Modified allyl benzoxazine resin composition, build-up film, preparation method therefor, and use thereof

Abstract

Provided are a modified allyl benzoxazine resin composition, a build-up film, a preparation method therefor, and use thereof. The modified allyl benzoxazine resin composition comprises a modified allyl benzoxazine resin, a functional resin, a curing agent, a curing accelerator, an inorganic filler, and an auxiliary agent. Raw materials for preparing the modified allyl benzoxazine resin comprise: a modifier and the allyl benzoxazine resin, the modifier comprising a first modifier, and the first modifier being an amine fluorine-containing compound. The build-up film comprises a modified allyl benzoxazine resin composition. The preparation method comprises coating the modified allyl benzoxazine resin composition on a substrate to form a resin composition coating. The build-up film is applied to a package substrate of a flip chip ball grid array.

Description

Modified allyl benzoxazine resin composition, thickening film, preparation method and application Technical Field

[0001] This application relates to the field of composite materials technology, and in particular to modified allyl benzoxazine resin compositions, layered films, 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] Compared with traditional packaging substrate technology, FCBGA carrier technology has higher integration, smaller package size, higher reliability and lower power consumption, which requires its main raw material, build-up film, to have better performance.

[0004] With the advent of the "Artificial Intelligence (AI)" era and the increase in information processing volume and speed, FCBGA substrates require lower dielectric constants and dielectric losses to reduce transmission losses. Furthermore, high water absorption in the packaging substrate can cause the "popcorn" phenomenon, leading to packaging failure. Therefore, FCBGA substrates place higher demands on the dielectric constant, dielectric loss, and water absorption of their fabrication materials.

[0005] Benzoxazine resins are widely used in electronic materials and other fields due to their high heat resistance, good flame retardancy, low water absorption, excellent dielectric properties, and the fact that no small molecules are released during curing and the volume shrinkage is almost zero. However, the dielectric and water absorption properties of compositions prepared from unmodified benzoxazine resins are still insufficient to meet the application requirements of laminated films.

[0006] Therefore, how to prepare resin compositions with low dielectric constant, dielectric loss and water absorption rate to meet the application requirements of laminated films has become an urgent problem to be solved in the industry. Summary of the Invention

[0007] Therefore, the main objective of this application is to provide a modified allyl benzoxazine resin composition with low dielectric constant, low dielectric loss and low water absorption to meet the application requirements of film-forming layers.

[0008] The first aspect of this application provides a modified allyl benzoxazine resin composition comprising the following components in parts by weight:

[0009] 10-40 parts of modified allyl benzoxazine resin;

[0010] 10-60 parts of functional resin;

[0011] 10-40 parts of curing agent;

[0012] 1-10 parts of curing accelerator;

[0013] Inorganic filler 50-300 parts;

[0014] 0-5 parts of auxiliary agent;

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

[0016] The modifier includes a first modifier; the first modifier is an amine-based fluorinated compound;

[0017] The fluorinated amine compound is 2,2-bis(4-allyloxyphenyl)hexafluoropropane.

[0018] In some embodiments, the preparation method of the modified allyl benzoxazine resin includes the following steps:

[0019] The modified allyl benzoxazine resin is prepared by mixing the modifier with an allyl benzoxazine resin and reacting it at 120-180°C.

[0020] In some embodiments, the reaction time is 1-3 hours.

[0021] In some embodiments, the allylbenzoxazine resin is selected from one or more of the following structures:

[0022]

[0023]

[0024] Where X is selected from -CHR1-, -CR2R3-, -SO2-, -O- or

[0025] R1, R2, and R3 are each independently selected from -H or -CH3.

[0026] In some embodiments, the modifier further includes a second modifier; the second modifier is an allyl compound.

[0027] In some embodiments, the allyl compound includes one or more of diallyl bisphenol A, diallyl bisphenol S, diallyl bisphenol F, and bisphenol A diallyl ether; the mass ratio of the first modifier to the second modifier is (3-6):1.

[0028] In some embodiments, the mass ratio of the modifier to the allyl benzoxazine resin is (60-150):100; optionally, the mass ratio of the modifier to the allyl benzoxazine resin is (80-120):100.

[0029] In some embodiments, the functional resin includes epoxy resin and / or benzoxazine 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 naphthalene type benzoxazine resin.

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

[0033] In some embodiments, the inorganic filler comprises modified spherical silica and / or modified spherical alumina.

[0034] 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; 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.

[0035] In some embodiments, the additives include one or more of dispersants, leveling agents, defoamers, treatment agents, and coupling agents.

[0036] A second aspect of this application provides a laminated film comprising the aforementioned modified allylbenzoxazine resin composition.

[0037] A third aspect of this application provides a method for preparing the aforementioned layered film, comprising the following steps:

[0038] A modified allylbenzoxazine resin composition is coated onto a substrate to form a resin composition coating, which is then heated and dried to prepare an extended film.

[0039] In some embodiments, the temperature for heating and drying is 70°C-160°C, and the time for heating and drying is 2 min-15 min.

[0040] In some embodiments, the substrate includes a plastic film and / or a metal film.

[0041] A fourth aspect of this application provides the application of the aforementioned modified allyl benzoxazine resin composition and the aforementioned build-up film in a packaging substrate for a flip-chip ball grid array.

[0042] A fifth aspect of this application provides a packaging substrate for a flip-chip ball grid array, comprising the aforementioned modified allyl benzoxazine resin composition and the aforementioned build-up film.

[0043] The beneficial effects of this application are:

[0044] This application modifies allyl benzoxazine resin using amine-based fluorinated compounds. Modified allyl benzoxazine resin is prepared through an addition reaction of amino groups and carbon-carbon double bonds. The selected amine-based fluorinated compounds have multiple rigid benzene rings and fluorine atoms. Due to the special molecular structure and chemical properties of the rigid benzene rings, they are difficult to form hydrogen bonds with water molecules. The presence of multiple rigid benzene rings can effectively reduce the water absorption rate of the resin. Furthermore, the fluorine atoms have extremely high electronegativity, which can effectively shield charges and reduce the dielectric constant and dielectric loss of the resin. This results in a modified allyl benzoxazine resin composition with low dielectric constant, low dielectric loss, and low water absorption rate, meeting the application requirements of film-forming layers. Detailed Implementation

[0045] 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.

[0046] 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.

[0047] 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.

[0048] 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.

[0049] In this description, "multiple" means two or more, such as two kinds, three kinds, etc., unless otherwise explicitly specified.

[0050] 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.

[0051] 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).

[0052] 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.

[0053] 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.

[0054] One aspect of this application provides a modified allyl benzoxazine resin composition comprising the following components in parts by weight:

[0055] 10-40 parts of modified allyl benzoxazine resin;

[0056] 10-60 parts of functional resin;

[0057] 10-40 parts of curing agent;

[0058] 1-10 parts of curing accelerator;

[0059] Inorganic filler 50-300 parts;

[0060] 0-5 parts of auxiliary agent;

[0061] The raw materials for preparing the modified allyl benzoxazine resin include: a modifier and allyl benzoxazine resin;

[0062] The modifier includes a first modifier; the first modifier is an amine-based fluorinated compound;

[0063] The fluorinated amine compound is 2,2-bis(4-allyloxyphenyl)hexafluoropropane.

[0064] The structure of 2,2-bis(4-allyloxyphenyl)hexafluoropropane is shown below:

[0065]

[0066] This application modifies allyl benzoxazine resin using amine-based fluorinated compounds. Modified allyl benzoxazine resin is prepared through an addition reaction of amino groups and carbon-carbon double bonds. The selected amine-based fluorinated compounds have multiple rigid benzene rings and fluorine atoms. Due to the special molecular structure and chemical properties of the rigid benzene rings, they are difficult to form hydrogen bonds with water molecules. The presence of multiple rigid benzene rings can effectively reduce the water absorption rate of the resin. Furthermore, the fluorine atoms have extremely high electronegativity, which can effectively shield charges and reduce the dielectric constant and dielectric loss of the resin. This results in a modified allyl benzoxazine resin composition with low dielectric constant, low dielectric loss, and low water absorption rate, meeting the application requirements of film-forming layers.

[0067] In some embodiments, the preparation method of the modified allyl benzoxazine resin includes the following steps:

[0068] The modified allyl benzoxazine resin is prepared by mixing the modifier with an allyl benzoxazine resin and reacting it at 120-180°C.

[0069] In some embodiments, the reaction time is 1-3 hours; the mass ratio of the modifier to the allyl benzoxazine resin is (60-150):100, more preferably, the mass ratio of the modifier to the allyl benzoxazine resin is (80-120):100.

[0070] Understandably, in this application, the modifier modifies the allyl benzoxazine resin through an addition reaction between the amino group and the double bond in the resin. The reaction temperature, reaction time, and their ratio can be adjusted according to actual needs. For example, increasing the reaction temperature can accelerate the reaction, extending the reaction time can increase the degree of reaction, and increasing the proportion of the modifier can increase the degree of modification. Specifically, the reaction temperature can be 120℃, 130℃, 140℃, 150℃, 160℃, 170℃, 180℃, etc., and the reaction time can be 1h, 1.5h, 2h, 2.5h, 3h, etc. The mass ratio of the modifier to the allyl benzoxazine resin can be 60:100, 70:100, 80:100, 90:100, 100:100, 110:100, 120:100, 130:100, 140:100, 150:100, 160:100, etc.

[0071] 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:

[0072]

[0073]

[0074] Where X is selected from -CHR1-, -CR2R3-, -SO2-, -O- or

[0075] R1, R2, and R3 are each independently selected from -H or -CH3.

[0076] Understandable This refers to a naphthalene ring that has been doubly substituted, with no limitation on the substitution site.

[0077] In some embodiments, the modifier further includes a second modifier; the second modifier is an allyl compound.

[0078] Understandably, in this application, the first modifier can be used alone or in combination with the second modifier, and the combination ratio is not limited.

[0079] In some embodiments, the allyl compound includes one or more of diallyl bisphenol A, diallyl bisphenol S, diallyl bisphenol F, and bisphenol A diallyl ether; 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.

[0080] In some embodiments, the functional resin includes epoxy resin and / or benzoxazine resin.

[0081] 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.

[0082] 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 naphthalene type benzoxazine resin.

[0083] The curing agent is not limited to a specific type. In some embodiments, the curing agent includes one or more of amine curing agents, phenolic curing agents, acid anhydride curing agents, cyanate ester curing agents, and reactive ester curing agents.

[0084] In some embodiments, the curing accelerator includes one or more of tertiary amine accelerators, imidazole accelerators, peroxide accelerators, organophosphorus accelerators, and transition metal carboxylate accelerators.

[0085] In some embodiments, the inorganic filler comprises modified spherical silica and / or modified spherical alumina.

[0086] 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; 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.

[0087] Understandably, there is no particular limitation on the average particle size of inorganic fillers, which can be 0.01μm-100μm, specifically 100μm, 50μm, 10μm, 5μm, 3μm, 1μm, 0.5μm, 0.1μm, 0.05μm, 0.01μm, etc.

[0088] In some embodiments, the additives include one or more of dispersants, leveling agents, defoamers, treatment agents, and coupling agents.

[0089] In some embodiments, the modified allyl benzoxazine resin composition comprises the following components in parts by weight:

[0090] 10-30 parts of modified allyl benzoxazine resin;

[0091] 10-50 parts of functional resin;

[0092] 10-30 parts of curing agent;

[0093] 1-5 parts of curing accelerator;

[0094] 50-250 parts of inorganic filler;

[0095] Additives: 1-5 parts.

[0096] A second aspect of this application provides a laminated film comprising the aforementioned modified allylbenzoxazine resin composition.

[0097] A third aspect of this application provides a method for preparing the aforementioned layered film, comprising the following steps:

[0098] A modified allylbenzoxazine resin composition is coated onto a substrate to form a resin composition coating, which is then heated and dried to prepare an extended film.

[0099] Understandably, the step of coating the modified allyl benzoxazine resin composition onto a support to form a resin composition coating can be as follows: dispersing the modified allyl benzoxazine 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; the mass ratio of the solvent to the modified allyl benzoxazine resin composition can be 1:1-5.

[0100] Understandably, solvent evaporation can be achieved during heating and drying.

[0101] In some embodiments, the temperature for heating and drying is 70°C-160°C, and the time for heating and drying is 2 min-15 min.

[0102] Understandably, there are no special limitations on the substrate. In some embodiments, the substrate includes a plastic film and / or a metal film. The plastic film includes, but is not limited to, polyethylene terephthalate (PET), polycarbonate (PC), polymethyl methacrylate (PMMA), etc.; the metal film may be copper foil or aluminum foil, etc.

[0103] Understandably, there are no special requirements for the thickness of the resin composition coating and the thickness of the substrate. For example, the thickness of the resin composition coating can be 5-150 μm, and the thickness of the substrate can be 3-105 μm.

[0104] A fourth aspect of this application provides the application of the aforementioned modified allyl benzoxazine resin composition and the aforementioned build-up film in a packaging substrate for a flip-chip ball grid array.

[0105] A fifth aspect of this application provides a packaging substrate for a flip-chip ball grid array, comprising the aforementioned modified allyl benzoxazine resin composition and the aforementioned build-up film.

[0106] In some embodiments, the packaging substrate satisfies at least one of the following properties: Tg ≥ 168°C; CTE ≤ 46 ppm / °C below Tg and CTE ≤ 125 ppm / °C above Tg; dielectric constant ≤ 3.71; dielectric loss ≤ 0.0114; water absorption ≤ 0.10%.

[0107] 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.

[0108] The sources of some components in the examples and comparative examples are as follows:

[0109] 2,2-Bis[4-(4-aminophenoxy)phenyl]hexafluoropropane: Tianjin Zhongtai, CAS: 69563-88-8;

[0110] Allyl benzoxazine resin: Dongcai Technology D148;

[0111] DCPD epoxy resin: DIC HP-7200H;

[0112] Reactive ester curing agent: DIC HPC-8000-65T;

[0113] Imidazole accelerator: Shikoku Kasei 2MI;

[0114] Spherical silica: Yaduma SO-C1;

[0115] Additive: BYK-1650 from BYK Chemicals.

[0116] The following are specific examples.

[0117] Example 1 of the synthesis of modified allyl benzoxazine resin

[0118] First, 80 parts of 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane were heated to a molten state, and then 100 parts of allylbenzoxazine resin were added. After prepolymerization at 150°C for 120 min, the mixture was cooled to room temperature to obtain modified allylbenzoxazine resin A.

[0119] Example 2 of the synthesis of modified allyl benzoxazine resin

[0120] First, 120 parts of 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane were heated to a molten state, and then 100 parts of allylbenzoxazine resin were added. After prepolymerization at 160°C for 140 min, the mixture was cooled to room temperature to obtain modified allylbenzoxazine resin B.

[0121] Example 3 of the synthesis of modified allyl benzoxazine resin

[0122] First, 100 parts of 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane were heated to a molten state, and then 100 parts of allylbenzoxazine resin were added. After prepolymerization at 150°C for 130 min, the mixture was cooled to room temperature to obtain modified allylbenzoxazine resin C.

[0123] Example 4 of the synthesis of modified allyl benzoxazine resin

[0124] First, 80 parts of 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane 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 prepolymerized at 150°C for 120 min and then cooled to room temperature to obtain modified allyl benzoxazine resin D.

[0125] Example 5 of the synthesis of modified allyl benzoxazine resin

[0126] First, 100 parts of allyl bisphenol A were heated to a molten state, and then 100 parts of allyl benzoxazine resin were added. After prepolymerization at 160°C for 130 min, the mixture was cooled to room temperature to obtain modified allyl benzoxazine resin E.

[0127] Example 1

[0128] By weight, 10 parts of modified allyl benzoxazine resin A, 50 parts of DCPD epoxy resin, 30 parts of reactive ester curing agent, 5 parts of imidazole accelerator, 250 parts of spherical silica and 5 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 being thoroughly stirred, the mixture was sprayed onto the surface of a PET film and then baked at 130°C for 8 minutes to obtain an extended film (PET film 38 μm, coating thickness 100 μm, the thickness is the same in other examples and comparative examples).

[0129] Example 2

[0130] By weight, 20 parts of modified allyl benzoxazine resin A, 30 parts of DCPD epoxy resin, 20 parts of reactive ester curing agent, 3 parts of imidazole accelerator, 150 parts of spherical silica and 3 parts 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 120°C for 8 minutes to obtain an extended film.

[0131] Example 3

[0132] By weight, 30 parts of modified allyl benzoxazine resin A, 10 parts of DCPD epoxy resin, 10 parts of reactive ester curing agent, 1 part of imidazole accelerator, 50 parts of spherical silica and 1 part of additive are dissolved in a mixed solvent of 80 parts of methyl ethyl ketone, toluene and propylene glycol methyl ether, wherein methyl ethyl ketone, 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 120°C for 8 minutes to obtain an extended film.

[0133] Example 4

[0134] By weight, 40 parts of modified allyl benzoxazine resin A, 60 parts of DCPD epoxy resin, 40 parts of reactive ester curing agent, 10 parts of imidazole accelerator, 300 parts of spherical silica and 5 parts of additives were dissolved in a mixed solvent of 150 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 surface of a PET film and then baked at 130°C for 10 minutes to obtain an extended film.

[0135] Example 5

[0136] By weight, 20 parts of modified allyl benzoxazine resin B, 30 parts of DCPD epoxy resin, 20 parts of reactive ester curing agent, 3 parts of imidazole accelerator, 150 parts of spherical silica and 3 parts 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 120°C for 8 minutes to obtain an extended film.

[0137] Example 6

[0138] By weight, 20 parts of modified allyl benzoxazine resin C, 30 parts of DCPD epoxy resin, 20 parts of reactive ester curing agent, 3 parts of imidazole accelerator, 150 parts of spherical silica and 3 parts 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 120°C for 8 minutes to obtain an extended film.

[0139] Example 7

[0140] By weight, 20 parts of modified allyl benzoxazine resin D, 30 parts of DCPD epoxy resin, 20 parts of reactive ester curing agent, 3 parts of imidazole accelerator, 150 parts of spherical silica and 3 parts 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 120°C for 8 minutes to obtain an extended film.

[0141] Comparative Example 1

[0142] By weight, 20 parts of modified allyl benzoxazine resin E, 30 parts of DCPD epoxy resin, 20 parts of reactive ester curing agent, 3 parts of imidazole accelerator, 150 parts of spherical silica and 3 parts 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 120°C for 8 minutes to obtain an extended film.

[0143] Comparative Example 2

[0144] By weight, 20 parts allylbenzoxazine, 30 parts DCPD epoxy resin, 20 parts reactive ester curing agent, 3 parts imidazole accelerator, 150 parts spherical silica and 3 parts 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 120°C for 8 minutes to obtain an extended film.

[0145] Comparative Example 3

[0146] By weight, 50 parts of modified allyl benzoxazine resin A, 30 parts of DCPD epoxy resin, 20 parts of reactive ester curing agent, 3 parts of imidazole accelerator, 150 parts of spherical silica and 3 parts 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 surface of a PET film and then baked at 120°C for 8 minutes to obtain an extended film.

[0147] The composition of the resin compositions in the above embodiments and comparative examples is shown in Table 1.

[0148] Table 1. Components of the Examples and Comparative Examples

[0149]

[0150] The thickened films obtained in Examples 1-7 and Comparative Examples 1-3 were tested using the following methods:

[0151] The laminated films (without the PET film) obtained in Examples 1-7 and Comparative Examples 1-3 were laminated onto copper foil with a thickness of 12 μm using a laminator. After removing the PET film, a copper foil with a thickness of 12 μm was applied on top. The laminated films were then placed in a programmable temperature and pressure controlled vacuum press and subjected to a vacuum condition (vacuum parameter <10 mBar) at 10 kgf / cm². 2 Under pressure, the substrate was completely cured at 100℃×30min+150℃×30min+190℃×120min to obtain the encapsulated substrate. Then, the performance was tested according to the following test standards, and the results are shown in Table 2.

[0152] 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).

[0153] 2. Electrical performance testing: Dielectric constant (Dk) and dielectric loss (Df) are tested according to IPC-TM-650 2.5.5.2;

[0154] 3. Water absorption rate: Tested according to IPC-TM650 2.6.2.1.

[0155] Table 2 Performance test results of Examples 1-7 and Comparative Examples 1-3

[0156]

[0157] As can be seen from Table 2, the encapsulation substrates prepared by the layered films in Examples 1-7 all have high Tg (≥168℃), low coefficient of thermal expansion (CTE≤46ppm / ℃ below Tg, CTE≤125ppm / ℃ above Tg), dielectric constant (≤3.71), dielectric loss (≤0.0114), and water absorption rate (≤0.10%), that is, they simultaneously have relatively ideal heat resistance, coefficient of thermal expansion, dielectric properties, and water absorption rate.

[0158] Comparing Example 2 and Comparative Example 1, it can be seen that using amine-based fluorinated compounds as modifiers, compared with using allyl bisphenol A as a modifier, is beneficial for reducing the coefficient of thermal expansion, dielectric properties, and water absorption, while improving heat resistance. Comparing Example 2 and Comparative Example 2, it can be seen that using modified allyl benzoxazine resin in Example 2, compared with using allyl benzoxazine resin in Comparative Example 2, can significantly improve the heat resistance of the laminated film and significantly reduce its coefficient of thermal expansion, dielectric properties, and water absorption. Comparing Example 2 and Comparative Example 3, 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.

[0159] 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.

[0160] The embodiments described above merely illustrate various 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 allylbenzoxazine resin composition, characterized in that, The components include the following parts by weight: The raw materials for preparing the modified allyl benzoxazine resin include: a modifier and allyl benzoxazine resin; The modifier includes a first modifier; the first modifier is an amine-based fluorinated compound; The structure of the fluorinated amine compound is shown below:

2. The modified allyl benzoxazine resin composition according to claim 1, characterized in that, The modifier further includes a second modifier; the second modifier is an allyl compound; Optionally, the mass ratio of the modifier to the allyl benzoxazine resin is (60-150):100; more preferably, the mass ratio of the modifier to the allyl benzoxazine resin is (80-120):

100. Optionally, the allyl compound includes one or more of diallyl bisphenol A, diallyl bisphenol S, diallyl bisphenol F, and bisphenol A diallyl ether; Optionally, the mass ratio of the first modifier to the second modifier is (3-6):

1.

3. The modified allyl benzoxazine resin composition according to claim 1, characterized in that, The preparation method of the modified allyl benzoxazine resin includes the following steps: The modifier is mixed with the allyl benzoxazine resin and reacted at 120-180°C to prepare the modified allyl benzoxazine resin. Optionally, the reaction time is 1-3 hours.

4. The modified allyl benzoxazine 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 -CHR1-, -CR2R3-, -SO2-, -O- or R1, R2, and R3 are each independently selected from -H or -CH3.

5. The modified allyl benzoxazine resin composition according to any one of claims 1-4, characterized in that, The functional resins include epoxy resins and / or benzoxazine resins; Optionally, 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. Optionally, 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 naphthalene type benzoxazine resin.

6. The modified allyl benzoxazine resin composition according to any one of claims 1-4, characterized in that, The curing agent includes 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 inorganic filler includes modified spherical silica and / or modified spherical alumina; And / or the additives include one or more of dispersants, leveling agents, defoamers, treatment agents and coupling agents.

7. The modified allyl benzoxazine resin composition according to claim 6, characterized in that, 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; 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.

8. A layering film, characterized in that, The modified allyl benzoxazine resin composition according to any one of claims 1-7.

9. The method for preparing the layered film as described in claim 8, characterized in that, Includes the following steps: A modified allylbenzoxazine resin composition is coated onto a substrate to form a resin composition coating, which is then heated and dried to prepare an extended film. Optionally, the heating and drying temperature is 70℃-160℃, and the heating and drying time is 2min-15min; Optionally, the substrate may include a plastic film and / or a metal film.

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

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