Toughened resin composition, layer-adding film, preparation method of layer-adding film and packaging substrate

Abstract

The invention relates to the technical field of packaging substrates, in particular to a toughened resin composition, a layer-adding film, a preparation method of the layer-adding film and a packaging substrate. The toughened resin composition is prepared from the following raw materials in parts by weight: 20 to 50 parts of toughened prepolymer, 10 to 40 parts of functional resin, 10 to 60 parts of curing agent, 1 to 10 parts of curing accelerator and 50 to 200 parts of inorganic filler, the toughening prepolymer is prepared from the following raw materials: acrylate type polyphenyl ether resin and amino organic silicon resin. The toughened resin composition provided by the invention is prepared into a layer-adding film, and the layer-adding film is excellent in anti-cracking performance, high in glass-transition temperature, good in heat resistance, low in water absorption rate, extremely high in dielectric property and suitable for preparing a high-performance packaging substrate.

Description

Technical Field

[0001] The present application relates to the technical field of packaging carriers, and in particular to a toughening resin composition, a build-up film and a preparation method thereof, and a packaging carrier. Background Art

[0002] As electronic products develop towards miniaturization, lightness, high functionality and high safety, electronic circuits are also developing towards multi-layer and high wiring density. Among them, Flip Chip Ball Grid Array (FCBGA) technology is an advanced packaging process that flips the chip upside down and attaches it to the carrier, and connects the chip and the carrier through solder balls to achieve electrical connection and signal transmission. FCBGA technology performs well in high speed, high density and high reliability, and is widely used in computer, communication, medical, consumer electronics and industrial control.

[0003] Compared with other packaging substrate technologies, FCBGA technology has higher integration, smaller packaging volume, higher reliability and lower power consumption, so it puts higher requirements on the performance of its main raw material, the build-up film, such as excellent mechanical properties, heat resistance and dielectric properties. With the advent of the artificial intelligence (AI) era, the amount of information processing and the speed of information transmission have exploded, and FCBGA packaging substrates also require lower dielectric constants and lower dielectric losses to reduce transmission losses. However, traditional resin compositions cannot have high heat resistance, high mechanical strength and excellent dielectric properties, and are difficult to be used in the preparation of FCBGA packaging substrates. Summary of the invention

[0004] Based on this, it is necessary to provide a toughened resin composition, a build-up film and a preparation method thereof, and a packaging carrier to solve the problem that traditional resin compositions cannot have high heat resistance, high mechanical strength and excellent dielectric properties and are difficult to be used in the preparation of FCBGA packaging carriers.

[0005] The above-mentioned purpose of the present application is achieved through the following technical solutions:

[0006] In a first aspect of the present application, a toughened resin composition is provided, comprising the following raw materials in parts by weight:

[0007] ;

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

[0009] (I);

[0010] Wherein, p is the degree of polymerization, and p is selected from any integer between 1 and 50;

[0011] Each occurrence of R is independently selected from one or more of an ether bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, and a substituted or unsubstituted dicyclopentadienyl group.

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

[0013] (III);

[0014] Wherein, 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 selected from C1-C3 alkylene.

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

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

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

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

[0020] In some embodiments, the epoxy resin includes one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, naphthalene epoxy resin, phosphorus-containing epoxy resin, unsaturated epoxy resin, phenolic epoxy resin, o-cresol 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 bisphenol A-type benzoxazine resin, bisphenol F-type benzoxazine resin, bisphenol S-type benzoxazine resin, main chain 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 an amine curing agent, a phenolic curing agent, an anhydride curing agent, a cyanate curing agent, an active ester curing agent, and an olefin curing agent.

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

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

[0026] In some embodiments, the toughened resin composition further comprises an additive and a solvent, wherein the additive comprises one or more of a dispersant, a leveling agent, a defoaming agent and a coupling agent.

[0027] In a second aspect of the present application, a build-up film is provided, comprising the toughening resin composition as described above.

[0028] In a third aspect of the present application, a method for preparing a build-up film is provided, comprising the following steps:

[0029] Covering the toughening resin composition as described above on a support to obtain a liquid film;

[0030] The liquid film is dried to obtain the build-up layer film.

[0031] In some embodiments, the drying process comprises the following steps: constant temperature drying at 100° C. to 200° C. for 5 min to 15 min.

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

[0033] In some embodiments, the thickness of the support body 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 of the present application, a packaging carrier is provided, comprising the toughening resin composition as described above, or comprising the build-up film as described above, or comprising a build-up film prepared by the method for preparing the build-up film as described above.

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

[0037] In the toughened resin composition provided by the present application, the acrylate functional group in the acrylate polyphenylene ether resin has high reactivity and can be combined with the amino group in the amino silicone resin, thereby grafting the organosiloxane side chain in the polyphenylene ether structure, so that the cured product exhibits excellent heat resistance and mechanical properties while maintaining good dielectric properties. At the same time, by rationally matching the toughened prepolymer, functional resin, curing agent, curing accelerator and inorganic filler in a specific ratio, not only can the number of polar groups in the composition be reduced, the dielectric constant and dielectric loss are effectively reduced, but also the heat resistance and mechanical properties of the composition can be significantly improved. Therefore, the toughened resin composition provided by the present application is made into a layered film, which has excellent crack resistance, high glass transition temperature, good heat resistance, low water absorption and extremely strong dielectric properties, and is suitable for preparing high-performance packaging carriers. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] In order to more clearly illustrate the technical solutions in the embodiments of the present application and to more completely understand the present application and its beneficial effects, the following is a brief introduction to the drawings required for the description of the embodiments. Obviously, the drawings described below are only some embodiments of the present application, and those skilled in the art can obtain other drawings based on these drawings without creative work.

[0039] Figure 1 This is a physical picture of the build-up film of Example 1 after cutting;

[0040] Figure 2 This is a physical picture of the build-up film of comparative example 1 after cutting. DETAILED DESCRIPTION

[0041] In order to facilitate the understanding of the present application, the present application is further described in detail below in conjunction with specific embodiments. However, the present application can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the understanding of the disclosure of the present application more thorough and comprehensive.

[0042] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art to which this application belongs. The terms used herein in the specification of this application are only for the purpose of describing specific embodiments and are not intended to limit this application.

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

[0044] When a numerical range is disclosed in this application, the above range is considered to be continuous and includes the minimum and maximum values ​​of the range, as well as every value between such minimum and maximum values. Further, when a range refers to an integer, every integer between the minimum and maximum values ​​of the range is included. In addition, when multiple ranges are provided to describe features or characteristics, the ranges can be combined. In other words, unless otherwise indicated, all ranges disclosed in this application should be understood to include any and all subranges included therein.

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

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

[0047] The temperature parameters in this application, unless otherwise specified, are allowed to be either constant temperature treatment or to vary within a certain temperature range. It should be understood that the constant temperature treatment allows the temperature to fluctuate within the accuracy range controlled by the instrument. Fluctuations within the range of ±5°C, ±4°C, ±3°C, ±2°C, and ±1°C are allowed.

[0048] In the present application, room temperature refers to indoor temperature, normal temperature or general temperature. Generally speaking, the range of room temperature can be any one of the following temperature intervals: 23°C ± 2°C, 25°C ± 5°C or 20°C ± 5°C.

[0049] the term

[0050] Unless otherwise specified or there is a contradiction, the terms and phrases used in this application have the following meanings:

[0051] In the present application, when a substituent with the same symbol appears multiple times, each substituent may be the same or different from each other. For example, when a general formula contains multiple R, R may be the same or different from each other.

[0052] "Substituted or unsubstituted" means that the defined group may be substituted or unsubstituted. When the defined group is substituted, it should be understood that the defined group may be substituted by one or more substituents acceptable in the art. Suitable substituents include but are not limited to: C1~C 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, silanyl, carbonyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, haloformyl, 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 understandable that R in -N(R)2 is independently substituted by groups acceptable in the art, including but not limited to: H, C1~C6 alkyl, cycloalkyl containing 3 to 8 ring atoms, heterocyclic group containing 3 to 8 ring atoms, aryl containing 5 to 10 ring atoms or heteroaryl containing 5 to 10 ring atoms.

[0053] The "number of ring atoms" refers to the number of atoms constituting the ring itself of a structural compound (e.g., a monocyclic compound, a condensed ring compound, a cross-linked compound, a carbocyclic compound, a heterocyclic compound) in which atoms are bonded to form a ring. When the ring is substituted by a substituent, the atoms contained in the substituent are not included in the ring atoms. The "number of ring atoms" described below is the same unless otherwise specified. For example, the number of ring atoms of a benzene ring is 6, the number of ring atoms of a naphthalene ring is 10, and the number of ring atoms of a thienyl group 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 a straight chain, branched and / or cyclic alkyl group. The carbon number of the alkyl group can be 1 to 50, 1 to 30, 1 to 20, 1 to 10 or 1 to 6. Phrases containing this term, for example, "C1 to C9 alkyl" refers to an alkyl group containing 1 to 9 carbon atoms, and each occurrence can be independently 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 with two monovalent radical centers derived from an alkyl group by removing a hydrogen atom, which can be a saturated branched alkyl group or a saturated straight-chain alkyl group. For example, "C1-C9 alkylene" means that the alkyl portion contains 1 to 9 carbon atoms, and each occurrence can be independently C1 alkylene, C4 alkylene, C5 alkylene, C6 alkylene, C7 alkylene, C8 alkylene 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 ring carbon atoms, which can be a monocyclic alkyl, a spirocyclic alkyl, or a bridged cycloalkyl. Phrases containing this term, for example, "C3~C9 cycloalkyl" refers to a cycloalkyl containing 3 to 9 carbon atoms, and each time it appears, it can be independently C3 cycloalkyl, C4 cycloalkyl, C5 cycloalkyl, C6 cycloalkyl, C7 cycloalkyl, C8 cycloalkyl or C9 cycloalkyl. Suitable examples include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl. In addition, "cycloalkyl" may also contain one or more double bonds, and representative examples of cycloalkyl containing double bonds include cyclopentenyl, cyclohexenyl, cyclopentadienyl, cyclohexadienyl, cyclobutadienyl and dicyclopentadienyl (DCPD) groups. Among them, the structure of dicyclopentadienyl or DCPD group is:

[0057] .

[0058] "Aryl" refers to an aromatic hydrocarbon group derived from an aromatic ring compound by removing a hydrogen atom. It can be a monocyclic aromatic group, a condensed aromatic group, or a polycyclic aromatic group. For polycyclic rings, at least one is an aromatic ring system. For example, "C5~C 20 "Aryl" refers to an aromatic group containing 5 to 20 carbon atoms, and each occurrence can be independently C5 aromatic group, C6 aromatic group, C 10 Aryl, C 14 Aryl, C 18 Aryl or C 20 Suitable examples include, but are not limited to, benzene, biphenyl, naphthalene, anthracene, phenanthrene, perylene, triphenylene, and derivatives thereof.

[0059] In a first aspect of the present application, a toughened resin composition is provided to solve the problem that traditional resin compositions cannot have high heat resistance, high mechanical strength and excellent dielectric properties and are difficult to be used in the preparation of FCBGA package carriers.

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

[0061] ;

[0062] The raw materials of the toughening prepolymer include acrylate polyphenylene ether resin and amino silicone resin. The amino silicone resin has a structure as shown in the general formula (I):

[0063] (I);

[0064] Wherein, p is the degree of polymerization, and p is selected from any integer between 1 and 50;

[0065] Each occurrence of R is independently selected from one or more of an ether bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, and a substituted or unsubstituted dicyclopentadienyl group.

[0066] Understandably, polyphenylene oxide (PPO) resin contains a large number of benzene rings in its molecular structure and does not contain strong polar groups. It has the characteristics of low dielectric constant (Dk) and low dielectric loss (Df), and has gradually become an ideal material for designing low dielectric constant and dielectric loss products. However, traditional polyphenylene oxide resins are mostly hydroxyl-terminated polyphenylene oxide resins, which have low reactivity of hydroxyl groups and are difficult to form a high cross-linking density curing system, resulting in poor mechanical properties and poor heat resistance, limiting its application in high-performance packaging substrates.

[0067] In the toughened resin composition provided by the present application, the acrylate functional group in the acrylate polyphenylene ether resin has high reactivity and can be combined with the amino group in the amino silicone resin, thereby grafting the organosiloxane side chain in the polyphenylene ether structure, so that the cured product exhibits excellent heat resistance and mechanical properties while maintaining good dielectric properties. At the same time, by rationally matching the toughened prepolymer, functional resin, curing agent, curing accelerator and inorganic filler in a specific ratio, not only can the number of polar groups in the composition be reduced, the dielectric constant and dielectric loss are effectively reduced, but also the heat resistance and mechanical properties of the composition can be significantly improved. Therefore, the toughened resin composition provided by the present application is made into a layered film, which has excellent crack resistance, high glass transition temperature, good heat resistance, low water absorption and extremely strong dielectric properties, and is suitable for preparing high-performance packaging carriers.

[0068] As an example, in the toughened resin composition, the weight parts of the toughening prepolymer include but are 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 can be further selected as 20 parts to 40 parts.

[0069] As an example, in the toughened resin composition, the weight of the functional resin includes but is 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 can be further selected as 10 parts to 30 parts.

[0070] As an example, in the toughened resin composition, the weight of the curing agent includes but is 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 can be further selected from 10 parts to 40 parts.

[0071] As an example, in the toughened resin composition, the weight of the curing accelerator includes but is 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 can be further selected as 1 part to 5 parts.

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

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

[0074] .

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

[0076] .

[0077] As an example, in the amino silicone resin, 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 an amino silicone resin, each occurrence of R is independently selected from one or more of an ether bond (-O-), a substituted or unsubstituted alkylene group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, and a substituted or unsubstituted dicyclopentadiene (DCPD) group. Wherein, "substituted or unsubstituted" means that the alkylene group, phenyl group, biphenyl group, naphthyl group, and DCPD group may be substituted or unsubstituted, and 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 group, nitro group, hydroxyl group, carboxyl group, ester group, or cyano group. Further optionally, each occurrence of R is independently selected from one or more of -O-, C1~C3 alkylene group, phenyl group, biphenyl group, naphthyl group, and dicyclopentadiene (DCPD) group. Wherein, C1~C3 alkylene includes but is not limited to: -CH2-, -CH(CH3)-, -CH2CH2-, -CH(CH2CH3)-, -CH2CH(CH3)-, -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 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 resin of Shin-etsu Chemical Industry Co., Ltd., and the model number may be any one of PAM-E, KF-8010, X-22-161A, X-22-161B, KF-8012, KF-8008, and X-22-1660B-3, and the physical properties are as follows:

[0083]

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

[0085] (III);

[0086] Wherein, 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 selected from C1~C3 alkylene;

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

[0089] As an example, in the acrylate polyphenylene ether resin, m and n are each independently selected from a positive integer, 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 not present, or Y is selected from a C1 alkylene, a C2 alkylene or a C3 alkylene, suitable examples of which include: -CH2-, -CH(CH3)-, -CH2CH2-, -CH(CH2CH3)-, -CH2CH(CH3)-, -CH2CH2CH2-.

[0090] In some embodiments, the mass ratio of the acrylate polyphenylene ether resin to the amino silicone resin is 100:(60-100). As an example, the mass ratio of the acrylate polyphenylene ether resin to the 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 polyphenylene ether resin and amino silicone resin, the content of polyphenylene ether structure, organosiloxane group and amino group in the toughened prepolymer can be regulated, thereby improving its compatibility, thermal expansion coefficient, glass transition temperature, mechanical properties and dielectric properties.

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

[0093] The acrylate polyphenylene ether resin and the amino silicone resin are mixed and prepolymerized at 100° C. to 180° C. for 90 min to 240 min to obtain a 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 can be further selected as 130°C to 140°C; the reaction time of the prepolymerization reaction includes but is not limited to 90min, 100min, 110min, 120min, 130min, 140min, 150min, 160min, 170min, 180min, 190min, 200min, 210min, 220min, 230min or 240min, and can be further selected as 120min to 150min.

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

[0096] As an example, the temperature of the heating 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 can further be 125°C~135°C.

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

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

[0099] It can be understood that the functional resin can be selected from any one of epoxy resin, benzoxazine resin and hydrocarbon resin, or can be selected 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 above functional resins, the molecular structure of benzoxazine resin contains benzene rings and six-membered oxazine rings, and the molecular polarity is low, which makes the dielectric constant relatively low and the dielectric loss small, and has excellent dielectric properties; the cross-linked network formed by curing of benzoxazine resin is relatively tight, the intermolecular force is strong, and the thermal expansion coefficient is low; at the same time, it has high heat resistance, the glass transition temperature is above 150°C, the curing shrinkage is almost 0, the halogen-free flame retardancy is good, the water absorption rate is low, and the elastic modulus is good. The molecular structure of hydrocarbon resin contains only two elements, carbon and hydrogen, does not contain heteroatoms, and has very few polar groups, and has good dielectric properties. Epoxy resin can be cured and cross-linked to form a network structure, which has excellent physical and mechanical properties, electrical insulation properties, bonding properties and processing properties, but its molecular structure contains polar groups such as epoxy and hydroxyl groups, which makes its dielectric constant and dielectric loss relatively high. By rationally matching functional resins of different components, the number of polar groups in the cured product of the toughened resin composition can be greatly reduced, further improving its dielectric properties, and maintaining a low thermal expansion coefficient, excellent heat resistance and good mechanical strength for the cured product.

[0101] In some embodiments, the epoxy resin includes one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, naphthalene epoxy resin, phosphorus-containing epoxy resin, unsaturated epoxy resin, phenolic epoxy resin, o-cresol 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 further selected from one or more of naphthalene 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 benzoxazine resin, phosphorus-containing benzoxazine resin, dicyclopentadiene benzoxazine resin, biphenyl benzoxazine resin, tetraphenol ethane benzoxazine resin and naphthalene benzoxazine resin, and can further be selected from one or more of phosphorus-containing benzoxazine resin, dicyclopentadiene benzoxazine resin, biphenyl benzoxazine resin and naphthalene 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 an amine curing agent, a phenolic curing agent, an anhydride curing agent, a cyanate curing agent, an active ester curing agent, and an olefin curing agent.

[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 aralkylphenol 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, benzophenonetetracarboxylic anhydride, glutaric anhydride, polyazetaic anhydride, dichloromaleic anhydride, trimellitic anhydride, pyromellitic anhydride, pyromellitic anhydride, dibenzophenonetetracarboxylic anhydride, dodecylmaleic anhydride, succinic anhydride, hexahydrophthalic anhydride and cyclopentanetetracarboxylic anhydride.

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

[0109] In some embodiments, the active ester curing agent includes one or more of bis(2-methacryloyloxyethyl)-3,3′-dithiodipropionate active ester and pentaerythritol tetrakis(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 a tertiary amine accelerator, an imidazole accelerator, a peroxide accelerator, an organic phosphorus accelerator, and a transition metal carboxylate accelerator.

[0112] In some embodiments, the tertiary amine accelerator includes 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-based accelerator includes one or more of benzoyl peroxide, di-tert-butyl peroxide, dicumyl peroxide (DCP), tert-butyl perbenzoate, 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 promoter includes one or more of manganese acetate, zinc octoate, zinc isooctanoate, zinc naphthenate, zinc acetylacetonate, stannous octoate, dibutyltin dilaurate, cobalt octoate, 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 appropriate inorganic fillers to the toughened resin composition can play a synergistic role with the toughened prepolymer and functional resin, significantly reducing the thermal expansion coefficient and improving the 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 silicon dioxide and the shape of the modified aluminum oxide are each independently selected from one or more of sphere, ellipsoid, strip, and amorphous, and can further be selected to be spherical.

[0122] It is understood that the average particle size of the inorganic filler is not particularly limited. In some embodiments, the average particle size of the inorganic filler is ≤10 μm, including but not limited to 10 μm, 5 μm, 3 μm, 1 μm, 0.5 μm, 0.1 μm, 0.05 μm or 0.01 μm.

[0123] In some embodiments, the toughened resin composition further comprises an additive and a solvent, wherein the additive comprises one or more of a dispersant, a leveling agent, a defoaming agent and a coupling agent.

[0124] Adding appropriate additives to the toughened resin composition can improve the dispersibility, fluidity, uniformity and bonding ability between different components of the toughened resin composition, improve the curing ability of the toughened resin composition, and enhance the various properties of its cured product. Adding solvents can improve the compatibility between multiple components and avoid the undesirable phenomenon of stratification or precipitation.

[0125] In some embodiments, the solvent includes one or more of 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 of butanone, toluene and propylene glycol methyl ether. Further optionally, in the solvent, the mass ratio of butanone, toluene and propylene glycol methyl ether is 1:1:1.

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

[0127] In some embodiments, among the auxiliary agents, the defoaming agent includes one or more of alcohol defoaming agents, fatty acid defoaming agents, fatty acid ester defoaming agents, phosphate defoaming agents, mineral oil defoaming agents, amide defoaming agents, polyether defoaming agents, silicone defoaming agents and polyether-modified silicone defoaming agents, and silicone defoaming agents can be further selected.

[0128] In some embodiments, the toughened resin composition further comprises the following raw materials in parts by weight: 80 to 200 parts of a solvent and 1 to 5 parts of an auxiliary agent.

[0129] As an example, in the toughened resin composition, the weight parts of the solvent include but are not limited to 80 parts, 90 parts, 100 parts, 110 parts, 120 parts, 130 parts, 140 parts, 150 parts, 160 parts, 170 parts, 180 parts, 190 parts or 200 parts, and can further be selected as 100 parts to 150 parts.

[0130] As an example, in the toughened resin composition, the weight of the additive includes but is 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 can be further selected as 3 parts to 5 parts.

[0131] In a second aspect of the present application, a build-up film is provided, comprising the toughening resin composition as described above.

[0132] In a third aspect of the present application, a method for preparing a build-up film is provided, which uses the toughening resin composition as described above.

[0133] In some embodiments, the method for preparing the build-up film comprises the following steps:

[0134] Covering the toughening resin composition as described above on a support to obtain a liquid film;

[0135] The liquid film is dried to obtain a build-up film.

[0136] In some embodiments, the method of coating the toughened resin composition on the support includes one or more of a coating method and a screen printing method, wherein the coating method includes one or more of a brushing method, a spin coating method, a spray coating method, a blade coating method, and a dip coating method.

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

[0138] As an example, the temperature of the drying process 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 130° C. to 150° C. The time of the drying process 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 10 min to 15 min.

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

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

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

[0142] It can be understood that the build-up film refers to a semi-cured product and / or cured product of the toughening resin composition. Generally, the support body only plays a supporting role in the preparation process of the build-up film, and the support body needs to be removed in the process of using the build-up film to make a packaging carrier. In addition, when the support body is a metal foil, it is also possible to choose not to remove the support body, but to directly make the package carrier from the combination formed by stacking the build-up film and the support body.

[0143] In a fourth aspect of the present application, a packaging carrier is provided, comprising the toughening resin composition as described above, or comprising the build-up film as described above, or comprising a build-up film prepared by the method for preparing the build-up film as described above.

[0144] In some embodiments, the number of the build-up layer films in the package carrier is one or more layers.

[0145] In some embodiments, one or both sides of each build-up layer film are coated with 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 3 μm to 105 μm, including but not limited to 3 μm, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm or 105 μm.

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

[0149] The following is further described in conjunction with specific examples and comparative examples. The raw materials involved in the following specific examples and comparative examples, unless otherwise specified, can all be sourced from commercial sources, the instruments used, unless otherwise specified, can all be sourced from commercial sources, and the processes involved, unless otherwise specified, are all routinely selected by those skilled in the art. Among them, the sources of some raw materials are as follows:

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

[0151] Acrylate polyphenylene ether resin: Sabic SA9000, the structure is shown in the general formula (III), the glass transition temperature is 160°C, the specific gravity is 1.02, the intrinsic viscosity is 0.09 dL / g, the number average molecular weight (Mn) is 2300, the vinyl functionality is 1.9, the dielectric constant (1MHz) is 2.54, and the dielectric loss (1MHz) is 0.0007;

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

[0153] Olefin curing agent: TAIC from Zhisheng 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, a silicone defoamer.

[0157] Example 1

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

[0159] (1) Preparation of toughened prepolymer:

[0160] Please refer to Table 1. By weight, 60 parts of amino silicone resin were taken and heated to a molten state at 130°C. Then, 100 parts of acrylate polyphenylene ether resin were added and prepolymerized at 135°C. After 120 minutes, the prepolymer was cooled to room temperature to obtain toughened prepolymer A.

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

[0162] Please refer to Table 2. According to parts by weight, 20 parts of toughened 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 auxiliary agent are dissolved in 100 parts of solvent (mixed by butanone, toluene and propylene glycol methyl ether in a mass ratio of 1:1:1), and stirred well to obtain a toughened resin composition in the form of a gel.

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

[0164] (4) Preparation of packaging substrate: Use a laminating machine to laminate the build-up film in the assembly onto a 12 μm thick copper foil, remove the PET film, and cover the build-up film with another 12 μm thick copper foil. Place the assembly in a programmable temperature and pressure controlled vacuum press and press the assembly under a vacuum state of ≤10 mBar and 10 kgf / cm 2 The build-up layer film was completely cured under vacuum hot pressing at 100°C for 30 min, vacuum hot pressing at 150°C for 30 min, and vacuum hot pressing at 190°C for 120 min to obtain a packaging carrier.

[0165] Example 2

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

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

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

[0169] Please refer to Table 2. In parts by weight, 30 parts of toughened 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 auxiliary agent are dissolved in 130 parts of solvent (mixed by butanone, toluene and propylene glycol methyl ether in a mass ratio of 1:1:1), and stirred well to obtain a toughened resin composition in a gel state.

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

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

[0172] Example 3

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

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

[0175] Please refer to Table 2. In parts by weight, 40 parts of toughened 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 auxiliary agent are dissolved in 120 parts of solvent (mixed by butanone, toluene and propylene glycol methyl ether in a mass ratio of 1:1:1), and stirred well to obtain a toughened resin composition in a gel state.

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

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

[0178] Example 4

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

[0180] (1) Preparation of toughened prepolymer:

[0181] Please refer to Table 1. By weight, 80 parts of amino silicone resin were taken and heated to a molten state at 130°C. Then, 100 parts of acrylate polyphenylene ether resin were added and prepolymerized at 140°C. After 150 minutes, the prepolymer was cooled to room temperature to obtain a toughened prepolymer B.

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

[0183] Please refer to Table 2. In parts by weight, 30 parts of toughened 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 auxiliary agent are dissolved in 130 parts of solvent (mixed by butanone, toluene and propylene glycol methyl ether in a mass ratio of 1:1:1), and stirred well to obtain a toughened resin composition in a gel state.

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

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

[0186] Example 5

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

[0188] (1) Preparation of toughened prepolymer:

[0189] Please refer to Table 1. By weight, 100 parts of amino silicone resin were taken and heated to a molten state at 130°C. Then, 100 parts of acrylate polyphenylene ether resin were added and prepolymerized at 130°C. After 140 minutes, the prepolymer was cooled to room temperature to obtain a toughened prepolymer C.

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

[0191] Please refer to Table 2. In parts by weight, 30 parts of toughened 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 auxiliary agent are dissolved in 130 parts of solvent (mixed by butanone, toluene and propylene glycol methyl ether in a mass ratio of 1:1:1), and stirred well to obtain a toughened resin composition in a gel state.

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

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

[0194] Comparative Example 1

[0195] The preparation method of the packaging substrate provided in this comparative example is as follows:

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

[0197] Please refer to Table 2. In parts by weight, 30 parts of acrylate 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 auxiliary agent are dissolved in 130 parts of solvent (mixed by butanone, toluene and propylene glycol methyl ether in a mass ratio of 1:1:1), and the mixture is fully stirred to obtain a toughened resin composition in the form of a gel.

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

[0199] (3) Preparation of packaging substrate: the same as step (4) of Example 1.

[0200] Comparative Example 2

[0201] The preparation method of the packaging substrate provided in this comparative example is as follows:

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

[0203] Please refer to Table 2. In parts by weight, 60 parts of toughened 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 auxiliary agent are dissolved in 130 parts of solvent (mixed by butanone, toluene and propylene glycol methyl ether in a mass ratio of 1:1:1), and stirred well to obtain a toughened resin composition in a gel state.

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

[0205] (3) Preparation of packaging substrate: the same as step (4) of Example 1.

[0206] Comparative Example 3

[0207] The preparation method of the packaging substrate provided in this comparative example is as follows:

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

[0209] Please refer to Table 2. In parts 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 auxiliary agent are dissolved in 130 parts of solvent (mixed by butanone, toluene and propylene glycol methyl ether in a mass ratio of 1:1:1), and the mixture is fully stirred to obtain a toughened resin composition in the form of a gel.

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

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

[0212] Test Case

[0213] 1. Test items:

[0214] 1. Thermomechanical analysis (TMA) test: According to IPC-TM-650 2.4.24.5 test, to obtain the glass transition temperature (Tg) of the package substrate.

[0215] 2. Heat resistance test: Test according to IPC-TM-650 2.4.13 to obtain the time that the package substrate can maintain stable performance under high temperature conditions. If the package substrate cannot maintain stable performance under high temperature conditions, it is easy to cause problems such as circuit short circuit and component damage, thereby affecting the normal operation of electronic equipment. The longer the package substrate maintains stable performance under high temperature conditions, the better its heat resistance.

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

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

[0218] 5. Cutting cracking degree test: Remove the copper foil from the fully cured package carrier, place the build-up film in a cutting machine for cutting, and observe and measure the crack width of the cut. The cut of the build-up film and other boards will crack after cutting. The smaller the crack width, the better the crack resistance and the higher the mechanical properties.

[0219] (II) Results analysis:

[0220] See also Figure 1 and Figure 2 The position indicated by the arrow in the figure is the incision of the build-up film. Figure 1 This is a real picture of the build-up layer film of Example 1 after cutting. The cut is basically free of cracks, and the crack width is about 0.5 mm; Figure 2 This is a physical picture of the build-up film of comparative example 1 after cutting. The cut is severely cracked, and the crack width is about 6 mm, indicating that the toughened resin composition of Example 1 has very excellent anti-cracking performance after curing.

[0221] As shown in Table 3, the packaging substrates of Examples 1 to 5 have Tg≥168°C, the time for maintaining stable performance under high temperature conditions is>1000s, 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 polyphenylene ether resin and amino silicone resin can significantly improve the heat resistance, dielectric properties and crack resistance of the toughening resin composition, so that the packaging substrate exhibits extremely high heat resistance, extremely low dielectric constant and dielectric loss, and higher mechanical properties, and is very suitable for preparing high-performance FCBGA substrates.

[0222] The difference between Comparative Example 1 and Example 2 is that the toughening prepolymer A is replaced with an equal mass of acrylic ester polyphenylene ether resin, resulting in a significant deterioration in the glass transition temperature, heat resistance, dielectric properties, water absorption and crack resistance of the packaging carrier.

[0223] In Comparative Example 2, the amount of toughening prepolymer A is increased, and the glass transition temperature, heat resistance, dielectric properties, water absorption and crack resistance of the packaging carrier are slightly improved compared with Comparative Example 1, but each performance is significantly lower than that of the packaging carriers of Examples 1 to 5, indicating that the amount of toughening prepolymer has a crucial influence on the heat resistance, dielectric properties and mechanical properties of the packaging carrier.

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

[0225] Table 1. Prepolymer formulation

[0226]

[0227] Table 2. Formulation of toughened resin composition

[0228]

[0229] Note: “-” means no addition.

[0230] Table 3. Test results of package substrate

[0231]

[0232] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described 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 above-described embodiments only express several implementation methods of the present application, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of protection of the present application. It should be pointed out that, for a person of ordinary skill in the art, several variations and improvements can be made without departing from the concept of the present application, and these all belong to the scope of protection of the present application. Therefore, the scope of protection of the present application shall be subject to the attached claims.

Claims

1. A toughened resin composition, characterized in that The invention comprises the following raw materials in parts by weight: ； The raw materials of the toughened prepolymer include acrylate polyphenylene ether resin and amino silicone resin, and the amino silicone resin has a structure as shown in the general formula (I): （Ⅰ）； Wherein, p is the degree of polymerization, and p is selected from any integer between 1 and 50; Each occurrence of R is independently selected from one or more of an ether bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, and a substituted or unsubstituted dicyclopentadienyl group.

2. The toughened resin composition according to claim 1, characterized in that The acrylate polyphenylene ether resin has a structure as shown in the general formula (III): （Ⅲ）； Wherein, 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 selected from C1-C3 alkylene.

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

4. The toughened resin composition according to any one of claims 1 to 3, characterized in that The preparation method of the toughened prepolymer comprises the following steps: The acrylate polyphenylene ether resin and the amino silicone resin are mixed and prepolymerized at 100° C. to 180° C. for 90 min to 240 min to obtain the toughened prepolymer.

5. The toughened resin composition according to any one of claims 1 to 3, characterized in that The functional resin includes one or more of epoxy resin, benzoxazine resin and hydrocarbon resin.

6. The toughened resin composition according to claim 5, characterized in that One or more of the following conditions are met: (1) The epoxy resin includes one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, naphthalene epoxy resin, phosphorus-containing epoxy resin, unsaturated epoxy resin, novolac epoxy resin, o-cresol novolac epoxy resin, bisphenol A novolac 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 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.

7. The toughened resin composition according to any one of claims 1 to 3, characterized in that One or more of the following conditions are met: (1) The curing agent includes one or more of an amine curing agent, a phenolic curing agent, an anhydride curing agent, a cyanate curing agent, an active ester curing agent and an olefin curing agent; (2) The curing accelerator includes one or more of a tertiary amine accelerator, an imidazole accelerator, a peroxide accelerator, an organic phosphorus accelerator and a transition metal carboxylate accelerator; (3) The inorganic filler includes one or more of modified silica and modified alumina.

8. The toughened resin composition according to any one of claims 1 to 3, characterized in that The toughened resin composition further comprises an auxiliary agent and a solvent, wherein the auxiliary agent comprises one or more of a dispersant, a leveling agent, a defoaming agent and a coupling agent.

9. A build-up film, characterized in that: The invention comprises a toughened resin composition as described in any one of claims 1 to 8.

10. A method for preparing a build-up film, characterized in that: The following steps are involved: Covering the toughening resin composition according to any one of claims 1 to 8 on a support to obtain a liquid film; The liquid film is dried to obtain the build-up layer film.

11. The method for preparing a build-up film according to claim 10, characterized in that: The drying process comprises the following steps: constant temperature drying at 100° C. to 200° C. for 5 min to 15 min.

12. The method for preparing a build-up film according to claim 10, characterized in that: One or more of the following conditions are met: (1) The support comprises one or more of a polymer film and a metal foil; (2) The thickness of the support is 3 μm to 105 μm; (3) The thickness of the liquid film is 5 μm to 150 μm.

13. A packaging carrier, characterized in that: It comprises the toughening resin composition as described in any one of claims 1 to 8, or comprises the build-up film as described in claim 9, or comprises the build-up film prepared by the preparation method of the build-up film as described in any one of claims 10 to 12.

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