a flexible substrate of a polyethylene terephthalate film (PET, O-type 188 mm purchased from Shinco Optoelectronic Materials) with a 25 μm wire rod to form a film layer with a film thickness of about 25 μm. After that, another soft substrate such as cellulose triacetate film (TAC, manufactured by L600), polyethylene terephthalate film (PEN, purchased from Teijin Chemical TEONEX® 100mm), or polyacrylic acid The amine film (PI, made by L700) was laminated with a laminator at room temperature (PET vs. TAC, PET vs. PEN, and PET vs. PI). The pressed test piece was irradiated with ultraviolet light (5,000 mJ/cm ² ) by a 365 nm mercury lamp, and then placed in an oven at 80° C. for 30 minutes to perform a hardening reaction. All test pieces are cut to a width of 2.5 cm and a length of 8 cm, and then tested with a double-column tensile machine (QC Teck) instrument for tear resistance (Peel strength) at a tensile rate of 254 mm/min (ASTM 1876-01 T-Peel Test is the test specification). The measurement standard of the glass transition temperature (Tg) of the above hardened resin composition is to cut the hardened sample to a weight of about 5 mg and place it in a special aluminum pan for the instrument, using a differential scanning thermal analyzer (model: TA INSTRUMENTS Q10), under a nitrogen atmosphere, the temperature was raised to 250°C at 20°C/min.

Example 2 100g of CH-BF-H1 resin composition, 1g of fumed silica R974 as a filler, 2g of thermal cationic initiator SI-60 (purchased from Sanshin Chemical Co., Ltd.) as a hardener , And mix at room temperature, use the Thinky stirring defoaming machine for mixing and defoaming. Next, the above resin composition was coated on a flexible substrate of a PET film or a PEN film with a 25 μm wire rod to form a film layer with a film thickness of about 25 μm. After that, it is laminated with another flexible substrate such as TAC, PEN, or PI at room temperature with a laminator (PET vs. TAC, PET vs. PEN, PET vs. PI, PEN vs. PI, and PEN vs. TAC). The pressed test piece was placed in an 80°C oven for 60 minutes to carry out the hardening reaction. All test pieces are cut to a width of 2.5 cm and a length of 8 cm, and then subjected to a tear test with a two-column tensile machine (QC Teck) instrument with a tensile rate of 254 mm/min (ASTM 1876-01 T-Peel Test is the test specification ). The measurement standard for the glass transition temperature (Tg) of the above-mentioned hardened resin composition is to cut the hardened sample, weigh about 5 mg, and place it in a special aluminum pan for the instrument, using a differential scanning thermal analyzer (model: TA INSTRUMENTS Q10), under a nitrogen atmosphere, the temperature was raised to 250°C at 20°C/min.

Example 3 is similar to Example 1, except that the resin composition is changed to 100 g of BD-BF-H1, 1 g of fumed silica R974, and 6 g of UV-type cationic initiator Chivacure 1176. The bonding method, hardening method, tear test, and Tg measurement of the remaining soft substrates are similar to those in Example 1.

Example 4 Similar to Example 1, except that the resin composition was changed to 100 g of BD-BA-H2, 1 g of fumed silica R974, and 6 g of UV-type cationic initiator Chivacure 1176. The bonding method, hardening method, tear test, and Tg measurement of the remaining soft substrates are similar to those in Example 1.

Example 5 Similar to Example 1, except that the resin composition was changed to 90g of BD-HY-H2, 1g of fumed silica R974, 5.4g of UV-type cationic initiator Chivacure 1176, and 10g of polyester acrylic Ester DM623 (purchased from Double Bond Chemical Company), and 0.4g of free radical initiator TPO (2,4,6-Trimethylbenzoyl-diphenyl-phosphineoxide, purchased from Mufeng Company). The bonding method, hardening method, tear test, and Tg measurement of the remaining soft substrates are similar to those in Example 1.

Example 6 Similar to Example 2, except that the resin composition was changed to 100 g of HD-BA-H1, 1 g of fumed silica R974, and 2 g of thermal cationic initiator SI-60. The bonding method, hardening method, tear test, and Tg measurement of the remaining soft substrates are similar to those in Example 2.

Example 7 Similar to Example 1, except that the resin composition was changed to 100 g of HD-BF-H2, 1 g of fumed silica R974, and 6 g of UV-type cationic initiator Chivacure 1176. The bonding method, hardening method, tear test, and Tg measurement of the remaining soft substrates are similar to those in Example 1.

Example 8 Similar to Example 1, except that the resin composition was changed to 100 g of ND-HY-H1, 1 g of fumed silica R974, and 6 g of UV-type cationic initiator Chivacure 1176. The bonding method, hardening method, tear test, and Tg measurement of the remaining soft substrates are similar to those in Example 1.

Example 9 Similar to Example 1, except that the resin composition was changed to 80g of ND-BA-H2, 1g of fumed silica R974, 4.8g of UV-type cationic initiator Chivacure 1176, 20g of polyester acrylic Ester DM623, and 0.8g of free radical initiator TPO. The bonding method, hardening method, tear test, and Tg measurement of the remaining soft substrates are similar to those in Example 1.

Example 10 Similar to Example 1, except that the resin composition was changed to 50g of CH-BA-H1, 50g of HD-BF-H2, 1g of fumed silica R974, and 6g of UV type cationic initiator Chivacure 1176. The bonding method, hardening method, tear test, and Tg measurement of the remaining soft substrates are similar to those in Example 1.

Comparative Example 1 is similar to Example 1, except that the resin composition is changed to 100 g of bisphenol A epoxy resin monomer BE-188L, 1 g of fumed silica R974, and 6 g of UV-type cationic initiator Chivacure 1176 . The bonding method, hardening method, tear test, and Tg measurement of the remaining soft substrates are similar to those in Example 1.

Comparative Example 2 is similar to Example 1, except that the resin composition is changed to 100 g of bisphenol F epoxy resin monomer 830S, 1 g of fumed silica R974, and 6 g of UV-type cationic initiator Chivacure 1176. The bonding method, hardening method, tear test, and Tg measurement of the remaining soft substrates are similar to those in Example 1.

Comparative Example 3 is similar to Example 1, except that the resin composition is changed to 50 g of 1,4-butanediol diglycidyl ether BDGE, 10 g of bisphenol A epoxy resin monomer BE-188L, and 40 g of bisphenol F Epoxy resin monomer 830S, 1g of fumed silica R974, and 6g of UV-type cationic initiator Chivacure 1176. The bonding method, hardening method, tear test, and Tg measurement of the remaining soft substrates are similar to those in Example 1.

Comparative Example 4 is similar to Example 2, except that the resin composition is changed to 50 g of 1,6-hexanediol diglycidyl ether HDGE, 50 g of bisphenol A epoxy resin monomer BE-188L, and 1 g of gas phase II Silicon oxide R974, and 2g of thermal cationic initiator SI-60. The bonding method, hardening method, tear test, and Tg measurement of the remaining soft substrates are similar to those in Example 2.

Table 1

Table 2

table 3

It can be seen from the examples and comparative examples in Tables 1 to 3 that after the epoxy resins in the examples are hardened, the adhesion to the flexible substrate can be significantly improved, especially the heterogeneous flexible substrate. Compared with the comparative example, the tear strength of PET vs. TAC in the examples is increased by 6-7 times, the tear strength of PET vs. PEN is increased by 4-5 times, and the tear strength of PET vs. PI is increased by 5-6 times The tear strength of PEN vs. PI is increased by 11-12 times, and the tear strength of PEN vs. TAC is increased by 4-5 times. In addition, the hardened resin composition in the examples has a first Tg lower than room temperature and a second Tg higher than room temperature.

Although this disclosure has been disclosed above in several embodiments, it is not intended to limit this disclosure. Anyone with ordinary knowledge in this technical field can make any changes and retouching without departing from the spirit and scope of this disclosure. Therefore, the scope of protection disclosed in this disclosure shall be deemed as defined by the scope of the attached patent application.

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Claims (19)

A resin composition, including: a bisphenol epoxy resin monomer, an aliphatic diglycidyl ether, an acid anhydride compound, and an oligomer formed by reacting with a catalyst, wherein the bisphenol epoxy resin monomer The molar ratio of the epoxy group of the body and the aliphatic diglycidyl ether to the anhydride group of the acid anhydride compound is between 3.5:1 and 8.8:1, wherein the bisphenol epoxy resin monomer and the fat The molar ratio of the family diglycidyl ether is between 0.3:1 and 1.3:1; and the viscosity of the resin composition at 25°C is 20 Pa. s to 80Pa. between s. The resin composition as described in item 1 of the patent application scope includes the unreacted bisphenol epoxy resin monomer and the aliphatic diglycidyl ether. The resin composition as described in item 1 of the patent application scope, wherein the bisphenol-type epoxy resin monomer includes bisphenol A epoxy resin monomer, hydrogenated bisphenol A epoxy resin monomer, bisphenol F epoxy resin Monomer, hydrogenated bisphenol F epoxy resin monomer, or a combination of the above. The resin composition as described in item 1 of the patent application scope, wherein the aliphatic diglycidyl ether includes ethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, Neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,4-cyclohexyl dimethanol diglycidyl ether, polypropylene glycol diglycidyl ether, or a combination thereof. The resin composition as described in item 1 of the patent application scope, wherein the acid anhydride compound includes 4-methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methylnadic anhydride, 1,2,4-benzenetricarboxylic anhydride, dodecene Succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, or a combination thereof. The resin composition as described in item 1 of the patent application scope, wherein the catalyst includes triethanolamine, dimethylbenzylamine, triphenylphosphine, or a combination thereof. The resin composition as described in item 1 of the patent application scope further includes a hardener. The resin composition as described in item 7 of the patent application, wherein the hardener includes a cationic initiator or an anionic initiator. The resin composition as described in item 7 of the patent application scope further includes an acrylate oligomer and a free radical initiator. The resin composition as described in item 7 of the patent application scope further includes a filler, an anti-foaming agent, a leveling agent, or a combination thereof. A hardened resin composition, wherein the resin composition includes: a bisphenol-type epoxy resin monomer, an aliphatic diglycidyl ether, an acid anhydride compound, an oligomer reacted with a catalyst; and a Hardener; wherein the molar ratio of the epoxy group of the bisphenol epoxy resin and the aliphatic diglycidyl ether to the anhydride group of the acid anhydride compound is between 3.5:1 and 8.8:1, wherein The molar ratio of the bisphenol epoxy resin monomer to the aliphatic diglycidyl ether is between 0.3:1 and 1.3:1; wherein the viscosity of the resin composition at 25°C is between 20 Pa. s to 80Pa. s; and where the resin composition hardened has a first glass transition temperature below room temperature and a second glass transition temperature above room temperature. The hardened resin composition as described in item 11 of the patent application range, wherein the resin composition includes the unreacted bisphenol-type epoxy resin monomer and the aliphatic diglycidyl ether. The hardened resin composition as described in item 11 of the patent application range, wherein the bisphenol-type epoxy resin monomer includes bisphenol A epoxy resin monomer, hydrogenated bisphenol A epoxy resin monomer, bisphenol F ring Oxygen resin monomer, hydrogenated bisphenol F epoxy resin monomer, or a combination thereof. The hardened resin composition as described in item 11 of the patent application range, wherein the aliphatic diglycidyl ether includes ethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether Ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,4-cyclohexyl dimethanol diglycidyl ether, polypropylene glycol diglycidyl ether, or a combination thereof. The hardened resin composition as described in item 11 of the patent application scope, wherein the acid anhydride compound includes 4-methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methylnadic anhydride, 1,2,4-benzenetricarboxylic anhydride, and ten Dienyl succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, or a combination thereof. The hardened resin composition as described in item 11 of the patent application range, wherein the catalyst includes triethanolamine, dimethylbenzylamine, triphenylphosphine, or a combination thereof. The hardened resin composition as described in item 11 of the patent application range, wherein the hardener includes a cationic initiator or an anionic initiator. The hardened resin composition as described in item 11 of the patent application scope, wherein the resin composition further includes an acrylate oligomer and a free radical initiator. The hardened resin composition as described in item 11 of the patent application scope, wherein the resin composition further includes a filler, an anti-foaming agent, a leveling agent, or a combination thereof.