Modified resin composition, film-increasing layer, and method for preparing and use thereof

Abstract

The application discloses a modified resin composition, a film-increasing layer and a preparation method and application thereof, and belongs to the technical field of composite materials. The modified resin composition comprises the following components: a modified allyl benzoxazine prepolymer, a functional resin, a curing agent, a curing accelerator, an inorganic filler, an organic filler and an auxiliary agent. The preparation raw material of the modified allyl benzoxazine prepolymer comprises an allyl compound and an allyl benzoxazine resin. The allyl compound comprises a first allyl compound, and the first allyl compound is triply naphthalene bisallyl ether. The resin composition provided by the application has low thermal expansion coefficient, low dielectric constant, low dielectric loss and low water absorption, can inhibit the warping of the film-increasing layer, and meets the application requirements of the film-increasing layer and a packaging substrate.

Description

Technical Field

[0001] This application relates to the field of composite materials technology, and in particular to modified resin compositions, film-forming layers, their preparation methods and applications. Background Technology

[0002] Flip Chip Ball Grid Array (FCBGA) substrate technology is an advanced packaging technology that involves flipping and mounting chips onto a substrate, connecting the chips and the substrate via solder balls to achieve electrical connections and signal transmission. FCBGA substrate technology offers advantages in high speed, high density, and high reliability, and is widely used in fields such as computers, communications, consumer electronics, medical devices, and industrial control.

[0003] As an essential packaging substrate for high-computing applications such as artificial intelligence, FCBGA packaging substrates significantly reduce lead length and area by inverting the chip and interconnecting it with bumps. This allows for the integration of a large number of electronic components in a smaller space, resulting in features such as small linewidth / spacing and numerous pins, effectively reducing dielectric loss and increasing component density. The insulating build-up film, with its good dimensional stability, excellent dielectric properties, durability, and reliability, is a core material in several advanced packaging technologies, including FCBGA packaging substrates.

[0004] Compared with traditional packaging substrate technology, FCBGA carrier technology has higher integration, smaller package size, higher reliability, and lower power consumption. This requires its main raw material, build-up film, to have better performance, such as lower coefficient of thermal expansion, lower warpage, lower dielectric constant, lower dielectric loss, and lower water absorption.

[0005] Therefore, how to provide resin compositions with low coefficient of thermal expansion, low dielectric constant, low dielectric loss and low water absorption rate, thereby effectively reducing the coefficient of thermal expansion, dielectric constant, dielectric loss and water absorption rate of the laminated film and inhibiting its warpage, has become an urgent problem to be solved in the industry. Summary of the Invention

[0006] Based on this, the main objective of this application is to provide a resin composition having a low coefficient of thermal expansion, a low dielectric constant, a low dielectric loss, and a low water absorption rate, thereby preparing a laminated film with a low coefficient of thermal expansion, a low dielectric constant, a low dielectric loss, a low water absorption rate, and low warpage.

[0007] One aspect of this application provides a modified resin composition comprising the following components in parts by weight;

[0008] 10-40 parts of modified allyl benzoxazine prepolymer;

[0009] 10-50 parts of functional resin;

[0010] 10-40 parts of curing agent;

[0011] 1-10 parts of curing accelerator;

[0012] Inorganic filler 50-300 parts;

[0013] 10-50 parts of organic filler;

[0014] 0-5 parts of auxiliary agent;

[0015] The raw materials for preparing the modified allyl benzoxazine prepolymer include: allyl compounds and allyl benzoxazine resin;

[0016] The allyl compound includes a first allyl compound, which is a trimenaphthalene dielyl ether, with the following structure:

[0017] .

[0018] In some embodiments, the allyl compound further includes a second allyl compound; the second allyl compound is selected from one or more of diallyl bisphenol A, diallyl bisphenol S, diallyl bisphenol F, and bisphenol A diallyl ether.

[0019] In some embodiments, the mass ratio of the allyl compound to the allyl benzoxazine resin is (0.8-1.2):1.

[0020] In some embodiments, the allylbenzoxazine resin is selected from one or more of the following structures:

[0021]

[0022]

[0023] Where X is selected from -CHR1-, -CR2R3-, -SO2-, -O- or ;

[0024] R1, R2, and R3 are each independently selected from -H or -CH3.

[0025] Understandable This refers to a naphthalene ring that has been doubly substituted, with no limitation on the substitution site.

[0026] In some embodiments, the preparation method of the modified allyl benzoxazine prepolymer includes the following steps:

[0027] The modified allyl benzoxazine prepolymer is prepared by mixing an allyl compound and an allyl benzoxazine resin and reacting and prepolymerizing at 120-180°C.

[0028] In some embodiments, the reaction time is 1-4 hours.

[0029] In some embodiments, the functional resin is one or more of epoxy resin, benzoxazine, and bismaleimide resin.

[0030] In some embodiments, the epoxy resin includes one or more of the following: naphthalene-type epoxy resin, bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, phosphorus-containing epoxy resin, unsaturated epoxy resin, phenolic 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.

[0031] In some embodiments, the benzoxazine resin includes one or more of the following: bisphenol A type benzoxazine resin, bisphenol F type benzoxazine resin, main-chain type benzoxazine resin, phosphorus-containing benzoxazine, bisphenol S type benzoxazine resin, dicyclopentadiene benzoxazine resin, biphenyl type benzoxazine resin, tetraphenol ethane benzoxazine resin, and naphthyl type benzoxazine resin.

[0032] In some embodiments, the curing agent is selected from one or more of amine curing agents, phenolic curing agents, acid anhydride curing agents, cyanate ester curing agents, and reactive ester curing agents.

[0033] In some embodiments, the curing accelerator is selected from one or more of tertiary amine accelerators, imidazole accelerators, peroxide accelerators, organophosphorus accelerators, and transition metal carboxylate accelerators.

[0034] In some embodiments, the inorganic filler is selected from modified spherical silica and / or modified spherical alumina.

[0035] In some embodiments, the modified spherical silica includes one or more of epoxy-modified spherical silica, aniline-modified spherical silica, vinyl-modified spherical silica, hollow spherical silica, acrylic-modified spherical silica, fluoroalkyl-modified spherical silica, and molybdate-modified spherical silica.

[0036] In some embodiments, the modified spherical alumina includes one or more of epoxy-modified spherical alumina, aniline-modified spherical alumina, vinyl-modified spherical alumina, hollow spherical alumina, acrylic-modified spherical alumina, fluoroalkyl-modified spherical alumina, and molybdate-modified spherical alumina.

[0037] In some embodiments, the organic filler is selected from one or more of organosilicon particles, core-shell rubber particles, and olefin elastomer particles.

[0038] In some embodiments, the additive is one or more of a dispersant, leveling agent, defoamer, treatment agent, and coupling agent.

[0039] In some embodiments, the modified resin composition comprises the following components in parts by weight;

[0040] 10-30 parts of modified allyl benzoxazine prepolymer;

[0041] 10-40 parts of functional resin;

[0042] 10-30 parts of curing agent;

[0043] 1-5 parts of curing accelerator;

[0044] 100-250 parts of inorganic filler;

[0045] 10-30 parts of organic filler;

[0046] Additives: 1-5 parts.

[0047] A second aspect of this application provides the use of the aforementioned modified resin composition in a multilayer film.

[0048] A third aspect of this application provides a layered film comprising the aforementioned modified resin composition.

[0049] A fourth aspect of this application provides a method for preparing the aforementioned layered film, comprising the following steps:

[0050] A modified resin composition is coated onto a support to form a resin composition coating, which is then cured to prepare a thickened film.

[0051] In some embodiments, the curing temperature is 70℃-160℃, and the curing time is 2min-15min.

[0052] In some embodiments, the support is selected from plastic film and / or metal film.

[0053] The fifth aspect of this application provides the application of the aforementioned modified resin composition and the aforementioned build-up film in a packaging substrate for a flip-chip ball grid array.

[0054] A sixth aspect of this application provides a packaging substrate for a flip-chip ball grid array, comprising a modified resin composition and the aforementioned build-up film.

[0055] The beneficial effects of this application are:

[0056] This application uses an allyl compound containing a naphthalene ring structure to prepolymerize an allyl benzoxazine resin to prepare a modified allyl benzoxazine prepolymer. This prepolymer is then combined with functional resins, organic fillers, and inorganic fillers to prepare a modified resin composition and a laminated film. The organic and inorganic fillers can reduce the shrinkage rate during curing and improve dimensional stability through filling and reinforcement. The introduction of a highly symmetrical and rigid naphthalene ring structure into the modified allyl benzoxazine prepolymer increases the steric hindrance and rigidity of the polymer chains and disrupts structural regularity. This effectively inhibits the movement of polymer chains during curing, ultimately significantly reducing the warpage, water absorption, and coefficient of thermal expansion of the laminated film, and achieving lower dielectric constant and dielectric loss. Detailed Implementation

[0057] To facilitate understanding of this application, a more comprehensive description of the application will be provided below with reference to specific embodiments. Preferred embodiments of the application are given below. However, the 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 thorough and complete understanding of the disclosure of this application.

[0058] 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. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0059] In this article, the technical features described in an open-ended manner include both closed technical solutions composed of the listed features and open technical solutions that include the listed features.

[0060] In this document, the terms “first” and “second” are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of technical features indicated.

[0061] In this description, "several" means two or more, such as two types, three types, etc., unless otherwise explicitly specified.

[0062] In this document, numerical ranges are referred to as continuous unless otherwise specified, and include the minimum and maximum values ​​of the range, as well as every value between the minimum and maximum values. Furthermore, when a 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 combined. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all subranges to which they are incorporated.

[0063] In this article, when referring to units for data ranges, if the unit is only followed by the right endpoint, it means that the units for the left and right endpoints are the same. For example, 500-600rpm means that the units for the left endpoint "500" and the right endpoint "600" are both rpm (revolutions per minute).

[0064] Unless otherwise specified, the temperature parameters in this document can be either constant temperature processing or processing within a certain temperature range. The constant temperature processing allows for temperature fluctuations within the precision range controlled by the instrument.

[0065] In this document, "optional," "preferred," and "ideal" refer to embodiments of this application that provide certain beneficial effects under certain circumstances. However, other embodiments may also be preferred under the same or other circumstances. Furthermore, the description of one or more preferred embodiments does not imply that other embodiments are unavailable, nor is it intended to exclude other embodiments from the scope of this application.

[0066] One aspect of this application provides a modified resin composition comprising the following components in parts by weight;

[0067] 10-40 parts of modified allyl benzoxazine prepolymer;

[0068] 10-50 parts of functional resin;

[0069] 10-40 parts of curing agent;

[0070] 1-10 parts of curing accelerator;

[0071] Inorganic filler 50-300 parts;

[0072] 10-50 parts of organic filler;

[0073] 0-5 parts of auxiliary agent;

[0074] The raw materials for preparing the modified allyl benzoxazine prepolymer include: allyl compounds and allyl benzoxazine resin;

[0075] The allyl compound includes a first allyl compound, which is a trimenaphthalene dielyl ether, with the following structure:

[0076] .

[0077] Understandably, the first allyl compound of this application has a highly symmetrical and rigid naphthalene ring structure. Modifying the allyl benzoxazine resin can increase the steric hindrance and rigidity of the polymer chains and disrupt structural regularity, thereby effectively inhibiting the movement of polymer chains during the curing process. This ultimately significantly reduces the warpage, water absorption, coefficient of thermal expansion, and dielectric parameters of the laminated film. The cured product exhibits extremely low coefficient of thermal expansion, low shrinkage, low water absorption, and high heat resistance. Furthermore, organic and inorganic fillers can reduce the shrinkage rate during curing and improve dimensional stability through filling and reinforcement effects.

[0078] This application uses an allyl compound containing a naphthalene ring structure to prepolymerize an allyl benzoxazine resin to prepare a modified allyl benzoxazine prepolymer. Combined with functional resins, organic fillers, inorganic fillers and other raw materials, a resin composition with low coefficient of thermal expansion, low dielectric constant, low dielectric loss and low water absorption can be prepared. This results in a build-up film with low coefficient of thermal expansion, low dielectric constant, low dielectric loss, low water absorption and low warpage, which can be used in build-up films and chip ball grid array packaging substrates.

[0079] In some embodiments, the mass ratio of the allyl compound to the allyl benzoxazine resin is (0.8-1.2):1.

[0080] In some embodiments, the allyl compound further includes a second allyl compound; the second allyl compound is selected from one or more of diallyl bisphenol A, diallyl bisphenol S, diallyl bisphenol F, and bisphenol A diallyl ether.

[0081] Understandably, the first modifier of this application can be used alone or in combination with the second modifier, and the combination ratio is not limited. For example, the mass ratio of the first modifier to the second modifier is (3-6):1, specifically 3:1, 4:1, 5:1, 6:1, etc.

[0082] It should be noted that the specific structure of the allyl benzoxazine resin in this application is not particularly required, as long as it contains double bonds. In some embodiments, the allyl benzoxazine resin is selected from one or more of the following structures:

[0083]

[0084]

[0085] Wherein, X is selected from -CHR1-, -CR2R3-, -SO2-, -O- or DCPD ring;

[0086] R1, R2, and R3 are each independently selected from -H or -CH3.

[0087] In some embodiments, the preparation method of the modified allyl benzoxazine prepolymer includes the following steps:

[0088] The modified allyl benzoxazine prepolymer is prepared by mixing an allyl compound and an allyl-type benzoxazine resin and reacting and prepolymerizing at 120-180°C. Specifically, the reaction temperature can be 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, etc.

[0089] Understandably, the step of mixing the allyl compound and the allyl-type benzoxazine resin can specifically be: heating the allyl compound to melt, and then adding the allyl-type benzoxazine resin to mix.

[0090] Understandably, the reaction time and raw material ratio can be adjusted according to actual needs, and there are no special limitations. For example, the reaction time can be 1-4 hours, specifically 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, etc.; the mass ratio of allyl compound to allyl benzoxazine resin can be (60-150):100, more preferably (80-120):100, specifically 60:100, 70:100, 80:100, 90:100, 100:100, 110:100, 120:100, 130:100, 140:100, 150:100, 160:100, etc.

[0091] In some embodiments, the functional resin is one or more of epoxy resin, benzoxazine, and bismaleimide resin.

[0092] The epoxy resin is not limited to a specific type. In some embodiments, the epoxy resin includes one or more of the following: naphthalene-type epoxy resin, bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, phosphorus-containing epoxy resin, unsaturated epoxy resin, phenolic 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.

[0093] The benzoxazine resin is not limited to a specific type. In some embodiments, the benzoxazine resin includes one or more of the following: bisphenol A type benzoxazine resin, bisphenol F type benzoxazine resin, main chain type benzoxazine resin, phosphorus-containing benzoxazine, bisphenol S type benzoxazine resin, dicyclopentadiene benzoxazine resin, biphenyl type benzoxazine resin, tetraphenol ethane benzoxazine resin, and naphthyl type benzoxazine resin.

[0094] The specific type of the bismaleimide resin is not limited, as long as it contains two maleimide structures. In some embodiments, the bismaleimide resin includes one or more of N,N'-(4,4'-methylenediphenyl)bismaleimide, N,N'-(1,4-phenylene)bismaleimide, N,N'-(4-methyl-1,3-phenylene)bismaleimide, N,N'-m-phenylenebismaleimide, di(4-maleimide-phenyl)methane, 2,2-di(4-(4-maleimide-phenoxy)-phenyl)propane, di(3,5-dimethyl-4-maleimide-phenyl)methane, di(3-ethyl-5-methyl-4-maleimide-phenyl)methane, di(3,5-diethyl-4-maleimide-phenyl)methane, polyphenylmethane bismaleimide, and bismaleimides containing a biphenyl structure.

[0095] The curing agent is not limited to a specific type. In some embodiments, the curing agent is selected from one or more of amine curing agents, phenolic curing agents, acid anhydride curing agents, cyanate ester curing agents, and reactive ester curing agents.

[0096] Preferably, the curing accelerator is selected from one or more of tertiary amine accelerators, imidazole accelerators, peroxide accelerators, organophosphorus accelerators, and transition metal carboxylate accelerators.

[0097] In some embodiments, the inorganic filler is selected from modified spherical silica and / or modified spherical alumina.

[0098] Optionally, the modified spherical silica includes one or more of epoxy-modified spherical silica, aniline-modified spherical silica, vinyl-modified spherical silica, hollow spherical silica, acrylic-modified spherical silica, fluoroalkyl-modified spherical silica, and molybdate-modified spherical silica.

[0099] Optionally, the modified spherical alumina includes one or more of epoxy-modified spherical alumina, aniline-modified spherical alumina, vinyl-modified spherical alumina, hollow spherical alumina, acrylic-modified spherical alumina, fluoroalkyl-modified spherical alumina, and molybdate-modified spherical alumina.

[0100] The average particle size of the inorganic filler is not particularly limited and can be 0.01-10μm, specifically 10μm, 5μm, 3μm, 1μm, 0.5μm, 0.1μm, 0.05μm, 0.01μm, etc.

[0101] In some embodiments, the organic filler is selected from one or more of organosilicon particles, core-shell rubber particles, and olefin elastomer particles.

[0102] The average particle size of the organic filler is not particularly limited and can be 10-1000nm, specifically 10nm, 50nm, 100nm, 200nm, 300nm, 500nm, 1000nm, etc.

[0103] In some embodiments, the additive is one or more of a dispersant, leveling agent, defoamer, treatment agent, and coupling agent.

[0104] In some embodiments, the modified resin composition comprises the following components in parts by weight;

[0105] 10-30 parts of modified allyl benzoxazine prepolymer;

[0106] 10-40 parts of functional resin;

[0107] 10-30 parts of curing agent;

[0108] 1-5 parts of curing accelerator;

[0109] 100-250 parts of inorganic filler;

[0110] 10-30 parts of organic filler;

[0111] Additives: 1-5 parts.

[0112] A second aspect of this application provides the use of the aforementioned modified resin composition in a multilayer film.

[0113] A third aspect of this application provides a layered film comprising the aforementioned modified resin composition.

[0114] A fourth aspect of this application provides a method for preparing the aforementioned layered film, comprising the following steps:

[0115] A modified resin composition is coated onto a support to form a resin composition coating, which is then cured to prepare a thickened film.

[0116] Understandably, the step of coating the modified resin composition onto a support to form a resin composition coating can be as follows: dispersing the modified resin composition in a solvent to prepare a dispersion, and then coating it onto the support to form a resin composition coating. The coating method can include spraying, blade coating, roller coating, etc. The solvent can include one or more of ethanol, acetone, cyclohexanone, butanone, toluene, xylene, N,N-dimethylformamide, N,N-dimethylacetamide, and propylene glycol methyl ether.

[0117] Understandably, solvent evaporation can also occur during the curing process.

[0118] In some embodiments, the curing temperature is 70℃-160℃, and the curing time is 2min-15min.

[0119] In some embodiments, the support is selected from plastic film and / or metal film.

[0120] The plastic film includes, but is not limited to, polyethylene terephthalate (PET), polycarbonate (PC), polymethyl methacrylate (PMMA), etc.; the metal film can be copper foil or aluminum foil, etc.; the thickness of the support is preferably, but not limited to, 3-105 μm; the thickness of the resin composition coating is preferably, but not limited to, 5-150 μm.

[0121] The fifth aspect of this application provides the application of the aforementioned modified resin composition and the aforementioned build-up film in a chip-mounted ball grid array packaging substrate.

[0122] A sixth aspect of this application provides a packaging substrate for a flip-chip ball grid array, comprising a modified resin composition and the aforementioned build-up film.

[0123] In some embodiments, the encapsulation carrier meets at least one of the following properties: Tg ≥ 173°C; CTE ≤ 35 ppm / °C below Tg, and CTE ≤ 85 ppm / °C above Tg; warpage ≤ 0.28 mm; Dk ≤ 3.67, Df ≤ 0.0128; water absorption ≤ 0.12%.

[0124] It is worth noting that the raw materials used in the embodiments of this application are all ordinary commercially available products, and their sources are not specifically limited.

[0125] The sources of some components in the examples and comparative examples are as follows:

[0126] Trinaphthalene dielyl ether: purchased from DIC Company;

[0127] Allylbenzoxazine: Huaibei Oasis LZ-32;

[0128] Biphenyl epoxy resin: Nippon Kayaku NC3000H;

[0129] Phenolic curing agent: Shandong Shengquan PF8711;

[0130] Imidazole accelerator: Shikoku Kasei 2MI;

[0131] Spherical silica: Yaduma SO-C1;

[0132] Core-shell rubber granules: UMG Corporation B0603;

[0133] Additive: BYK-1650 from BYK Chemicals.

[0134] The following are specific examples.

[0135] Example 1 of the synthesis of modified allylbenzoxazine prepolymer

[0136] First, 80 parts of trinaphthalene dielyl ether were heated to a molten state, and then 100 parts of allyl benzoxazine resin were added. The mixture was reacted and prepolymerized at 150°C for 120 min and then cooled to room temperature to obtain modified allyl benzoxazine prepolymer A.

[0137] Example 2 of the synthesis of modified allyl benzoxazine prepolymer

[0138] First, 100 parts of trinaphthalene dielyl ether were heated to a molten state, and then 100 parts of allyl benzoxazine resin were added. The reaction was carried out at 150°C for 140 min and then cooled to room temperature to obtain modified allyl benzoxazine prepolymer B.

[0139] Example 3 of the synthesis of modified allylbenzoxazine prepolymer

[0140] First, 120 parts of trinaphthalene dielyl ether were heated to a molten state, and then 100 parts of allyl benzoxazine resin were added. The mixture was reacted and prepolymerized at 160°C for 100 min and then cooled to room temperature to obtain modified allyl benzoxazine prepolymer C.

[0141] Example 4 of the synthesis of modified allyl benzoxazine prepolymer

[0142] First, 80 parts of trinaphthalene dielyl ether and 20 parts of allyl bisphenol A were heated to a molten state. Then, 100 parts of allyl benzoxazine resin were added. The mixture was reacted and prepolymerized at 150°C for 150 min and then cooled to room temperature to obtain modified allyl benzoxazine prepolymer D.

[0143] Example 1

[0144] By weight, 10 parts of modified allyl benzoxazine prepolymer A, 40 parts of biphenyl epoxy resin, 30 parts of phenolic curing agent, 5 parts of imidazole accelerator, 250 parts of spherical silica, 10 parts of core-shell particles, and 3 parts of additives were dissolved in a mixed solvent of 120 parts of methyl ethyl ketone, toluene, and propylene glycol methyl ether, wherein the methyl ethyl ketone, toluene, and propylene glycol methyl ether were mixed in a mass ratio of 1:1:1. After thorough mixing, the solution was sprayed onto the surface of a PET film and then baked at 130°C for 5 minutes to obtain an extended film (PET film thickness 38 μm, coating thickness 100 μm; the film thicknesses of other examples and comparative examples are the same).

[0145] Example 2

[0146] By weight, 20 parts of modified allyl benzoxazine prepolymer A, 30 parts of biphenyl epoxy resin, 20 parts of phenolic curing agent, 3 parts of imidazole accelerator, 200 parts of spherical silica, 15 parts of core-shell particles and 1 part of additives are dissolved in 100 parts of a mixed solvent of butanone, toluene and propylene glycol methyl ether, wherein butanone, toluene and propylene glycol methyl ether are mixed in a mass ratio of 1:1:1. After being thoroughly stirred, the mixture is sprayed onto the surface of a PET film and then baked at 140°C for 5 minutes to obtain an extended film.

[0147] Example 3

[0148] By weight, 30 parts of modified allyl benzoxazine prepolymer A, 10 parts of biphenyl epoxy resin, 10 parts of phenolic curing agent, 1 part of imidazole accelerator, 100 parts of spherical silica, 30 parts of core-shell particles and 5 parts of additives were dissolved in a mixed solvent of 110 parts of methyl ethyl ketone, toluene and propylene glycol methyl ether, wherein methyl ethyl ketone, toluene and propylene glycol methyl ether were mixed in a mass ratio of 1:1:1. After being thoroughly stirred, the mixture was sprayed onto the surface of a PET film and then baked at 150°C for 6 minutes to obtain an extended film.

[0149] Example 4

[0150] By weight, 40 parts of modified allyl benzoxazine prepolymer A, 30 parts of biphenyl epoxy resin, 20 parts of phenolic curing agent, 3 parts of imidazole accelerator, 200 parts of spherical silica, 15 parts of core-shell particles and 1 part of additives are dissolved in 100 parts of a mixed solvent of butanone, toluene and propylene glycol methyl ether, wherein butanone, toluene and propylene glycol methyl ether are mixed in a mass ratio of 1:1:1. After being thoroughly stirred, the mixture is sprayed onto the surface of a PET film and then baked at 150°C for 3 minutes to obtain an extended film.

[0151] Example 5

[0152] By weight, 20 parts of modified allyl benzoxazine prepolymer B, 30 parts of biphenyl epoxy resin, 20 parts of phenolic curing agent, 3 parts of imidazole accelerator, 200 parts of spherical silica, 15 parts of core-shell particles and 1 part of additives were dissolved in 100 parts of a mixed solvent of butanone, toluene and propylene glycol methyl ether, wherein butanone, toluene and propylene glycol methyl ether were mixed in a mass ratio of 1:1:1. After being thoroughly stirred, the mixture was sprayed onto the surface of a PET film and then baked at 145°C for 5 minutes to obtain an extended film.

[0153] Example 6

[0154] By weight, 20 parts of modified allyl benzoxazine prepolymer C, 30 parts of biphenyl epoxy resin, 20 parts of phenolic curing agent, 3 parts of imidazole accelerator, 200 parts of spherical silica, 15 parts of core-shell particles and 1 part of additives are dissolved in 100 parts of a mixed solvent of butanone, toluene and propylene glycol methyl ether, wherein butanone, toluene and propylene glycol methyl ether are mixed in a mass ratio of 1:1:1. After being thoroughly stirred, the mixture is sprayed onto the surface of a PET film and then baked at 140°C for 5 minutes to obtain an extended film.

[0155] Example 7

[0156] By weight, 20 parts of modified allyl benzoxazine prepolymer D, 30 parts of biphenyl epoxy resin, 20 parts of phenolic curing agent, 3 parts of imidazole accelerator, 200 parts of spherical silica, 15 parts of core-shell particles and 1 part of additives are dissolved in 100 parts of a mixed solvent of butanone, toluene and propylene glycol methyl ether, wherein butanone, toluene and propylene glycol methyl ether are mixed in a mass ratio of 1:1:1. After being thoroughly stirred, the mixture is sprayed onto the surface of a PET film and then baked at 150°C for 5 minutes to obtain an extended film.

[0157] Comparative Example 1

[0158] By weight, 20 parts allylbenzoxazine, 30 parts biphenyl epoxy resin, 20 parts phenolic curing agent, 3 parts imidazole accelerator, 200 parts spherical silica, 15 parts core-shell particles and 1 part additive are dissolved in 100 parts of a mixed solvent of butanone, toluene and propylene glycol methyl ether, wherein butanone, toluene and propylene glycol methyl ether are mixed in a mass ratio of 1:1:1. After being thoroughly stirred, the mixture is sprayed onto the PET surface and then baked at 150℃ for 5 minutes to obtain a thickened film.

[0159] Comparative Example 2

[0160] By weight, 60 parts of modified allyl benzoxazine prepolymer A, 30 parts of biphenyl epoxy resin, 20 parts of phenolic curing agent, 3 parts of imidazole accelerator, 200 parts of spherical silica, 15 parts of core-shell particles and 1 part of additives were dissolved in a mixed solvent of 100 parts of methyl ethyl ketone, toluene and propylene glycol methyl ether, wherein the methyl ethyl ketone, toluene and propylene glycol methyl ether were mixed in a mass ratio of 1:1:1. After being thoroughly stirred, the mixture was sprayed onto the PET surface and then baked at 160℃ for 5 minutes to obtain a thickened film.

[0161] The composition of the modified resin compositions in the above embodiments and comparative examples is shown in Table 1.

[0162] Table 1. Composition of the modified resin compositions in the examples and comparative examples

[0163]

[0164] The thickened films obtained in Examples 1-7 and Comparative Examples 1-2 were tested using the following methods:

[0165] The obtained laminated film (without the PET film) was laminated onto a 12μm thick copper foil using a laminator. After removing the PET film, a 12μm thick copper foil was then applied over it. The laminate was placed in a programmable temperature and pressure controlled vacuum press and cured completely under vacuum (vacuum parameters <10 mBar) and a pressure of 10 kgf / cm² for 100℃×30min+160℃×30min+200℃×120min to obtain the encapsulation substrate. Performance tests were conducted according to the following test standards, and the results are shown in Table 2.

[0166] 1. TMA test: Glass transition temperature (Tg) and coefficient of thermal expansion (CTE) are tested according to IPC-TM-650 2.4.24.5. CTE includes CTE below Tg (Before TG) and CTE above Tg (After TG).

[0167] 2. Warpage test: Tested according to IPC-TM-650 2.4.22.1;

[0168] 3. Electrical performance testing: Dielectric constant (Dk) and dielectric loss (Df) are tested according to IPC-TM-650 2.5.5.2;

[0169] 4. Water absorption rate: Tested according to IPC-TM650 2.6.2.1;

[0170] Table 2 Performance test results of Examples 1-7 and Comparative Examples 1-2

[0171]

[0172] As can be seen, the packaging substrates of Examples 1-7 have a Tg ≥ 173℃, a CTE ≤ 35ppm / ℃ below Tg, a CTE ≤ 85ppm / ℃ above Tg, a warpage ≤ 0.28mm, a Dk ≤ 3.67, a Df ≤ 0.0128, and a water absorption rate ≤ 0.12%, exhibiting extremely low coefficient of thermal expansion, low dielectric constant, low valence point loss, low water absorption rate, and high heat resistance.

[0173] Comparing Examples 1-7 with Comparative Example 1, it can be found that modifying allyl benzoxazine with trinaphthalene dielyl ether can significantly increase Tg (by more than 23°C) and significantly reduce CTE (CTE reduced by 25-38 ppm / °C below Tg, and CTE reduced by 45-60 ppm / °C above Tg), warpage (reduced by 1-1.08 mm), Dk (reduced by 0.32-0.39), Df (reduced by more than 0.1362), and water absorption (reduced by 0.76%-0.8%). Therefore, modifying allyl benzoxazine with trinaphthalene dielyl ether can greatly improve heat resistance and reduce the coefficient of thermal expansion, dielectric constant, valence point loss, and water absorption, thus meeting application requirements.

[0174] Comparing Examples 1-4 with Comparative Example 2, it can be seen that excessive use of modified allyl benzoxazine resin will lead to deterioration of overall performance. The amount of modified allyl benzoxazine resin should be 10-40 parts.

[0175] 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.

[0176] The embodiments described above are merely illustrative of several implementation methods of this application, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. 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 all fall within the protection scope of this application. Therefore, the protection scope of this patent application should be determined by the appended claims.

Claims

1. A modified resin composition, characterized in that, The components include the following parts by weight: 10-30 parts of modified allyl benzoxazine prepolymer; 10-40 parts of functional resin; 10-30 parts of curing agent; 1-5 parts of curing accelerator; 100-250 parts of inorganic filler; 10-30 parts of organic filler; 1-5 parts of auxiliary agent; The raw materials for preparing the modified allyl benzoxazine prepolymer include: allyl compounds and allyl benzoxazine resin; The allyl compound includes a first allyl compound, which is a trimenaphthalene dielyl ether, with the following structure: ； The mass ratio of the allyl compound to the allyl benzoxazine resin is (0.8-1.2):1; The functional resin is one or more of epoxy resin, benzoxazine and bismaleimide resin; The inorganic filler is selected from modified spherical silica and / or modified spherical alumina; The organic filler is selected from one or more of organosilicon particles, core-shell rubber particles, and olefin elastomer particles.

2. The modified resin composition according to claim 1, characterized in that, The allyl compound further includes a second allyl compound; the second allyl compound is selected from one or more of diallyl bisphenol A, diallyl bisphenol S, diallyl bisphenol F, and bisphenol A diallyl ether.

3. The modified resin composition according to claim 1, characterized in that, The allylbenzoxazine resin is selected from one or more of the following structures: Where X is selected from -CR2R3-, -SO2-, -O- or ; R2 and R3 are each independently selected from -H or -CH3; And / or, the preparation method of the modified allylbenzoxazine prepolymer includes the following steps: The modified allyl benzoxazine prepolymer is prepared by mixing an allyl compound and an allyl benzoxazine resin and reacting and prepolymerizing at 120-180°C.

4. The modified resin composition according to any one of claims 1-3, characterized in that, The curing agent is selected from one or more of amine curing agents, phenolic curing agents, acid anhydride curing agents, cyanate ester curing agents, and reactive ester curing agents; And / or, the additive is one or more of the following: dispersant, leveling agent, defoamer, treatment agent, and coupling agent.

5. The use of the modified resin composition according to any one of claims 1-4 in a thickened film.

6. A layering film, characterized in that, Includes the modified resin composition according to any one of claims 1-4.

7. The method for preparing the layered film as described in claim 6, characterized in that, Includes the following steps: A modified resin composition is coated onto a support to form a resin composition coating, which is then cured to prepare a thickened film.

8. The preparation method according to claim 7, characterized in that, The curing temperature is 70℃-160℃, and the curing time is 2min-15min; And / or, the support is selected from plastic film and / or metal film.

9. The application of the modified resin composition according to any one of claims 1-4, the layering film according to claim 6, or the layering film prepared by the preparation method according to claim 7 or 8 in the packaging substrate of a flip chip ball grid array.

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