Modified resin composition, film increasing layer as well as preparation method and application of film increasing layer

Abstract

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

Description

Technical Field

[0001] The present application relates to the technical field of composite materials, and in particular to a modified resin composition, a film-building layer, and a preparation method and application thereof. Background Art

[0002] Flip chip ball grid array (FCBGA) substrate technology is an advanced packaging technology, which is a technology that flips the chip upside down and attaches it to the substrate, connects the chip and the substrate through solder balls, and realizes electrical connection and signal transmission. FCBGA substrate technology has advantages in high speed, high density, high reliability, etc., and is widely used in computer, communication, consumer electronics, medical, industrial control and other fields.

[0003] As an essential packaging substrate for high-computing power application fields such as artificial intelligence, FCBGA packaging substrates greatly reduce the length and area of ​​leads by inverting the chip and interconnecting it with bumps, thereby carrying a large number of electronic components in a smaller space. Therefore, it has the characteristics of small line width / line spacing and numerous pins, which can effectively reduce dielectric loss and increase component density. Among them, the insulating layer film with good dimensional stability, excellent dielectric properties, durability and reliability is the core key material of several advanced packaging technologies including FCBGA packaging substrates.

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

[0005] Therefore, how to provide a resin composition with low thermal expansion coefficient, low dielectric constant, low dielectric loss and low water absorption, so as to effectively reduce the thermal expansion coefficient, dielectric constant, dielectric loss and water absorption of the build-up film and inhibit its warping, has become an urgent problem to be solved in the industry. Summary of the invention

[0006] Based on this, the main purpose of the present application is to provide a resin composition with low thermal expansion coefficient, low dielectric constant, low dielectric loss and low water absorption, so as to prepare a build-up film with low thermal expansion coefficient, low dielectric constant, low dielectric loss, low water absorption and low warping.

[0007] In one aspect of the present application, a modified resin composition is provided, which comprises 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] 50-300 parts of inorganic filler;

[0013] 10-50 parts of organic filler;

[0014] Additives 0-5 parts;

[0015] The raw materials for preparing the modified allylbenzoxazine prepolymer include: an allyl compound and an allylbenzoxazine resin;

[0016] The allyl compound includes a first allyl compound, and the first allyl compound is terpene bisallyl ether, and its structure is as follows:

[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 bisallyl 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] Wherein X is selected from -CHR 1 -,-CR 2 R 3 -,-SO 2 -, -O- or ;

[0024] R 1 , R 2 , R 3 Each independently selected from -H or -CH 3 .

[0025] Understandable, It refers to a disubstituted naphthalene ring, and the substitution site is not limited.

[0026] In some embodiments, the method for preparing the modified allylbenzoxazine prepolymer comprises the following steps:

[0027] The allyl compound and the allyl benzoxazine resin are mixed and prepolymerized at 120-180° C. to prepare the modified allyl benzoxazine prepolymer.

[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 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-formaldehyde 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 bisphenol A benzoxazine resin, bisphenol F benzoxazine resin, main chain benzoxazine resin, phosphorus-containing benzoxazine, bisphenol S benzoxazine resin, dicyclopentadiene benzoxazine resin, biphenyl benzoxazine resin, tetraphenol ethane benzoxazine resin, and naphthalene benzoxazine resin.

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

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

[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 silicone particles, core-shell rubber particles, and olefin elastomer particles.

[0038] In some embodiments, the auxiliary agent is one or more of a dispersant, a leveling agent, a defoaming agent, a treating agent and a coupling agent.

[0039] In some embodiments, the modified resin composition includes 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] 1-5 parts of additives.

[0047] The second aspect of the present application provides the use of the aforementioned modified resin composition in a build-up film.

[0048] The third aspect of the present application provides a build-up film, comprising the aforementioned modified resin composition.

[0049] The fourth aspect of the present application provides a method for preparing the aforementioned build-up film, comprising the following steps:

[0050] The modified resin composition is coated on a support to form a resin composition coating, which is then cured to prepare a build-up film.

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

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

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

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

[0055] The beneficial effects of this application are:

[0056] The present application adopts an allyl compound containing a naphthalene ring structure and an allyl benzoxazine resin to prepolymerize to prepare a modified allyl benzoxazine prepolymer, and combines it with functional resins, organic fillers, inorganic fillers and other raw materials to prepare a modified resin composition and a build-up film. Among them, the organic filler and the inorganic filler can reduce the shrinkage rate of the system during curing and improve the dimensional stability through filling, reinforcement and other effects. After the highly symmetrical and highly rigid naphthalene ring structure is introduced into the modified allyl benzoxazine prepolymer, the steric hindrance of the polymer chain and the rigidity of the polymer chain segment are increased, and the structural regularity is destroyed, which can effectively inhibit the movement of the polymer chain segment during the curing process, and ultimately greatly reduce the warping, water absorption and thermal expansion coefficient of the build-up film, and obtain a lower dielectric constant and dielectric loss. DETAILED DESCRIPTION

[0057] In order to facilitate the understanding of the present application, the present application will be described more comprehensively below in conjunction with specific embodiments. Preferred embodiments of the present application are provided hereinafter. However, the present application can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the understanding of the disclosure of the present application more thorough and comprehensive.

[0058] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art to which this application belongs. The terms used herein in the specification of this application are only for the purpose of describing specific embodiments and are not intended to limit this application. The term "and / or" used herein includes any and all combinations of one or more of the related listed items.

[0059] In this article, the technical features described in an open manner include closed technical solutions composed of the listed features, and also include open technical solutions containing the listed features.

[0060] In this article, the terms "first" and "second" are used for descriptive purposes only and should not be understood as indicating or implying relative importance or implicitly indicating the quantity of the indicated technical features.

[0061] In the description herein, “several” means two or more, such as two, three, etc., unless otherwise clearly and specifically defined.

[0062] Herein, when it comes to numerical ranges, unless otherwise specified, the numerical ranges are deemed to be continuous and include the minimum and maximum values ​​of the range, as well as every value between such minimum and maximum values. Further, when a range refers to an integer, every integer between the minimum and maximum values ​​of the range is included. In addition, when multiple ranges are provided to describe features or characteristics, the ranges can be merged. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all subranges included therein.

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

[0064] The temperature parameters herein, unless otherwise specified, allow for both constant temperature treatment and treatment within a certain temperature range. The constant temperature treatment allows for temperature fluctuations within the precision range of instrument control.

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

[0066] In one aspect of the present application, a modified resin composition is provided, which comprises 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] 50-300 parts of inorganic filler;

[0072] 10-50 parts of organic filler;

[0073] Additives 0-5 parts;

[0074] The raw materials for preparing the modified allylbenzoxazine prepolymer include: an allyl compound and an allylbenzoxazine resin;

[0075] The allyl compound includes a first allyl compound, and the first allyl compound is terpene bisallyl ether, and its structure is as follows:

[0076] .

[0077] It is understandable that the first allyl compound of the present application has a highly symmetrical and highly rigid naphthalene ring structure. After the allyl benzoxazine resin is modified, the steric hindrance of the polymer chain and the rigidity of the polymer segment can be increased, and the structural regularity can be destroyed, thereby effectively inhibiting the movement of the polymer segment during the curing process, and ultimately greatly reducing the warping, water absorption, thermal expansion coefficient and dielectric parameters of the build-up film. The cured product has the characteristics of extremely low thermal expansion coefficient, low shrinkage, low water absorption and high heat resistance. Organic fillers and inorganic fillers can reduce the shrinkage of the system during curing and improve dimensional stability through filling, reinforcement and other effects.

[0078] The present application adopts an allyl compound containing a naphthalene ring structure and an allyl benzoxazine resin to prepolymerize to prepare a modified allyl benzoxazine prepolymer, and combines it with functional resins, organic fillers, inorganic fillers and other raw materials to prepare a resin composition with low thermal expansion coefficient, low dielectric constant, low dielectric loss and low water absorption, thereby preparing a build-up film with low thermal expansion coefficient, low dielectric constant, low dielectric loss, low water absorption and low warpage, and realizing the application of the build-up film and chip ball grid array packaging substrate.

[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 bisallyl ether.

[0081] It is understandable that the first modifier of the present 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 there is no special requirement for the specific structure of the allylbenzoxazine resin in the present application, as long as it contains a double bond. In some embodiments, the allylbenzoxazine resin is selected from one or more of the following structures:

[0083]

[0084]

[0085] Wherein X is selected from -CHR 1 -,-CR 2 R 3 -,-SO 2 -, -O- or DCPD ring;

[0086] R 1 , R 2 , R 3 Each independently selected from -H or -CH 3 .

[0087] In some embodiments, the method for preparing the modified allylbenzoxazine prepolymer comprises the following steps:

[0088] The allyl compound and the allyl benzoxazine resin are mixed and prepolymerized at 120-180° C. to prepare the modified allyl benzoxazine prepolymer. Specifically, the reaction temperature can be 120° C., 130° C., 140° C., 150° C., 160° C., 170° C., 180° C., etc.

[0089] It is understandable that the step of mixing the allyl compound and the allyl benzoxazine resin may specifically be: heating the allyl compound until it is melted, and then adding the allyl benzoxazine resin to mix.

[0090] It is understandable that the reaction time and the ratio of raw materials can be adjusted according to actual needs and are not particularly limited. 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 the allyl compound to the allyl benzoxazine resin can be (60-150):100, 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 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 bisphenol A benzoxazine resin, bisphenol F benzoxazine resin, main chain benzoxazine resin, phosphorus-containing benzoxazine, bisphenol S benzoxazine resin, dicyclopentadiene benzoxazine resin, biphenyl benzoxazine resin, tetraphenol ethane benzoxazine resin, and naphthalene benzoxazine resin.

[0094] The bismaleimide resin is not limited to a specific type, 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-phenylene bismaleimide, bis(4-maleimidophenyl) methane, 2, 2-bis(4-(4-maleimidophenoxy)-phenyl) propane, bis(3, 5-dimethyl-4-maleimidophenyl) methane, bis(3-ethyl-5-methyl-4-maleimidophenyl) methane, bis(3, 5-diethyl-4-maleimidophenyl) methane, polyphenylmethane bismaleimide and bismaleimide containing 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 an amine curing agent, a phenolic curing agent, an acid anhydride curing agent, a cyanate curing agent, and an active ester curing agent.

[0096] Preferably, the curing accelerator is selected from one or more of tertiary amine accelerators, imidazole accelerators, peroxide accelerators, organic phosphorus 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 may be 0.01-10 μm, specifically 10 μm, 5 μm, 3 μm, 1 μm, 0.5 μm, 0.1 μm, 0.05 μm, 0.01 μm, etc.

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

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

[0103] In some embodiments, the auxiliary agent is one or more of a dispersant, a leveling agent, a defoaming agent, a treating agent and a coupling agent.

[0104] In some embodiments, the modified resin composition includes 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] 1-5 parts of additives.

[0112] The second aspect of the present application provides the use of the aforementioned modified resin composition in a build-up film.

[0113] The third aspect of the present application provides a build-up film, comprising the aforementioned modified resin composition.

[0114] The fourth aspect of the present application provides a method for preparing the aforementioned build-up film, comprising the following steps:

[0115] The modified resin composition is coated on a support to form a resin composition coating, which is then cured to prepare a build-up film.

[0116] It is understandable that the step of coating the modified resin composition on the support to form the resin composition coating may be: the modified resin composition is dispersed in a solvent to prepare a dispersion, and then coated on the support to form the resin composition coating. The coating method may include spraying, scraping, roller coating, etc. The solvent may include one or more of ethanol, acetone, cyclohexanone, butanone, toluene, xylene, N, N-dimethylformamide, N, N-dimethylacetamide and propylene glycol methyl ether.

[0117] It is understandable that during the curing process, the solvent can be volatilized at the same time.

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

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

[0120] Among them, 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 body is preferably but not limited to 3-105μm; the thickness of the resin composition coating is preferably but not limited to 5-150μm.

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

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

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

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

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

[0126] Trinaphthalene bisallyl ether: purchased from DIC Corporation;

[0127] Allylbenzoxazine: Huaibei Oasis LZ-32;

[0128] Biphenyl epoxy resin: Nippon Kayaku NC3000H;

[0129] Phenolic curing agent: Shandong Shengquan PF8711;

[0130] Imidazole accelerator: Shikoku Chemical 2MI;

[0131] Spherical silica: Yaduma SO-C1;

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

[0133] Additive: BYK-1650.

[0134] The following are specific embodiments.

[0135] Synthesis Example 1 of Modified Allylbenzoxazine Prepolymer

[0136] First, 80 parts of terphenyl naphthalene bisallyl ether were heated to a molten state, and then 100 parts of allyl benzoxazine resin were added, and the mixture was prepolymerized at 150° C. for 120 minutes and then cooled to room temperature to obtain a modified allyl benzoxazine prepolymer A.

[0137] Synthesis Example 2 of Modified Allylbenzoxazine Prepolymer

[0138] First, 100 parts of terphenyl naphthalene bisallyl ether were heated to a molten state, and then 100 parts of allyl benzoxazine resin were added, and the mixture was prepolymerized at 150° C. for 140 minutes and then cooled to room temperature to obtain a modified allyl benzoxazine prepolymer B.

[0139] Synthesis Example 3 of Modified Allylbenzoxazine Prepolymer

[0140] First, 120 parts of terphenyl naphthalene bisallyl ether were heated to a molten state, and then 100 parts of allyl benzoxazine resin were added, and the mixture was prepolymerized at 160° C. for 100 minutes and then cooled to room temperature to obtain a modified allyl benzoxazine prepolymer C.

[0141] Synthesis Example 4 of Modified Allylbenzoxazine Prepolymer

[0142] First, 80 parts of tert-butyl bisallyl ether and 20 parts of allyl bisphenol A were heated to a molten state, and then 100 parts of allyl benzoxazine resin were added, and the mixture was prepolymerized at 150° C. for 150 minutes and then cooled to room temperature to obtain a modified allyl benzoxazine prepolymer D.

[0143] Example 1

[0144] Calculated 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 are dissolved in 120 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, stirred well and sprayed on the surface of the PET film, and then baked at 130°C for 5 minutes to obtain a build-up film (PET film thickness 38 μm, coating thickness 100 μm, other embodiments and comparative examples have the same film thickness).

[0145] Example 2

[0146] Calculated 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 auxiliary agent 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, stirred thoroughly and evenly, sprayed on the surface of the PET film, and then baked at 140°C for 5 minutes to obtain a build-up layer film.

[0147] Example 3

[0148] Calculated 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 are dissolved in 110 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, stirred thoroughly and evenly, sprayed on the surface of the PET film, and then baked at 150°C for 6 minutes to obtain a build-up layer film.

[0149] Example 4

[0150] Calculated 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 auxiliary agent 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, stirred thoroughly and evenly, sprayed on the surface of the PET film, and then baked at 150°C for 3 minutes to obtain a build-up layer film.

[0151] Example 5

[0152] Calculated 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 auxiliary agent 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, stirred thoroughly and evenly, sprayed on the surface of the PET film, and then baked at 145°C for 5 minutes to obtain a build-up layer film.

[0153] Example 6

[0154] Calculated 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 auxiliary agent 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, stirred thoroughly and evenly, sprayed on the surface of the PET film, and then baked at 140°C for 5 minutes to obtain a build-up layer film.

[0155] Example 7

[0156] Calculated 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 auxiliary agent 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, stirred thoroughly and evenly, sprayed on the surface of the PET film, and then baked at 150°C for 5 minutes to obtain a build-up layer film.

[0157] Comparative Example 1

[0158] Calculated by weight, 20 parts of allyl benzoxazine, 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 auxiliary agent 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, stirred thoroughly and evenly, sprayed on the PET surface, and then baked at 150°C for 5 minutes to obtain a build-up layer film.

[0159] Comparative Example 2

[0160] Calculated 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 auxiliary agent 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, stirred thoroughly and evenly, sprayed on the PET surface, and then baked at 160°C for 5 minutes to obtain a build-up layer film.

[0161] The components of the modified resin compositions in the above examples and comparative examples are shown in Table 1.

[0162] Table 1 Compositions of modified resin compositions in Examples and Comparative Examples

[0163]

[0164] The build-up films obtained in Examples 1-7 and Comparative Examples 1-2 were tested, and the testing method was as follows:

[0165] The obtained build-up layer film (the side without PET film) was bonded to a copper foil with a thickness of 12μm by a bonding machine, and then the PET film was removed and then covered with a copper foil with a thickness of 12μm. The film was placed in a vacuum press with programmable temperature and pressure control, and cured completely at 100℃×30min+160℃×30min+200℃×120min in a vacuum state (vacuum parameters are <10 mBar) and a pressure of 10kgf / cm² to obtain a package carrier. The performance test was carried out according to the following test standards. 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, where 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 test: Dielectric constant (Dk) and dielectric loss (Df) are tested according to IPC-TM-650 2.5.5.2;

[0169] 4. Water absorption: 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] It can be seen that the Tg of the packaging carrier of Examples 1-7 is ≥173°C, the CTE below Tg is ≤35ppm / °C, the CTE above Tg is ≤85ppm / °C, the warpage is ≤0.28mm, Dk≤3.67, Df≤0.0128, and the water absorption rate is ≤0.12%. It has extremely low thermal expansion coefficient, low dielectric constant, low price point loss, low water absorption rate and high heat resistance.

[0173] By comparing Examples 1-7 and Comparative Example 1, it can be found that after allylbenzoxazine is modified with trimerized naphthalene bisallyl ether, Tg can be significantly increased (increased by more than 23°C), and CTE (CTE below Tg is reduced by 25-38ppm / °C, and CTE above Tg is reduced by 45-60ppm / °C), 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%) are significantly reduced. It can be seen that modifying allylbenzoxazine with trimerized naphthalene bisallyl ether can greatly improve heat resistance, reduce thermal expansion coefficient, low dielectric constant, low price point loss, and low water absorption, thereby meeting application requirements.

[0174] By comparing Examples 1-4 and Comparative Example 2, it can be seen that when the amount of the modified allyl benzoxazine resin is too much, the overall performance will be deteriorated, and the amount of the modified allyl benzoxazine resin is preferably 10-40 parts.

[0175] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0176] The above-mentioned embodiments only express several implementation methods of the present application, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be pointed out that, for a person of ordinary skill in the art, several variations and improvements can be made without departing from the concept of the present application, and these all belong to the protection scope of the present application. Therefore, the protection scope of the patent of the present application shall be subject to the attached claims.

Claims

1. A modified resin composition, characterized in that The composition comprises the following components in parts by weight: 10-40 parts of modified allyl benzoxazine prepolymer; 10-50 parts of functional resin; 10-40 parts of curing agent; 1-10 parts of curing accelerator; 50-300 parts of inorganic filler; 10-50 parts of organic filler; Additives 0-5 parts; The raw materials for preparing the modified allylbenzoxazine prepolymer include: an allyl compound and an allylbenzoxazine resin; The allyl compound includes a first allyl compound, and the first allyl compound is terpene bisallyl ether, and its structure is as follows: 。 2. The modified resin composition according to claim 1, characterized in that The allyl compound further comprises 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 bisallyl ether; And / or the mass ratio of the allyl compound to the allyl benzoxazine resin is (0.8-1.2):

1.

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: Wherein, X is selected from -CHR1-, -CR2R3-, -SO2-, -O- or ; R1, R2, R3 are independently selected from -H or -CH3; And / or the preparation method of the modified allylbenzoxazine prepolymer comprises the following steps: The allyl compound and the allyl benzoxazine resin are mixed and prepolymerized at 120-180° C. to prepare the modified allyl benzoxazine prepolymer.

4. The modified resin composition according to any one of claims 1 to 3, characterized in that The functional resin is one or more of epoxy resin, benzoxazine and bismaleimide resin; and / or the curing agent is selected from one or more of an amine curing agent, a phenolic curing agent, an anhydride curing agent, a cyanate curing agent and an active ester curing agent; and / or the inorganic filler is selected from modified spherical silica and / or modified spherical alumina; and / or the organic filler is selected from one or more of silicone particles, core-shell rubber particles and olefin elastomer particles; And / or the auxiliary agent is one or more of a dispersant, a leveling agent, a defoaming agent, a treating agent and a coupling agent.

5. The modified resin composition according to any one of claims 1 to 3, characterized in that: The modified resin composition comprises the following components in 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 additives.

6. Use of the modified resin composition according to any one of claims 1 to 5 in a build-up film.

7. A build-up film, characterized in that: The modified resin composition comprises any one of claims 1 to 5.

8. The method for preparing a build-up film according to claim 7, characterized in that: The steps include: The modified resin composition is coated on a support to form a resin composition coating, which is then cured to prepare a build-up film.

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

10. Use of the modified resin composition according to any one of claims 1 to 5, the build-up film according to claim 7, and the build-up film prepared by the preparation method according to claims 8 to 9 in a packaging substrate of a flip chip ball grid array.

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