Polymer and application thereof

Abstract

The embodiment of the invention provides a polymer which comprises a structural unit as shown in a formula (I): # imgabs0 #, in the formula (I), R1 is selected from no bond, single bond, dimethyl methylene, trifluoromethyl methylene, methylene, sulfuryl or oxygen; r2 is selected from H or substituted or non-substituted acyl; r3 is selected from H or-O-Rf, wherein Rf is selected from H, substituted or non-substituted alkyl, substituted or non-substituted alkenyl, substituted or non-substituted aryl, or substituted or non-substituted acyl; r4 is selected from H, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or-(CH2) 3-Si (CH3) 2-Ra; n is a positive integer, and m is equal to 0 or 1. The polymer can be used in an epoxy resin composition, so that a cured product of the epoxy resin composition shows low dielectric constant and dielectric loss at high frequency, and has good heat resistance.

Description

Technical Field

[0001] The embodiments of the present application relate to the technical field of low dielectric material preparation, and in particular, to a polymer and its application. Background Art

[0002] In high-frequency communication technology, in order to ensure the quality of communication signals during high-speed transmission, dielectric materials with low dielectric constant D are usually used. k and dielectric loss D f High-frequency low-dielectric materials are used for interlayer insulation to prepare high-frequency communication electronic components. Epoxy resin compositions composed of epoxy resin and its curing agent are a widely used low-dielectric material and have been used as base resins for high-frequency printed circuit boards or interlayer insulation for integrated circuits. However, with the rapid development of 5G communication technology, the miniaturization of line width and line spacing has put forward higher requirements on the heat resistance and low dielectric properties of epoxy resin materials used for interlayer insulation. Summary of the invention

[0003] In view of this, an embodiment of the present application provides a polymer, which is used in an epoxy resin composition, so that the cured epoxy resin composition can exhibit a low dielectric constant and dielectric loss at high frequencies and have good heat resistance. The obtained epoxy resin composition is used in the preparation of an electronic substrate, which can improve the signal transmission quality of the electronic substrate and improve the reliability of the electronic substrate.

[0004] Specifically, the first aspect of the embodiment of the present application provides a polymer, wherein the polymer includes a structural unit represented by formula (I):

[0005]

[0006] In formula (I), R1 is selected from a bondless group, a single bond, dimethylmethylene (-C(CH3)2-), trifluoromethylmethylene (-C(CF3)2-), methylene (-CH2-), sulfacyl (-SO2-) or oxygen; R2 is selected from H or a substituted or unsubstituted acyl group; R3 is selected from H or -OR f , where R f R4 is selected from H, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted aryl, or substituted or unsubstituted acyl; R4 is selected from H, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, or -(CH2)3-Si(CH3)2-Ra, R4 can be connected to the carbon atom on the benzene ring to form a ring, wherein R a is selected from benzocyclobutenyl, aryltrifluorovinyl ether, styryl, phenyl, or substituted or unsubstituted alkyl;

[0007] n is a positive integer, m=0 or 1.

[0008] The polymer provided in the embodiments of the present application has a special polyarylether structure. Introducing the polymer into an epoxy resin composition can optimize the dielectric properties, heat resistance and hydrophobic properties of the epoxy resin composition. The obtained epoxy resin composition is used for the preparation of electronic substrates, which can improve the transmission efficiency of signals, reduce the loss in the signal transmission process, and improve the reliability of the electronic substrate.

[0009] In the embodiment of the present application, in R2 and R3, the substituted or unsubstituted acyl group is represented by: -O=CR; wherein R is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group. R2 being a substituted or unsubstituted acyl group is beneficial to the improvement of the crosslinking density of the polymer, thereby improving the heat resistance of the resin composition.

[0010] In the embodiment of the present application, the substituent group in the substituted alkyl group includes a halogen atom, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group; the substituent group in the substituted alkenyl group includes a halogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group; the substituent group in the substituted aryl group includes a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group. Alkyl, alkenyl and aryl groups substituted with different groups can provide a richer polymer structure to better achieve fine-tuning of the performance of the epoxy resin composition and better meet different application requirements.

[0011] In the embodiment of the present application, the substituted or unsubstituted aryl group includes a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted heteroaryl group. When R2, R3, and R4 contain a substituted or unsubstituted aryl group, the side chain rigidity is relatively large, which can improve the thermal stability of the polymer molecular structure.

[0012] In the embodiment of the present application, the number average molecular weight Mn of the polymer is 500-50000. In some embodiments, the number average molecular weight Mn of the polymer is 500-20000. In some embodiments, the number average molecular weight Mn of the polymer is 500-10000. In some embodiments, the number average molecular weight Mn of the polymer is 500-5000. The polymer has a suitable molecular weight, which is conducive to achieving good dispersion thereof in the resin composition, and is also conducive to controlling the viscosity of the resin composition as a whole to remain at a low level.

[0013] The second aspect of the embodiment of the present application provides a resin composition, including an epoxy resin and a curing agent, wherein the curing agent includes the polymer described in the first aspect of the embodiment of the present application. The polymer described in the first aspect of the embodiment of the present application is used as a curing agent to prepare the resin composition, which can effectively improve the dielectric properties and heat resistance of the resin composition. The obtained resin composition is used in the preparation of an electronic substrate, which can improve the signal transmission quality of the electronic substrate and improve the reliability of the electronic substrate.

[0014] In the embodiment of the present application, the mass percentage of the epoxy resin in the resin composition is 1%-50%. The suitable epoxy resin content can enable the resin composition to meet the basic physical properties of electronic substrate applications, better realize the strong combination of the resin composition with other components when used as an interlayer dielectric layer, and improve the reliability of the electronic substrate.

[0015] In the embodiment of the present application, in the resin composition, the mass percentage of the curing agent is 1%-50%. In some embodiments, in the resin composition, the mass percentage of the curing agent is 5%-45%. In some embodiments, in the resin composition, the mass percentage of the curing agent is 10%-40%. The appropriate curing agent content can enable the resin composition to be cured smoothly and obtain the basic physical properties that meet the application of electronic substrates.

[0016] In the embodiment of the present application, in the resin composition, the mass percentage of the polymer is 1%-30%. In some embodiments, in the resin composition, the mass percentage of the polymer is 2%-25%. In some embodiments, in the resin composition, the mass percentage of the polymer is 3%-20%.

[0017] In the embodiment of the present application, the epoxy resin includes liquid epoxy resin and solid epoxy resin. Using liquid epoxy resin and solid epoxy resin at the same time is conducive to making the resin composition take into account the advantages of liquid epoxy resin and solid epoxy resin, thereby improving the comprehensive performance of the resin composition.

[0018] In the embodiment of the present application, the weight ratio of the liquid epoxy resin to the solid epoxy resin is 0.1 to 10. Controlling the liquid epoxy resin and the solid epoxy resin in a suitable ratio is conducive to making the resin composition have good fluidity and processability, and better meet the application requirements in the preparation of electronic substrates.

[0019] In the embodiment of the present application, the resin composition further comprises a film-forming resin, and the film-forming resin comprises a polyphenylene oxide resin. The film-forming resin is a resin having film-forming properties. Adding the film-forming resin to the resin composition is beneficial to promoting the curing of the resin composition to form a film and improving the quality of the film layer.

[0020] In the embodiment of the present application, the polyphenoxy resin may be selected from bisphenol A type polyphenoxy resin and bisphenol A bisphenol F mixed type polyphenoxy resin.

[0021] In the embodiment of the present application, the weight average molecular weight of the polyphenylene oxide resin is 50000 g / mol-60000 g / mol. A suitable weight average molecular weight is conducive to making the polyphenylene oxide resin obtain better film-forming properties.

[0022] In some embodiments of the present application, the curing agent in the epoxy resin composition only includes the polymer provided in the embodiments of the present application. In other embodiments of the present application, the curing agent also includes an active ester. The active ester is used in combination with the polymer provided in the embodiments of the present application as a curing agent.

[0023] In the embodiment of the present application, the active ester includes one or more of bisphenol A type active ester, dicyclopentadiene type active ester, and bisphenol AF cyanate ester.

[0024] In the embodiment of the present application, the resin composition further comprises an inorganic filler. The addition of the inorganic filler can effectively improve the mechanical properties, thermal deformation temperature and wear resistance of the cured product of the resin composition, reduce the thermal expansion coefficient of the resin composition, reduce thermal stress, and can also reduce water absorption, molding shrinkage, and resin overflow, thereby improving the reliability of the electronic substrate prepared using the resin composition.

[0025] In the embodiment of the present application, the average particle size of the inorganic filler is 0.1 μm-1 μm, and the cut-off particle size is 1 μm-5 μm. The inorganic filler has a smaller size, which is conducive to better realization of fine circuit preparation.

[0026] In the embodiment of the present application, in the resin composition, the mass percentage of the inorganic filler is 20%-90%. In some embodiments, in the resin composition, the mass percentage of the inorganic filler is 25%-85%. In some embodiments, in the resin composition, the mass percentage of the inorganic filler is 30%-80%. The addition of an appropriate amount of inorganic filler is beneficial to reducing the thermal expansion coefficient and viscosity of the resin composition, so that the cured product of the resin composition obtains suitable mechanical properties, etc., and improves the reliability of the electronic substrate.

[0027] In the embodiment of the present application, the resin composition further includes additives, which include one or more of a catalyst (i.e., a curing accelerator), a leveling agent, a stabilizer, a diluent, a toughening agent, a colorant, a coupling agent, a stress modifier, a dispersant, an ion trap, a flame retardant, and a release agent. According to the performance requirements of the resin composition, the above-mentioned additives can be added in appropriate amounts to improve the relevant properties of the resin composition.

[0028] The third aspect of the embodiment of the present application provides a resin composition sheet, comprising a resin composition layer obtained by curing the resin composition described in the second aspect of the embodiment of the present application. The resin composition layer has a lower dielectric constant and dielectric loss, and has good heat resistance. The resin composition layer is provided in an electronic substrate as an interlayer dielectric, which can improve the reliability of the electronic substrate.

[0029] In the embodiment of the present application, the resin composition sheet further includes a support layer for supporting the resin composition layer.

[0030] The fourth aspect of the embodiment of the present application provides the use of the resin composition described in the second aspect or the resin composition sheet described in the third aspect in electronic packaging or semiconductor packaging. The resin composition can be used as an interlayer insulating material in electronic packaging or semiconductor packaging to improve the signal transmission performance of the device and improve the packaging reliability.

[0031] A fifth aspect of the embodiments of the present application provides an electronic substrate, which includes a cured product of the resin composition described in the second aspect of the embodiments of the present application.

[0032] In the embodiment of the present application, the electronic substrate includes a base plate, a conductive metal disposed on the base plate, and an interlayer dielectric disposed between the conductive metals, wherein the interlayer dielectric includes the solidified material. The interlayer dielectric is an electrical insulating layer between different metal layers, and the interlayer dielectric can act as an isolation film between two layers of conductive metal or adjacent metal lines. The solidified material of the resin composition has a lower dielectric constant and dielectric loss, and has good heat resistance. It is disposed in the electronic substrate as an interlayer dielectric, which can improve the signal transmission quality of the electronic substrate and improve the reliability of the electronic substrate.

[0033] The sixth aspect of the embodiment of the present application provides a semiconductor device, wherein the semiconductor device comprises a cured product of the resin composition described in the second aspect of the embodiment of the present application. The cured product of the resin composition of the embodiment of the present application can improve the performance of the semiconductor device.

[0034] The present application also provides an electronic device, which includes the electronic substrate described in the fifth aspect of the present application, or includes the semiconductor device described in the sixth aspect of the present application. The electronic substrate and semiconductor device of the present application can improve the high-frequency signal transmission quality of the electronic substrate and improve the reliability of the electronic substrate. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 A schematic diagram of the structure of a resin composition sheet 10 provided in an embodiment of the present application;

[0036] Figure 2 A schematic diagram of the structure of an electronic substrate 100 provided in one embodiment of the present application;

[0037] Figure 3 This is a schematic structural diagram of an electronic substrate 100 provided in another embodiment of the present application. DETAILED DESCRIPTION

[0038] The embodiments of the present application will be described below in conjunction with the drawings in the embodiments of the present application.

[0039] In high-frequency communication technology, in order to ensure the quality of communication signals during high-speed transmission, dielectric materials with low dielectric constant D are usually used. k and dielectric loss D f High-frequency low-dielectric materials are used for interlayer insulation to prepare high-frequency communication electronic components. Epoxy resin compositions composed of epoxy resins and their curing agents are a type of widely used low-dielectric materials, which have been used as base resins for high-frequency printed circuit boards or dielectric layers for integrated circuits. However, with the rapid development of 5G communication technology, the miniaturization of line width and line spacing has put forward higher requirements on the heat resistance and low dielectric properties of epoxy resin materials used for interlayer insulation. In view of this, an embodiment of the present application provides a polymer, which is used in an epoxy resin composition, and can make the cured product of the epoxy resin composition exhibit low dielectric constant and dielectric loss at high frequencies, and has good heat resistance. The obtained epoxy resin composition is used for the preparation of electronic substrates, which can reduce the delay of signal transmission, improve the signal transmission quality of electronic substrates, and improve the reliability of electronic substrates.

[0040] The present application provides a polymer, which includes a structural unit shown in formula (I):

[0041]

[0042] In formula (I), R1 is selected from a bondless group, a single bond, dimethylmethylene (-C(CH3)2-), trifluoromethylmethylene (-C(CF3)2-), methylene (-CH2-), sulfacyl (-SO2-) or oxygen (-O-); R2 is selected from H or a substituted or unsubstituted acyl group; R3 is selected from H or -OR f , where R f R4 is selected from H, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted aryl, or substituted or unsubstituted acyl; R4 is selected from H, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, or -(CH2)3-Si(CH3)2-Ra, R4 can be connected to the carbon atom on the benzene ring to form a ring, wherein R a is selected from benzocyclobutenyl, aryltrifluorovinyl ether, styryl, phenyl, or substituted or unsubstituted alkyl;

[0043] n is a positive integer, m=0 or 1.

[0044] The polymer provided in the embodiments of the present application has a special polyarylether structure. Introducing the polymer into an epoxy resin composition can optimize the dielectric properties, heat resistance and hydrophobic properties of the epoxy resin composition. The obtained epoxy resin composition is used for the preparation of electronic substrates, which can improve the transmission efficiency of signals, reduce the loss in the signal transmission process, and improve the reliability of the electronic substrate.

[0045] For the convenience of description, the unit with a repeating number of n in formula (I) is defined as an A unit, and the unit with a repeating number of m is defined as a B unit.

[0046] In the embodiment of the present application, R1 can be bondless, single bond, dimethylmethylene (-C(CH3)2-), trifluoromethylmethylene (-C(CF3)2-), methylene (-CH2-), sulfacyl (-SO2-) or oxygen (-O-). R1 ​​can be connected to each vacant carbon on the benzene ring where it is located. For example, R1 can be connected to the para position of the oxygen atom on the benzene ring where it is located, or it can be connected to the meta position of the oxygen atom. Among them, R1 is bondless, that is, R1 means that there is no chemical bond. At this time, the two benzene rings where R1 is located are connected together. In some embodiments, the structure of formula (I) can be:

[0047]

[0048] R1 being a single bond means that the two benzene rings where R1 is located are connected by a single bond. In this case, the structure of formula (I) can be:

[0049]

[0050] In the embodiment of the present application, the substituted or unsubstituted alkyl group may be, but is not limited to, a substituted or unsubstituted C1 to C10 alkyl group, i.e., a substituted or unsubstituted C1, C2, C3, C4, C5, C6, C7, C8, C9, C10 alkyl group, i.e., a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted butyl group, a substituted or unsubstituted pentyl group, a substituted or unsubstituted hexyl group, etc. The substituted or unsubstituted alkyl group may be a straight chain, a branched chain, or a cyclic structure. In the embodiment of the present application, the substituent group in the substituted alkyl group may be a halogen atom, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group. The halogen atom may be, for example, fluorine, chlorine, bromine, or iodine.

[0051] In the embodiments of the present application, the substituted or unsubstituted alkenyl group may be, but is not limited to, a substituted or unsubstituted C1 to C10 alkene group, i.e., a substituted or unsubstituted C1, C2, C3, C4, C5, C6, C7, C8, C9, C10 alkenyl group, i.e., a substituted or unsubstituted vinyl group, a substituted or unsubstituted propenyl group, a substituted or unsubstituted butenyl group, a substituted or unsubstituted pentenyl group, a substituted or unsubstituted hexenyl group, etc. The substituted or unsubstituted alkenyl group may be a straight chain, a branched chain, or a cyclic structure. In the embodiments of the present application, the substituent group in the substituted alkenyl group may include a halogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.

[0052] In the embodiments of the present application, the substituted or unsubstituted aryl group may include, but is not limited to, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, or substituted or unsubstituted heteroaryl. In the embodiments of the present application, the substituent group in the substituted aryl group may include halogen atoms, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl. The substituted or unsubstituted aryl group has high rigidity, which is conducive to improving the stability of the polymer molecular structure.

[0053] In the embodiment of the present application, the substituted or unsubstituted acyl group can be represented by: -O=CR, wherein R is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group. The substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, or substituted or unsubstituted aryl group in R can be as described above. When R2 is a substituted or unsubstituted alkyl group, the flexibility and solubility of the polymer can be improved as required. When R2 is a substituted or unsubstituted alkenyl group, post-crosslinking can be performed to increase heat resistance, and crosslinking of the double bond system can improve the heat resistance and dielectric properties of olefin resins.

[0054] It should be noted that in the embodiments of the present application, unless otherwise specified, substituted or unsubstituted alkyl groups, substituted or unsubstituted alkenyl groups, substituted or unsubstituted aryl groups, or substituted or unsubstituted acyl groups, and halogen atoms may be as described above and will not be described in detail in the subsequent text.

[0055] In the embodiment of the present application, R2 can be selected from H or substituted or unsubstituted acyl. When R2 is H, the hydroxyl group can directly participate in the subsequent crosslinking and modification. When R2 is a substituted or unsubstituted acyl group, it can be crosslinked with epoxy resin to improve the dielectric properties and heat resistance of epoxy resin. In some embodiments of the present application, when R2 is a substituted acyl group, R is a group containing a double bond. By introducing crosslinkable groups such as ester groups and double bonds into the polymer through R2, it is beneficial to improve the crosslinking density of the polymer, thereby improving the heat resistance of the resin composition. In some embodiments, R2 is a substituted or unsubstituted aryl acyl group, such as a substituted or unsubstituted benzoyl group, a substituted or unsubstituted phenylacetyl group. The epoxy resin is crosslinked with the ester group, which is beneficial to reducing the overall polarizability of the epoxy resin composition after curing and improving the stability of the polymer molecular structure. In some embodiments, the substituent groups in the substituted alkyl, substituted alkenyl, and substituted aryl in R are fluorine-containing groups, and the introduction of fluorine-containing groups is beneficial to improving the dielectric properties of the resin composition. In some embodiments, R is phenyl, naphthyl, phenylvinyl, trifluoromethylphenyl, or tert-butylphenyl.

[0056] In the embodiment of the present application, R3 can be selected from H or -OR f , where R fis selected from H, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted aryl, or substituted or unsubstituted acyl. R3 may be connected to each vacant carbon on the benzene ring where it is located, for example, it may be connected to the ortho, meta or para position of the bridge oxygen bond (-O-). R f When it is H, the hydroxyl group can directly participate in the subsequent crosslinking and modification, thus better realizing the regulation of polymer properties. f When it is a substituted or unsubstituted alkyl group, the flexibility and solubility of the polymer can be improved as required, and the polymer can also be further modified. f is a substituted or unsubstituted C4 to C10 alkyl group, or a substituted or unsubstituted C4 to C10 alkenyl group. Introducing a slightly longer flexible segment into the polymer through R3 is beneficial to improving the solubility of the polymer, improving the toughness of the resin composition, and improving the heat resistance of the resin composition. f When it is a substituted or unsubstituted alkenyl group, it can be post-crosslinked to increase heat resistance. Double bond system crosslinking can improve the heat resistance and dielectric properties of olefin resins. In some embodiments of the present application, R f is a substituted or unsubstituted acyl group, R f The substituted or unsubstituted acyl group can cross-link with the epoxy resin to improve the dielectric properties of the epoxy resin, and is also conducive to increasing the cross-linking density of the polymer, thereby improving the heat resistance of the resin composition. f The acyl group in is a substituted or unsubstituted aryl acyl group, such as a substituted or unsubstituted benzoyl group, a substituted or unsubstituted phenylacetyl group, and the substituted or unsubstituted aryl acyl group is beneficial to improving the stability of the polymer molecular structure. f It is H, methyl, vinyl, allyl, propargyl, phenyl, styryl, benzocyclobutenyl, etc.

[0057] In the embodiment of the present application, R4 can be selected from H, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, or -(CH2)3-Si(CH3)2-Ra, and R4 can be connected to the carbon atom on the benzene ring to form a ring, wherein R a Selected from benzocyclobutenyl, aryl trifluorovinyl ether, styryl, phenyl, or substituted or unsubstituted alkyl. R4 can be connected to each vacant carbon on the phenyl ring where it is located, for example, it can be connected to the ortho position, meta position or para position of the oxygen atom on the phenyl ring where it is located. It can be understood that R4 and R1 are connected to different carbon positions. In the embodiment of the present application, the two R4 in the A unit can be the same or different groups.

[0058] In the embodiment of the present application, R1 in unit A and the two ring structures connected by R1 and R1 in unit B and the two ring structures connected by R1 can be completely the same structure or different structures. In some embodiments, the two R1 in formula (I) are the same group. In some embodiments, the four R4 in formula (I) are the same group.

[0059] In the embodiment of the present application, the B unit may be connected to each vacant carbon on the benzene ring where R3 is located through an oxygen atom, for example, it may be connected to the para or meta position of the bridging oxygen bond in the A unit.

[0060] The embodiments of the present application can provide a richer polymer structure by introducing alkyl, alkenyl, aryl, acyl, etc. substituted with different substituent groups into the polymer structure, thereby achieving fine-tuning of various properties of the epoxy resin composition and better meeting different application requirements.

[0061] In the embodiments of the present application, n can be an integer from 1 to 100. In some embodiments, n is an integer from 1 to 80. In some embodiments, n is an integer from 1 to 50. In some embodiments, n is an integer from 1 to 20.

[0062] In the embodiment of the present application, the number average molecular weight Mn of the polymer can be in the range of 500-50000. In some embodiments, the number average molecular weight Mn of the polymer is 500-20000. In some embodiments, the number average molecular weight Mn of the polymer is 500-10000. In some embodiments, the number average molecular weight Mn of the polymer is 500-5000. The polymer has a suitable molecular weight, which is conducive to achieving good dispersion thereof in the resin composition, and is also conducive to controlling the viscosity of the resin composition as a whole to remain at a low level, which is conducive to its application.

[0063] The polymer with a special polyether structure provided in the above-mentioned embodiment of the present application can be used as a curing agent for the preparation of an epoxy resin composition to improve the dielectric properties and heat resistance of the epoxy resin composition. The resin composition can be used as an interlayer insulating material in the field of electronic manufacturing for the preparation of components such as electronic substrates, which can effectively improve the signal transmission quality and service reliability of the electronic substrate.

[0064] The present application also provides a method for preparing the above polymer, which is used to prepare the above polymer having the structure of formula (I). The formation of the diaryl ether structure (Ar-O-Ar) can be obtained by SN2 nucleophilic substitution of halogenated aromatic hydrocarbons and transition metal-catalyzed coupling reaction.

[0065] In some embodiments of the present application, for a polymer having a structure of formula (I) in which R2 is H and R3 is not OH, that is, polymer P1, the preparation process may include:

[0066] (1) reacting raw material M1 with raw material M2 in a solvent under the action of a base and in the presence of a catalyst and a ligand to obtain polymer P1;

[0067] Raw materials M1: Raw material M2:

[0068] Polymer P1:

[0069] Wherein, R1 in the raw material M1 and the polymer P1 is selected from a bondless group, a single bond, a dimethylmethylene group (-C(CH3)2-), a trifluoromethylmethylene group (-C(CF3)2-), a methylene group (-CH2-), a sulfonyl group (-SO2-) or an oxygen group (-O-), R4 is selected from H, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and R4 can be connected to the carbon atom on the benzene ring where it is located to form a ring; R3 in the raw material M2 and the polymer P1 is selected from H or -OR f , where R f is selected from substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, or substituted or unsubstituted aryl; in the polymer P1, n is a positive integer, and m=0 or 1.

[0070] In some embodiments of the present application, for a polymer having a structure of formula (I) in which R2 is H and R3 is OH, that is, polymer P2, the preparation process may include:

[0071] (1) polymer P1 wherein R3 is -O-CH3 is subjected to demethoxylation under the action of a demethoxylating agent to obtain polymer P2; the demethoxylating agent may be B(C6F5)3, thiol or acid;

[0072] Polymer P2:

[0073] R1 in polymer P2 is selected from bondless, single bond, dimethylmethylene (-C(CH3)2-), trifluoromethylmethylene (-C(CF3)2-), methylene (-CH2-), sulfonyl (-SO2-) or oxygen (-O-), R4 is selected from H, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, and R4 can be connected to the carbon atom on the benzene ring where it is located to form a ring; n is a positive integer, m=0 or 1.

[0074] In some embodiments of the present application, for a polymer having a structure of formula (I) in which R2 is not H, that is, polymer P3, the preparation process may include:

[0075] (1) reacting a polymer P1 wherein R3 is H or a polymer P2 with a halide or an acyl halide compound to obtain a polymer P3;

[0076] Polymer P3:

[0077] R1 in polymer P3 is selected from no bond, single bond, dimethylmethylene (-C(CH3)2-), trifluoromethylmethylene (-C(CF3)2-), methylene (-CH2-), sulfonyl (-SO2-) or oxygen (-O-), R2 is selected from substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, or substituted or unsubstituted aryl, or substituted or unsubstituted acyl; R3 is H or -OR f , where R f R4 is selected from H, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, or substituted or unsubstituted aryl, or substituted or unsubstituted acyl, R4 is selected from H, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, R4 can be connected to the carbon atom on the benzene ring where it is located to form a ring; n is a positive integer, m=0 or 1.

[0078] In some embodiments of the present application, for a polymer having a structure of formula (I) in which R2 is H, R3 is not OH, and R4 is -(CH2)3-Si(CH3)2-Ra, i.e., polymer P5, the preparation process may include:

[0079] (1) reacting raw material M3 with raw material M2 in a solvent under the action of a base and in the presence of a catalyst and a ligand to obtain polymer P4;

[0080] Raw material M3: Raw material M2:

[0081] Polymer P4:

[0082] (2) reacting polymer P4 with a silicon hydride compound SiH(CH3)2-Ra to obtain polymer P5;

[0083] Polymer P5:

[0084] Among them, R1 in the raw material M3, polymer P4, and polymer P5 is selected from a bondless, single bond, dimethylmethylene (-C(CH3)2-), trifluoromethylmethylene (-C(CF3)2-), methylene (-CH2-), sulfacyl (-SO2-) or oxygen (-O-), n is a positive integer, and m=0 or 1; R3 in the raw material M2, polymer P4, and polymer P5 is H or -OR f , where R f R in polymer P5 and SiH(CH3)2-Ra is selected from substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, or substituted or unsubstituted aryl; a It is selected from benzocyclobutenyl, aryltrifluorovinyl ether, styryl, phenyl, or substituted or unsubstituted alkyl.

[0085] In some embodiments of the present application, for a polymer having a structure of formula (I) in which R2 is H, R3 is OH, and R4 is -(CH2)3-Si(CH3)2-Ra, i.e., polymer P7, the preparation process may include:

[0086] (1) polymer P4 wherein R3 is -O-CH3 is subjected to demethoxylation under the action of a demethoxylating agent to obtain polymer P6; the demethoxylating agent may be B(C6F5)3, thiol or acid;

[0087] Polymer P6:

[0088] (2) reacting polymer P6 with a silicon hydride compound SiH(CH3)2-Ra to obtain polymer P7;

[0089] Polymer P7:

[0090] Wherein, R1 in polymer P4, polymer P6, and polymer P7 is selected from the group consisting of no bond, single bond, dimethylmethylene (-C(CH3)2-), trifluoromethylmethylene (-C(CF3)2-), methylene (-CH2-), sulfacyl (-SO2-), or oxygen (-O-); n is a positive integer, m=0 or 1; R1 in polymer P7 and SiH(CH3)2-Ra a It is selected from benzocyclobutenyl, aryltrifluorovinyl ether, styryl, phenyl, or substituted or unsubstituted alkyl.

[0091] In some embodiments of the present application, for a polymer having a structure of formula (I) in which R2 is not H, that is, polymer P9, the preparation process may include:

[0092] (1) reacting polymer P4 wherein R3 is H or polymer P6 with a halide or an acyl halide compound to obtain polymer P8;

[0093] Polymer P8:

[0094] (2) reacting polymer P8 with a silicon hydride compound SiH(CH3)2-Ra to obtain polymer P9;

[0095] Polymer P9:

[0096] R1 in polymer P4, polymer P6, polymer P8, and polymer P9 is selected from the group consisting of no bond, single bond, dimethylmethylene (-C(CH3)2-), trifluoromethylmethylene (-C(CF3)2-), methylene (-CH2-), sulfonyl (-SO2-), or oxygen (-O-); n is a positive integer, and m=0 or 1; R2 in polymer P8 and polymer P9 is selected from the group consisting of substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, or substituted or unsubstituted aryl, or substituted or unsubstituted acyl, and R3 is selected from the group consisting of H or -OR f , where R f is selected from H, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted aryl, or substituted or unsubstituted acyl; R in polymer P9 and SiH(CH3)2-Ra a It is selected from benzocyclobutenyl, aryltrifluorovinyl ether, styryl, phenyl, or substituted or unsubstituted alkyl.

[0097] In the above-mentioned preparation method of the embodiment of the present application, the solvent may be but is not limited to 1,4-dioxane, acetonitrile, toluene, ethyl acetate, dichloromethane, dimethylformamide, etc. The base may be but is not limited to sodium hydroxide, cesium carbonate, potassium phosphate, potassium dihydrogen phosphate, etc. The catalyst may be but is not limited to copper salts (such as CuCl, CuBr, CuI, etc.), palladium salts, rhodium salts, etc. The ligand can stabilize the catalyst activity and increase the catalyst life. The ligand may be but is not limited to (2-pyridine) acetone, nitrogen-containing multidentate ligands, etc. In the preparation process of the above-mentioned polymer P1 and polymer P4, an antioxidant may also be added. The antioxidant may increase the catalyst life, increase the reaction efficiency, and reduce the reaction temperature. The antioxidant may be but is not limited to sodium ascorbate;

[0098] It can be understood that the polymers of the embodiments of the present application can be prepared by the above method, or prepared based on the above method combined with common preparation knowledge known in the art.

[0099] The present application also provides a resin composition, including an epoxy resin and a curing agent, wherein the curing agent includes the polymer provided in the present application. The resin composition is prepared by using the polymer in the present application as a curing agent, which can effectively improve the dielectric properties and heat resistance of the resin composition. The obtained resin composition is used in the preparation of an electronic substrate, which can improve the signal transmission quality of the electronic substrate and improve the reliability of the electronic substrate.

[0100] In the embodiment of the present application, in the resin composition, the mass percentage of epoxy resin is 1%-50%. In some embodiments, the mass percentage of epoxy resin is 1%, 4%, 6%, 10%, 12%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%. Suitable epoxy resin content can enable the resin composition to meet the basic physical properties of electronic substrate applications, better realize the strong combination of the resin composition as an interlayer dielectric layer with other components, and improve the reliability of the electronic substrate.

[0101] In the embodiment of the present application, the mass percentage of the curing agent in the resin composition is 1%-50%. In some embodiments, the mass percentage of the curing agent in the resin composition is 5%-45%. In some embodiments, the mass percentage of the curing agent in the resin composition is 10%-40%. In some embodiments, the mass percentage of the curing agent in the resin composition is 20%-30%. In some embodiments, the mass percentage of the curing agent in the resin composition is 10%-20%. Suitable curing agent content can enable the resin composition to be cured smoothly and obtain the basic physical properties that meet the application of electronic substrates.

[0102] In the embodiment of the present application, in the resin composition, the mass percentage of the polymer is 1%-30%. In some embodiments, in the resin composition, the mass percentage of the polymer is 2%-25%. In some embodiments, in the resin composition, the mass percentage of the polymer is 3%-20%. In some embodiments, in the resin composition, the mass percentage of the polymer is 5%-15%. The introduction of a suitable polymer into the resin composition can better improve the dielectric properties and heat resistance of the resin composition, and at the same time, the comprehensive performance of the resin composition can be better improved by introducing other components.

[0103] In some embodiments of the present application, the epoxy resin includes a liquid epoxy resin and a solid epoxy resin, that is, liquid epoxy resin and solid epoxy resin are added to the resin combination at the same time. The use of liquid epoxy resin and solid epoxy resin at the same time is conducive to making the resin combination take into account the advantages of liquid epoxy resin and solid epoxy resin, and improves the comprehensive performance of the resin combination. The liquid epoxy resin can be one or more of bisphenol A type epoxy resin and bisphenol F type epoxy resin. The solid epoxy resin can be one or more of biphenyl type epoxy resin, naphthalene ring type epoxy resin, dicyclopentadiene type epoxy resin, phenolic type epoxy resin, etc.

[0104] In some embodiments of the present application, the weight ratio of liquid epoxy resin to solid epoxy resin is 0.1-10. In some embodiments, the weight ratio of liquid epoxy resin to solid epoxy resin is 1-8. In some embodiments, the weight ratio of liquid epoxy resin to solid epoxy resin is 1.1-5. In some embodiments, the weight ratio of liquid epoxy resin to solid epoxy resin is 1.2-3. Controlling the liquid epoxy resin and the solid epoxy resin in a suitable ratio is conducive to making the resin composition take into account good fluidity and processability, and better meet the application requirements in the preparation of electronic substrates. Among them, controlling the amount of liquid epoxy resin to be appropriately higher than the amount of solid epoxy resin can make the resin composition better adapt to the preparation of various narrow line width and narrow line spacing electronic substrates, and better meet the packaging requirements of complex and fine structures.

[0105] In some embodiments of the present application, the resin composition also includes a film-forming resin, which is a resin with film-forming properties. Adding a film-forming resin to the resin composition is conducive to promoting the curing of the resin composition to form a film, improving the quality of the film layer, and then improving the quality of the electronic product. The film-forming resin may include a polyphenylene oxide resin. The polyphenylene oxide resin may be selected from bisphenol A type polyphenylene oxide resin and bisphenol A bisphenol F mixed type polyphenylene oxide resin.

[0106] In the embodiment of the present application, the weight average molecular weight of the polyphenylene oxide resin may be 50000 g / mol-60000 g / mol. A suitable weight average molecular weight is conducive to obtaining better film-forming properties of the polyphenylene oxide resin, and can also make the polyphenylene oxide resin better dispersed and the resin composition obtain suitable viscosity.

[0107] In some embodiments of the present application, the curing agent in the resin composition only includes the polymer provided in the examples of the present application, that is, the polymer provided in the present application is used alone as a curing agent and added to the resin composition.

[0108] In some other embodiments of the present application, the curing agent in the resin composition further comprises an active ester. The active ester as a curing agent can effectively improve the curing efficiency and curing degree of the resin composition. The active ester may be, but is not limited to, one or more of bisphenol A type active ester, dicyclopentadiene type active ester, and bisphenol AF cyanate ester.

[0109] In some embodiments of the present application, the bisphenol A type active ester includes an active ester having a structure shown in formula (i):

[0110]

[0111] The active ester molecules represented by formula (i) have relatively large rigidity and good heat resistance, which is beneficial to improving the heat resistance of the resin composition.

[0112] In the embodiment of the present application, the active ester having the structure shown in formula (i) can be prepared by the following method:

[0113]

[0114] Bisphenol A phenolic resin Benzoyl chloride Bisphenol A active ester

[0115] In a 500mL three-necked flask, 5g (41.3mmol) of bisphenol A phenolic resin and 200mL of ethyl acetate were added and stirred to dissolve, 0.95g (4.17mmol) of triethylbenzyl ammonium chloride was added, 20mL (172.1mmol) of excess benzoyl chloride was added dropwise in batches, 40mL of 10% sodium hydroxide aqueous solution was added dropwise, and the reaction was carried out at room temperature for 5h. The hydroxyl group disappeared by infrared detection, and the esterification reaction was complete. Sodium hydroxide aqueous solution was added to the system to adjust the pH to neutral to weak alkalinity. The reaction solution was extracted with ethyl acetate and water three times, the organic phase was collected, dried with anhydrous sodium sulfate, and concentrated, the concentrated solution was added dropwise to ethanol for sedimentation, the precipitate was collected, and dried to obtain a bisphenol A active ester having a structure shown in formula (i).

[0116] In the embodiment of the present application, the resin composition further includes an inorganic filler. The inorganic filler may be one or more of silicon dioxide, aluminum oxide, magnesium oxide, aluminum nitride, and silicon nitride. The addition of the inorganic filler can effectively improve the mechanical properties, thermal deformation temperature, and wear resistance of the resin composition cured product, reduce the thermal expansion coefficient of the resin composition, reduce thermal stress, and can also reduce water absorption, reduce molding shrinkage, and reduce resin overflow, thereby improving the reliability of the electronic substrate prepared using the resin composition.

[0117] In some embodiments of the present application, the inorganic filler includes silica surface-modified by a modifier, such as a silane coupling agent, which may be an amine alkoxysilane compound. The surface-modified silica can better combine with the polymer system.

[0118] In the embodiment of the present application, the average particle size of the inorganic filler is 0.1 μm-1 μm, and the cut-off particle size is 1 μm-5 μm. The inorganic filler has a smaller size, which is conducive to better realization of fine circuit preparation.

[0119] In the embodiment of the present application, in the resin composition, the mass percentage of the inorganic filler can be 20%-90%. In some embodiments, in the resin composition, the mass percentage of the inorganic filler is 25%-85%. In some embodiments, in the resin composition, the mass percentage of the inorganic filler is 30%-80%. In some embodiments, the mass percentage of the inorganic filler is 60%-90%. In some embodiments, the mass percentage of the inorganic filler is 70%-80%. The addition of an appropriate amount of inorganic filler is conducive to reducing the thermal expansion coefficient and viscosity of the resin composition, so that the cured product of the resin composition obtains suitable mechanical properties, etc., and improves the reliability of the electronic substrate. Among them, controlling the inorganic filler in a suitable higher content range can enable the resin composition to better take into account low thermal expansion coefficient, high glass transition temperature Tg, low viscosity and suitable mechanical properties, thereby ensuring that the resin composition can better achieve narrow gap filling and improve the reliability of electronic substrate packaging.

[0120] In the embodiment of the present application, the resin composition also includes additives, and the additives may include one or more of a catalyst (i.e., a curing accelerator), a leveling agent, a stabilizer, a diluent, a toughening agent, a colorant, a coupling agent, a stress modifier, a dispersant, an ion trap, a flame retardant, and a release agent. Wherein the catalyst may be, for example, but not limited to, 4-dimethylaminopyridine, cobalt acetylacetonate (II). According to the performance requirements of the resin composition, the above-mentioned additives may be added in an appropriate amount to improve the relevant properties of the resin composition.

[0121] See also Figure 1 , the embodiment of the present application also provides a resin composition sheet 10, including a resin composition layer 11 obtained by curing reaction of the resin composition described above in the embodiment of the present application. The resin composition layer has a lower dielectric constant and dielectric loss, and has good heat resistance. The resin composition layer is arranged in the electronic substrate as an interlayer medium, which can improve the reliability of the electronic substrate. In the embodiment of the present application, the resin composition sheet 10 also includes a support layer 12 for carrying the resin composition layer 11, and the support layer 12 can be a release film, such as a polyethylene terephthalate (PET) film. The thickness of the resin composition layer 11 in the resin composition sheet 10 can be set according to actual needs.

[0122] The present application embodiment also provides the application of the above-mentioned resin composition in electronic packaging or semiconductor packaging. The resin composition can be used as an interlayer medium in an electronic substrate to improve the signal transmission quality of the electronic substrate and improve the reliability of the electronic substrate. The resin composition can be used as a packaging material for semiconductor packaging to improve the signal transmission performance of semiconductor devices and improve packaging reliability. When used in electronic packaging or semiconductor packaging, the resin composition layer can be cured in the target structure by hot pressing.

[0123] See also Figure 2and Figure 3 , the embodiment of the present application provides an electronic substrate 100, and the electronic substrate 100 includes the cured product of the resin composition described above in the embodiment of the present application. The electronic substrate is a carrier for semiconductor chip packaging, a support for electronic components, and constitutes the basis of the electronic circuit. From small chips and electronic components to large circuit systems and electronic equipment, the above-mentioned electronic substrate is required. According to the application level, electronic substrates can be divided into several categories such as packaging substrates, module substrates, ordinary printed circuit boards, and assembly motherboards. According to the different stages of the electronic manufacturing process of the electronic substrate, it is divided into the first-level substrate, which is a substrate used in the field of semiconductor and electronic module manufacturing, usually called a packaging substrate or IC substrate, IC packaging substrate, IC packaging carrier; the second-level substrate is a substrate used for board manufacturing in the field of electronic assembly, usually called a printed circuit board, or PCB for short; the third-level substrate is a substrate used in the field of electronic whole machine assembly, generally called a main board or motherboard. According to the electronic manufacturing industry, electronic substrates can be divided into electronic packaging substrates and electronic assembly substrates. The resin composition of the embodiment of the present application can be used as an interlayer insulating material in an electronic substrate. The electronic substrate can be, for example, but not limited to, used in the packaging of large CPU (Central Processing Unit), GPU (Graphics Processing Unit) chips such as cloud, base station, AI (Artificial Intelligence), big data, etc.

[0124] In some embodiments of the present application, the electronic substrate 100 includes a base plate 101, a plurality of (two or more) conductive metal structures 102 disposed on the base plate 101, and an interlayer dielectric 103 disposed between two adjacent conductive metal structures 102, wherein the interlayer dielectric 103 includes a cured product of the resin composition described in the embodiment of the present application. The conductive metal structure 102 may be a conductive metal layer (e.g. Figure 1 As shown), conductive metal wires (as Figure 2 As shown), the cured product has a lower dielectric constant and dielectric loss and better heat resistance. It is arranged in an electronic substrate as an interlayer medium to improve the signal transmission quality of the electronic substrate and improve the reliability of the electronic substrate.

[0125] The embodiment of the present application further provides a semiconductor device, which includes a cured product of the resin composition described above in the embodiment of the present application.

[0126] The embodiment of the present application further provides an electronic device, which includes the electronic substrate 100 described above in the embodiment of the present application, or includes the semiconductor device described above in the embodiment of the present application.

[0127] The embodiments of the present application are further described below with reference to a plurality of embodiments.

[0128] Polymer Preparation Example 1

[0129] Synthesis of polymer 1

[0130]

[0131] Under nitrogen protection, add magnetic stirring, 10g (50mmol) of compound 1, 6g (25mmol) of compound 2a, 0.245g (2.5mmol) of CuCl, 0.84g (3mmol) of ligand L, 1.98g (10mmol) of sodium ascorbate, 32.6g (100mmol) of cesium carbonate, and 50mL of 1,4-dioxane to a 250mL dry three-necked flask. After the addition is complete, stir at 100°C for 24 hours. Filter the filtrate with diatomaceous earth, concentrate, and distill under reduced pressure. The filtrate is precipitated in water to obtain a light brown polymer 1 with a yield of 80% (M n =1500, PDI (polymer dispersibility index) =1.31). 1 H NMR (CDCl3, 400MHz,) δ7.87 (s, 1H), 7.45-6.59 (m, 10H), 3.94 (dd, J = 32.8, 11.8Hz, 2H).

[0132] Synthesis of polymer 2

[0133]

[0134] Take 6.6g (8.39mmol) of product P1 and add it to a 500mL three-necked flask and add 120mL of dichloromethane to stir and dissolve, add 0.19g (0.83mmol) of triethylbenzyl ammonium chloride, add 3mL (25.8mmol) of excess benzoyl chloride in batches, add 10mL of 10% sodium hydroxide aqueous solution, react at room temperature for 5h, and detect the disappearance of hydroxyl groups by infrared detection, indicating that the esterification reaction is complete. Add sodium hydroxide aqueous solution to the system to adjust the pH to neutral to weak alkalinity. Extract the reaction solution three times with dichloromethane and water, collect the organic phase, dry it with anhydrous sodium sulfate, and concentrate it. Add the concentrated solution dropwise into ethanol for sedimentation, collect the precipitate, wash it twice with ethanol again, and finally filter and dry it to obtain polymer 2.

[0135] Polymer Preparation Example 2

[0136] Synthesis of polymer 3

[0137]

[0138] Under nitrogen protection, add magnetic stirring, 10 g (50 mmol) of compound 1, 6.648 g (25 mmol) of compound 2b, 0.245 g (2.5 mmol) of CuCl, 0.84 g (3 mmol) of ligand L, 1.98 g (10 mmol) of sodium ascorbate, 32.6 g (100 mmol) of cesium carbonate, and 50 mL of 1,4-dioxane to a 250 mL dry three-necked flask. After the addition is complete, stir at 100°C for 24 hours. Filter with diatomaceous earth to obtain the filtrate, concentrate, and distill under reduced pressure. The precipitated in water obtains a light yellow polymer 3 (Mn = 1600, PDI = 1.37). 1 H NMR (CDCl3, 400MHz,) δ7.75 (s, 1H), 7.22-6.84 (m, 10H), 6.15 (ddd, J = 21.9, 12.6, 8.8Hz, 3H), 3.91 (d, J = 15.5Hz, 2H), 3.67 (dd, J = 15.9, 5.4Hz, 3H).

[0139] Synthesis of polymer 4

[0140]

[0141] 4 g of polymer 3, 0.08 g (0.01 mmol) of B(C6F5)3, and 3 mL of toluene were added to a 100 mL round-bottom flask, and 2 mL (3 mmol) of Et3SiH dissolved in 1 mL of toluene was added dropwise under stirring. After the addition was complete, the mixture was vigorously stirred at room temperature for 2 hours. The solvent was removed under reduced pressure, hydrochloric acid was added and stirred for half an hour, and the pH was adjusted to neutral with ethanol. The solvent was removed under reduced pressure to obtain a light yellow polymer 4. 1 H NMR (DMSO, 400MHz,) δ9.37 (s, 1H), 6.98 (dddd, J = 26.9, 18.4, 14.3, 7.7Hz, 10H), 6.42-5.72 (m, 3H), 3.77 (d, J = 13.4Hz, 2H).

[0142] Synthesis of polymer 5

[0143]

[0144] 3g (14mmol) of polymer 4 was added to a 500mL three-necked flask and 150mL of ethyl acetate (EA) was added to stir and dissolve, 0.5g (2.1mmol) of triethylbenzylammonium chloride (TEBAC) was added, 10mL (86mmol) of excess benzoyl chloride was added dropwise in batches, 20mL of 10% sodium hydroxide aqueous solution was added dropwise, and the reaction was carried out at room temperature for 6h. The hydroxyl group disappeared by infrared detection, and the esterification reaction was complete. Sodium hydroxide aqueous solution was added to the system to adjust the pH to neutral to weak alkalinity. The reaction solution was extracted with dichloromethane and water three times, the organic phase was collected, dried with anhydrous sodium sulfate, and concentrated, the concentrated solution was added dropwise to ethanol for sedimentation, the precipitate was collected, and it was washed twice with ethanol again, and finally filtered and dried to obtain polymer 5.

[0145] Resin composition example 1

[0146] Bisphenol A epoxy resin, DCPD epoxy resin (dicyclopentadiene phenol epoxy resin), polyphenoxy resin, polymer 2, active ester of bisphenol A of formula (i), 4-dimethylaminopyridine and silicon powder (spherical silica surface-treated with an amine alkoxysilane compound) were dissolved in a mixed solvent of butanone, toluene and cyclohexanone, and uniformly dispersed by a high-speed rotating mixer to obtain a resin composition. The weight parts of each component are shown in Table 1.

[0147] Resin composition example 2

[0148] Bisphenol A epoxy resin, DCPD epoxy resin, polyphenylene oxide resin, polymer 5, active ester of bisphenol A of formula (i), 4-dimethylaminopyridine and silicon powder (spherical silica surface-treated with an amine alkoxysilane compound) were dissolved in a mixed solvent of butanone, toluene and cyclohexanone, and uniformly dispersed by a high-speed rotating mixer to obtain a resin composition. The weight parts of each component are shown in Table 1.

[0149] Resin composition example 3

[0150] The only difference from the resin composition example 1 is the component contents, as shown in Table 1.

[0151] Resin composition example 4

[0152] The only difference from the resin composition example 2 is the component contents, as shown in Table 1.

[0153] Comparative Example 1

[0154] Bisphenol A epoxy resin, DCPD epoxy resin, polyphenylene oxide resin, active ester of bisphenol A of formula (i), 4-dimethylaminopyridine and silicon powder were dissolved in a mixed solvent of butanone, toluene and cyclohexanone, and uniformly dispersed by a high-speed rotating mixer to obtain a resin composition. The weight parts of each component are shown in Table 1.

[0155] Comparative Example 2

[0156] Bisphenol A epoxy resin, DCPD epoxy resin, polyphenylene oxide resin, bisphenol AF cyanate, cobalt (II) acetylacetonate, 4-dimethylaminopyridine and silicon powder were dissolved in a mixed solvent of butanone, toluene and cyclohexanone, and uniformly dispersed by a high-speed rotary mixer to obtain a resin composition. The weight parts of each component are shown in Table 1.

[0157] Comparative Example 3

[0158] Bisphenol A epoxy resin, DCPD epoxy resin, polyphenylene oxide resin, commercial dicyclopentadiene active ester, 4-dimethylaminopyridine and silicon powder were dissolved in a mixed solvent of butanone, toluene and cyclohexanone, and uniformly dispersed by a high-speed rotating mixer to obtain a resin composition. The weight parts of each component are shown in Table 1.

[0159] Comparative Example 4

[0160] Bisphenol A epoxy resin, DCPD epoxy resin, polyphenylene oxide resin, bisphenol AF cyanate, commercial dicyclopentadiene active ester, cobalt (II) acetylacetonate, 4-dimethylaminopyridine and silicon powder were dissolved in a mixed solvent of butanone, toluene and cyclohexanone, and uniformly dispersed by a high-speed rotary mixer to obtain a resin composition. The weight parts of each component are shown in Table 1.

[0161] Among them, the epoxy group equivalent of bisphenol A epoxy resin is 170g, the epoxy group equivalent of DCPD epoxy resin is 268g, the ester group equivalent of polymer 2 is 895g, the ester group equivalent of polymer 2 is 337g, the ester group equivalent of bisphenol A active ester is 225g, the cyanate group equivalent of bisphenol AF cyanate ester is 220g, and the ester group equivalent of commercial dicyclopentadiene active ester is 220g.

[0162] Preparation of resin composition sheet:

[0163] A polyethylene terephthalate film having a release layer was used as a support layer (38 μm thick), and the resin compositions obtained in Resin Composition Examples 1-4 and Comparative Examples 1-4 were uniformly applied on the release layer of the support so that the thickness of the resin composition layer after drying was 40 μm. Then, the resin composition was dried at 80° C. to 100° C. (90° C. on average) for 5 minutes to obtain a resin composition sheet including a support layer and a resin composition layer, wherein the thickness of the resin composition layer was 40 μm.

[0164] Preparation of cured resin

[0165] The resin compositions prepared in the above Examples 1-4 and Comparative Examples 1-4 were placed on a PET film and cured at 190°C for 90 minutes, and then the PET film was peeled off to obtain a cured film of the same thickness; the dielectric constant (Dk) and dielectric loss tangent (Df) of the cured film at 10 GHz were measured using the SPDR resonant cavity method. The cured film was subjected to a thermal gravimetric test using a thermal gravimetric analyzer (TGA) in an air atmosphere at a heating rate of 10°C / min, and T was recorded. 5d (5% thermal weight loss temperature), that is, the temperature at which the sample loses 5% of its mass during heating. The water absorption rate of the cured film was measured by immersion in 100°C boiling water for 5 hours. The properties of the cured films of Examples 1-4 and Comparative Examples 1-4 are shown in Table 2.

[0166] Table 1

[0167]

[0168]

[0169] Table 2

[0170]

[0171] It can be seen from the results in Table 2 that compared with the cured films obtained after curing the resin compositions of Comparative Examples 1-4, the resin compositions of Examples 1-4 of the present application have a lower dielectric constant and dielectric loss after curing the resin compositions due to the addition of a polymer having a polyarylether structure, and T 5d The resin composition is used in electronic packaging to effectively improve the quality of communication signal transmission and the service reliability of electronic equipment.

[0172] It should be understood that the first, second and various numerical numbers involved in this document are only distinguished for the convenience of description and are not used to limit the scope of the present application.

[0173] In this application, "and / or" describes the association relationship of associated objects, indicating that there can be three relationships. For example, A and / or B can mean: A exists alone, A and B exist at the same time, and B exists alone, where A and B can be singular or plural. The character " / " generally indicates that the associated objects are in an "or" relationship.

[0174] In this application, "at least one" means one or more, and "plurality" means two or more. "At least one of the following" or similar expressions refers to any combination of these items, including any combination of single items or plural items. For example, "at least one of a, b, or c", or "at least one of a, b, and c" can all mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, c can be single or multiple, respectively.

[0175] In this application, “-” represents a range value, including the endpoint values ​​at both ends. For example, the value of a can be 0.5-15, which means that the value of a can be between 0.5 and 15, and includes the endpoint values ​​0.5 and 15.

[0176] It should be understood that in the various embodiments of the present application, the size of the serial numbers of the above-mentioned processes does not mean the order of execution, some or all of the steps can be executed in parallel or sequentially, and the execution order of each process should be determined by its function and internal logic, and should not constitute any limitation on the implementation process of the embodiments of the present application.

Claims

1. A polymer, characterized in that The polymer comprises a structural unit represented by formula (I): In formula (I), R1 is selected from a bondless group, a single bond, a dimethylmethylene group, a trifluoromethylmethylene group, a methylene group, a sulfonyl group or an oxygen group; R2 is selected from a H group or a substituted or unsubstituted acyl group; R3 is selected from a H group or -OR f , where R f R4 is selected from H, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted aryl, or substituted or unsubstituted acyl; R4 is selected from H, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, or -(CH2)3-Si(CH3)2-Ra, R4 can be connected to the carbon atom on the benzene ring to form a ring, wherein R a is selected from benzocyclobutenyl, aryltrifluorovinyl ether, styryl, phenyl, or substituted or unsubstituted alkyl; n is a positive integer, m=0 or 1.

2. The polymer according to claim 1, characterized in that The substituted or unsubstituted acyl group is represented by: -O=CR; wherein R is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group.

3. The polymer according to claim 1 or 2, characterized in that The substituent groups in the substituted alkyl include halogen atoms, substituted or unsubstituted alkenyl groups, or substituted or unsubstituted aryl groups; the substituent groups in the substituted alkenyl groups include halogen atoms, substituted or unsubstituted alkyl groups, or substituted or unsubstituted aryl groups; the substituent groups in the substituted aryl groups include halogen atoms, substituted or unsubstituted alkyl groups, or substituted or unsubstituted alkenyl groups.

4. The polymer according to any one of claims 1 to 3, characterized in that The substituted or unsubstituted aryl group includes a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted heteroaryl group.

5. The polymer according to any one of claims 1 to 4, characterized in that The number average molecular weight of the polymer is 500-50,000.

6. A resin composition, characterized in that The invention comprises an epoxy resin and a curing agent, wherein the curing agent comprises the polymer according to any one of claims 1 to 5.

7. The resin composition according to claim 6, characterized in that In the resin composition, the mass percentage of the epoxy resin is 1%-50%.

8. The resin composition according to claim 6 or 7, characterized in that In the resin composition, the mass percentage of the curing agent is 1%-50%.

9. The resin composition according to any one of claims 6 to 8, characterized in that In the resin composition, the mass percentage of the polymer is 1%-30%.

10. The resin composition according to any one of claims 6 to 9, characterized in that The epoxy resin includes liquid epoxy resin and solid epoxy resin.

11. The resin composition according to claim 10, characterized in that The weight ratio of the liquid epoxy resin to the solid epoxy resin is 0.1-10.

12. The resin composition according to any one of claims 6 to 11, characterized in that The resin composition further comprises a film-forming resin, and the film-forming resin comprises a polyphenylene oxide resin.

13. The resin composition according to claim 12, characterized in that The weight average molecular weight of the polyphenylene oxide resin is 50000 g / mol-60000 g / mol.

14. The resin composition according to any one of claims 6 to 13, characterized in that The curing agent also includes an active ester.

15. The resin composition according to claim 14, characterized in that The active ester includes one or more of bisphenol A type active ester, dicyclopentadiene type active ester and bisphenol AF cyanate ester.

16. The resin composition according to any one of claims 6 to 15, characterized in that The resin composition further includes an inorganic filler.

17. The resin composition according to claim 16, characterized in that The average particle size of the inorganic filler is 0.1 μm-1 μm, and the cut-off particle size is 1 μm-5 μm.

18. The resin composition according to claim 16 or 17, characterized in that In the resin composition, the mass percentage of the inorganic filler is 20%-90%.

19. The resin composition according to any one of claims 6 to 18, characterized in that The resin composition further comprises additives, which include one or more of a catalyst, a leveling agent, a stabilizer, a diluent, a toughening agent, a colorant, a coupling agent, a stress modifier, a dispersant, an ion capture agent, a flame retardant, and a release agent.

20. A resin composition sheet, characterized in that: A resin composition layer comprising a resin composition according to any one of claims 6 to 19 obtained by curing reaction.

21. The resin composition sheet according to claim 20, characterized in that The invention also comprises a supporting layer for supporting the resin composition layer.

22. Use of the resin composition according to any one of claims 6 to 19 or the resin composition sheet according to any one of claims 20 to 21 in semiconductor packaging or electronic packaging.

23. An electronic substrate, characterized in that: The electronic substrate comprises a cured product of the resin composition according to any one of claims 6 to 19.

24. The electronic substrate according to claim 23, characterized in that The electronic substrate comprises a bottom plate, a conductive metal arranged on the bottom plate, and an interlayer dielectric arranged between the conductive metals, wherein the interlayer dielectric comprises the solidified material.

25. A semiconductor device, characterized in that: The semiconductor device comprises a cured product of the resin composition according to any one of claims 6 to 19.

26. An electronic device, characterized in that: The electronic device includes the electronic substrate according to claim 23 or 24, or includes the semiconductor device according to claim 25.

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