WO2023208180A1

WO2023208180A1 - Epoxy resin, method for preparing same, and resin composition thereof

Info

Publication number: WO2023208180A1
Application number: PCT/CN2023/091523
Authority: WO
Inventors: 徐伟娜; 刘成杰; 张鹏博; 张军营
Original assignee: 华为技术有限公司; 北京化工大学
Priority date: 2022-04-29
Filing date: 2023-04-28
Publication date: 2023-11-02
Also published as: CN117003991A

Abstract

Provided in the embodiments of the present application is an epoxy resin, comprising a cyclic siloxane ring and at least one group represented by formula (A) linked to a silicon atom on the cyclic siloxane ring, wherein in formula (A), Z is a substituted or unsubstituted arylene; n is an integer greater than or equal to 2. The molecular structure of the epoxy resin has both a cyclic siloxane ring and an epoxy group containing an arylene structure represented by formula (A) linked to the cyclic siloxane ring. The epoxy resin can feature low viscosity, low dielectric, low water absorption, high flexibility, and higher glass transition temperature Tg, and can be applied to the field of electronic sealed packaging as a sealed packaging material so as to effectively improve the reliability of sealed packaging.

Description

Epoxy resin and preparation method and resin composition thereof

This application claims priority to the Chinese patent application filed with the China Patent Office on April 29, 2022, with application number 202210483848.9 and the application name "Epoxy Resin and Preparation Method and Resin Composition", the entire content of which is incorporated by reference. in this application.

Technical field

The embodiments of the present application relate to the technical field of epoxy resin for sealed packaging, and in particular to an epoxy resin and its preparation method and resin composition.

Background technique

Epoxy resin compositions are widely used in the field of electronic sealing packaging as sealing packaging materials. Epoxy resin compositions used as sealing packaging materials generally require the ability to achieve narrow gap filling, high flexibility, low dielectric, and high reliability. Among them, to achieve narrow gap filling, the epoxy resin composition needs to have low viscosity characteristics. In order to reduce the viscosity of the system, the existing conventional method is to add a large amount of diluent or solvent to the epoxy resin composition system, and the addition of a large amount of diluent will cause The Tg (glass transition temperature) of the system decreases, and the addition of a large amount of solvent will cause bubbles due to volatilization and difficulty in post-processing. The realization of high flexibility generally requires the addition of toughening agents, but the increase in toughening agents will lead to a decrease in the Tg of the system. The decrease in Tg will increase the risk of softening of the cured epoxy resin composition at high temperatures, reduce the safety and reliability of the device, and cannot better match the current development of highly integrated electronic equipment.

Therefore, it is necessary to provide an epoxy resin composition that can have properties such as low viscosity, low dielectric, and low water absorption, and can maintain the Tg of the system at a high level while achieving high flexibility.

Contents of the invention

In view of this, embodiments of the present application provide an epoxy resin and a resin composition. The resin composition has low viscosity, low dielectric, and low water absorption properties, and can maintain the Tg of the system at 100% while achieving high flexibility. higher level.

Specifically, the first aspect of the embodiment of the present application provides an epoxy resin, which includes a cyclic siloxane ring and at least one formula (A) connected to a silicon atom on the cyclic siloxane ring. ),

In formula (A), Z is a substituted or unsubstituted arylene group; n is an integer greater than or equal to 2.

The above-mentioned epoxy resin provided in the embodiment of the present application is a silicone epoxy resin, and its molecular structure has both a cyclic siloxane ring and an arylene group represented by formula (A) connected to the cyclic siloxane ring. The epoxy group of the structure, among which the cyclic siloxane ring can loosen the entire molecular chain of the epoxy resin, reduce the force and entanglement between the molecular chains, increase the free volume, and can effectively reduce the viscosity and improve the Flexibility, and reduce the water absorption and dielectric properties of the epoxy resin; the epoxy group containing the arylene structure shown in formula (A) has a certain rigidity and can better maintain the Tg of the epoxy resin at a higher level. High level; under the joint action of the two types of group structures, the silicone epoxy resin in the embodiment of the present application can maintain the Tg of the system at a high level while improving flexibility, and has low viscosity and low dielectric properties. , low water absorption properties, thereby better meeting the sealing packaging needs of semiconductor devices and electronic devices.

In the embodiment of the present application, the substituted or unsubstituted arylene group includes any one of a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, and a substituted or unsubstituted fused ring aryl group. kind. Z is a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted fused ring aryl group, which can make the epoxy group shown in formula (A) have a certain rigidity, so that it can Working synergistically with the cyclic siloxane ring, the epoxy resin obtains good flexibility while maintaining the glass transition temperature Tg of the epoxy resin at a high level.

In the embodiment of the present application, the substituent groups on the substituted arylene include substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted Any of aryl groups and substituted or unsubstituted aryloxy groups, adjacent substituent groups may be connected to form a ring. The arylene structure containing the above substituent groups is relatively stable, and the raw materials are easily available, which is beneficial to the preparation of epoxy resin. The selection of multiple substituent groups can produce more types of epoxy resins, which is conducive to fine-tuning the performance of epoxy resins to meet the application needs of different scenarios.

In some embodiments of the present application, Z is a substituted or unsubstituted phenylene group, and the formula (A) is represented by formula (A1):

In formula (A1), the four _R1s are independently selected from a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, and a substituted or unsubstituted aryl group. Any one of the group, substituted or unsubstituted aryloxy group, adjacent R ₁ can be connected to form a ring. Z is a substituted or unsubstituted phenylene group. The raw materials are relatively easy to obtain, and it is beneficial for the epoxy resin to obtain better low viscosity characteristics when obtaining a higher glass transition temperature Tg, which is beneficial to the application process of the epoxy resin. processing operations.

In some embodiments of the present application, Z is a substituted or unsubstituted biphenylene group, and the formula (A) is represented by formula (A2):

In formula (A2), 4 R ₂ and 4 R ₃ are independently selected from hydrogen atoms, substituted or unsubstituted alkyl groups, substituted or unsubstituted cycloalkyl groups, substituted or unsubstituted alkoxy groups, substituted Or any one of unsubstituted aryl, substituted or unsubstituted aryloxy, adjacent R ₂ can be connected to form a ring, adjacent R ₃ can be connected to form a ring; R is a bridging group, and R is selected From any one of single bonds, oxygen atoms, sulfur atoms, disulfide bonds, sulfone groups, substituted or unsubstituted alkylene groups, substituted or unsubstituted alkyleneoxy groups; m is 1 or 2; n is greater than Or an integer equal to 2. When Z is a substituted or unsubstituted biphenylene group, it is beneficial to increase the glass transition temperature Tg of the epoxy resin.

In the embodiment of the present application, the substituted or unsubstituted fused ring aryl group includes a substituted or unsubstituted naphthylene group, a substituted or unsubstituted binaphthylene group, a substituted or unsubstituted anthracene group, a substituted or unsubstituted anthracenylene group, Substituted phenylene, substituted or unsubstituted fluorenylene, substituted or unsubstituted pyrenylene, or substituted or unsubstituted perylene.

In some embodiments of the present application, Z is a substituted or unsubstituted naphthylene group, and the formula (A) is represented by formula (A3):

In formula (A3), 6 R ₄ are independently selected from a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, and a substituted or unsubstituted aryl group. any one of the group, substituted or unsubstituted aryloxy group, Adjacent R ₄ can be connected to form a ring; n is an integer greater than or equal to 2. When Z is a substituted or unsubstituted naphthylene group, it is beneficial to increase the glass transition temperature Tg of the epoxy resin.

In the embodiment of the present application, the epoxy resin has a structure represented by formula (I):

In formula (I), R ₅ is a hydrogen atom or a group represented by formula (A). Among a R ₅ , at least one R ₅ is a group represented by formula (A); a is greater than or equal to an integer of 3.

In the embodiment of the present application, among the a R _5s , b R _5s are groups represented by formula (A), 1≤b≤a.

In the embodiment of the present application, a is an integer from 3 to 6.

In the molecular structure of epoxy resin, the greater the number of -Si-O- in the cyclic siloxane ring, the more conducive it is to obtain high flexibility, low viscosity and other properties; the greater the content of the groups shown in formula (A), the The more conducive to keeping Tg at a higher level. In the embodiment of the present application, by selecting epoxy siloxane rings with different silicon atom contents, controllable adjustment of the group content represented by formula (A) in the entire molecular structure of the epoxy resin can be achieved, thereby better achieving viscosity, Adjustment of flexibility, dielectric properties, water absorption and glass transition temperature Tg.

In some embodiments of the present application, the epoxy resin includes any compound represented by formula (1) to formula (4):

In Formula (1) to Formula (4), Z is a substituted or unsubstituted arylene group; n is an integer greater than or equal to 2.

The epoxy resin represented by formula (1) to formula (4) has an appropriate amount of -Si-O-, which can make the epoxy resin obtain a lower viscosity, and make the epoxy resin structure more stable and easy to prepare; and the above The silicon atoms on the cyclic siloxane ring of the epoxy resin are all connected with groups represented by formula (A), which is beneficial to maintaining the glass transition temperature Tg of the epoxy resin at a high level.

In the embodiment of the present application, the substituted or unsubstituted alkyl group is a substituted or unsubstituted C ₁ -C ₁₀ alkyl group; the substituted or unsubstituted cycloalkyl group is a substituted or unsubstituted C ₃ -C ₁₀ Cycloalkyl; the substituted or unsubstituted alkoxy group is a substituted or unsubstituted C ₁ -C ₁₀ alkoxy group; the substituted or unsubstituted aryl group is a substituted or unsubstituted C ₆ -C ₂₀ aryl group group; the substituted or unsubstituted aryloxy group is a substituted or unsubstituted C ₆ -C ₂₀ aryloxy group. Substituent groups suitable for the number of carbon atoms make the raw materials more accessible, the molecular chain simpler, and the epoxy resin easier to prepare.

In the embodiment of the present application, the substituted alkyl group includes any one of epoxyalkyl group, epoxyalkyl ether group, arylalkyl group and aminoalkyl group.

In the embodiment of the present application, when adjacent substituent groups on the substituted or unsubstituted arylene group are connected to form a ring, they may be connected to form an aromatic ring.

The second aspect of the embodiments of the present application provides a method for preparing epoxy resin, including:

The first raw material represented by formula (a) and cyclic siloxane are added to a solvent, and a hydrosilylation reaction occurs under the action of a platinum catalyst to obtain an epoxy resin. The epoxy resin includes a cyclic siloxane ring. and at least one group represented by formula (A) connected to a silicon atom on the cyclic siloxane ring,

In formula (a) and formula (A), Z is a substituted or unsubstituted arylene group; n is an integer greater than or equal to 2.

The preparation method of epoxy resin provided in the embodiments of the present application has a simple process, is easy to control, and can realize industrial production.

In the embodiment of the present application, the cyclic siloxane includes a interconnected -Si-O-, and the molar ratio of the first raw material represented by the formula (a) to the cyclic siloxane is ( a:1) to (1.2a:1). By controlling the molar amount of the first raw material to be equal to or slightly larger than the cyclic siloxane, the cyclic siloxane can be reacted more completely without excessive waste of the first raw material.

In the embodiment of the present application, the platinum catalyst includes at least one of Castor platinum catalyst and chloroplatinic acid; the amount of the platinum catalyst is 15 ppm of the total mass of the first raw material and the cyclic siloxane. -30ppm; the solvent includes one or more of tetrahydrofuran and toluene. Platinum catalyst can catalyze the above reaction very well, and controlling the amount of platinum catalyst at a suitable content can better make the reaction proceed quickly and smoothly.

In the embodiment of the present application, the preparation process of the first raw material represented by formula (a) includes:

Mix the precursor represented by formula (a-1), epichlorohydrin, and alkali, and react under the action of an ammonium salt catalyst at 60°C-80°C to obtain the first raw material represented by formula (a);

In formula (a-1), Z is a substituted or unsubstituted arylene group; n is an integer greater than or equal to 2.

In the embodiment of the present application, the molar ratio of the precursor represented by formula (a-1), epichlorohydrin, alkali and ammonium salt catalyst is 1:(4-15):(1.5-5):(0.01 -0.3). Controlling each raw material at an appropriate ratio is conducive to the smooth progress of the above reaction and improves the yield.

The second aspect of the embodiments of the present application provides a resin composition, which includes the epoxy resin and the curing agent described in the first aspect of the embodiments of the present application. The resin composition of the embodiment of the present application will solidify when heated, and the cured product obtained by curing can have low dielectricity, low water absorption, high flexibility and a high glass transition temperature Tg. The resin composition can be applied In the field of electronic sealing packaging, it improves the reliability of sealing packaging. At the same time, due to the low viscosity of epoxy resin, good processing performance can be obtained.

In the embodiment of the present application, the resin composition further includes a filler. The addition of fillers can improve the warpage of the cured resin composition during the sealing and packaging process.

In the embodiment of the present application, the resin composition further includes at least one of a curing accelerator and an auxiliary agent. Curing promotion The additive is beneficial to the curing of the resin composition, and the additive can be various substances that are beneficial to improving the properties of the cured product obtained by curing.

In the embodiment of the present application, the resin composition includes the following mass percentages of each component: the epoxy resin: 1%-50%, the curing agent: 1%-70%, and the filler: 0-95 %, curing accelerator: 0-10%, additives: 0-10%.

In the embodiment of the present application, the resin composition also includes other epoxy resins.

The third aspect of the embodiments of the present application provides a cured product, which includes a cured product of the resin composition described in the second aspect of the embodiments of the present application. The cured product can have low dielectricity, low water absorption, high flexibility and high glass transition temperature Tg.

The fourth aspect of the embodiment of the present application provides a sealed packaging material for sealing packaging of semiconductor devices or electronic devices. The sealed packaging material includes the resin composition and/or the resin described in the second aspect of the embodiment of the present application. The cured product of the composition. After curing, the sealed packaging material can have low dielectricity, low water absorption, high flexibility and high glass transition temperature Tg, which can improve the reliability of sealed packaging.

The fifth aspect of the embodiment of the present application provides a sealed package, including a sealed package of a semiconductor or a sealed package of an electronic device, and the sealed package includes the cured product described in the third aspect of the embodiment of the present application. The sealed package containing the cured product of the above-mentioned resin composition in the embodiment of the present application has high reliability.

The sixth aspect of the embodiment of the present application provides a semiconductor sealed package, including a substrate, a chip disposed on the substrate, and a plastic package for sealing and packaging the chip. The plastic package includes the components of the third aspect of the embodiment of the present application. The above-mentioned cured product. The semiconductor sealing package containing the cured product of the above-mentioned resin composition in the embodiment of the present application has high reliability.

In the embodiment of the present application, a plurality of welding bumps are provided on a side surface of the chip facing the substrate, and a bottom filling glue layer is provided between the welding bumps. The bottom filling glue layer includes the cured product. .

An embodiment of the present application also provides an electronic device. The electronic device includes the sealed package described in the fifth aspect of the embodiment of the present application, or the semiconductor sealed package described in the sixth aspect of the embodiment of the present application. Electronic equipment including the above-mentioned sealed package in embodiments of the present application has high reliability.

Description of the drawings

Figure 1 is a schematic structural diagram of a sealed package 100 provided by an embodiment of the present application;

Figure 2 is a schematic structural diagram of an electronic device 200 provided by an embodiment of the present application;

Figure 3 is the infrared spectrum of tetramethylcyclotetrasiloxane (D4H), eugenol-based epoxy resin (EUEP), and silicone epoxy resin A in Example 1 of the present application;

Figure 4 is the nuclear magnetic resonance spectrum of silicone epoxy resin A in Example 1 of the present application;

Figure 5 is the viscosity curve of eugenol-based epoxy resin (EUEP) and silicone epoxy resin A in Example 1 of the present application;

Figure 6 shows the dielectric property results of the cured product of the resin composition prepared in Example 1 of the present application.

Detailed ways

The embodiments of the present application will be described below with reference to the drawings in the embodiments of the present application.

Epoxy resin compositions are used as sealing packaging (ie, encapsulation) materials for sealing packaging of semiconductor devices and electronic devices. They are usually required to have high flexibility to improve adhesion and sealing packaging reliability, and at the same time have a high glass transition Temperature Tg (generally greater than 120°C) to meet usage requirements. However, currently, in order to improve the flexibility of epoxy resin systems, toughening agents are usually added to the system. However, the increase of toughening agents will cause the Tg of the system to decrease, that is, it is difficult for existing epoxy resin systems to maintain high flexibility. and higher Tg. In order to solve the above problems, embodiments of the present application provide an epoxy resin, which can maintain the Tg of the system at a high level while improving flexibility, and has low viscosity, low dielectric, and low water absorption characteristics, so that it can Better meet the sealing packaging needs of semiconductor devices and electronic devices.

Specifically, embodiments of the present application provide an epoxy resin, which includes a cyclic siloxane ring and at least one group represented by formula (A) connected to a silicon atom on the cyclic siloxane ring. ,

In formula (I), R ₅ is a hydrogen atom or a group represented by formula (A). Among a R ₅ , at least one R ₅ is a group represented by formula (A); a is greater than or equal to 3. integer.

In the embodiments of the present application, the cyclic siloxane ring may include more than 3 interconnected -Si-O-; in some embodiments, the cyclic siloxane ring may include 3-6 interconnected -Si -O-; that is, in formula (I), a can be an integer from 3 to 6. Specifically, in one embodiment, a is 3, and the cyclic siloxane ring includes 3 interconnected -Si-O-; in one embodiment, a is 4, and the cyclic siloxane ring includes 4 interconnected ones. -Si-O-; In one embodiment, a is 5, and the cyclic siloxane ring includes 5 interconnected -Si-O-; In one embodiment, a is 6, and the cyclic siloxane ring includes 6 interconnected -Si-O-. In the molecular structure of epoxy resin, the greater the number of -Si-O- in the cyclic siloxane ring, the more conducive it is to obtain high flexibility, low viscosity and other properties; the greater the content of the groups shown in formula (A), the The more conducive to keeping Tg at a higher level. In the embodiment of the present application, by selecting epoxy siloxane rings with different silicon atom contents, controllable adjustment of the group content represented by formula (A) in the entire molecular structure of the epoxy resin can be achieved, thereby better achieving viscosity, Adjustment of flexibility, dielectric properties, water absorption and glass transition temperature Tg.

In the embodiment of the present application, among a R _5s , b R _5s may be groups represented by formula (A), 1≤b≤a, that is, they may be part or all of the cyclic siloxane ring. A group represented by formula (A) is connected to the silicon atom. For example, when a is 4, and the cyclic siloxane ring includes 4 interconnected -Si-O-, there can be 1, 2, 3 or 4 silicon atoms connected with the formula (A) The group, that is, b can be an integer from 1 to 4. For another example, when a is 5 and the cyclic siloxane ring includes 5 interconnected -Si-O-, there can be 1, 2, 3, 4 or 5 silicon atoms connected with the formula ( The group shown in A), that is, b, can be an integer from 1 to 5.

In some embodiments of the present application, when all silicon atoms on the cyclic siloxane ring are connected with groups represented by formula (A), the epoxy resin can be represented by formula (1) to formula (4) Either structure:

The epoxy resin represented by formula (1) to formula (4) has an appropriate amount of -Si-O-, which can make the epoxy resin obtain a lower viscosity, and make the epoxy resin structure more stable and easy to prepare; and the above The silicon atoms on the cyclic siloxane ring of the epoxy resin are all connected with groups represented by formula (A), which is beneficial to maintaining the Tg of the epoxy resin at a high level.

In the embodiment of the present application, when some silicon atoms on the cyclic siloxane ring are connected with groups represented by formula (A), a is 4, that is, the cyclic siloxane ring includes 4 interconnected -Si-O- is an example. The epoxy resin can have any structure shown in formula (5) to formula (7):

In Formula (5) to Formula (7), Z is a substituted or unsubstituted arylene group; n is an integer greater than or equal to 2.

In the embodiment of the present application, in formula (A), n may be an integer greater than or equal to 2. In some embodiments, n may be an integer from 2 to 5. Specifically, n may be 2, 3, 4 or 5.

In the embodiment of the present application, the substituted or unsubstituted arylene group may include any one of substituted or unsubstituted phenylene groups, substituted or unsubstituted biphenylene groups, and substituted or unsubstituted fused ring aryl groups. kind. Z is substituted or unsubstituted phenylene, The substituted or unsubstituted biphenylene group and the substituted or unsubstituted fused ring aryl group can make the epoxy group shown in formula (A) have a certain rigidity, so that it can cooperate with the cyclic siloxane ring to make The epoxy resin obtains good flexibility while maintaining the glass transition temperature Tg of the epoxy resin at a high level. When Z is a substituted or unsubstituted phenylene group, it is beneficial for the epoxy resin to obtain better low viscosity characteristics when obtaining a higher glass transition temperature Tg, which is beneficial to the processing of the epoxy resin during the application process.

In the embodiment of the present application, the substituent groups on the substituted arylene group may include substituted or unsubstituted alkyl groups, substituted or unsubstituted cycloalkyl groups, substituted or unsubstituted alkoxy groups, substituted or unsubstituted Any of aryl groups and substituted or unsubstituted aryloxy groups, adjacent substituent groups may be connected to form a ring. The arylene structure containing the above substituent groups is relatively stable, and the raw materials are easily available, which is beneficial to the preparation of epoxy resin. The selection of multiple substituent groups can produce more types of epoxy resins, which is conducive to fine-tuning the performance of epoxy resins to meet the application needs of different scenarios.

In the embodiment of the present application, the substituted or unsubstituted alkyl group may be a substituted or unsubstituted C ₁ -C ₁₀ alkyl group, such as, but not limited to, a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, Substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted pentyl, substituted or unsubstituted hexyl, substituted or unsubstituted heptyl, substituted or unsubstituted octyl, etc. The substituted alkyl group may be any one of epoxyalkyl group, epoxyalkyl ether group, arylalkyl group and aminoalkyl group. The epoxyalkyl ether group may be, for example, but is not limited to

In the embodiment of the present application, the substituted or unsubstituted cycloalkyl group may be a substituted or unsubstituted C ₃ -C ₁₀ cycloalkyl group. Specifically, it may be, but is not limited to, a substituted or unsubstituted cyclopropyl group, a substituted or unsubstituted cyclopropyl group. cyclobutyl, substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl.

In the embodiments of the present application, the substituted or unsubstituted alkoxy group may be a substituted or unsubstituted C ₁ -C ₁₀ alkoxy group. For example, it may be, but is not limited to, a substituted or unsubstituted methaneoxy group, a substituted or unsubstituted alkoxy group. ethyloxy group, substituted or unsubstituted propyloxy group, substituted or unsubstituted butyloxy group, substituted or unsubstituted pentyloxy group, substituted or unsubstituted hexyl alkoxy group.

In the embodiment of the present application, the substituted or unsubstituted aryl group may be a substituted or unsubstituted C ₆ -C ₂₀ aryl group. For example, it may be, but is not limited to, a substituted or unsubstituted phenyl group or a substituted or unsubstituted anthracenyl group. , substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthrenyl. In the embodiment of the present application, the substituted or unsubstituted aryloxy group may be a substituted or unsubstituted C ₆ -C ₂₀ aryloxy group, for example, but is not limited to a substituted or unsubstituted phenoxy group.

The above-mentioned substituent groups with a suitable number of carbon atoms make the raw materials more accessible, the molecular chain simpler, and the epoxy resin easier to prepare.

In some embodiments of the present application, Z is a substituted or unsubstituted phenylene group, and the epoxyalkyl ether group and the alkylene group are located in the para position of the benzene ring. In this case, formula (A) can be expressed as formula (A1):

In other embodiments of the present application, when Z is a substituted or unsubstituted phenylene group, the epoxy alkyl ether group and the alkylene group can also be So it is the ortho position or the meta position.

In some embodiments of the present application, in formula (A1), four R _1s are all hydrogen atoms. In some embodiments of the present application, in formula (A1), part of the four R _1s is a hydrogen atom, and the other part is an alkoxy group.

In some embodiments of the present application, in formula (A1), adjacent R _1s may be connected to form a ring. Specifically, adjacent R _1's may be connected to form an aromatic ring. The above-mentioned connected aromatic ring may specifically be a benzene ring, and the benzene ring may be connected to the benzene ring structure on the main chain in formula (A). Among them, when two adjacent R _1s in formula (A1) are connected to form a benzene ring structure, the specific structure of the benzene ring structure and the benzene ring structure on the main chain in formula (A1) and the ring connection are as follows:

When two adjacent R _1s in formula (A1) are connected to form a benzene ring structure, the specific structure of the benzene ring structure and the benzene ring structure on the main chain in formula (A1) and the ring connection are as follows:

In some embodiments of the present application, Z is a substituted or unsubstituted biphenylene group. In this case, formula (A) can be expressed as formula (A2):

In formula (A2), 4 R ₂ and 4 R ₃ are independently selected from hydrogen atoms, substituted or unsubstituted alkyl groups, substituted or unsubstituted cycloalkyl groups, substituted or unsubstituted alkoxy groups, substituted Or any one of unsubstituted aryl, substituted or unsubstituted aryloxy, adjacent R ₂ can be connected to form a ring, adjacent R ₃ can be connected to form a ring; R is a bridging group, which can be Single bond, oxygen atom (O), sulfur atom (S), disulfide bond (-SS-), sulfone group (-SO ₂ -), substituted or unsubstituted alkylene group, substituted or unsubstituted alkylene oxygen Any one of the bases; m is 1 or 2; n is an integer greater than or equal to 2. The substituted or unsubstituted alkylene group can be, but is not limited to, methylene (-CH ₂ -), ethylene (-CH ₂ CH ₂ -), propylene (-CH ₂ CH ₂ CH ₂ -) , isopropylene (-C(CH ₃ ) ₂ -), phenyl substituted methylene (-CHC ₆ H ₅ -), etc.; the substituted or unsubstituted alkyleneoxy group can specifically be, but is not limited to, methyleneoxy group (-O-CH ₂ -), ethyleneoxy group (-O-CH ₂ CH ₂ -). When Z is a substituted or unsubstituted biphenylene group, it is beneficial to increase the glass transition temperature Tg of the epoxy resin.

In some embodiments of the present application, in formula (A2), m=1. In this case, formula (A) can be expressed as formula (A2-1):

In formula (A2-1), 4 R ₂ and 4 R ₃ are each independently selected from a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, and a substituted or unsubstituted alkoxy group. , substituted or unsubstituted aryl group, substituted or unsubstituted aryloxy group Any of them, adjacent R ₂ can be connected to form a ring, and adjacent R ₃ can be connected to form a ring; R is a bridging group, which can be a single bond, an oxygen atom (O), a sulfur atom (S), or a dihydrogen atom. Any one of sulfur bond (-SS-), sulfone group (-SO ₂ -), substituted or unsubstituted alkylene group, substituted or unsubstituted alkyleneoxy group; m is 1 or 2; n is greater than Or an integer equal to 2. In some embodiments of the present application, in formula (A2-1), 4 R ₂ and 4 R ₃ are both hydrogen atoms. In some embodiments of the present application, in formula (A2-1), 4 R ₂ and 4 R ₃ are partly hydrogen atoms, and the other part is an alkoxy group.

In the embodiment of the present application, the substituted or unsubstituted fused ring aryl group may include a substituted or unsubstituted naphthylene group, a substituted or unsubstituted binaphthylene group, a substituted or unsubstituted anthracenylene group, a substituted or unsubstituted anthracenylene group, Substituted phenylene, substituted or unsubstituted fluorenylene, substituted or unsubstituted pyrenylene, or substituted or unsubstituted perylene.

In some embodiments of the present application, Z is a substituted or unsubstituted naphthylene group, and the epoxy alkyl ether group and the alkylene group are respectively located on the 1st carbon and the 5th carbon of the naphthalene ring. In this case, formula (A) can Expressed as formula (A3):

In formula (A3), the six substituent groups R ₄ on the naphthalene ring are independently selected from hydrogen atoms, substituted or unsubstituted alkyl groups, substituted or unsubstituted cycloalkyl groups, and substituted or unsubstituted alkoxy groups. , any one of substituted or unsubstituted aryl groups, substituted or unsubstituted aryloxy groups, adjacent R ₄ can be connected to form a ring; n is an integer greater than or equal to 2. In some embodiments of the present application, in formula (A3), 6 R ₄ are all hydrogen atoms. In some embodiments of the present application, in formula (A1), some of the six R _4s are hydrogen atoms, and the other part is an alkoxy group. When Z is a substituted or unsubstituted naphthylene group, it is beneficial to increase the glass transition temperature Tg of the epoxy resin.

In some embodiments of the present application, Z is a substituted or unsubstituted naphthylene group, and the epoxyalkyl ether group and the alkylene group can also be located on other carbon atoms of the naphthalene ring respectively.

Illustratively, the group represented by formula (A) in the embodiment of the present application can specifically be a group represented by the following formula (A-1) to formula (A-10):

Accordingly, the embodiments of the present application provide a method for preparing the above-mentioned epoxy resin, which includes the following steps:

The first raw material represented by formula (a) and cyclic siloxane are added to a solvent, and a hydrosilylation reaction occurs under the action of a platinum catalyst to obtain an epoxy resin. The epoxy resin includes a cyclic siloxane ring and at least A group represented by formula (A) connected to a silicon atom on a cyclic siloxane ring,

It can be understood that the specific selection of Z in formula (a) is consistent with that in formula (A), and will not be described again here.

In the embodiment of the present application, the first raw material represented by formula (a) is essentially an epoxy resin containing double bonds. The silicone epoxy resin in the embodiment of the present application is composed of the first raw material represented by formula (a) and Cyclic siloxanes are obtained by hydrosilylation reactions. Modification of the first raw material represented by formula (a) through hydrosilation reaction can eliminate the consumption of epoxy groups, thereby increasing the crosslinking density of the epoxy resin after curing.

In the embodiment of the present application, the cyclic siloxane includes a interconnected -Si-O-. When it is expected that each of the a silicon atoms can be connected to a group represented by formula (A), The molar ratio of the first raw material represented by formula (a) to the cyclic siloxane may be (a:1) to (1.2a:1). By controlling the molar amount of the first raw material to be equal to or slightly larger than the cyclic siloxane, the cyclic siloxane can be reacted more completely without excessive waste of the first raw material. It should be noted that during the actual preparation process, depending on the degree of hydrosilylation, epoxy resins containing different amounts of groups represented by formula (A) may be obtained, and the final prepared product may also contain different amounts of groups represented by formula (A). A mixture of epoxy resins having groups represented by (A). Taking cyclic siloxane including 4 interconnected -Si-O- as an example, depending on the degree of hydrosilylation, it is possible to obtain the monosubstituted epoxy resin represented by the aforementioned formula (5), and the monosubstituted epoxy resin represented by the formula (6). The disubstituted epoxy resin represented by formula (7), the trisubstituted epoxy resin represented by formula (7), the four-substituted epoxy resin represented by formula (2), or a mixture of two or more different epoxy resins mentioned above.

In the embodiment of the present application, the platinum catalyst can improve the rate and reaction efficiency of the hydrosilylation reaction. The platinum catalyst may specifically include Castor platinum catalyst (ie, KZstedt catalyst, specifically a siloxane complex of Pt), chloroplatinic acid (H ₂ PtCl ₆ ·6H ₂ O), and other available platinum catalysts. of at least one. In the embodiment of the present application, the amount of catalyst used may be 15 ppm to 30 ppm based on the total mass of the above-mentioned first raw material and cyclic siloxane. Specifically, it may be 15 ppm, 20 ppm, 25 ppm, or 30 ppm. Controlling the amount of platinum catalyst at a suitable content can better enable the reaction to proceed quickly and smoothly without causing waste. In the embodiment of the present application, the solvent may include one or more of tetrahydrofuran, toluene, and xylene.

In the embodiment of the present application, the reaction temperature of the above-mentioned hydrosilylation reaction can be 100°C-120°C, for example, it can be 100°C, 110°C, 120°C, etc.; the reaction time can be 2-4 hours, for example, it can be 2 hours, 3 hours, 4 hours Wait. In the embodiment of the present application, after the hydrosilylation reaction is completed, an adsorbent, such as activated carbon, may be used to remove the catalyst. After the catalyst is removed, the final product may be obtained through suction filtration and vacuum distillation. Specifically, after suction filtration, the lower clear liquid obtained by suction filtration is subjected to the following post-processing: the lower clear liquid is distilled under reduced pressure, and then an equal volume of a second solvent (such as methyl isobutyl ketone, or a solvent thereof) is added. Mix n-butanol) to dissolve the crude resin product, and add water 1.5-3 times the volume of the crude resin product to thoroughly mix and wash with water, let it stand, remove the water phase, collect the oil phase, and complete one water washing operation; The oil phase is repeatedly washed with water - left to stand - and the water phase is removed (usually repeated 3-6 times) until the pH of the water phase reaches neutral, and finally distilled under reduced pressure to remove the second solvent to obtain the final required Silicone epoxy resin. For example, the temperature of vacuum distillation can be 80-90°C, and the time can be 0.5h-1.5h.

In the embodiment of the present application, the preparation process of the first raw material represented by formula (a) may include the following steps:

Mix the precursor represented by formula (a-1), epichlorohydrin, and alkali, and react under the action of an ammonium salt catalyst at 60°C-80°C in an inert gas atmosphere to obtain the third compound represented by formula (a). a raw material;

In formula (a-1), Z is a substituted or unsubstituted arylene group; n is an integer greater than or equal to 2. Understandably, the selection of Z in formula (a-1) is consistent with that in formula (A), and will not be described again here.

In the embodiment of the present application, the base may be an alkali metal hydroxide, such as one or more of sodium hydroxide and potassium hydroxide. In the embodiment of the present application, the ammonium salt catalyst is a quaternary ammonium salt. Specific examples include but are not limited to tetramethylammonium bromide, tetramethylammonium chloride, tetraethylammonium bromide, tetrapropylammonium bromide, and tetramethylammonium bromide. Butylammonium bromide, tetrabutylammonium chloride, cetylamine bromide, cetyltrimethylammonium chloride, trioctylmethylammonium chloride, trioctylethylammonium bromide, Tetramethylbenzylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium chloride, benzyltriethylammonium bromide, benzyltriethylammonium chloride, benzyltributyl One or more of ammonium bromide, benzyltributylammonium chloride, phenyltrimethylammonium bromide, and phenyltrimethylammonium chloride.

In the embodiment of the present application, the molar ratio of the precursor represented by formula (a-1), epichlorohydrin, base and ammonium salt catalyst can be 1:(4-15):(1.5-5):(0.01- 0.3). In some embodiments, the molar ratio of the precursor represented by formula (a-1), epichlorohydrin, base and ammonium salt catalyst can be 1:(6-10):(2.5-4):(0.1-0.2 ). Controlling each raw material at an appropriate ratio is conducive to the smooth progress of the above reaction and improves the yield.

In the embodiment of the present application, the reaction temperature during the preparation process of the first raw material represented by formula (a) can be specifically 60°C, 65°C, 70°C, 75°C, 80°C, etc.; the reaction time can be 2-3 hours. , specifically, it can be 2 hours, 2.5 hours, 3 hours, etc. The inert gas atmosphere may be a nitrogen atmosphere, for example.

Taking the preparation of silicone epoxy resin a as an example, its synthesis route is shown in reaction formula (1):

The embodiments of the present application also provide a resin composition, which includes the epoxy resin and the curing agent described in the embodiments of the present application. The resin composition can be obtained by mixing the epoxy resin and the curing agent mentioned in the embodiments of the present application. The above-mentioned epoxy resin in the embodiments of the present application is helpful for the resin composition to obtain low dielectric properties. In some embodiments, the dielectric constant of the resin composition is below 3. The resin composition of the embodiment of the present application will solidify when heated, and the cured product obtained by curing can have low dielectricity, low water absorption, high flexibility and a high glass transition temperature Tg. The resin composition can be applied In the field of electronic sealing packaging, it improves the reliability of sealing packaging. At the same time, due to the low viscosity of epoxy resin, good processing performance can be obtained.

In the embodiment of the present application, the curing agent may include one or more of anhydride curing agents, amine curing agents, and phenolic curing agents. Exemplarily, the acid anhydride curing agent may be hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, alkyl hexahydrophthalic anhydride One or more of acid anhydride, tetrahydrophthalic anhydride, succinic anhydride, methylnadic anhydride, 5-norbornene-2,3-dioic anhydride, and trialkyl tetrahydrophthalic anhydride. For example, the amine curing agent may be polyetheramine, isophoronediamine, 3,3’-dimethyl-4,4’-diamino-dicyclohexylmethane, etc.

In some embodiments of the present application, the resin composition may include fillers. The addition of fillers can make the cured product formed by the resin composition after curing have a lower linear expansion coefficient and higher impact strength. The fillers include, but are not limited to, one or more of silica, aluminum oxide, magnesium oxide, zinc oxide, zirconium oxide, titanium dioxide, etc.

In some embodiments of the present application, the resin composition further includes at least one of a curing accelerator and an auxiliary agent. Among them, the curing accelerator includes but is not limited to one of tertiary amines (such as N,N-dimethylbenzylamine, etc.), imidazole, and modified imidazole (such as dimethylimidazole, 1-phenyldimethylimidazole, etc.) Kind or variety. Auxiliary agents may include one or more of defoaming agents, leveling agents, dispersants, flame retardants, release agents, colorants, ion trapping agents, stress absorbers, thickeners, flow improvers, etc.

In the embodiment of the present application, the above-mentioned resin composition may include each component with the following mass percentage: silicone epoxy resin in the embodiment of the present application: 1%-50%, curing agent: 1%-70%, filler: 0-95%, curing accelerator: 0-10%, additives: 0-10%. In some embodiments, the quality of the silicone epoxy resin in the resin composition according to the embodiments of the present application is Specifically, the component content may be 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 10%, 12%, 15%, 20%, 25%, 30%, 40% , 50%, etc. In some embodiments, the mass percentage of the filler in the resin composition can be 50%-93%, specifically, it can be 50%, 60%, 70%, 80%, 85%, 88%, 90%. , 91%, 92%, 93%, etc. The mass percentage of the curing agent in the resin composition may be 1%-10%, and further may be 2%-8%. The mass percentage of the curing accelerator in the resin composition may be 0.1%-1%, for example, 0.5%-1%.

In some embodiments of the present application, the resin composition includes the following components by mass: Examples of the present application: silicone epoxy resin: 3%-10%, curing agent: 1%-8%, filler: 80% -92%, curing accelerator: 0.1%-1%, additives: 0-10%. At this time, the resin composition is more suitable for use as a plastic package for sealing packages.

In some embodiments of the present application, the resin composition may further include other epoxy resins. That is, the silicone epoxy resin in the embodiment of this application is used in combination with other epoxy resins.

The resin composition in the embodiments of the present application will be cured when heated, that is, the epoxy resin and the curing agent in the resin composition may react chemically to form a three-dimensional network polymer. The resin composition is converted into a cured product of a certain shape after curing, and the cured product may be in the form of a film, a sheet, or a three-dimensional structure. The epoxy resin in the embodiment of the present application is helpful for the cured product of the resin composition to obtain low water absorption, high flexibility and high Tg.

The resin composition mentioned above in this application is usually in liquid state. The liquid resin composition can be directly used as liquid glue, and can form a glue layer after being coated and solidified. In addition, the resin composition can also be converted into a solid molding compound that is easy to store (the epoxy resin is not completely cross-linked and solidified) after being kneaded, aged, etc., and the molding compound can be in the form of granules, sheets, or lumps. etc., which can then be transformed into a solidified object of a certain shape through common molding processes, usually into a three-dimensional structure. In addition, molding compounds generally contain fillers, and liquid glue may or may not contain fillers. The above-mentioned epoxy resin in the embodiments of the present application has low viscosity, so it is beneficial for the liquid resin composition to obtain low viscosity, thereby allowing the liquid resin composition to obtain a wider process window, which is beneficial to operation and application at different temperatures. In some embodiments, the resin composition may have a viscosity of less than 10 Pa.s at room temperature.

Embodiments of the present application provide a sealing packaging material for sealing packaging of semiconductor devices or electronic devices. The sealing packaging material includes the above-mentioned resin composition and/or the cured product of the above-mentioned resin composition.

Please refer to FIG. 1 , which is a schematic structural diagram of a sealed package 100 in an embodiment of the present application. The sealed package 100 may be a semiconductor sealed package or an electronic device sealed package, and the sealed package 100 includes the cured product described above in the embodiment of the present application. Specifically, the sealed package 100 includes a substrate 10 , components 20 provided on the substrate 10 , and a plastic package 30 that seals and packages the substrate 10 and the components 20 . The component 20 may be one or more of a chip, a transistor (such as a diode, a triode), an LED, a resistor-capacitor element (such as a resistor, a capacitor, an inductor), etc. The following takes the component 20 as a chip as an example for detailed description. The surface of the chip 20 facing the substrate 10 may have a plurality of solder bumps (eg, solder balls) 40 , and the chip 20 may be attached to the surface of the substrate 10 by remelting the solder bumps 40 . In some embodiments, an underfill glue layer 50 is also provided in the gap between the solder bumps 40 to fill the space between the chip 20 and the substrate 10 to provide a more stable connection. Wherein, the plastic package 30 and/or the underfill layer 50 adopt the resin composition of the embodiment of the present application, that is, the plastic package 30 and/or the underfill layer 50 include a cured product of the resin composition. In some embodiments, the plastic encapsulation body 30 includes a cured product of a resin composition; in some embodiments, the underfill glue layer 50 includes a cured product of a resin composition; in some embodiments, both the plastic encapsulation body 30 and the underfill glue layer 50 include Cured product of resin composition. The plastic body 30 can be processed into a certain structural appearance by using common molding processes such as transfer molding, compression molding, or injection molding from a molding compound containing epoxy resin and fillers. And the epoxy resin is cross-linked and solidified during the molding process. The underfill glue layer 50 can be formed by applying liquid glue containing epoxy resin and then solidifying. In some embodiments, the substrate 10 may also be made of the epoxy resin provided in the embodiments of this application.

The sealed package of this application is sealed and packaged using the epoxy resin provided in the embodiment of this application, and has high reliability.

Referring to FIG. 2 , an embodiment of the present application also provides an electronic device 200 . The electronic device 200 includes a housing 201 and a sealed package 100 disposed in the housing 201 . The electronic device 200 may be a mobile phone, a tablet computer, a notebook computer, a portable computer, a smart wearable product, a car, or other products.

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

In this application, "and/or" describes the relationship between associated objects, indicating that there can be three relationships, for example, A and/or B, which can mean: A exists alone, A and B exist simultaneously, and B exists alone. , where A and B can be singular or plural.

In this application, "at least one" refers to one or more, and "plurality" refers to two or more.

The embodiments of the present application will be further described below in multiple embodiments.

Example 1

Preparation of silicone epoxy resin A: (1) Add the raw materials into a 500mL three-necked bottle according to the following formula: eugenol: epichlorohydrin: sodium hydroxide: tetramethylammonium bromide = 40g: 230g: 35g: 0.7g, and react The temperature is maintained at 65-70°C. After refluxing for 2.5 hours, the unreacted epichlorohydrin is evaporated, and methyl isobutyl ketone is added to fully dissolve it. Then a certain amount of deionized water is added to separate layers to obtain the supernatant. The supernatant was washed with deionized water several times until pH=7, and then dried under vacuum to obtain eugenol-based epoxy resin (EUEP for short).

(2) Add 2.7g tetramethylcyclotetrasiloxane (D4H) and an appropriate amount of toluene into a 250mL single-neck bottle, and add a mixture of 10g eugenol-based epoxy resin, 0.06g platinum catalyst and toluene at 110°C. Reflux the reaction for 3 hours, then add 5% of the total mass of activated carbon to the reaction system and continue stirring for 40 minutes. Filter with suction to remove the activated carbon adsorbed with the platinum catalyst. The lower liquid obtained by suction filtration is distilled under reduced pressure to obtain silicone epoxy resin A. .

The above reaction process is as follows:

Preparation of the resin composition: Add 5.11g of the curing agent methylhexahydrophthalic anhydride and 0.1g of the catalyst dimethylbenzylamine BDMA to 10g of the silicone epoxy resin A prepared in Example 1, and stir evenly to obtain a resin composition.

Curing of the resin composition: Pour the above resin composition into a mold after removing bubbles, and react at 105°C for 5 hours, 160°C for 4 hours, and 200°C for 1 hour to obtain a cured product.

Figure 3 is the infrared spectrum of tetramethylcyclotetrasiloxane (D4H), eugenol-based epoxy resin (EUEP), and silicone epoxy resin A in Example 1 of the present application; Figure 4 is Example 1 of the present application. NMR spectrum of silicone epoxy resin A. It can be seen from the characterization results in Figures 3 and 4 that silicone epoxy resin A was prepared in this application.

Example 2

Preparation of silicone epoxy resin B: (1) Add the raw materials into a 500mL three-necked bottle according to the following formula: eugenol: epichlorohydrin: sodium hydroxide: tetramethylammonium bromide = 40g: 230g: 35g: 0.7g, and react The temperature is maintained at 65-70°C. After refluxing for 2.5 hours, the unreacted epichlorohydrin is evaporated, and methyl isobutyl ketone is added to fully dissolve it. Then a certain amount of deionized water is added to separate layers to obtain the supernatant. The supernatant was washed with deionized water several times until pH=7, and then dried under vacuum to obtain eugenol-based epoxy resin.

(2) Add 2.5g trimethylcyclotrisiloxane (CAS: 13269-39-1) and an appropriate amount of toluene into a 250mL single-neck bottle, and mix 10g eugenol-based epoxy resin and 0.06g platinum catalyst at 110°C. Add the mixture of toluene and reflux for 3 hours, then add 5% of the total mass of activated carbon to the reaction system and continue stirring for 40 minutes. Filter with suction to remove the activated carbon adsorbed with the platinum catalyst. The lower liquid obtained by suction filtration is distilled under reduced pressure to obtain Silicone epoxy resin B.

Silicone epoxy resin B:

Preparation of the resin composition: Add 5g of the curing agent methylhexahydrophthalic anhydride and 0.1g of the catalyst dimethylbenzylamine BDMA to 10g of the silicone epoxy resin B prepared in Example 2, and stir evenly to obtain a resin composition.

Example 3

Preparation of silicone epoxy resin C: (1) Add the raw materials according to 4-allylphenol: epichlorohydrin: sodium hydroxide: tetramethylammonium bromide = 35g: 230g: 35g: 0.7g into 500mL three ports In the bottle, the reaction temperature is maintained at 65-70°C. After refluxing for 2.5 hours, the unreacted epichlorohydrin is evaporated, then methyl isobutyl ketone is added to fully dissolve it, and then a certain amount of deionized water is added to separate the layers to obtain the above The supernatant was washed with deionized water several times until pH=7, and then dried under vacuum to obtain 4-vinylphenyl glycidyl ether.

(2) Add 2.2g pentamethylcyclopentasiloxane and an appropriate amount of toluene into a 250mL single-neck bottle, add a mixture of 10g 4-vinylphenyl glycidyl ether, 0.06g platinum catalyst and toluene at 110°C, and reflux React for 3 hours, then add 5% of the total mass of activated carbon to the reaction system and continue stirring for 40 minutes. Filter with suction to remove the activated carbon adsorbed with the platinum catalyst. The lower liquid obtained by suction filtration is distilled under reduced pressure to obtain silicone epoxy resin C.

Silicone epoxy resin C:

Preparation of the resin composition: Add 5g of the curing agent methylhexahydrophthalic anhydride and 0.1g of the catalyst dimethylbenzylamine BDMA to 9g of the silicone epoxy resin C prepared in Example 3, and stir evenly to obtain a resin composition.

Example 4

Preparation of silicone epoxy resin D: (1) Combine the raw materials as follows: 5-allyl-1-naphthol: epichlorohydrin: sodium hydroxide: tetramethylammonium bromide = 55g: 230g: 35g: 0.7g Add it to a 500mL three-necked flask, maintain the reaction temperature at 65-70°C, reflux for 2.5 hours, spin off the unreacted epichlorohydrin, add methyl isobutyl ketone to fully dissolve it, and then add a certain amount of deionized water. layer to obtain a supernatant, which is washed with deionized water several times until pH=7, and then dried in a vacuum to obtain a naphthalene-based epoxy resin.

(2) Add 2.7g tetramethylcyclotetrasiloxane (D4H) and an appropriate amount of toluene into a 250mL single-neck bottle, add a mixture of 15g naphthalene epoxy resin, 0.06g platinum catalyst and toluene at 110°C, and reflux React for 3 hours, then add 5% of the total mass of activated carbon to the reaction system and continue stirring for 40 minutes. Filter with suction to remove the activated carbon adsorbed with the platinum catalyst. The lower liquid obtained by suction filtration is distilled under reduced pressure to obtain silicone epoxy resin D.

Silicone epoxy resin D:

Preparation of the resin composition: Add 5g of the curing agent methylhexahydrophthalic anhydride and 0.1g of the catalyst dimethylbenzylamine BDMA to 9g of the silicone epoxy resin D prepared in Example 4, and stir evenly to obtain a resin composition.

Example 5

Preparation of silicone epoxy resin E: (1) Combine the raw materials as follows: 4-hydroxy-4'-allylbiphenyl: epichlorohydrin: sodium hydroxide: tetramethylammonium bromide = 50g: 230g: 35g: Add 0.7g into a 500mL three-necked flask, maintain the reaction temperature at 65-70°C, reflux for 2.5 hours, spin off the unreacted epichlorohydrin, add methyl isobutyl ketone to fully dissolve it, and then add quantitative deionization Separate the water layers to obtain a supernatant, wash the supernatant with deionized water several times until pH=7, and then vacuum-dry to obtain biphenyl epoxy resin.

(2) Add 2.7g tetramethylcyclotetrasiloxane (D4H) and an appropriate amount of toluene into a 250mL single-neck bottle, add a mixture of 13g biphenyl epoxy resin, 0.06g platinum catalyst and toluene at 110°C, and reflux React for 3 hours, then add 5% of the total mass of activated carbon to the reaction system and continue stirring for 40 minutes. Filter with suction to remove the activated carbon adsorbed with the platinum catalyst. Use suction filtration. The obtained lower liquid was distilled under reduced pressure to obtain silicone epoxy resin E.

Silicone Epoxy Resin E:

Preparation of the resin composition: Add 5g of the curing agent methylhexahydrophthalic anhydride and 0.1g of the catalyst dimethylbenzylamine BDMA to 8.5g of the silicone epoxy resin E prepared in Example 5, and stir evenly to obtain a resin composition.

Comparative example 1

A kind of bisphenol A type epoxy resin, its structural formula is shown as the following formula (i):

A resin composition: the bisphenol A type epoxy resin of Comparative Example 1 is mixed with methylhexahydrophthalic anhydride and the catalyst dimethylbenzylamine BDMA to obtain a resin composition.

The silicone epoxy resin prepared in Examples 1 to 5 of the present application and the bisphenol A-type epoxy resin in Comparative Example 1 were subjected to a viscosity test. The cured products of the resin composition prepared in Examples 1 to 5 of the present application and the cured product of the resin composition of Comparative Example 1 were subjected to dielectric property test, elastic modulus test, glass transition temperature Tg test and water absorption test. . The viscosity of the epoxy resin at room temperature, the dielectric constant of the cured resin composition at 5 MHz, the elastic modulus at 25°C, the glass transition temperature Tg, and the water absorption are shown in Table 1. Among them, the viscosity of the epoxy resin is measured with a viscometer; the dielectric properties of the cured product of the resin composition are measured with a spectrum analyzer, and the test frequency is 5MHz; the elastic modulus of the cured product of the resin composition is measured with a three-point universal testing machine The bending mode is used for testing; Tg is tested using a dynamic thermomechanical analyzer; the water absorption test is tested using the PCT test (commonly known as the pressure cooker cooking test or saturated steam test).

Table 1 Summary of test results of each embodiment and comparative example

It can be known from the results in Table 1 that the epoxy resins of Examples 1-5 of the present application have lower viscosity at room temperature, lower than the viscosity of the epoxy resin of Comparative Example 1, and lower than the viscosity of the mainstream liquid epoxy resin currently on the market. . In addition, Figure 5 shows the application practice Viscosity curves of eugenol-based epoxy resin (EUEP) and silicone epoxy resin A in Example 1. It can be seen from Figure 5 that compared with eugenol-based epoxy resin (EUEP), the viscosity of the silicone epoxy resin A in Example 1 of the present application is significantly reduced. The viscosity of silicone epoxy resin A in Example 1 of this application is only 0.1 Pa.s at room temperature.

It can be seen from the results in Table 1 that the dielectric constant (Dk) of the cured products of the resin compositions of Examples 1-5 of the present application is 3.0 or less at 5 MHz, while the cured product of the resin composition of Comparative Example 1 is The dielectric constant (Dk) at 5 MHz is 3.4, and the dielectric constant of the cured products of the resin compositions of Examples 1-5 of the present application is significantly lower than that of Comparative Example 1. It can be seen from this that the cured product of the resin composition in the embodiment of the present application has obvious low dielectric properties. Figure 6 shows the dielectric property results of the cured product of the resin composition prepared in Example 1 of the present application. It can be seen from Figure 6 that at 5 MHz, the dielectric constant (Dk) of the cured product of the resin composition prepared in Example 1 of the present application is about 2.9, the dielectric loss is about 0.012, and it has low dielectric properties.

It can be seen from the results in Table 1 that the elastic modulus of the cured products of the resin compositions of Examples 1-5 of the present application is low, which is lower than that of the currently commonly used bisphenol A epoxy resin composition shown in Comparative Example 1. The elastic modulus of the material is 3.0 GPa. Therefore, the resin composition of the embodiment of the present application has low modulus properties, that is, it has high flexibility, which can improve the peeling force of the chip during chip sealing and packaging and improve the reliability of the chip.

It can be known from the results in Table 1 that the glass transition temperature Tg of the cured resin compositions of Examples 1-5 of the present application is greater than or equal to 120°C. It has a higher glass transition temperature Tg, which can improve its application in electronics. Safety and reliability in the field of sealed packaging.

It can be known from the results in Table 1 that the water absorption rates of the cured products of the resin compositions of Examples 1-5 of the present application are low, all below 0.15%, which is lower than the currently commonly used bisphenol A epoxy shown in Comparative Example 1. The cured product of the resin composition has a water absorption rate of 0.2%. Therefore, the resin composition in the embodiment of the present application has low water absorption performance, which can improve the safety and reliability of its application in the field of electronic sealing packaging.

The epoxy resin provided in the embodiments of the present application can have low viscosity at room temperature, low dielectric properties, good flexibility, high glass transition temperature Tg and low water absorption, because the epoxy resin molecular structure also contains cyclic silica. An alkane ring and an epoxy group containing an arylene structure connected to a cyclic siloxane ring. The cyclic siloxane ring can loosen the entire molecular chain of the epoxy resin and reduce the friction between the molecular chains. The force and entanglement increase the free volume, which can effectively reduce the viscosity, improve the flexibility, and reduce the water absorption and dielectric properties of the epoxy resin; the epoxy group containing the arylene structure has a certain rigidity and can better Keep the Tg of the epoxy resin at a high level; under the joint action of the two types of group structures, the silicone epoxy resin in the embodiments of the present application can maintain the Tg of the system at a high level while improving flexibility. , and has low viscosity, low dielectric, and low water absorption properties, which can better meet the sealing packaging needs of semiconductor devices and electronic devices.

Claims

An epoxy resin, characterized in that the epoxy resin includes a cyclic siloxane ring and at least one group represented by formula (A) connected to a silicon atom on the cyclic siloxane ring,

In formula (A), Z is a substituted or unsubstituted arylene group; n is an integer greater than or equal to 2.
The epoxy resin of claim 1, wherein the substituted or unsubstituted arylene group includes a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted arylene group, Any of the subfused ring aromatic groups.
The epoxy resin of claim 1 or 2, wherein the substituent groups on the substituted arylene group include substituted or unsubstituted alkyl groups, substituted or unsubstituted cycloalkyl groups, substituted or unsubstituted cycloalkyl groups, Any one of a substituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, and adjacent substituent groups can be connected to form a ring.
The epoxy resin of claim 2 or 3, wherein Z is a substituted or unsubstituted phenylene group, and the formula (A) is expressed as formula (A1):

In formula (A1), the four R1s are independently selected from a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, and a substituted or unsubstituted aryl group. Any one of the group, substituted or unsubstituted aryloxy group, adjacent R 1 can be connected to form a ring.
The epoxy resin of claim 2 or 3, wherein Z is a substituted or unsubstituted biphenylene group, and the formula (A) is expressed as formula (A2):

In formula (A2), 4 R 2 and 4 R 3 are independently selected from hydrogen atoms, substituted or unsubstituted alkyl groups, substituted or unsubstituted cycloalkyl groups, substituted or unsubstituted alkoxy groups, substituted Or any one of unsubstituted aryl, substituted or unsubstituted aryloxy, adjacent R 2 can be connected to form a ring, adjacent R 3 can be connected to form a ring; R is a bridging group, and R is selected From any one of single bonds, oxygen atoms, sulfur atoms, disulfide bonds, sulfone groups, substituted or unsubstituted alkylene groups, substituted or unsubstituted alkyleneoxy groups; m is 1 or 2; n is greater than Or an integer equal to 2.
The epoxy resin of claim 2 or 3, wherein the substituted or unsubstituted fused ring aryl group includes a substituted or unsubstituted naphthylene group, a substituted or unsubstituted binaphthylene group, a substituted Or an unsubstituted anthracenylene group, a substituted or unsubstituted phenylene group, a substituted or unsubstituted fluorenylene group, a substituted or unsubstituted pyrenylene group, or a substituted or unsubstituted perylene group.
The epoxy resin of claim 6, wherein Z is a substituted or unsubstituted naphthylene group, and the formula (A) is represented by formula (A3):

In formula (A3), 6 R 4 are independently selected from a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, and a substituted or unsubstituted aryl group. Any one of the group, substituted or unsubstituted aryloxy group, adjacent R 4 can be connected to form a ring; n is an integer greater than or equal to 2.
The epoxy resin according to any one of claims 1 to 7, characterized in that the epoxy resin has a structure represented by formula (I):

In formula (I), R 5 is a hydrogen atom or a group represented by formula (A). Among a R 5 , at least one R 5 is a group represented by formula (A); a is greater than or equal to an integer of 3.
The epoxy resin of claim 8, wherein among the a R 5s , b R 5s are groups represented by formula (A), 1≤b≤a.
The epoxy resin according to claim 8 or 9, wherein a is an integer from 3 to 6.
The epoxy resin according to any one of claims 1 to 10, characterized in that the epoxy resin includes any compound represented by formula (1) to formula (4):

In Formula (1) to Formula (4), Z is a substituted or unsubstituted arylene group; n is an integer greater than or equal to 2.
The epoxy resin of claim 3, wherein the substituted or unsubstituted alkyl group is a substituted or unsubstituted C 1 -C 10 alkyl group; the substituted or unsubstituted cycloalkyl group is a substituted Or unsubstituted C 3 -C 10 cycloalkyl; the substituted or unsubstituted alkoxy group is a substituted or unsubstituted C 1 -C 10 alkoxy group; the substituted or unsubstituted aryl group is a substituted or Unsubstituted C 6 -C 20 aryl group; the substituted or unsubstituted aryloxy group is a substituted or unsubstituted C 6 -C 20 aryloxy group.
The epoxy resin according to claim 3 or 12, wherein the substituted alkyl group includes any one of epoxyalkyl group, epoxyalkyl ether group, arylalkyl group and aminoalkyl group. .
A method for preparing epoxy resin, characterized by including:

The first raw material represented by formula (a) and cyclic siloxane are added to a solvent, and a hydrosilylation reaction occurs under the action of a platinum catalyst to obtain an epoxy resin. The epoxy resin includes a cyclic siloxane ring. and at least one group represented by formula (A) connected to a silicon atom on the cyclic siloxane ring,

In formula (a) and formula (A), Z is a substituted or unsubstituted arylene group; n is an integer greater than or equal to 2.
The preparation method of claim 14, wherein the cyclic siloxane includes a number of interconnected -Si-O-, and the first raw material represented by formula (a) and the cyclic siloxane The molar ratio of siloxane is (a:1) to (1.2a:1).
The preparation method according to claim 14, wherein the platinum catalyst includes at least one of castor platinum catalyst and chloroplatinic acid; the amount of the platinum catalyst is the amount of the first raw material and the ring. 15ppm-30ppm of the total mass of siloxane; the solvent includes one or more of tetrahydrofuran and toluene.
The preparation method according to claim 14, characterized in that the preparation process of the first raw material represented by formula (a) includes:

Mix the precursor represented by formula (a-1), epichlorohydrin, and alkali, and react under the action of an ammonium salt catalyst at 60°C-80°C to obtain the first raw material represented by formula (a);
H 2 C=(CH 2 ) n-1 -Z-OH formula (a-1)

In formula (a-1), Z is a substituted or unsubstituted arylene group; n is an integer greater than or equal to 2.
The preparation method according to claim 17, characterized in that the molar ratio of the precursor represented by the formula (a-1), epichlorohydrin, alkali and ammonium salt catalyst is 1: (4-15): (1.5-5): (0.01-0.3).
A resin composition, characterized in that the resin composition includes the epoxy resin and curing agent according to any one of claims 1-13.
The resin composition of claim 19, further comprising a filler.
The resin composition according to claim 19 or 20, characterized in that the resin composition further includes at least one of a curing accelerator and an auxiliary agent.
The resin composition according to any one of claims 19 to 21, characterized in that the resin composition includes the following mass percentages of each component: the epoxy resin: 1%-50%, the Curing agent: 1%-70%, filler: 0-95%, curing accelerator: 0-10%, additives: 0-10%.
The resin composition according to any one of claims 19 to 22, characterized in that the resin composition further includes other epoxy resins.
A cured product, characterized in that the cured product includes a cured product of the resin composition according to any one of claims 19 to 23.
A sealing packaging material for sealing packaging of semiconductor devices or electronic devices, characterized in that the sealing packaging material includes the resin composition of any one of claims 19-23 and/or a portion of the resin composition. solidified material.
A sealed package, including a semiconductor sealed package or an electronic device sealed package, characterized in that the sealed package includes the cured product according to claim 24.
A semiconductor sealed package, characterized in that it includes a substrate, a chip disposed on the substrate, and a plastic package for sealing and packaging the chip, and the plastic package includes the cured product according to claim 24.
The semiconductor sealing package of claim 27, wherein a plurality of welding bumps are provided on a side surface of the chip facing the substrate, and a bottom filling adhesive layer is provided between the welding bumps. The underfill glue layer includes the cured product.
An electronic device, characterized in that the electronic device includes the sealed package of claim 26 or the semiconductor sealed package of any one of claims 27-28.