Toughened resin composition, build-up film, method for manufacturing the same, and package substrate

Abstract

The application relates to the technical field of packaging boards, in particular to a toughened resin composition, a build-up film and a preparation method thereof and a packaging board. The toughened resin composition comprises the following raw materials in parts by weight: 20-50 parts of a toughened prepolymer, 10-40 parts of a functional resin, 10-60 parts of a curing agent, 1-10 parts of a curing accelerator and 50-200 parts of inorganic fillers; the raw materials of the toughened prepolymer comprise an acrylate type polyphenyl ether resin and an amino organosilicon resin. The toughened resin composition is made into a build-up film, the build-up film has excellent anti-cracking performance, high glass transition temperature, good heat resistance, low water absorption and extremely strong dielectric performance, and is suitable for preparing high-performance packaging boards.

Description

Technical Field

[0001] This application relates to the field of encapsulation substrate technology, and in particular to a toughening resin composition, a layered film, a method for preparing the same, and an encapsulation substrate. Background Technology

[0002] As electronic products evolve towards miniaturization, thinner and lighter designs, higher functionality, and enhanced security, electronic circuits are also developing towards multilayering and higher wiring density. Among these advancements, Flip Chip Ball Grid Array (FCBGA) technology is an advanced packaging process that involves flipping a chip upside down and attaching it to a carrier board, connecting the chip and the board via solder balls to achieve electrical connection and signal transmission. FCBGA technology excels in high speed, high density, and high reliability, and is widely used in fields such as computers, communications, medical devices, consumer electronics, and industrial control.

[0003] Compared to other packaging substrate technologies, FCBGA technology offers higher integration, smaller package size, higher reliability, and lower power consumption. Therefore, it places higher demands on the performance of its main raw material, the build-up film, requiring excellent mechanical properties, heat resistance, and dielectric properties. With the advent of the artificial intelligence (AI) era, the amount of information processed and the speed of information transmission are exploding, requiring FCBGA packaging substrates to have lower dielectric constants and lower dielectric losses to reduce transmission losses. However, traditional resin compositions cannot simultaneously possess high heat resistance, high mechanical strength, and excellent dielectric properties, making them difficult to apply in the fabrication of FCBGA packaging substrates. Summary of the Invention

[0004] Therefore, it is necessary to provide a toughening resin composition, a layered film, a method for preparing the same, and a packaging substrate to solve the problem that traditional resin compositions cannot simultaneously possess high heat resistance, high mechanical strength, and excellent dielectric properties, making them difficult to apply to the preparation of FCBGA packaging substrates.

[0005] The above-mentioned objective of this application is achieved through the following technical solution:

[0006] In a first aspect, this application provides a toughening resin composition comprising the following raw materials in parts by weight:

[0007] ;

[0008] The raw materials for the toughening prepolymer include acrylate-type polyphenylene ether resin and amino silicone resin, wherein the amino silicone resin has a structure as shown in general formula (I):

[0009] (I);

[0010] Where p is the degree of aggregation, and p is selected from any integer from 1 to 50;

[0011] Each time R appears, it is independently selected from one or more of the following: ether bond, substituted or unsubstituted alkylene group, substituted or unsubstituted phenyl group, substituted or unsubstituted biphenyl group, substituted or unsubstituted naphthyl group, and substituted or unsubstituted dicyclopentadienyl group.

[0012] In some embodiments, the acrylate-type polyphenylene ether resin has a structure as shown in general formula (III):

[0013] (III);

[0014] Where m and n are each independently selected from positive integers, and the sum of m and n is 5 to 60;

[0015] Y is absent, or is selected from C1~C3 alkylene groups.

[0016] In some embodiments, the mass ratio of the acrylate-type polyphenylene ether resin to the amino silicone resin is 100:(60~100).

[0017] In some embodiments, the method for preparing the toughened prepolymer includes the following steps:

[0018] The acrylate-type polyphenylene ether resin and the amino silicone resin are mixed and prepolymerized at 100℃~180℃ for 90min~240min to obtain the toughened prepolymer.

[0019] In some embodiments, the functional resin includes one or more of epoxy resin, benzoxazine resin, and hydrocarbon resin.

[0020] In some embodiments, the epoxy resin includes one or more of the following: bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthalene type epoxy resin, phosphorus-containing epoxy resin, unsaturated epoxy resin, phenolic type epoxy resin, o-cresol type epoxy resin, bisphenol A phenolic epoxy resin, multifunctional epoxy resin, alicyclic epoxy resin, resorcinol epoxy resin, rubber-modified epoxy resin, biphenyl epoxy resin, and dicyclopentadiene epoxy resin.

[0021] In some embodiments, the benzoxazine resin includes one or more of the following: bisphenol A type benzoxazine resin, bisphenol F type benzoxazine resin, bisphenol S type benzoxazine resin, main-chain type benzoxazine resin, phosphorus-containing benzoxazine resin, dicyclopentadiene benzoxazine resin, biphenyl type benzoxazine resin, tetraphenol ethane benzoxazine resin, and naphthalene type benzoxazine resin.

[0022] In some embodiments, the hydrocarbon resin includes one or more of polybutadiene and styrene-butadiene copolymer.

[0023] In some embodiments, the curing agent includes one or more of amine curing agents, phenolic curing agents, acid anhydride curing agents, cyanate ester curing agents, reactive ester curing agents, and olefin curing agents.

[0024] In some embodiments, the curing accelerator includes one or more of tertiary amine accelerators, imidazole accelerators, peroxide accelerators, organophosphorus accelerators, and transition metal carboxylate accelerators.

[0025] In some embodiments, the inorganic filler includes one or more of modified silica and modified alumina.

[0026] In some embodiments, the toughening resin composition further includes additives and solvents, the additives including one or more of dispersants, leveling agents, defoamers, and coupling agents.

[0027] In a second aspect, this application provides a laminated film comprising the toughening resin composition described above.

[0028] A third aspect of this application provides a method for preparing an extended film, comprising the following steps:

[0029] The toughening resin composition described above is applied to the support to obtain a liquid film;

[0030] The liquid film is dried to obtain the layered film.

[0031] In some embodiments, the drying process includes the following steps: drying at a constant temperature of 100℃~200℃ for 5min~15min.

[0032] In some embodiments, the support comprises one or more of a polymer film and a metal foil.

[0033] In some embodiments, the thickness of the support is 3 μm to 105 μm.

[0034] In some embodiments, the thickness of the liquid film is 5 μm to 150 μm.

[0035] In a fourth aspect, this application provides an encapsulation substrate comprising the toughening resin composition as described above, or comprising the laminate as described above, or comprising the laminate prepared by the method described above.

[0036] This application has at least the following beneficial effects:

[0037] In the toughening resin composition provided in this application, the acrylate functional groups in the acrylate-type polyphenylene ether resin have high reactivity and can combine with the amino groups in the amino organosilicon resin, thereby grafting organosiloxane branches into the polyphenylene ether structure. This results in the cured product exhibiting excellent heat resistance and mechanical properties while maintaining good dielectric properties. Furthermore, by rationally combining the toughening prepolymer, functional resin, curing agent, curing accelerator, and inorganic filler in specific proportions, not only can the number of polar groups in the composition be reduced, effectively lowering the dielectric constant and dielectric loss, but the heat resistance and mechanical properties of the composition can also be significantly improved. Therefore, the toughening resin composition provided in this application, when used to prepare a laminated film, exhibits excellent crack resistance, high glass transition temperature, good heat resistance, low water absorption, and extremely strong dielectric properties, making it suitable for preparing high-performance encapsulation substrates. Attached Figure Description

[0038] To more clearly illustrate the technical solutions in the embodiments of this application and to more completely understand this application and its beneficial effects, the drawings used in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0039] Figure 1 This is a photograph of the cut laminated film from Example 1.

[0040] Figure 2 This is a picture of the actual product after cutting the laminated film of Comparative Example 1. Detailed Implementation

[0041] To facilitate understanding of this application, the following detailed description is provided in conjunction with specific embodiments. However, this application can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a more thorough and complete understanding of the disclosure of this application.

[0042] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application.

[0043] In this application, "and / or" means any and all combinations of one or more of the related listed items. "At least one" means one or more, such as one, two, or more. "Multiple" or "several" means at least two, such as two, three, etc., and "multi-layered" means at least two layers, such as two, three, etc., unless otherwise expressly and specifically defined. In the description of this application, "several" means at least one, such as one, two, etc., unless otherwise expressly and specifically defined.

[0044] When a numerical range is disclosed in this application, the range is considered continuous and includes the minimum and maximum values ​​of the range, as well as every value between the minimum and maximum values. Furthermore, when the range refers to an integer, it includes every integer between the minimum and maximum values ​​of the range. Additionally, when multiple ranges are provided to describe a feature or characteristic, the ranges may be merged. In other words, unless otherwise specified, all ranges disclosed in this application should be understood to include any and all subranges to which they are included.

[0045] Unless otherwise specified, all steps in this application may be performed sequentially or randomly. For example, the method includes steps (a) and (b), indicating that the method may include steps (a) and (b) performed sequentially, or it may include steps (b) and (a) performed sequentially. For example, the method may also include step (c), indicating that step (c) may be added to the method in any order. For example, the method may include steps (a), (b), and (c), or it may include steps (a), (c), and (b), or it may include steps (c), (a), and (b), etc.

[0046] In this application, "above" or "below" includes the number itself. For example, "below 1" includes 1.

[0047] Unless otherwise specified, the temperature parameters in this application are permitted to be either constant-temperature treatment or variations within a certain temperature range. It should be understood that the constant-temperature treatment allows temperature fluctuations within the precision range of the instrument control, such as ±5℃, ±4℃, ±3℃, ±2℃, or ±1℃.

[0048] In this application, room temperature refers to indoor temperature, normal temperature, or general temperature. Generally, room temperature can be any of the following temperature ranges: 23℃±2℃, 25℃±5℃, or 20℃±5℃.

[0049] the term

[0050] Unless otherwise stated or in case of conflict, the terms or phrases used in this application shall have the following meanings:

[0051] In this application, when a substituent of the same symbol appears multiple times, the substituents may be the same or different from each other. If the general formula contains multiple R, then the R may be the same or different from each other.

[0052] "Substituted or unsubstituted" indicates that the defined group may or may not be substituted. When the defined group is substituted, it should be understood that the defined group can be substituted by one or more substituents acceptable in the art, suitable substituents including but not limited to: C1~C1. 30 Alkyl, cycloalkyl containing 3 to 20 ring atoms, heterocyclic group containing 3 to 20 ring atoms, aryl containing 6 to 20 ring atoms, heteroaryl containing 5 to 20 ring atoms, silyl, carbonyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, halocarbamoyl, formyl, amino (-N(R)2), cyano, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxyl, trifluoromethyl, nitro or halogen, and the above groups may be further substituted by substituents acceptable in the art; it is understood that each R in -N(R)2 is independently substituted by a group acceptable in the art, including but not limited to: H, C1 to C6 alkyl, cycloalkyl containing 3 to 8 ring atoms, heterocyclic group containing 3 to 8 ring atoms, aryl or heteroaryl containing 5 to 10 ring atoms.

[0053] "Number of ring atoms" refers to the number of atoms in the ring itself of a compound formed by atomic bonds (e.g., monocyclic compounds, fused-ring compounds, cross-linked compounds, carbocyclic compounds, heterocyclic compounds). When the ring is substituted by a substituent, the atoms contained in the substituent are not included in the ring-forming atoms. The same applies to the "number of ring atoms" as described below unless otherwise specified. For example, the number of ring atoms in a benzene ring is 6, in a naphthalene ring it is 10, and in a thiophene group it is 5.

[0054] "Alkyl" refers to a monovalent residue formed by the loss of a hydrogen atom from a saturated hydrocarbon containing a primary (normal) carbon atom, a secondary carbon atom, a tertiary carbon atom, a quaternary carbon atom, or a combination thereof. Alkyl can represent straight-chain, branched, and / or cyclic alkyl. The number of carbon atoms in an alkyl group can be 1–50, 1–30, 1–20, 1–10, or 1–6. Phrases containing this term, such as "C1–C9 alkyl," refer to alkyl groups containing 1–9 carbon atoms, and each occurrence can independently be C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, C7 alkyl, C8 alkyl, or C9 alkyl. Suitable examples include, but are not limited to: methyl (Me, -CH3), ethyl (Et, -CH2CH3), 1-propyl (n-Pr, n-propyl, -CH2CH2CH3), 2-propyl (i-Pr, i-propyl, -CH(CH3)2), 1-butyl (n-Bu, n-butyl, -CH2CH2CH2CH3), 2-methyl-1-propyl (i-Bu, i-butyl, -CH2CH(CH3)2), 2-butyl (s-Bu, s-butyl, -CH(C H3)CH2CH3), 2-methyl-2-propyl (t-Bu, t-butyl, -C(CH3)3), 1-pentyl (n-pentyl, -CH2CH2CH2CH2CH3), 2-pentyl (-CH(CH3)CH2CH2CH3), 3-pentyl (-CH(CH2CH3)2), 2-methyl-2-butyl (-C(CH3)2CH2CH3), 3-methyl-2-butyl (-CH(CH3)CH(CH3)2), 3-methyl-1-butyl (- CH2CH2CH(CH3)2), 2-methyl-1-butyl (-CH2CH(CH3)CH2CH3), 1-hexyl (-CH2CH2CH2CH2CH2CH3), 2-hexyl (-CH(CH3)CH2CH2CH2CH3), 3-hexyl (-CH(CH2CH3)(CH2CH2CH3)), 2-methyl-2-pentyl (-C(CH3)2CH2CH2CH3), 3-methyl-2-pentyl (-CH(CH3)CH( CH3)CH2CH3), 4-methyl-2-pentyl (-CH(CH3)CH2CH(CH3)2), 3-methyl-3-pentyl (-C(CH3)(CH2CH3)2), 2-methyl-3-pentyl (-CH(CH2CH3)CH(CH3)2), 2,3-dimethyl-2-butyl (-C(CH3)2CH(CH3)2), 3,3-dimethyl-2-butyl (-CH(CH3)C(CH3)3, octyl (-(CH2)7CH3).

[0055] "Alkylene" refers to a hydrocarbon group derived from an alkyl group by removing one hydrogen atom, forming a group with two monovalent groups. It can be a saturated branched alkyl group or a saturated straight-chain alkyl group. For example, "C1-C9 alkylene" refers to an alkyl group containing 1-9 carbon atoms, and each occurrence can be independently C1, C4, C5, C6, C7, C8, or C9 alkylene. Suitable examples include, but are not limited to: methylene (-CH2-), 1,1-ethyl (-CH(CH3)-), 1,2-ethyl (-CH2CH2-), 1,1-propyl (-CH(CH2CH3)-), 1,2-propyl (-CH2CH(CH3)-), 1,3-propyl (-CH2CH2CH2-), and 1,4-butyl (-CH2CH2CH2CH2-).

[0056] "Cycloalkyl" refers to a non-aromatic hydrocarbon containing a ring of carbon atoms, which can be monocycloalkyl, spirocycloalkyl, or bridged cycloalkyl. Phrases containing this term, such as "C3-C9 cycloalkyl," refer to cycloalkyl groups containing 3 to 9 carbon atoms, and each occurrence can independently be C3, C4, C5, C6, C7, C8, or C9 cycloalkyl. Suitable examples include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl. Additionally, "cycloalkyl" may contain one or more double bonds; representative examples of cycloalkyl groups containing double bonds include cyclopentenyl, cyclohexenyl, cyclopentadienyl, cyclohexadienyl, cyclobutadienyl, and dicyclopentadienyl (DCPD) group. The structure of the dicyclopentadienyl or DCPD group is as follows:

[0057] .

[0058] "Aryl" refers to an aromatic hydrocarbon group derived from an aromatic ring compound by removing one hydrogen atom. It can be a monocyclic aryl, a fused-ring aryl, or a polycyclic aryl. For polycyclic compounds, at least one ring must be an aromatic ring system. For example, "C5~C..." 20 "Aryl" refers to an aryl group containing 5 to 20 carbon atoms. Each time it appears, it can independently be C5 aryl, C6 aryl, C7 aryl, C8 aryl, C9 ... 10 Aryl, C 14 Aryl, C 18 Aryl or C 20 Aryl groups. Suitable examples include, but are not limited to: benzene, biphenyl, naphthalene, anthracene, phenanthrene, dinaphthalene, triphenylene and their derivatives.

[0059] In a first aspect, this application provides a toughening resin composition to solve the problem that traditional resin compositions cannot simultaneously possess high heat resistance, high mechanical strength, and excellent dielectric properties, making them difficult to apply to the preparation of FCBGA packaging substrates.

[0060] In some embodiments, the toughening resin composition comprises the following raw materials in parts by weight:

[0061] ;

[0062] The raw materials for the toughening prepolymer include acrylate-type polyphenylene ether resin and amino silicone resin, the amino silicone resin having a structure as shown in general formula (I):

[0063] (I);

[0064] Where p is the degree of aggregation, and p is selected from any integer from 1 to 50;

[0065] Each time R appears, it is independently selected from one or more of the following: ether bond, substituted or unsubstituted alkylene group, substituted or unsubstituted phenyl group, substituted or unsubstituted biphenyl group, substituted or unsubstituted naphthyl group, and substituted or unsubstituted dicyclopentadienyl group.

[0066] Understandably, polyphenylene ether (PPO) resins contain a large number of benzene rings in their molecular structure and lack strongly polar groups, resulting in low dielectric constant (Dk) and low dielectric loss (Df). This makes them increasingly ideal materials for products with low dielectric constant and low dielectric loss. However, traditional PPO resins are mostly hydroxyl-terminated, with low reactivity of hydroxyl groups, making it difficult to form a high-crosslink density curing system. This leads to poor mechanical properties and heat resistance, limiting their application in high-performance encapsulation substrates.

[0067] In the toughening resin composition provided in this application, the acrylate functional groups in the acrylate-type polyphenylene ether resin have high reactivity and can combine with the amino groups in the amino organosilicon resin, thereby grafting organosiloxane branches into the polyphenylene ether structure. This results in the cured product exhibiting excellent heat resistance and mechanical properties while maintaining good dielectric properties. Furthermore, by rationally combining the toughening prepolymer, functional resin, curing agent, curing accelerator, and inorganic filler in specific proportions, not only can the number of polar groups in the composition be reduced, effectively lowering the dielectric constant and dielectric loss, but the heat resistance and mechanical properties of the composition can also be significantly improved. Therefore, the toughening resin composition provided in this application, when used to prepare a laminated film, exhibits excellent crack resistance, high glass transition temperature, good heat resistance, low water absorption, and extremely strong dielectric properties, making it suitable for preparing high-performance encapsulation substrates.

[0068] As an example, in the toughening resin composition, the toughening prepolymer may be present in parts by weight including but not limited to 20 parts, 22 parts, 25 parts, 28 parts, 30 parts, 32 parts, 35 parts, 38 parts, 40 parts, 42 parts, 45 parts, 48 ​​parts or 50 parts, and may further be 20 parts to 40 parts.

[0069] As an example, in the toughening resin composition, the functional resin is present in parts by weight including but not limited to 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, 28 parts, 30 parts, 32 parts, 35 parts, 38 parts or 40 parts, and may further be selected as 10 parts to 30 parts.

[0070] As an example, in the toughening resin composition, the curing agent is present in parts by weight including but not limited to 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, 28 parts, 30 parts, 32 parts, 35 parts, 38 parts, 40 parts, 42 parts, 45 parts, 48 ​​parts, 50 parts, 52 parts, 55 parts, 58 parts or 60 parts, and may further be selected as 10 parts to 40 parts.

[0071] As an example, in the toughening resin composition, the curing accelerator is present in parts by weight including but not limited to 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts or 10 parts, and may further be 1 part to 5 parts.

[0072] As an example, in the toughening resin composition, the inorganic filler may be present in parts by weight of, but not limited to, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190 or 200 parts, and may further be selected as 50 to 150 parts.

[0073] In some embodiments, the toughening resin composition comprises the following raw materials in parts by weight:

[0074] .

[0075] In some embodiments, the toughening resin composition comprises the following raw materials in parts by weight:

[0076] .

[0077] As an example, in amino silicone resins, p is a polymer, and the value of p includes, but is not limited to, 1, 2, 5, 8, 10, 12, 15, 18, 20, 22, 25, 28, 30, 32, 35, 38, 40, 42, 45, 48 or 50.

[0078] As an example, in amino silicone resins, each occurrence of R is independently selected from one or more of the following: ether bond (-O-), substituted or unsubstituted alkylene group, substituted or unsubstituted phenyl group, substituted or unsubstituted biphenyl group, substituted or unsubstituted naphthyl group, and substituted or unsubstituted dicyclopentadienyl (DCPD) group. "Substituted or unsubstituted" indicates that the alkylene group, phenyl group, biphenyl group, naphthyl group, and DCPD group may or may not be substituted. Suitable substituents include, but are not limited to: C1-C6 alkyl group, C1-C6 alkoxy group, cycloalkyl group containing 3-8 ring atoms, heterocyclic group containing 3-8 ring atoms, aryl group containing 6-10 ring atoms, heteroaryl group containing 5-10 ring atoms, halogen, amino, nitro, hydroxyl, carboxyl, ester, or cyano group. Further optionally, each occurrence of R is independently selected from one or more of the following: -O-, C1-C3 alkylene group, phenyl group, biphenyl group, naphthyl group, and dicyclopentadienyl (DCPD) group. Among them, C1~C3 alkylene groups include, but are not limited to: -CH2-, -CH(CH3)-, -CH2CH2-, -CH(CH2CH3)-, -CH2CH(CH3)-, and -CH2CH2CH2-. Further, optionally, each occurrence of R is independently selected from -O- or -CH2-.

[0079] In some embodiments, the amino silicone resin has a structure as shown in general formula (II-1) or (II-2):

[0080] (Ⅱ-1);

[0081] (Ⅱ-2).

[0082] In some embodiments, the amino silicone resin is selected from the amino silicone resins of Shin-Etsu Chemical Industry Co., Ltd., and the model can be any one of PAM-E, KF-8010, X-22-161A, X-22-161B, KF-8012, KF-8008, and X-22-1660B-3, with the following physical properties:

[0083]

[0084] In some embodiments, the acrylate-type polyphenylene ether resin has a structure as shown in general formula (III):

[0085] (III);

[0086] Where m and n are each independently selected from positive integers, and the sum of m and n is 5 to 60;

[0087] Y is absent, or is selected from C1~C3 alkylene groups;

[0088] Polyphenylene ether (PPO) resin contains a large number of benzene rings in its molecular structure and does not contain strongly polar groups, which endows it with excellent properties such as high glass transition temperature (Tg), low coefficient of thermal expansion (CTE), low dielectric constant (Dk), and low dissipation factor (Df). Modifying traditional PPO resin by introducing acrylate groups at both ends can improve its reactivity in prepolymerization and curing reactions, improve its compatibility with functional resins, and reduce its melt viscosity.

[0089] As an example, in acrylate-type polyphenylene ether resins, m and n are each independently selected from positive integers, and the sum of m and n includes, but is not limited to, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, or 60; Y is absent, or Y is selected from C1 alkylene, C2 alkylene, or C3 alkylene, suitable examples including: -CH2-, -CH(CH3)-, -CH2CH2-, -CH(CH2CH3)-, -CH2CH(CH3)-, -CH2CH2CH2-.

[0090] In some embodiments, the mass ratio of acrylate-type polyphenylene ether resin to amino silicone resin is 100:(60~100). As an example, the mass ratio of acrylate-type polyphenylene ether resin to amino silicone resin includes, but is not limited to, 100:60, 100:65, 100:70, 100:75, 100:80, 100:85, 100:90, 100:95 or 100:100.

[0091] By controlling the mass ratio of acrylate-type polyphenylene ether resin and amino organosilicon resin, the content of polyphenylene ether structure, organosilicon alkyl groups and amino groups in the toughened prepolymer can be adjusted, thereby improving its compatibility, coefficient of thermal expansion, glass transition temperature, mechanical properties and dielectric properties.

[0092] In some embodiments, the method for preparing the toughened prepolymer includes the following steps:

[0093] Acrylic polyphenylene ether resin and amino silicone resin are mixed and prepolymerized at 100℃~180℃ for 90min~240min to obtain toughened prepolymer.

[0094] As an example, the reaction temperature of the prepolymerization reaction includes, but is not limited to, 100°C, 105°C, 110°C, 115°C, 120°C, 125°C, 130°C, 135°C, 140°C, 145°C, 150°C, 155°C, 160°C, 165°C, 170°C, 175°C, or 180°C, and may further be selected as 130°C to 140°C; the reaction time of the prepolymerization reaction includes, but is not limited to, 90 min, 100 min, 110 min, 120 min, 130 min, 140 min, 150 min, 160 min, 170 min, 180 min, 190 min, 200 min, 210 min, 220 min, 230 min, or 240 min, and may further be selected as 120 min to 150 min.

[0095] In some embodiments, the method of mixing acrylate-type polyphenylene ether resin and amino silicone resin includes the following steps: heating at 100°C to 150°C to melt the amino silicone resin, and then adding the acrylate-type polyphenylene ether resin.

[0096] As an example, the temperature of the heat treatment includes, but is not limited to, 100°C, 105°C, 110°C, 115°C, 120°C, 125°C, 130°C, 135°C, 140°C, 145°C or 150°C, and may further be selected as 125°C to 135°C.

[0097] In some embodiments, a step of cooling to room temperature is further included after the prepolymerization reaction.

[0098] In some embodiments, the functional resin includes one or more of epoxy resin, benzoxazine resin, and hydrocarbon resin.

[0099] Understandably, the functional resin may be selected from any one of epoxy resin, benzoxazine resin and hydrocarbon resin, or from at least two of epoxy resin, benzoxazine resin and hydrocarbon resin, such as epoxy resin and benzoxazine resin, epoxy resin and hydrocarbon resin, benzoxazine resin and hydrocarbon resin.

[0100] Among the aforementioned functional resins, benzoxazine resins possess a benzene ring and a six-membered oxazine ring in their molecular structure, resulting in low molecular polarity, a relatively low dielectric constant, and low dielectric loss, thus exhibiting excellent dielectric properties. The cross-linked network formed by the curing of benzoxazine resins is relatively compact, with strong intermolecular forces and a low coefficient of thermal expansion. Simultaneously, it exhibits high heat resistance, a glass transition temperature above 150℃, almost zero curing shrinkage, good halogen-free flame retardancy, low water absorption, and good elastic modulus. Hydrocarbon resins contain only carbon and hydrogen elements in their molecular structure, lacking heteroatoms and having very few polar groups, thus possessing good dielectric properties. Epoxy resins can cure and cross-link to form a network structure, exhibiting excellent physical and mechanical properties, electrical insulation properties, adhesive properties, and processability. However, the presence of polar groups such as epoxy and hydroxyl groups in their molecular structure results in relatively high dielectric constants and dielectric losses. By rationally combining functional resins of different components, the number of polar groups in the cured product of the toughening resin composition can be greatly reduced, further improving its dielectric properties and enabling the cured product to maintain a low coefficient of thermal expansion, excellent heat resistance, and good mechanical strength.

[0101] In some embodiments, the epoxy resin includes one or more of bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthalene type epoxy resin, phosphorus-containing epoxy resin, unsaturated epoxy resin, phenolic type epoxy resin, o-cresol type epoxy resin, bisphenol A phenolic epoxy resin, multifunctional epoxy resin, alicyclic epoxy resin, resorcinol epoxy resin, rubber-modified epoxy resin, biphenyl epoxy resin, and dicyclopentadiene epoxy resin, and may further be selected as one or more of naphthalene type epoxy resin, phosphorus-containing epoxy resin, biphenyl epoxy resin, and dicyclopentadiene epoxy resin.

[0102] In some embodiments, the benzoxazine resin includes one or more of bisphenol A type benzoxazine resin, bisphenol F type benzoxazine resin, bisphenol S type benzoxazine resin, main-chain type benzoxazine resin, phosphorus-containing benzoxazine resin, dicyclopentadiene benzoxazine resin, biphenyl type benzoxazine resin, tetraphenol ethane benzoxazine resin, and naphthyl type benzoxazine resin, and may further be selected as one or more of phosphorus-containing benzoxazine resin, dicyclopentadiene benzoxazine resin, biphenyl type benzoxazine resin, and naphthyl type benzoxazine resin.

[0103] In some embodiments, the hydrocarbon resin includes one or more of polybutadiene and styrene-butadiene copolymer, and may further be polybutadiene.

[0104] In some embodiments, the curing agent includes one or more of amine curing agents, phenolic curing agents, acid anhydride curing agents, cyanate ester curing agents, reactive ester curing agents, and olefin curing agents.

[0105] In some embodiments, the amine curing agent includes one or more of ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenyl sulfone, dicyandiamide, polyetheramine, and polyamide.

[0106] In some embodiments, the phenolic curing agent includes one or more of linear phenol-formaldehyde resin, linear bisphenol A-formaldehyde resin, linear o-cresol-formaldehyde resin, neophenol resin, biphenyl arylphenol resin, halogen-free flame-retardant nitrogen-containing phenolic resin, and halogen-free flame-retardant phosphorus-containing phenolic resin.

[0107] In some embodiments, the anhydride curing agent includes one or more of phthalic anhydride, styrene-maleic anhydride copolymer, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, maleic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, benzophenone tetracarboxylic anhydride, glutaric anhydride, polyazelaic anhydride, dichloromaleic anhydride, trimellitic anhydride, pyromellitic anhydride, trimellitic dianhydride, benzophenone tetracarboxylic anhydride, dodecyl maleic anhydride, succinic anhydride, hexahydrophthalic anhydride, and cyclopentanetetracarboxylic anhydride.

[0108] In some embodiments, the cyanate curing agent includes one or more of the following: bisphenol A cyanate resin, bisphenol F cyanate resin, bisphenol S cyanate resin, bisphenol M cyanate resin, bisphenol E cyanate resin, phenolic cyanate resin, biphenyl cyanate resin, naphthalene cyanate resin, polyfunctional cyanate resin, and dicyclopentadiene bisphenol cyanate resin.

[0109] In some embodiments, the active ester curing agent includes one or more of bis(2-methacryloyloxyethyl) active ester of 3,3′-dithiodipropionate and pentaerythritol tetra(3-mercaptopropionate) active ester.

[0110] In some embodiments, the olefin curing agent includes one or more of pentaerythritol triacrylate, triallyl cyanurate (TAC), trimethylolpropane trimethacrylate, tripropylene glycol diacrylate, and triallyl isocyanurate (TAIC).

[0111] In some embodiments, the curing accelerator includes one or more of tertiary amine accelerators, imidazole accelerators, peroxide accelerators, organophosphorus accelerators, and transition metal carboxylate accelerators.

[0112] In some embodiments, tertiary amine accelerators include one or more of triethylamine, benzyldimethylamine, tris(dimethylaminomethyl)phenol, triethylenediamine, and dimethylaniline.

[0113] In some embodiments, the imidazole accelerator includes one or more of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and 1-cyano-2-methylimidazole.

[0114] In some embodiments, the peroxide accelerator includes one or more of benzoyl peroxide, di-tert-butyl peroxide, dicumyl peroxide (DCP), tert-butyl peroxide, and tert-butyl peroxyoctanoate.

[0115] In some embodiments, the organophosphorus accelerator includes one or more of triphenylphosphine and tributyl phosphate.

[0116] In some embodiments, the transition metal carboxylate accelerator includes one or more of manganese acetate, zinc octanoate, zinc isooctanoate, zinc naphthenate, zinc acetylacetonate, stannous octanoate, dibutyltin dilaurate, cobalt octanoate, cobalt naphthenate, cobalt acetylacetonate, aluminum acetylacetonate, copper acetylacetonate, and nickel acetylacetonate.

[0117] In some embodiments, the inorganic filler includes one or more of modified silica and modified alumina.

[0118] Adding suitable inorganic fillers to toughening resin compositions can have a synergistic effect with toughening prepolymers and functional resins, significantly reducing the coefficient of thermal expansion and improving mechanical strength.

[0119] In some embodiments, the modified silica includes one or more of epoxy-modified silica, aniline-modified silica, vinyl-modified silica, hollow silica, acrylic (polymethyl methacrylate, PMMA)-modified silica, fluoroalkyl-modified silica, and molybdate-modified silica.

[0120] In some embodiments, the modified alumina includes one or more of epoxy-modified alumina, aniline-modified alumina, vinyl-modified alumina, hollow alumina, acrylic (polymethyl methacrylate, PMMA)-modified alumina, fluoroalkyl-modified alumina, and molybdate-modified alumina.

[0121] In some embodiments, the shape of the modified silica and the shape of the modified alumina are each independently selected from one or more of spherical, ellipsoidal, strip-shaped and amorphous shapes, and are further selected as spherical.

[0122] Understandably, there is no particular limitation on the average particle size of the inorganic filler. In some embodiments, the average particle size of the inorganic filler is ≤10μm, including but not limited to 10μm, 5μm, 3μm, 1μm, 0.5μm, 0.1μm, 0.05μm or 0.01μm.

[0123] In some embodiments, the toughening resin composition further includes additives and solvents, the additives including one or more of dispersants, leveling agents, defoamers, and coupling agents.

[0124] Adding suitable additives to toughening resin compositions can improve their dispersibility, flowability, uniformity, and bonding ability between different components, as well as their curing ability, thereby enhancing the various properties of the cured product. Adding solvents can improve the compatibility between multiple components and prevent undesirable phenomena such as layering or precipitation.

[0125] In some embodiments, the solvent includes one or more selected from ethanol, acetone, cyclohexanone, butanone, toluene, xylene, N,N-dimethylformamide, N,N-dimethylacetamide, and propylene glycol methyl ether. Further optionally, the solvent includes one or more selected from butanone, toluene, and propylene glycol methyl ether. Even more optionally, the mass ratio of butanone, toluene, and propylene glycol methyl ether in the solvent is 1:1:1.

[0126] In some embodiments, the coupling agent in the additive includes one or more of silane coupling agents, titanate coupling agents, aluminate coupling agents, and zirconate coupling agents, and may further be a silane coupling agent.

[0127] In some embodiments, the defoamer in the additives includes one or more of alcohol defoamers, fatty acid defoamers, fatty acid ester defoamers, phosphate ester defoamers, mineral oil defoamers, amide defoamers, polyether defoamers, silicone defoamers, and polyether-modified silicone defoamers, and may further be selected as silicone defoamers.

[0128] In some embodiments, the toughening resin composition further includes the following raw materials in parts by weight: 80 to 200 parts of solvent and 1 to 5 parts of additives.

[0129] As an example, in the toughening resin composition, the solvent may be present in parts by weight of, but not limited to, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190 or 200 parts, and may further be 100 to 150 parts.

[0130] As an example, in the toughening resin composition, the parts by weight of the additive include, but are not limited to, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts or 5 parts, and may further be 3 to 5 parts.

[0131] In a second aspect, this application provides a laminated film comprising the toughening resin composition described above.

[0132] In a third aspect, this application provides a method for preparing a layered film, which uses the toughening resin composition described above.

[0133] In some embodiments, the method for preparing the layered film includes the following steps:

[0134] The toughening resin composition described above is applied to the support to obtain a liquid film;

[0135] The liquid film is dried to obtain the extended film.

[0136] In some embodiments, the method of coating the toughening resin composition onto the support includes one or more of coating and screen printing. The coating method includes one or more of brushing, spin coating, spraying, scraping, and dip coating.

[0137] In some embodiments, the drying process includes the following steps: drying at a constant temperature of 100°C to 200°C for 5 min to 15 min.

[0138] As an example, the drying temperature includes, but is not limited to, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C, or 200°C, and may further be selected as 130°C to 150°C. The drying time includes, but is not limited to, 5 min, 6 min, 7 min, 8 min, 9 min, 10 min, 11 min, 12 min, 13 min, 14 min, or 15 min, and may further be selected as 10 min to 15 min.

[0139] In some embodiments, the thickness of the liquid film is 5μm to 150μm, including but not limited to 5μm, 10μm, 20μm, 30μm, 40μm, 50μm, 60μm, 70μm, 80μm, 90μm, 100μm, 110μm, 120μm, 130μm, 140μm or 150μm.

[0140] In some embodiments, the thickness of the support is 3μm to 105μm, including but not limited to 3μm, 10μm, 20μm, 30μm, 40μm, 50μm, 60μm, 70μm, 80μm, 90μm, 100μm or 105μm.

[0141] In some embodiments, the support comprises one or more of a polymer film and a metal foil. Optionally, the polymer film comprises one or more of polyethylene terephthalate (PET) film, polycarbonate (PC) film, and polymethyl methacrylate (PMMA) film; the metal foil comprises one or more of copper foil and aluminum foil.

[0142] Understandably, a build-up film refers to the semi-cured and / or cured product of a toughening resin composition. Typically, the support only serves a supporting function during the preparation of the build-up film; it must be removed when the build-up film is used to fabricate an encapsulation carrier. Alternatively, when the support is a metal foil, it is possible to choose not to remove the support and instead directly fabricate the encapsulation carrier from the combination of the build-up film and the support.

[0143] In a fourth aspect, this application provides an encapsulation substrate comprising the toughening resin composition as described above, or comprising the laminate as described above, or comprising the laminate prepared by the method described above.

[0144] In some embodiments, the number of layers of the add-on film in the encapsulation carrier is one or more.

[0145] In some embodiments, one or both sides of each layered film are covered with a metal foil.

[0146] In some embodiments, the metal foil includes one or more of copper foil and aluminum foil.

[0147] In some embodiments, the thickness of the metal foil is 3μm to 105μm, including but not limited to 3μm, 10μm, 20μm, 30μm, 40μm, 50μm, 60μm, 70μm, 80μm, 90μm, 100μm or 105μm.

[0148] In some embodiments, the method for preparing the encapsulation carrier includes vacuum hot pressing.

[0149] The following detailed description, along with specific embodiments and comparative examples, further illustrates the process. Unless otherwise specified, all raw materials and instruments used in these embodiments and comparative examples are commercially available. Unless otherwise specified, all processes involved are conventionally chosen by those skilled in the art. The sources of some raw materials are shown below:

[0150] Amino silicone resin: Shin-Etsu Chemical Industry Co., Ltd. X-22-161Bl;

[0151] Acrylic polyphenylene ether resin: Sabiq SA9000, with the structure shown in general formula (Ⅲ), has a glass transition temperature of 160℃, a specific gravity of 1.02, an intrinsic viscosity of 0.09 dL / g, a number-average molecular weight (Mn) of 2300, a vinyl functionality of 1.9, a dielectric constant (1MHz) of 2.54, and a dielectric loss (1MHz) of 0.0007.

[0152] Dicyclopentadiene (DCPD) benzoxazine resin: Klöln KZH-5031MP70;

[0153] Olefin curing agent: TAIC Technology;

[0154] Peroxide curing accelerator: Nouryon DCP;

[0155] Vinyl-modified spherical silica: Yaduma, model SO-C1, average particle size 0.4μm;

[0156] Additive: BYK-1650 from BYK Chemicals, which is an organosilicone defoamer.

[0157] Example 1

[0158] The specific method for preparing the packaging carrier provided in this embodiment is as follows:

[0159] (1) Preparation of toughened prepolymer:

[0160] Please refer to Table 1. Take 60 parts by weight of amino silicone resin, heat it to a molten state at 130°C, then add 100 parts of acrylate-type polyphenylene ether resin, carry out a prepolymerization reaction at 135°C, and cool it to room temperature after 120 min to obtain toughened prepolymer A.

[0161] (2) Preparation of toughening resin composition:

[0162] Please refer to Table 2. By weight, 20 parts of toughening prepolymer A, 10 parts of DCPD benzoxazine resin, 10 parts of olefin curing agent, 3 parts of peroxide curing accelerator, 100 parts of vinyl-modified spherical silica and 1 part of additive are dissolved in 100 parts of solvent (a mixture of butanone, toluene and propylene glycol methyl ether in a mass ratio of 1:1:1) and stirred thoroughly to obtain a gel-like toughening resin composition.

[0163] (3) Preparation of the toughening film: The toughening resin composition is sprayed onto one surface of the PET film and baked at 140°C for 10 min to obtain the toughening film. The toughening film and the PET film are stacked to form a composite.

[0164] (4) Preparation of the encapsulation substrate: The enhancement film in the assembly is laminated onto a copper foil with a thickness of 12 μm using a laminator. The PET film is removed, and another copper foil with a thickness of 12 μm is covered on the enhancement film. The substrate is then placed in a programmable temperature and pressure controlled vacuum press and subjected to a vacuum state of ≤10 mBar and 10 kgf / cm². 2 Under pressure, vacuum hot pressing is performed at 100℃ for 30 minutes, at 150℃ for 30 minutes, and at 190℃ for 120 minutes to completely cure the extension film and obtain the encapsulation carrier plate.

[0165] Example 2

[0166] The specific method for preparing the packaging carrier provided in this embodiment is as follows:

[0167] (1) Preparation of toughened prepolymer: Same as in Example 1.

[0168] (2) Preparation of toughening resin composition:

[0169] Please refer to Table 2. By weight, 30 parts of toughening prepolymer A, 30 parts of DCPD benzoxazine resin, 25 parts of olefin curing agent, 5 parts of peroxide curing accelerator, 150 parts of vinyl-modified spherical silica and 3 parts of additives are dissolved in 130 parts of solvent (a mixture of butanone, toluene and propylene glycol methyl ether in a mass ratio of 1:1:1) and stirred thoroughly to obtain a gel-like toughening resin composition.

[0170] (3) Preparation of the toughening film: The toughening resin composition is sprayed onto one surface of the PET film and baked at 140°C for 14 min to obtain the toughening film. The toughening film and the PET film are stacked to form a composite.

[0171] (4) Preparation of the encapsulation substrate: Same as in Example 1.

[0172] Example 3

[0173] (1) Preparation of toughened prepolymer: Same as in Example 1.

[0174] (2) Preparation of toughening resin composition:

[0175] Please refer to Table 2. By weight, 40 parts of toughening prepolymer A, 20 parts of DCPD benzoxazine resin, 40 parts of olefin curing agent, 1 part of peroxide curing accelerator, 50 parts of vinyl-modified spherical silica and 5 parts of additives are dissolved in 120 parts of solvent (a mixture of butanone, toluene and propylene glycol methyl ether in a mass ratio of 1:1:1) and stirred thoroughly to obtain a gel-like toughening resin composition.

[0176] (3) Preparation of the toughening film: The toughening resin composition is sprayed onto one surface of the PET film and baked at 130°C for 13 min to obtain the toughening film. The toughening film and the PET film are stacked to form a composite.

[0177] (4) Preparation of the encapsulation substrate: Same as in Example 1.

[0178] Example 4

[0179] The specific method for preparing the packaging carrier provided in this embodiment is as follows:

[0180] (1) Preparation of toughened prepolymer:

[0181] Please refer to Table 1. Take 80 parts by weight of amino silicone resin, heat it to a molten state at 130°C, then add 100 parts of acrylate-type polyphenylene ether resin, carry out a prepolymerization reaction at 140°C, and cool it to room temperature after 150 min to obtain toughened prepolymer B.

[0182] (2) Preparation of toughening resin composition:

[0183] Please refer to Table 2. By weight, 30 parts of toughening prepolymer B, 30 parts of DCPD benzoxazine resin, 25 parts of olefin curing agent, 5 parts of peroxide curing accelerator, 150 parts of vinyl-modified spherical silica and 3 parts of additives are dissolved in 130 parts of solvent (a mixture of butanone, toluene and propylene glycol methyl ether in a mass ratio of 1:1:1) and stirred thoroughly to obtain a gel-like toughening resin composition.

[0184] (3) Preparation of the toughening film: The toughening resin composition is sprayed onto one surface of the PET film and baked at 145°C for 14 min to obtain the toughening film. The toughening film and the PET film are stacked to form a composite.

[0185] (4) Preparation of the encapsulation substrate: Same as in Example 1.

[0186] Example 5

[0187] The specific method for preparing the packaging carrier provided in this embodiment is as follows:

[0188] (1) Preparation of toughened prepolymer:

[0189] Please refer to Table 1. Take 100 parts by weight of amino silicone resin, heat it to a molten state at 130°C, then add 100 parts of acrylate-type polyphenylene ether resin, carry out a prepolymerization reaction at 130°C, and cool it to room temperature after 140 min to obtain toughened prepolymer C.

[0190] (2) Preparation of toughening resin composition:

[0191] Please refer to Table 2. By weight, 30 parts of toughening prepolymer C, 30 parts of DCPD benzoxazine resin, 25 parts of olefin curing agent, 5 parts of peroxide curing accelerator, 150 parts of vinyl-modified spherical silica and 3 parts of additives are dissolved in 130 parts of solvent (a mixture of butanone, toluene and propylene glycol methyl ether in a mass ratio of 1:1:1) and stirred thoroughly to obtain a gel-like toughening resin composition.

[0192] (3) Preparation of the toughening film: The toughening resin composition is sprayed onto one surface of the PET film and baked at 150°C for 14 min to obtain the toughening film. The toughening film and the PET film are stacked to form a composite.

[0193] (4) Preparation of the encapsulation substrate: Same as in Example 1.

[0194] Comparative Example 1

[0195] The specific method for preparing the packaging carrier provided in this comparative example is as follows:

[0196] (1) Preparation of toughening resin composition:

[0197] Please refer to Table 2. By weight, 30 parts of acrylate-type polyphenylene ether resin, 30 parts of DCPD benzoxazine resin, 25 parts of olefin curing agent, 5 parts of peroxide curing accelerator, 150 parts of vinyl-modified spherical silica and 3 parts of additives are dissolved in 130 parts of solvent (a mixture of butanone, toluene and propylene glycol methyl ether in a mass ratio of 1:1:1) and stirred thoroughly to obtain a gel-like toughening resin composition.

[0198] (2) Preparation of the toughening film: The toughening resin composition is sprayed onto one surface of the PET film and baked at 140°C for 12 min to obtain the toughening film. The toughening film and the PET film are stacked to form a composite.

[0199] (3) Preparation of the encapsulation substrate: Same as step (4) in Example 1.

[0200] Comparative Example 2

[0201] The specific method for preparing the packaging carrier provided in this comparative example is as follows:

[0202] (1) Preparation of toughening resin composition:

[0203] Please refer to Table 2. By weight, 60 parts of toughening prepolymer A, 30 parts of DCPD benzoxazine resin, 25 parts of olefin curing agent, 5 parts of peroxide curing accelerator, 150 parts of vinyl-modified spherical silica and 3 parts of additives are dissolved in 130 parts of solvent (a mixture of butanone, toluene and propylene glycol methyl ether in a mass ratio of 1:1:1) and stirred thoroughly to obtain a gel-like toughening resin composition.

[0204] (2) Preparation of the toughening film: The toughening resin composition is sprayed onto one surface of the PET film and baked at 140°C for 15 min to obtain the toughening film. The toughening film and the PET film are stacked to form a composite.

[0205] (3) Preparation of the encapsulation substrate: Same as step (4) in Example 1.

[0206] Comparative Example 3

[0207] The specific method for preparing the packaging carrier provided in this comparative example is as follows:

[0208] (1) Preparation of toughening resin composition:

[0209] Please refer to Table 2. By weight, 30 parts of amino silicone resin, 30 parts of DCPD benzoxazine resin, 25 parts of olefin curing agent, 5 parts of peroxide curing accelerator, 150 parts of vinyl-modified spherical silica and 3 parts of additives are dissolved in 130 parts of solvent (a mixture of butanone, toluene and propylene glycol methyl ether in a mass ratio of 1:1:1) and stirred thoroughly to obtain a gel-like toughening resin composition.

[0210] (3) Preparation of the toughening film: The toughening resin composition is sprayed onto one surface of the PET film and baked at 140°C for 14 min to obtain the toughening film. The toughening film and the PET film are stacked to form a composite.

[0211] (4) Preparation of the encapsulation substrate: Same as in Example 1.

[0212] Test case

[0213] (a) Test items:

[0214] 1. Thermomechanical analysis (TMA) test: The glass transition temperature (Tg) of the packaging substrate is obtained by testing according to IPC-TM-650 2.4.24.5.

[0215] 2. Heat Resistance Test: Tested according to IPC-TM-650 2.4.13 to determine the time the packaging substrate maintains stable performance under high temperature conditions. If the packaging substrate cannot maintain stable performance under high temperature conditions, it can easily cause short circuits, component damage, and other problems, thus affecting the normal operation of electronic devices. The longer the packaging substrate maintains stable performance under high temperature conditions, the better its heat resistance.

[0216] 3. Dielectric performance testing: According to IPC-TM-650 2.5.5.2, the dielectric constant (Dk) and dielectric loss (Df) of the package substrate are obtained.

[0217] 4. Water absorption rate: Tested according to IPC-TM650 2.6.2.1.

[0218] 5. Cutting Crack Test: Remove the copper foil from the fully cured encapsulation substrate, place the extension film in a cutting machine for cutting, and observe and measure the crack width of the cut. Cracks will occur at the cut edges of extension films and other materials after cutting. The smaller the crack width, the better the crack resistance and the higher the mechanical properties.

[0219] (II) Results Analysis:

[0220] Please see Figure 1 and Figure 2 The location indicated by the arrow in the diagram is the incision point of the layered membrane. Figure 1 The image shows the actual product of the laminated film after cutting in Example 1. The cut is basically undamaged, with a crack width of approximately 0.5 mm. Figure 2 The image shows the actual product of the thickened film of Comparative Example 1 after cutting. The cut is severely cracked, with a crack width of about 6 mm; this indicates that the toughening resin composition of Example 1 has excellent crack resistance after curing.

[0221] Table 3 shows that the encapsulation substrates of Examples 1-5 have a Tg ≥ 168℃, maintain stable performance for > 1000s under high temperature conditions, Dk ≤ 3.64, Df ≤ 0.0075, water absorption ≤ 0.10%, and crack width ≤ 1.2mm. This indicates that adding an appropriate amount of toughening prepolymer obtained by reacting acrylate-type polyphenylene ether resin and amino silicone resin can significantly improve the heat resistance, dielectric properties, and crack resistance of the toughening resin composition. This results in the encapsulation substrate exhibiting extremely high heat resistance, extremely low dielectric constant and dielectric loss, and higher mechanical properties, making it very suitable for preparing high-performance FCBGA substrates.

[0222] The difference between Comparative Example 1 and Example 2 is that toughening prepolymer A was replaced with an equal mass of acrylate-type polyphenylene ether resin, which resulted in a significant deterioration in the glass transition temperature, heat resistance, dielectric properties, water absorption and crack resistance of the encapsulation substrate.

[0223] Comparative Example 2 increased the amount of toughening prepolymer A. The glass transition temperature, heat resistance, dielectric properties, water absorption and crack resistance of the encapsulation substrate were slightly improved compared with Comparative Example 1. However, all properties were significantly lower than those of the encapsulation substrates of Examples 1 to 5, indicating that the amount of toughening prepolymer has a crucial impact on the heat resistance, dielectric properties and mechanical properties of the encapsulation substrate.

[0224] The difference between Comparative Example 3 and Example 2 is that toughening prepolymer A was replaced with an equal mass of amino silicone resin, which also resulted in a significant deterioration in the glass transition temperature, heat resistance, dielectric properties, water absorption and crack resistance of the encapsulation substrate.

[0225] Table 1. Formulation of prepolymers

[0226]

[0227] Table 2. Formulation of toughening resin composition

[0228]

[0229] Note: "-" indicates that no addition is needed.

[0230] Table 3. Test results of the packaging substrate

[0231]

[0232] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0233] The embodiments described above are merely illustrative of several implementation methods of this application, and while the descriptions are specific and detailed, they should not be construed as limiting the scope of protection of this application. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of this application, and these modifications and improvements all fall within the scope of protection of this application. Therefore, the scope of protection of this application should be determined by the appended claims.

Claims

1. A toughening resin composition, characterized in that, The ingredients include the following parts by weight: ； The functional resin includes one or more of epoxy resin, benzoxazine resin and hydrocarbon resin; The raw materials for the toughening prepolymer include acrylate-type polyphenylene ether resin and amino silicone resin, wherein the amino silicone resin has a structure as shown in general formula (I): （Ⅰ）； Where p is the degree of aggregation, and p is selected from any integer from 1 to 50; Each time R appears, it is independently selected from one or more of the following: ether bond, substituted or unsubstituted alkylene group, substituted or unsubstituted phenyl group, substituted or unsubstituted biphenyl group, substituted or unsubstituted naphthyl group, and substituted or unsubstituted dicyclopentadienyl group; The mass ratio of the acrylate-type polyphenylene ether resin to the amino organosilicon resin is 100:(60~100). The method for preparing the toughened prepolymer includes the following steps: The acrylate-type polyphenylene ether resin and the amino silicone resin are mixed and prepolymerized at 100℃~180℃ for 90min~240min to obtain the toughened prepolymer.

2. The toughening resin composition according to claim 1, characterized in that, The acrylate-type polyphenylene ether resin has a structure as shown in general formula (III): （Ⅲ）； Where m and n are each independently selected from positive integers, and the sum of m and n is 5 to 60; Y is absent, or is selected from C1~C3 alkylene groups.

3. The toughening resin composition according to claim 2, characterized in that, The mass ratio of the acrylate-type polyphenylene ether resin to the amino organosilicon resin is 100:(60~80).

4. The toughening resin composition according to any one of claims 1 to 3, characterized in that, The method for preparing the toughened prepolymer includes the following steps: The acrylate-type polyphenylene ether resin and the amino silicone resin are mixed and prepolymerized at 130°C to 140°C for 120 min to 150 min to obtain the toughened prepolymer.

5. The toughening resin composition according to claim 1, characterized in that, One or more of the following conditions must be met: (1) The epoxy resin includes one or more of the following: bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthalene type epoxy resin, phosphorus-containing epoxy resin, unsaturated epoxy resin, phenolic type epoxy resin, o-cresol type epoxy resin, bisphenol A phenolic epoxy resin, multifunctional epoxy resin, alicyclic epoxy resin, resorcinol epoxy resin, rubber modified epoxy resin, biphenyl epoxy resin and dicyclopentadiene epoxy resin; (2) The benzoxazine resin includes one or more of the following: bisphenol A type benzoxazine resin, bisphenol F type benzoxazine resin, bisphenol S type benzoxazine resin, main chain type benzoxazine resin, phosphorus-containing benzoxazine resin, dicyclopentadiene benzoxazine resin, biphenyl type benzoxazine resin, tetraphenol ethane benzoxazine resin, and naphthalene type benzoxazine resin; (3) The hydrocarbon resin includes one or more of polybutadiene and styrene-butadiene copolymer.

6. The toughening resin composition according to any one of claims 1 to 3, characterized in that, One or more of the following conditions must be met: (1) The curing agent includes one or more of the following: amine curing agents, phenolic curing agents, acid anhydride curing agents, cyanate ester curing agents, reactive ester curing agents, and olefin curing agents; (2) The curing accelerator includes one or more of the following: tertiary amine accelerators, imidazole accelerators, peroxide accelerators, organophosphorus accelerators, and transition metal carboxylates; (3) The inorganic filler includes one or more of modified silica and modified alumina.

7. The toughening resin composition according to any one of claims 1 to 3, characterized in that, The toughening resin composition further includes additives and solvents, wherein the additives include one or more of dispersants, leveling agents, defoamers, and coupling agents.

8. A layering film, characterized in that, The toughening resin composition includes any one of claims 1 to 7.

9. A method for preparing a layered film, characterized in that, Includes the following steps: A liquid film is obtained by covering the support with the toughening resin composition as described in any one of claims 1 to 7; The liquid film is dried to obtain the layered film.

10. The method for preparing the layered film as described in claim 9, characterized in that, The drying process includes the following steps: drying at a constant temperature of 100℃~200℃ for 5min~15min.

11. The method for preparing the layered film as described in claim 9, characterized in that, One or more of the following conditions must be met: (1) The support comprises one or more of a polymer film and a metal foil; (2) The thickness of the support is 3μm~105μm; (3) The thickness of the liquid film is 5μm~150μm.

12. A packaging carrier board, characterized in that, It includes the toughening resin composition as described in any one of claims 1 to 7, or the thickening film as described in claim 8, or the thickening film prepared by the method for preparing the thickening film as described in any one of claims 9 to 11.

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