Resin composition and application thereof, layer-adding film and preparation method and application thereof

Abstract

The invention provides a resin composition and application thereof, a layer-adding film and a preparation method and application thereof, and belongs to the technical field of composite materials. The resin composition is prepared from the following components in parts by mass: 10 to 30 parts of modified benzoxazine prepolymer; 10 to 40 parts of modified polyphenyl ether resin; 1-5 parts of an initiator; and 100 to 300 parts of an inorganic filler. The modified benzoxazine prepolymer is synthesized from raw materials including allyl benzoxazine and a diamine compound containing a benzocyclobutene structure. According to the present invention, the diamine compound containing the benzocyclobutene structure is adopted to modify the allyl benzoxazine, and the mass parts of the modified benzoxazine prepolymer, the modified polyphenyl ether resin, the initiator and the inorganic filler in the resin composition are controlled, such that the dielectric property and the heat resistance of the resin composition can be significantly improved; and the film-forming property is excellent, and the requirement of a layer-adding film is met.

Description

Technical Field

[0001] This application relates to the field of composite materials technology, and in particular to resin compositions and their applications, as well as laminated films, their preparation methods, and their applications. Background Technology

[0002] Flip-chip ball grid array (FC-BGA) substrate technology is a semiconductor packaging technology that enables electrical connections and signal transmission, and is widely used in fields such as computers, communications, consumer electronics, medical and industrial control.

[0003] Enhancement films are key materials in the semi-additive process (SAP) manufacturing of FC-BGA substrates, offering advantages such as higher integration density, smaller package size, higher reliability, and lower power consumption. However, enhancement films prepared from traditional resin compositions commonly exhibit dielectric property deviations, which can lead to significant dielectric losses and heat generation in high-frequency and high-speed applications, severely impacting their application in integrated circuits.

[0004] Therefore, how to improve the dielectric properties of resin compositions to meet the application requirements of laminated films has become an urgent problem to be solved. Summary of the Invention

[0005] Therefore, the main objective of this application is to provide resin compositions and their applications, as well as methods for preparing and using laminated films, to improve the dielectric properties of the resin compositions and meet the application requirements of laminated films for dielectric properties.

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

[0007] 10-30 parts of modified benzoxazine prepolymer;

[0008] 10-40 parts of modified polyphenylene ether resin;

[0009] 1-5 parts of initiator; and

[0010] Inorganic filler 100-300 parts;

[0011] The modified benzoxazine prepolymer is synthesized from raw materials including allylbenzoxazine and diamine compounds containing a benzocyclobutene structure.

[0012] In some embodiments, the diamine compound containing a benzocyclobutene structure includes at least one of the compounds with the structure shown in Formula 1:

[0013] Formula 1;

[0014] Wherein, R1 and R2 are independently selected from any of the following structures:

[0015] , ,

[0016] , .

[0017] In some embodiments, the allylbenzoxazine comprises at least one of compounds with the structure shown below:

[0018] , ,

[0019] ;

[0020] Among them, R3 is selected from -CR4R5-, -SO2-, -O-, , , , or ;

[0021] R4 and R5 are independently selected from -H or -CH3.

[0022] In some embodiments, the modified benzoxazine prepolymer is prepared by the following method:

[0023] The modified benzoxazine prepolymer is prepared by polymerizing the allylbenzoxazine and the diamine compound containing the benzocyclobutene structure.

[0024] In some embodiments, the mass ratio of the allylbenzoxazine to the diamine compound containing the benzocyclobutene structure is 1:(0.6-1.2).

[0025] In some embodiments, the conditions for the polymerization reaction include a reaction temperature of 100-200°C and a reaction time of 60-150 min.

[0026] In some embodiments, the modified polyphenylene ether resin includes at least one of vinyl benzyl ether modified polyphenylene ether resin, allyl modified polyphenylene ether resin, and methyl polyacrylate modified bisphenol A type polyphenylene ether resin.

[0027] In some embodiments, the initiator includes a peroxide initiator.

[0028] In some embodiments, the peroxide initiator includes at least one of dicumyl peroxide, benzoyl peroxide, di-tert-butyl peroxide, and dilauryl peroxide.

[0029] In some embodiments, the inorganic filler includes at least one selected from zirconium vanadate, zirconium tungstate, hafnium tungstate, microcrystalline glass, nepheline, silica, quartz, mica powder, titanium dioxide, magnesium oxide, magnesium hydroxide, talc, alumina, silicon carbide, boron nitride, aluminum nitride, molybdenum oxide, barium sulfate, zinc molybdate, zinc borate, zinc stannate, zinc oxide, strontium titanate, barium titanate, calcium titanate, and clay.

[0030] A second aspect of this application provides the use of the resin composition described in the first aspect in the preparation of a thickened film.

[0031] A third aspect of this application provides a laminated film comprising: the resin composition described in the first aspect.

[0032] In a fourth aspect, this application provides a method for preparing an extended film, comprising the following steps:

[0033] The resin composition described in the first aspect is coated onto a support and dried to prepare the thickened film.

[0034] In some embodiments, the step of coating the resin composition onto the support specifically includes:

[0035] The resin composition is dissolved in a solvent to prepare a coating solution, which is then coated onto a support.

[0036] In some embodiments, the solvent includes at least one of butanone, toluene, and propylene glycol methyl ether.

[0037] In some embodiments, the support comprises a plastic film and / or a metal film.

[0038] In some embodiments, the plastic film includes at least one of polyethylene terephthalate, polycarbonate, and polymethyl methacrylate.

[0039] In some embodiments, the metal film includes copper foil or aluminum foil.

[0040] In some embodiments, the thickness of the augmentation film is 13-150 μm.

[0041] In some embodiments, the drying conditions include a temperature of 50-160°C and a time of 1-10 minutes.

[0042] The fifth aspect of this application provides the application of the resin composition described in the first aspect, the build-up film described in the third aspect, or the build-up film prepared by the preparation method described in the fourth aspect in the packaging substrate of a flip-chip ball grid array.

[0043] Compared with traditional technologies, this application has at least the following beneficial effects:

[0044] This application significantly reduces the dielectric constant and dielectric loss of the resin composition by controlling the mass fractions of modified benzoxazine prepolymer, modified polyphenylene ether resin, initiator, and inorganic filler, while also exhibiting excellent film-forming properties and heat resistance, thus meeting the requirements for layered films. Specifically, this application uses a diamine compound containing a benzocyclobutene structure to modify allylbenzoxazine. The modified benzoxazine prepolymer prepared has a wide optical band gap in its benzocyclobutene structure, which can restrict electronic transitions and polarization processes. Its high resistivity also reduces leakage current, thereby lowering dielectric loss. Detailed Implementation

[0045] The present application will be further described in detail below with reference to the embodiments and examples. These embodiments and examples are for illustrative purposes only and are not intended to limit the scope of the present application. The purpose of providing these embodiments and examples is to enable a more thorough and comprehensive understanding of the disclosure of the present application. It should also be understood that the present application can be implemented in many different forms and is not limited to the embodiments and examples described herein. Those skilled in the art can make various modifications or alterations without departing from the spirit of the present application, and the equivalent forms obtained also fall within the protection scope of the present application. Furthermore, numerous specific details are set forth in the following description to provide a fuller understanding of the present application. It should be understood that the present application can be implemented without one or more of these details.

[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] To address the common problem of dielectric property deviations in traditional resin compositions used for build-up films, which easily lead to significant dielectric losses and heat generation in high-frequency and high-speed applications, severely impacting their use in integrated circuits, this application addresses this issue. By controlling the mass fractions of modified benzoxazine prepolymer, modified polyphenylene ether resin, initiator, and inorganic filler in the resin composition, the dielectric constant and dielectric loss of the resin composition can be significantly reduced, while maintaining excellent film-forming properties and heat resistance, thus meeting the requirements for build-up films. Specifically, by modifying allylbenzoxazine with a diamine compound containing a benzocyclobutene structure, the prepared modified benzoxazine prepolymer exhibits a wide optical band gap, which restricts electronic transitions and polarization processes. Its high resistivity reduces leakage current, thereby lowering dielectric losses.

[0048] In a first aspect, this application provides a resin composition comprising the following components in parts by weight:

[0049] 10-30 parts of modified benzoxazine prepolymer;

[0050] 10-40 parts of modified polyphenylene ether resin;

[0051] 1-5 parts of initiator; and

[0052] Inorganic filler 100-300 parts;

[0053] The modified benzoxazine prepolymer is synthesized from raw materials including allylbenzoxazine and diamine compounds containing a benzocyclobutene structure.

[0054] The dielectric properties, heat resistance, and film-forming properties of the resin composition can be improved by controlling the mass fraction of each component in the resin composition as described in this application. Specifically, by modifying allylbenzoxazine with a diamine compound containing a benzocyclobutene structure, the modified benzoxazine prepolymer exhibits a wide optical band gap in the benzocyclobutene structure, which restricts electronic transitions and polarization processes. Simultaneously, its high resistivity reduces leakage current, thereby lowering dielectric loss.

[0055] In some embodiments, the diamine compound containing a benzocyclobutene structure includes at least one of the compounds with the structure shown in Formula 1:

[0056] Formula 1;

[0057] Wherein, R1 and R2 are independently selected from any of the following structures:

[0058] , ,

[0059] , .

[0060] In some embodiments, the diamine compound containing a benzocyclobutene structure has the structure shown below:

[0061] .

[0062] In some embodiments, the allylbenzoxazine comprises at least one of compounds with the structure shown below:

[0063] , ,

[0064] ;

[0065] Among them, R3 is selected from -CR4R5-, -SO2-, -O-, , , , or ;

[0066] R4 and R5 are independently selected from -H or -CH3.

[0067] In some embodiments, the modified benzoxazine prepolymer in the resin composition is 10-30 parts by mass, which can be 10 parts, 15 parts, 20 parts, 25 parts or 30 parts.

[0068] The modified polyphenylene ether resin is in the range of 10-40 parts by weight, and can be 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts or 40 parts.

[0069] The initiator is present in 1-5 parts by mass, and can be 1 part, 2 parts, 3 parts, 4 parts or 5 parts;

[0070] The inorganic filler has a mass fraction of 100-300 parts, which can be 100 parts, 150 parts, 200 parts, 250 parts or 300 parts.

[0071] This application can significantly reduce the dielectric constant and dielectric loss of the resin composition by controlling the mass fractions of modified benzoxazine prepolymer, modified polyphenylene ether resin, initiator and inorganic filler in the resin composition, while also possessing excellent film-forming properties and heat resistance, thereby meeting the requirements of laminated films.

[0072] In some embodiments, the modified benzoxazine prepolymer is prepared by the following method:

[0073] The modified benzoxazine prepolymer is prepared by polymerizing the allylbenzoxazine and the diamine compound containing the benzocyclobutene structure.

[0074] In some embodiments, the mass ratio of the allylbenzoxazine to the diamine compound containing the benzocyclobutene structure is 1:(0.6-1.2), which can be 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, 1:1.1 or 1:1.2.

[0075] In some embodiments, the conditions for the polymerization reaction include: a reaction temperature of 100-200°C, which can be 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C, or 200°C; and a reaction time of 60-150 min, which can be 60 min, 70 min, 80 min, 90 min, 100 min, 110 min, 120 min, 130 min, 140 min, or 150 min.

[0076] In some embodiments, the modified polyphenylene ether resin includes at least one of vinyl benzyl ether modified polyphenylene ether resin, allyl modified polyphenylene ether resin, and methyl polyacrylate modified bisphenol A type polyphenylene ether resin.

[0077] In some embodiments, the initiator includes a peroxide initiator.

[0078] In some embodiments, the peroxide initiator includes at least one of dicumyl peroxide, benzoyl peroxide, di-tert-butyl peroxide, and dilauryl peroxide.

[0079] In some embodiments, the inorganic filler includes at least one selected from zirconium vanadate, zirconium tungstate, hafnium tungstate, microcrystalline glass, nepheline, silica, quartz, mica powder, titanium dioxide, magnesium oxide, magnesium hydroxide, talc, alumina, silicon carbide, boron nitride, aluminum nitride, molybdenum oxide, barium sulfate, zinc molybdate, zinc borate, zinc stannate, zinc oxide, strontium titanate, barium titanate, calcium titanate, and clay.

[0080] In some embodiments, the clay includes kaolin.

[0081] In some embodiments, the inorganic filler is silicon dioxide, which includes spherical silicon dioxide.

[0082] A second aspect of this application provides the use of the resin composition described in the first aspect in the preparation of a thickened film.

[0083] A third aspect of this application provides a laminated film comprising: the resin composition described in the first aspect.

[0084] In a fourth aspect, this application provides a method for preparing an extended film, comprising the following steps:

[0085] The resin composition described in the first aspect is coated onto a support and dried to prepare the thickened film.

[0086] After drying, a coating is formed on the support to obtain the laminated film.

[0087] In some embodiments, the thickness of the coating is 10-150 μm, and can be 10 μm, 30 μm, 70 μm, 90 μm, 110 μm, 130 μm or 150 μm.

[0088] In some embodiments, the step of coating the resin composition onto the support specifically includes:

[0089] The resin composition is dissolved in a solvent to prepare a coating solution, which is then coated onto a support.

[0090] In some embodiments, the solvent includes at least one of butanone, toluene, and propylene glycol methyl ether.

[0091] In some embodiments, the solvent includes butanone, toluene, and propylene glycol methyl ether, wherein the mass ratio of butanone, toluene, and propylene glycol methyl ether is (1-2):(1-2):(1-2), which can be 1:1:2, 1:1:1, 1:2:1, or 2:2:1.

[0092] In some embodiments, the support comprises a plastic film and / or a metal film.

[0093] In some embodiments, the plastic film includes at least one of polyethylene terephthalate (PET), polycarbonate (PC), and polymethyl methacrylate (PMMA).

[0094] In some embodiments, the metal film includes copper foil or aluminum foil.

[0095] In some embodiments, the thickness of the support is 3-105 μm, and can be 3 μm, 30 μm, 38 μm, 60 μm, 80 μm, 100 μm or 105 μm.

[0096] In some embodiments, the drying conditions include: a temperature of 50-160°C, which can be 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, or 160°C; and a time of 1-10 min, which can be 1 min, 2 min, 3 min, 4 min, 5 min, 6 min, 8 min, or 10 min.

[0097] In some implementations, drying is carried out by baking.

[0098] In some embodiments, the thickness of the augmentation film is 13-150 μm, and can be 13 μm, 30 μm, 50 μm, 70 μm, 90 μm, 110 μm, 130 μm or 150 μm.

[0099] The fifth aspect of this application provides the application of the resin composition described in the first aspect, the build-up film described in the third aspect, or the build-up film prepared by the preparation method described in the fourth aspect in the packaging substrate of a flip-chip ball grid array.

[0100] The build-up film described in this application has excellent film-forming properties and dielectric properties, which can meet the performance requirements of FC-BGA packaging substrates.

[0101] The embodiments of this application will be described in detail below with reference to examples. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of this application. For experimental methods in the following embodiments where specific conditions are not specified, please refer to the guidelines given in this application, or follow experimental manuals or conventional conditions in the art, or follow the conditions recommended by the manufacturer, or refer to experimental methods known in the art.

[0102] As an example, the source of raw materials in this application is as follows:

[0103] Bisphenol A type allylbenzoxazine: purchased from Dongcai Technology, model number D146;

[0104] DCPD type allylbenzoxazine: purchased from Kolon Chemical, model KZH-5031MP70;

[0105] Allyl-modified polyphenylene ether resin: purchased from Taiwan Jin Yi, model PP501;

[0106] Dicumyl peroxide: purchased from Wanqian Chemical;

[0107] Spherical silica: purchased from Yaduma, model SO-C1, D50 is 0.3μm;

[0108] PET support: purchased from Toray Industries, Japan, model S105.

[0109] Basic Example 1

[0110] The preparation method of diamine compounds containing a benzocyclobutene structure is as follows:

[0111] 0.26 mol of benzocyclobutene 2,5-dicarboxylic acid and 0.0011 mol of benzyltriethylammonium chloride were added to 800 mL of thionyl chloride. The mixture was stirred until homogeneous at room temperature (25 °C), then refluxed and stirred for 24 h until homogenized. The solution was then evaporated under reduced pressure to obtain a solid intermediate product of acyl chloride. This solid intermediate product was dissolved in 600 mL of dichloromethane to prepare an acyl chloride intermediate product solution. 2.6 mol of 4,4'-diaminodiphenylmethane was dissolved in 500 mL of dichloromethane, and 0.2 mol of pyridine was added and mixed with the acyl chloride intermediate product solution. The mixture was stirred at room temperature (25 °C) for 12 h. The precipitate was filtered, and the obtained precipitate was washed with deionized water and dichloromethane to remove excess 4,4'-diaminodiphenylmethane. After drying, the resulting solid was a diamine compound containing a benzocyclobutene structure, as shown below:

[0112] .

[0113] Basic Implementation Example 2

[0114] 100 parts of the diamine compound containing the benzocyclobutene structure prepared in Basic Example 1 were heated to a molten state, and 100 parts of bisphenol A type allylbenzoxazine were added. The polymerization reaction was carried out at 135°C. After reacting for 1 hour, the mixture was cooled to room temperature to obtain modified benzoxazine prepolymer A.

[0115] The structure of bisphenol A type allylbenzoxazine is as follows:

[0116] .

[0117] Basic Example 3

[0118] 100 parts of the diamine compound containing the benzocyclobutene structure prepared in Basic Example 1 were heated to a molten state, and 100 parts of DCPD type allylbenzoxazine were added. The polymerization reaction was carried out at 135°C. After reacting for 1 hour, the mixture was cooled to room temperature to obtain modified benzoxazine prepolymer B.

[0119] The structure of DCPD-type allylbenzoxazine is as follows:

[0120] .

[0121] Example 1

[0122] The resin composition consists of the following components in parts by weight:

[0123] 20 parts of modified benzoxazine prepolymer A, 25 parts of allyl modified polyphenylene ether resin, 1 part of dicumyl peroxide and 300 parts of spherical silica.

[0124] By mass, 20 parts of modified benzoxazine prepolymer A, 25 parts of allyl modified polyphenylene ether resin, 1 part of dicumyl peroxide, and 300 parts of spherical silica were dissolved in 70 parts of solvent (composed of butanone, toluene, and propylene glycol methyl ether in a mass ratio of 1:1:1). After thorough mixing, the solution was sprayed onto the surface of a 38 μm thick PET support and then baked at 120 °C for 5 min to obtain a 50 μm thick extension film (excluding the PET support).

[0125] Example 2

[0126] The resin composition consists of the following components in parts by weight:

[0127] 10 parts modified benzoxazine prepolymer A, 40 parts allyl modified polyphenylene ether resin, 3 parts dicumyl peroxide and 200 parts spherical silica.

[0128] By mass, 10 parts of modified benzoxazine prepolymer A, 40 parts of allyl modified polyphenylene ether resin, 3 parts of dicumyl peroxide, and 200 parts of spherical silica were dissolved in 70 parts of solvent (composed of butanone, toluene, and propylene glycol methyl ether in a mass ratio of 1:1:1). After thorough mixing, the solution was sprayed onto the surface of a PET support with a thickness of 38 μm and then baked at 120 °C for 5 min to obtain a 50 μm thick extension film (excluding the PET support).

[0129] Example 3

[0130] The resin composition consists of the following components in parts by weight:

[0131] 30 parts modified benzoxazine prepolymer A, 10 parts allyl modified polyphenylene ether resin, 5 parts dicumyl peroxide and 100 parts spherical silica.

[0132] By mass, 30 parts of modified benzoxazine prepolymer A, 10 parts of allyl modified polyphenylene ether resin, 5 parts of dicumyl peroxide, and 100 parts of spherical silica were dissolved in 70 parts of solvent (composed of butanone, toluene, and propylene glycol methyl ether in a mass ratio of 1:1:1). After thorough mixing, the solution was sprayed onto the surface of a PET support with a thickness of 38 μm and then baked at 120 °C for 5 min to obtain a 50 μm thick extension film (excluding the PET support).

[0133] Example 4

[0134] The resin composition consists of the following components in parts by weight:

[0135] 20 parts of modified benzoxazine prepolymer B, 25 parts of allyl modified polyphenylene ether resin, 1 part of dicumyl peroxide and 300 parts of spherical silica.

[0136] By mass, 20 parts of modified benzoxazine prepolymer B, 25 parts of allyl modified polyphenylene ether resin, 1 part of dicumyl peroxide, and 300 parts of spherical silica were dissolved in 70 parts of solvent (composed of butanone, toluene, and propylene glycol methyl ether in a mass ratio of 1:1:1). After thorough mixing, the solution was sprayed onto the surface of a 38 μm thick PET support and then baked at 120 °C for 5 min to obtain a 50 μm thick extension film (excluding the PET support).

[0137] Comparative Example 1

[0138] The resin composition consists of the following components in parts by weight:

[0139] 40 parts modified benzoxazine prepolymer A, 25 parts allyl modified polyphenylene ether resin, 1 part dicumyl peroxide and 300 parts spherical silica.

[0140] By mass, 40 parts of modified benzoxazine prepolymer A, 25 parts of allyl modified polyphenylene ether resin, 1 part of dicumyl peroxide, and 300 parts of spherical silica were dissolved in 70 parts of solvent (composed of butanone, toluene, and propylene glycol methyl ether in a mass ratio of 1:1:1). After thorough mixing, the solution was sprayed onto the surface of a PET support with a thickness of 38 μm and then baked at 120 °C for 5 min to obtain a 50 μm thick extension film (excluding the PET support).

[0141] Comparative Example 2

[0142] The resin composition consists of the following components in parts by weight:

[0143] The mixture consisted of 20 parts of allyl benzoxazine used in Basic Example 2, 25 parts of allyl modified polyphenylene ether resin, 1 part of dicumyl peroxide, and 300 parts of spherical silica.

[0144] By mass percentage, 20 parts of allyl benzoxazine used in Basic Example 2, 25 parts of allyl modified polyphenylene ether resin, 1 part of dicumyl peroxide, and 300 parts of spherical silica were dissolved in 70 parts of solvent (composed of butanone, toluene, and propylene glycol methyl ether in a mass ratio of 1:1:1). After thorough mixing, the solution was sprayed onto the surface of a PET support with a thickness of 38 μm and then baked at 120°C for 5 min to obtain a 50 μm thick extension film (excluding the PET support).

[0145] Comparative Example 3

[0146] The resin composition consists of the following components in parts by weight:

[0147] 45 parts allyl-modified polyphenylene ether resin, 1 part dicumyl peroxide and 300 parts spherical silica.

[0148] By mass, 45 parts of allyl modified polyphenylene ether resin, 1 part of dicumyl peroxide, and 300 parts of spherical silica were dissolved in 70 parts of solvent (composed of butanone, toluene, and propylene glycol methyl ether in a mass ratio of 1:1:1). After thorough mixing, the solution was sprayed onto the surface of a PET support with a thickness of 38 μm and then baked at 120 °C for 5 min to obtain a 50 μm thick extension film (excluding the PET support).

[0149] Comparative Example 4

[0150] The resin composition consists of the following components in parts by weight:

[0151] 45 parts of modified benzoxazine prepolymer A, 1 part of dicumyl peroxide and 300 parts of spherical silica.

[0152] By mass, 45 parts of modified benzoxazine prepolymer A, 1 part of dicumyl peroxide, and 300 parts of spherical silica were dissolved in 70 parts of solvent (composed of butanone, toluene, and propylene glycol methyl ether in a mass ratio of 1:1:1). After thorough mixing, the solution was sprayed onto the surface of a PET support with a thickness of 38 μm and then baked at 120 °C for 5 min to obtain a 50 μm thick extension film (excluding the PET support).

[0153] The composition of the resin compositions of Examples 1-4 and Comparative Examples 1-4 is shown in Table 1.

[0154] Table 1 Composition of the resin composition

[0155]

[0156] " / " indicates that it was not added.

[0157] Experimental Example 1

[0158] The performance of the thickened films obtained in Examples 1-4 and Comparative Examples 1-4 was tested using the following methods:

[0159] After the extension film is laminated onto a 12μm thick copper foil using a vacuum laminator, the PET support film on the surface of the extension film is removed, and then a 12μm thick copper foil is applied. The laminate is then placed in a programmable temperature and pressure controlled vacuum press under vacuum conditions (vacuum parameters <10mBar) and 8kgf / cm². 2Under pressure, the film was cured at 180℃ for 30 min, then at 210℃ for 120 min until complete curing, thus preparing the test sample. The dielectric constant (Dk) and loss factor (Df) of the test sample were tested according to IPC-TM-650 2.5.5.2 to determine its dielectric properties. The film-forming properties of the laminated film were assessed by comparing whether surface shrinkage occurred during curing; if shrinkage was observed, the film-forming properties were poor; if no shrinkage occurred, the film-forming properties were good. The DMA Tg (glass transition temperature) of the test sample was tested using Dynamic Mechanical Analysis (DMA) technology according to IPC-TM-650 2.4.24.4.

[0160] The results are shown in Table 2.

[0161] Table 2 Performance test results of the extended membrane

[0162]

[0163] The results in Table 2 show that, compared with Comparative Examples 1-4, the layered films of Examples 1-4 of this application have excellent dielectric properties and good film-forming properties.

[0164] Compared to Comparative Example 1, which used 40 parts by mass of modified benzoxazine prepolymer, Example 1 of this application used 20 parts by mass of modified benzoxazine prepolymer. Measurements at 10 GHz showed that the dielectric constant of the laminated film decreased from 3.3 to 3.1; the loss factor decreased from 0.0057 to 0.0045, a reduction of 21%; and the glass transition temperature increased from 195°C to 210°C. This indicates that by controlling the mass fraction of the modified benzoxazine prepolymer, this application can significantly improve the dielectric and heat resistance properties of the laminated film, thereby significantly improving its transport efficiency and stability.

[0165] Compared to Comparative Example 2, which used allylbenzoxazine, Example 1 of this application used a modified benzoxazine prepolymer. Measurements at 10 GHz showed that the dielectric constant of the layered film decreased from 3.6 to 3.1; the loss factor decreased from 0.0102 to 0.0045, a reduction of 56%; and the glass transition temperature increased from 190°C to 210°C. This indicates that by using a modified benzoxazine prepolymer, this application can significantly improve the dielectric and heat resistance properties of the layered film, thereby significantly improving its transport efficiency and stability.

[0166] Compared to Comparative Examples 3-4, which used only one of modified benzoxazine prepolymer A and allyl modified polyphenylene ether resin, the resin composition of Example 1, which used both modified benzoxazine prepolymer A and allyl modified polyphenylene ether resin, resulted in a reduction in the dielectric constant of the laminated film from 3.4-35 to 3.1, a reduction in the loss factor from 0.0071-0.0082 to 0.0045 (a decrease of 37%-45%), and an increase in the glass transition temperature from 165-178°C to 210°C (an increase of 18%-27%). This indicates that the use of modified benzoxazine prepolymer A and allyl modified polyphenylene ether resin in this application, in synergy, can significantly improve the dielectric properties, heat resistance, and film-forming properties of the laminated film.

[0167] 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.

[0168] 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 patent application. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of this application, and these 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 resin composition, characterized in that, The components include the following parts by mass: 10-30 parts of modified benzoxazine prepolymer; 10-40 parts of modified polyphenylene ether resin; 1-5 parts of initiator; and Inorganic filler 100-300 parts; The modified benzoxazine prepolymer is synthesized from raw materials including allylbenzoxazine and diamine compounds containing a benzocyclobutene structure.

2. The resin composition according to claim 1, characterized in that, The diamine compounds containing a benzocyclobutene structure include at least one of the compounds with the structure shown in Formula 1: Formula 1; Wherein, R1 and R2 are independently selected from any of the following structures: 、 、 、 。 3. The resin composition according to claim 1, characterized in that, The allylbenzoxazine comprises at least one of the compounds with the structure shown in the following formula: 、 、 ； Among them, R3 is selected from -CR4R5-, -SO2-, -O-, , , , or ; R4 and R5 are independently selected from -H or -CH3.

4. The resin composition according to any one of claims 1-3, characterized in that, The modified benzoxazine prepolymer was prepared by the following method: The modified benzoxazine prepolymer was prepared by polymerizing the allylbenzoxazine and the diamine compound containing a benzocyclobutene structure. Optionally, the mass ratio of the allylbenzoxazine to the diamine compound containing the benzocyclobutene structure is 1:(0.6-1.2). Optionally, the conditions for the polymerization reaction include: a reaction temperature of 100-200℃ and a reaction time of 60-150 min.

5. The resin composition according to claim 1, characterized in that, It meets at least one of the following characteristics: (1) The modified polyphenylene ether resin includes at least one of vinyl benzyl ether modified polyphenylene ether resin, allyl modified polyphenylene ether resin and methyl polyacrylate modified bisphenol A type polyphenylene ether resin; (2) The initiator includes a peroxide initiator; Optionally, the peroxide initiator includes at least one of dicumyl peroxide, benzoyl peroxide, di-tert-butyl peroxide, and dilauryl peroxide; (3) The inorganic filler includes at least one of zirconium vanadate, zirconium tungstate, hafnium tungstate, microcrystalline glass, nepheline, silicon dioxide, quartz, mica powder, titanium dioxide, magnesium oxide, magnesium hydroxide, talc, aluminum oxide, silicon carbide, boron nitride, aluminum nitride, molybdenum oxide, barium sulfate, zinc molybdate, zinc borate, zinc stannate, zinc oxide, strontium titanate, barium titanate, calcium titanate, and clay.

6. Use of the resin composition according to any one of claims 1-5 in the preparation of a thickening film.

7. A layering film, characterized in that, include: The resin composition according to any one of claims 1-5.

8. A method for preparing a layered film, characterized in that, Includes the following steps: The resin composition as described in any one of claims 1-5 is coated onto a support and dried to prepare the laminated film.

9. The method for preparing the layered film according to claim 8, characterized in that, It meets at least one of the following characteristics: (1) The step of coating the resin composition onto the support specifically includes: The resin composition is dissolved in a solvent to prepare a coating solution, and then the coating solution is coated onto the support. Optionally, the solvent includes at least one of butanone, toluene, and propylene glycol methyl ether; (2) The support body includes a plastic film and / or a metal film; Optionally, the plastic film includes at least one of polyethylene terephthalate, polycarbonate, and polymethyl methacrylate; Optionally, the metal film includes copper foil or aluminum foil; (3) The thickness of the layered film is 13-150 μm; (4) Drying conditions include: temperature of 50-160℃; time of 1-10min.

10. The use of the resin composition according to any one of claims 1-5, the layering film according to claim 7, or the layering film prepared by the preparation method according to any one of claims 8-9 in the packaging substrate of a flip chip ball grid array.

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