A phenolic resin, an epoxy resin and their cured products

Abstract

The specific implementation mode of the present invention provides a phenolic resin, an epoxy resin and a cured product thereof. The phenolic resin further introduces a hydroxyl-substituted or halomethyl-substituted benzaldehyde structure into the phenolic resin structure introducing a benzene ring or a biphenyl structure, and this structure can further improve the high-temperature moisture and heat stability of its epoxy resin encapsulation material.

Description

Technical Field

[0001] The present invention belongs to the field of polymer cured resin materials, and particularly relates to a phenolic resin, an epoxy resin and a cured product thereof. Background Art

[0002] As a packaging material for semiconductors, epoxy resins are usually used for curing and sealing. Among them, resins formed by cresol novolak type epoxy resins, phenol novolak curing agents and inorganic fillers such as silica are widely used for packaging. By introducing a benzene ring or a biphenyl structure into the epoxy resin and / or phenolic resin curing agent of the epoxy resin curing and sealing material, its flame retardancy and high temperature resistance can be greatly improved. With the emerging development of industries such as new energy vehicles, consumer electronics, Internet of Things, and 5G, the performance requirements for integrated circuits and semiconductors are also continuously developing towards low dimensions and high power according to Moore's law. Therefore, higher requirements are put forward for the high temperature and humidity resistance stability of semiconductor-related materials. How to further improve the high temperature and humidity resistance stability of epoxy resin packaging materials has become an extremely important issue. Summary of the Invention

[0003] The specific embodiments of the present invention provide a phenolic resin, an epoxy resin and a cured product thereof with excellent high temperature and humidity resistance stability. The specific solutions are as follows:

[0004] A phenolic resin having a structure shown in the following formula (1),

[0005] A-(B-A) m1 (1)

[0007] wherein, m1 is an integer from 1 to 10,

[0008] A has a structure shown in the following formula (2),

[0009]

[0010] In formula (2), R 1 is a substituted or unsubstituted phenylene group, or a substituted or unsubstituted biphenylene group, and n1 is an integer from 1 to 10,

[0011] n1 in m1 + 1 A's can be the same or different;

[0012] B has a structure shown in the following formula (3),

[0013]

[0014] In formula (3), R 2 is a hydroxyl group or CX 3 , and X is a halogen atom.

[0015] Optionally, the R 2 is ortho- or para-substituted hydroxy, or ortho- or para-substituted trifluoromethyl.

[0016] The preparation method of the phenolic resin as described above includes the following steps:

[0017] 1) React 400-500 parts by weight of the benzene or biphenyl compound shown in the following formula (4) with 1000 parts by weight of phenol. After the reaction, remove the excessive phenol under reduced pressure.

[0018] Y-CH 2 R 1 CH 2 -Y (4)

[0020] In formula (4), Y is a halogen atom, a hydroxy group or a C 1-4 alkoxy group, and R 1 is a substituted or unsubstituted phenylene group, or a substituted or unsubstituted biphenylene group;

[0021] 2) Add 20-60 parts by weight of the substituted benzaldehyde shown in formula (5) to the product of step 1), and react to obtain the phenolic resin.

[0022]

[0023] In formula (5), R 2 is a hydroxy group or CX 3 , and X is a halogen atom.

[0024] An epoxy resin has a structure shown in the following formula (6).

[0025] C-(D-C) m2 (6)

[0027] Wherein, m2 is an integer from 1 to 10.

[0028] C has a structure shown in the following formula (7).

[0029]

[0030] In formula (7), R 1 is a substituted or unsubstituted phenylene group, or a substituted or unsubstituted biphenylene group, n2 is an integer from 1 to 10.

[0031] n2 among m2 + 1 Cs can be the same or different.

[0032] D has a structure shown in the following formula (8).

[0033]

[0034] In formula (8), R 2 is or CX 3 , where X is a halogen atom.

[0035] Optionally, the R 2 is an ortho- or para-substituted hydroxyl group, or an ortho- or para-substituted trifluoromethyl group.

[0036] The preparation method of the epoxy resin as described above, the epoxy resin is obtained by reacting the phenolic resin with epichlorohydrin.

[0037] An epoxy resin composition, the epoxy resin composition includes the phenolic resin and the epoxy resin as described above.

[0038] An epoxy resin cured product, the epoxy resin cured product is cured from the epoxy resin composition as described above.

[0039] Optionally, the glass transition temperature of the cured product is 135 - 146 °C, and the water absorption rate is 0.4 - 0.7.

[0040] A semiconductor device, the semiconductor includes the epoxy resin cured product as described above.

[0041] The phenolic resin in the specific embodiment of the present invention has the structure shown in formula (1), and it further introduces the structural unit shown in formula (3) into the structural unit shown in formula (2), and this structure can further improve the high-temperature and high-humidity stability of its epoxy resin encapsulation material. Specific Embodiment

[0042] The specific embodiment of the present invention provides a phenolic resin having the structure shown in the following formula (1),

[0043] A-(B-A) m1 (1)

[0045] wherein, m1 is an integer from 1 to 10,

[0046] A has the structure shown in the following formula (2),

[0047]

[0048] In formula (2), R 1 is a substituted or unsubstituted phenylene group, or a substituted or unsubstituted biphenylene group, n1 is an integer from 1 to 10,

[0049] n1 in m1 + 1 A's can be the same or different;

[0050] B has the structure shown in the following formula (3),

[0051]

[0052] In formula (3), R 2 is a hydroxyl group or CX 3 , where X is a halogen atom.

[0053] For the phenolic resin in the specific embodiments of the present invention, by introducing a benzaldehyde structure onto the phenolic resin structure shown in formula (2), the high-temperature moisture and heat stability of its epoxy resin encapsulation material can be further improved, meeting the continuous development requirements of the performance of integrated circuits and semiconductors towards low dimensions and high power in accordance with Moore's law. The benzaldehyde structure is as shown in formula (3), and the benzene ring structure of the benzaldehyde has a hydroxyl substituent or a CX 3 substituent. When the substituent is not present, for example, in the case of only benzaldehyde, it may not be able to effectively react with the phenolic resin shown in formula (2), and ultimately, the further improvement of performance cannot be effectively obtained.

[0054] For the phenolic resin in the specific embodiments of the present invention, in some specific embodiments, R in the benzaldehyde structure shown in formula (3) 2 is a hydroxyl group. In some specific embodiments, R in the benzaldehyde structure shown in formula (3) 2 is CX 3 . Considering more excellent high-temperature and high-humidity resistance performance, R in the benzaldehyde structure shown in formula (3) 2 is CX 3 .

[0055] For the phenolic resin in the specific embodiments of the present invention, in some specific embodiments, the R 2 is an ortho- or para-substituted hydroxyl group. In some specific embodiments, the R 2 is an ortho- or para-substituted trifluoromethyl group.

[0056] For the phenolic resin in the specific embodiments of the present invention, in some specific embodiments, the R 1 is an unsubstituted phenylene group or an unsubstituted biphenylene group, that is, a phenylene group without substituents or a biphenylene group without substituents. In some specific embodiments, the R 1 is a substituted phenylene group or a substituted biphenylene group, that is, the benzene ring of the phenylene group or biphenylene group has substituents, such as methyl, ethyl, hydroxyl, carboxyl, or amino, etc. Considering better high-temperature and moisture resistance, the R 1 is an unsubstituted biphenylene group.

[0057] The phenolic resin of the specific embodiment of the present invention, in some specific embodiments, the phenolic resin has the structure shown in formula (1), where m1 is an integer from 1 to 10, for example, m1 is 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10. In some specific embodiments, the phenolic resin has the structure shown in formula (1), and m1 is multiple integers from 1 to 10, that is, the phenolic resin is a mixture of multiple m1 values being integers from 1 to 10. For example, in some specific embodiments, the phenolic resin simultaneously includes the structures shown in formula (1) with m1 values of 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10.

[0058] For the phenolic resin of the specific embodiment of the present invention, n1 among m1 + 1 A's can be the same or different. In some specific embodiments, in the structural unit A having the structure shown in formula (2) in formula (1), the n1 values among m1 + 1 structural units A are the same. In some specific embodiments, in the structural unit A having the structure shown in formula (2) in formula (1), the n1 values among m1 + 1 structural units A are not the same. For example, the value of n1 in one structural unit A is 1, and the value of n1 in another structural unit A is 2 or 3, etc.

[0059] The specific embodiment of the present invention also provides a preparation method of the above phenolic resin, including the following steps:

[0060] 1) React 400 - 500 parts by weight of the benzene or biphenyl compound shown in the following formula (4) with 1000 parts by weight of phenol, and after the reaction, remove the excessive phenol under reduced pressure.

[0061] Y-CH 2 R 1 CH 2 -Y (4)

[0063] In formula (4), Y is a halogen atom, a hydroxyl group or an alkoxy group of C 1-4 and R 1 is a substituted or unsubstituted phenylene group, or a substituted or unsubstituted biphenylene group;

[0064] 2) Add 20 - 60 parts by weight of the substituted benzaldehyde shown in formula (5) to the product of step 1), and react to obtain the phenolic resin.

[0065]

[0066] In formula (5), R 2 is a hydroxyl group or CX 3 , and X is a halogen atom.

[0067] The preparation method of the phenolic resin according to the specific embodiments of the present invention. In some specific embodiments, the benzene or biphenyl compound represented by the formula (4) reacts with phenol under the catalysis of an acid catalyst. The acid catalyst can be an organic acid or an inorganic acid, such as methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid or sulfuric acid, etc. In some specific embodiments, the reaction temperature is 20 - 120 °C and the reaction time is 20 - 20 h.

[0068] The preparation method of the phenolic resin according to the specific embodiments of the present invention. In some specific embodiments, the benzene or biphenyl compound represented by the formula (4) is 1,4-dichlorobenzene, 1,4-diethoxybenzene, 4,4'-bis(chloromethyl)-1,1'-biphenyl, 4,4'-bis(bromomethyl)-1,1'-biphenyl, 4,4'-bis(methoxymethyl)-1,1'-biphenyl, 4,4'-bis(ethoxymethyl)-1,1'-biphenyl, etc.

[0069] The preparation method of the phenolic resin according to the specific embodiments of the present invention. In some specific embodiments, the reaction in step 1) is carried out without a solvent. In some specific embodiments, the reaction in step 1) is carried out in the presence of a solvent. The solvent can be, for example, methanol, ethanol, isopropanol, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, etc.

[0070] The preparation method of the phenolic resin according to the specific embodiments of the present invention. In some specific embodiments, the reaction in step 2) is carried out in the presence of a solvent. The solvent can be, for example, aromatic hydrocarbons such as toluene, xylene, or methyl ethyl ketone, methyl isobutyl ketone (MIBK), etc.

[0071] The preparation method of the phenolic resin according to the specific embodiments of the present invention. In some specific embodiments, the reaction temperature in step 2) is 100 - 150 °C and the reaction time is 5 - 10 h.

[0072] The preparation method of the phenolic resin according to the specific embodiments of the present invention. In formula (5), R 2 is a hydroxyl group or CX 3 , where X is a halogen atom. Compared with the case without the substituent, for example, in the case of only benzaldehyde, it can effectively react with the phenolic resin represented by the formula (2), and effectively obtain a further improvement in performance.

[0073] The preparation method of the phenolic resin according to the specific embodiments of the present invention. In some specific embodiments, after the reaction in step 2) is completed, it further includes the steps of washing the product to neutral and removing the reaction solvent.

[0074] The specific embodiments of the present invention further provide an epoxy resin having the structure shown in the following formula (6),

[0075] C-(D-C) m2 (6)

[0077] Among them, m2 is an integer from 1 to 10,

[0078] C has the structure shown in the following formula (7),

[0079]

[0080] In formula (7), R 1 is a substituted or unsubstituted phenylene group, or a substituted or unsubstituted biphenylene group, n2 is an integer from 1 to 10, and n2 in m2 + 1 Cs can be the same or different

[0081] D has the structure shown in the following formula (8),

[0082]

[0083] In formula (8), R 2 is or CX 3 , and X is a halogen atom.

[0084] For the epoxy resin in the specific embodiments of the present invention, in some specific embodiments, the epoxy resin has the structure shown in formula (6), where m2 takes a value of one of the integers from 1 to 10. For example, m2 takes a value of 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10. In some specific embodiments, the epoxy resin has the structure shown in formula (6), and m2 takes multiple values of the integers from 1 to 10, that is, the epoxy resin is a mixture of multiple values of m2 being the integers from 1 to 10. For example, in some specific embodiments, the epoxy resin simultaneously includes the structures shown in formula (6) with m2 taking values of 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10.

[0085] For the epoxy resin in the specific embodiments of the present invention, n2 in m2 + 1 Cs can be the same or different. In some specific embodiments, in the structural unit C having the structure shown in formula (7) in formula (6), n2 values in m2 + 1 structural units C are the same. In some specific embodiments, in the structural unit C having the structure shown in formula (7) in formula (6), n2 values in m2 + 1 structural units C are different. For example, the value of n2 in one structural unit C is 1, and the value of n2 in another structural unit C is 2 or 3, etc.

[0086] For the epoxy resin in the specific embodiments of the present invention, in some specific embodiments, R 2 in the benzaldehyde structure shown in formula (8) is a hydroxyl group. In some specific embodiments, R 2 in the benzaldehyde structure shown in formula (8) is CX3 , considering the more excellent high temperature and high humidity resistance performance, in the benzaldehyde structure shown in formula (8), R 2 is CX 3 .

[0087] For the epoxy resin of the specific embodiments of the present invention, in some specific embodiments, the R 2 is a hydroxyl group substituted at the ortho or para position. In some specific embodiments, the R 2 is a trifluoromethyl group substituted at the ortho or para position.

[0088] The specific embodiments of the present invention also provide a preparation method of the epoxy resin. In some specific embodiments, the epoxy resin is prepared by reacting the aforementioned phenolic resin with epichlorohydrin (C3H5XO: X is a halogen atom).

[0089] For the preparation method of the epoxy resin of the specific embodiments of the present invention, in some specific embodiments, the epoxy resin is prepared by glycidyl etherification in epihalohydrin in the presence of an alkali metal hydroxide. In some specific embodiments, the reaction temperature is 50 - 150 °C and the reaction time is 2 - 20 h. In some specific embodiments, the reaction is carried out in a solvent, such as a solvent like toluene or xylene.

[0090] For the preparation method of the epoxy resin of the specific embodiments of the present invention, in some specific embodiments, in the preparation method of the epoxy resin, the phenolic resin is 200 - 400 parts by weight and the epihalohydrin is 1000 - 1200 parts by weight.

[0091] For the preparation method of the phenolic resin of the specific embodiments of the present invention, in some specific embodiments, the preparation method of the epoxy resin further includes the steps of washing the product to neutrality, removing the excessive epihalohydrin and the reaction solvent.

[0092] The specific embodiments of the present invention also provide an epoxy resin composition, which includes the aforementioned phenolic resin and epoxy resin.

[0093] For the epoxy resin composition of the specific embodiments of the present invention, in some specific embodiments, the epoxy resin composition may further include other phenolic resins, such as phenol phenolic resin, cresol phenolic resin or triphenylmethane resin, etc. In some specific embodiments, the epoxy resin composition may further include other epoxy resins, such as o-cresol novolac epoxy resin, triphenylmethane epoxy resin, naphthol epoxy resin, naphthol aralkyl resin, etc.

[0094] The epoxy resin composition of the specific embodiments of the present invention, in some specific embodiments, the epoxy resin composition further includes a curing accelerator for curing the epoxy resin with a phenolic resin. As the curing accelerator, for example, organic phosphine compounds and their borate salts, tertiary amines, quaternary ammonium salts, imidazoles and their tetraphenyl borate salts, etc. Specifically, for example, triphenylphosphine.

[0095] The epoxy resin composition of the specific embodiments of the present invention, in some specific embodiments, further includes other components, such as inorganic fillers, other resin compositions, additives, etc.

[0096] The specific embodiments of the present invention further provide an epoxy resin cured product, which is cured from the epoxy resin composition as described above. In some specific embodiments, the epoxy resin cured product has particularly excellent high-temperature and high-humidity stability. The glass transition temperature of the cured product is 135-146 °C. Specifically, for example, it can be 135 °C, 136 °C, 137 °C, 138 °C, 139, 140 °C, 141 °C, 142 °C, 143 °C, 144, 145 °C or 146 °C, etc. The water absorption rate is 0.4-0.7. Specifically, for example, 0.4, 0.5, 0.6 or 0.7, etc.

[0097] The specific embodiments of the present invention further provide a semiconductor device, which includes the epoxy resin cured product as described above. The epoxy resin is used for sealing and encapsulating the semiconductor device. The semiconductor device can be, for example, an integrated circuit, a large-scale integrated circuit, a transistor, a thyristor, a diode, a solid-state imaging element, etc.

[0098] The following examples are to further illustrate the effects of the present invention, but are not limited thereto, and are only used for illustration and strengthening of understanding.

[0099] Examples

[0100] Test description:

[0101] Glass transition (Tg): Using Hitachi analytical instrument TMA 7100, heat up to 200 °C at a heating rate of 2 °C / min, then cool down to 30 °C at a cooling rate of 2 °C / min, and then heat up to 200 °C again at a heating rate of 2 °C / min. Integrate and read the glass transition temperature under the second heating.

[0102] Water absorption rate: Prepare the sample into a disk with a diameter of 5 cm * 4 mm thickness, place it in boiling hot water at 100 degrees for 24 hours, and then weigh the percentage increase in weight (wt%).

[0103] Example 1

[0104] In a four-necked flask equipped with a stirrer, a thermometer and a condenser, 1000 parts of phenol and 1 part of concentrated sulfuric acid were placed; under stirring, 484 parts of 4,4'-biphenyldimethyl dimethyl ether were added together at 100 °C. The resulting reactants were reacted at 50 °C for 10 hours. After the reaction was completed, unreacted phenol was completely removed by vacuum distillation at a temperature not exceeding 230 °C. The temperature was lowered to below 120 °C, and then 30 parts of o-hydroxybenzaldehyde and 500 parts of MIBK solvent were added, dissolved thoroughly, and reacted at 130 °C. After the reaction was completed, another 500 parts of MIBK were added, and the mixture was washed with water several times until the water was neutral, and then MIBK was removed under heating and vacuum conditions. Finally, 702 parts of a phenolic resin (P1) with a softening point of 80 °C and a hydroxyl equivalent of 176 q / eq was obtained.

[0105] In a four-necked flask equipped with a stirrer, a thermometer and a condenser, 353 parts of the phenolic resin (P1) prepared above, 1120 parts of epichlorohydrin and 300 parts of toluene were placed to prepare a solution. The solution was heated to 50 °C, and then 82 parts of flaky sodium hydroxide (purity 99 wt%) were added within 90 minutes. Then the temperature was raised to 60 °C and the reaction was carried out for 8 hours. Then the reaction mixture was washed repeatedly with water until the washing water became neutral. Then the excess epichlorohydrin was distilled off from the organic layer under heating and reduced pressure. Then 900 parts of MIBK were added to dissolve it, and the mixed solution was heated to 70 °C. 20 parts of a 20 wt% aqueous sodium hydroxide solution were added and reacted for 2 hours. Then the obtained reaction mixture was washed repeatedly with water until the washing water became neutral. Then under reduced pressure conditions at 180 - 200 °C, MIBK was distilled off to obtain 466 parts of an epoxy resin (E1) with an epoxy equivalent of 233 g / eq and a softening point of 70 °C.

[0106] 100 parts of phenolic resin (P1), 75 parts of epoxy resin (E1) and 1 part of triphenylphosphine were mixed evenly using a stirrer. After die-casting the composition for 200 seconds, it was cured at 160 °C for 2 hours and then cured at 180 °C for 6 hours to obtain a cured product. The glass transition temperature of the cured product was measured to be 138 °C, and its water absorption rate was measured to be 0.67.

[0107] Example 2

[0108] In a four-necked flask equipped with a stirrer, a thermometer and a condenser, 1000 parts of phenol and 1 part of concentrated sulfuric acid were placed; under stirring, it was added together with 484 parts of 4,4'-biphenyldimethyldimethylether at 100 °C, and the reactants thus obtained were reacted at 50 °C for 10 hours. After the reaction was completed, unreacted phenol was completely removed by vacuum distillation at no more than 230 °C, cooled to below 120 °C, then 50 parts of 3-(trifluoromethyl)benzaldehyde and 500 parts of MIBK solvent were added, dissolved thoroughly, and reacted at 130 °C. After the reaction was completed, another 500 parts of MIBK were added, washed with water several times until the water was neutral, and then MIBK was removed under heating and vacuum conditions. Finally, 722 parts of a phenolic resin (P2) with a softening point of 84 °C and a hydroxyl equivalent of 212 q / eq were obtained.

[0109] In a four-necked flask equipped with a stirrer, a thermometer and a condenser, 424 parts of the phenolic resin (P2) prepared above, 1120 parts of epichlorohydrin and 300 parts of toluene were placed to prepare a solution. The solution was heated to 50 °C, then 82 parts of flaky sodium hydroxide (purity 99 wt%) were added over a period of 90 minutes, then the temperature was raised to 60 °C and reacted for 8 hours. Then the reaction mixture was washed repeatedly with water until the washing water became neutral. Then the excess epichlorohydrin was distilled off from the organic layer under heating and reduced pressure. Then 900 parts of MIBK were added to dissolve it, the mixed solution was heated to 70 °C, 20 parts of 20 wt% sodium hydroxide aqueous solution were added and reacted for 2 hours. Then the obtained reaction mixture was washed repeatedly with water until the washing water became neutral. Then under reduced pressure conditions of 180 - 200 °C, MIBK was distilled off to obtain 536 parts of an epoxy resin (E2) with an epoxy equivalent of 267 g / eq and a softening point of 75 °C.

[0110] 100 parts of phenolic resin (P2), 75 parts of epoxy resin (E2) and 1 part of triphenylphosphine were mixed evenly using a stirrer, and the composition was die-cast for 200 seconds and then cured at 160 °C for 2 hours and at 180 °C for 6 hours to obtain a cured product. The glass transition temperature of the cured product was measured to be 145 °C, and its water absorption rate was measured to be 0.43.

[0111] Comparative Example 1

[0112] In a four-necked flask equipped with a stirrer, a thermometer and a condenser, 1000 parts of phenol and 1 part of concentrated sulfuric acid were placed; under stirring, it was added together with 484 parts of 4,4'-biphenyldimethyldimethylether at 100 °C, and the reactants thus obtained were reacted at 50 °C for 10 hours. After the reaction was completed, unreacted phenol was completely removed by vacuum distillation at no more than 230 °C, 500 parts of MIBK were added, washed with water several times until the water was neutral, and then MIBK was removed under heating and vacuum conditions. Finally, 663 parts of a phenolic resin (P3) with a softening point of 60 °C and a hydroxyl equivalent of 204 q / eq were obtained.

[0113] In a four-necked flask equipped with a stirrer, a thermometer and a condenser, 408 parts of the phenolic resin (P3) prepared above, 1300 parts of epichlorohydrin and 350 parts of toluene were placed to prepare a solution. The solution was heated to 50 °C, and then 82 parts of flaky sodium hydroxide (purity 99 wt%) were added over a period of 90 minutes. Then the temperature was raised to 60 °C and the reaction was carried out for 8 hours. Then the reaction mixture was washed repeatedly with water until the wash water became neutral. Then the excess epichlorohydrin was distilled off from the organic layer under heating and reduced pressure. Then 900 parts of MIBK were added and dissolved, and the mixed solution was heated to 70 °C. 20 parts of a 20 wt% aqueous sodium hydroxide solution were added and the reaction was carried out for 2 hours. Then the obtained reaction mixture was washed repeatedly with water until the wash water became neutral. Then under reduced pressure at 180 - 200 °C, MIBK was distilled off to obtain 518 parts of an epoxy resin (E3) with an epoxy equivalent of 260 g / eq and a softening point of 50 °C.

[0114] 100 parts of phenolic resin (P3), 75 parts of epoxy resin (E3) and 1 part of triphenylphosphine were mixed uniformly using a stirrer. After die-casting the composition for 200 seconds, it was cured at 160 °C for 2 hours and then cured at 180 °C for 6 hours to obtain a cured product. The glass transition temperature of the cured product was measured to be 130 °C, and its water absorption rate was measured to be 0.65.

[0115] From the results of Example 1 and Comparative Example 1 above, it can be seen that after introducing the o-hydroxybenzaldehyde structure, the cured product of the phenolic resin with a biphenyl structure and its epoxy resin has a higher glass transition temperature, but its water absorption rate remains basically unchanged. In particular, as can be seen from the results of Example 2 above, after introducing the 3-(trifluoromethyl)benzaldehyde structure, the cured product of the phenolic resin with a biphenyl structure and its epoxy resin has an even higher glass transition temperature and a lower water absorption rate.

[0116] Although the present invention is disclosed as above, the present invention is not limited thereto. Any person skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the protection scope of the present invention should be determined by the scope defined in the claims.

Claims

1. A phenolic resin, characterized in that it has the structure shown in formula (1) below, A-(B-A) m1 (1) wherein, m1 is an integer from 1 to 10, A has the structure shown in formula (2) below, In formula (2), R 1 is a substituted or unsubstituted phenylene group, or a substituted or unsubstituted biphenylene group, and n1 is an integer from 1 to 10. n1 in m1 + 1 A's can be the same or different; B has the structure shown in formula (3) below, In formula (3), R 2 is hydroxyl or CX 3 , where X is a halogen atom; The phenolic resin is a mixture of multiple values of m1 being integers from 1 to 10.

2. The phenolic resin according to claim 1, characterized in that The R 2 is ortho- or para-substituted hydroxy, or ortho- or para-substituted trifluoromethyl.

3. An epoxy resin, characterized in that it has the structure shown in formula (6) below, C-(D-C) m2 (6) wherein, m2 is an integer from 1 to 10, C has the structure shown in formula (7) below, In formula (7), R 1 is a substituted or unsubstituted phenylene group, or a substituted or unsubstituted biphenylene group, and n2 is an integer from 1 to 10. n2 in m2 + 1 C's can be the same or different; D has the structure shown in formula (8) below, In formula (8), R 2 is or CX 3 , where X is a halogen atom; The epoxy resin is a mixture of multiple values of m2 being integers from 1 to 10.

4. The epoxy resin according to claim 3, characterized in that The R 2 is an ortho- or para-substituted hydroxyl group, or an ortho- or para-substituted trifluoromethyl group.

5. A method for preparing the epoxy resin according to claim 3, characterized in that The epoxy resin is obtained by reacting the phenolic resin according to claim 1 with epichlorohydrin.

6. An epoxy resin composition, characterized in that The epoxy resin composition includes the phenolic resin of claim 1 or 2 and the epoxy resin of claim 3 or 4.

7. An epoxy resin cured product, characterized in that The epoxy resin cured product is formed by curing the epoxy resin composition according to claim 6.

8. The epoxy resin cured product according to claim 7, characterized in that The glass transition temperature of the cured product is between 135 and 146 °C, and the water absorption rate is between 0.4 and 0.

7.

9. A semiconductor device, characterized in that The semiconductor includes the epoxy resin cured product according to claim 7.

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