Modified allyl benzoxazine resin composition, layer-adding film as well as preparation method and application of modified allyl benzoxazine resin composition and layer-adding film

Abstract

The invention discloses a modified allyl benzoxazine resin composition, a layer-adding film as well as a preparation method and application of the layer-adding film, and belongs to the technical field of composite materials. The modified allyl benzoxazine resin composition comprises modified allyl benzoxazine resin, functional resin, a curing agent, a curing accelerator, an inorganic filler and an auxiliary agent, the modified allyl benzoxazine resin is prepared from the following raw materials: a modifier and allyl benzoxazine resin, the modifier comprises a first modifier; the first modifier is an amine fluorine-containing compound; the amine fluorine-containing compound is 2, 2-bis (4-allyloxyphenyl) hexafluoropropane, and the amine fluorine-containing compound is 2, 2-bis (4-allyloxyphenyl) hexafluoropropane. According to the invention, the amine fluorine-containing compound is adopted to modify the allyl benzoxazine resin, so that the modified allyl benzoxazine resin composition with low dielectric constant, low dielectric loss and low water absorption rate can be prepared, and the application requirements of a film increasing layer are met.

Description

Technical Field

[0001] The present application relates to the technical field of composite materials, and in particular to a modified allylbenzoxazine resin composition, a build-up film, 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] Compared with traditional packaging substrate technology, FCBGA substrate technology has higher integration, smaller packaging volume, 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, the amount and speed of information processing have increased, and FCBGA substrates also require lower dielectric constants and dielectric losses to reduce transmission losses. In addition, in the package substrate, if the water absorption rate is high, it will cause the "popcorn" phenomenon and make the package fail. Therefore, FCBGA substrates have higher requirements for the dielectric constant, dielectric loss and water absorption rate of their preparation materials.

[0005] Benzoxazine resins are widely used in electronic materials and other fields because of their high heat resistance, good flame retardancy, low water absorption, excellent dielectric properties, no small molecule release during curing, and almost zero volume shrinkage. However, the dielectric properties and water absorption properties of the composition prepared from unmodified benzoxazine resins are still difficult to meet the application requirements of build-up films.

[0006] Therefore, how to prepare a resin composition with low dielectric constant, dielectric loss and water absorption to meet the application requirements of build-up films has become an urgent problem to be solved in the industry. Summary of the invention

[0007] Based on this, the main purpose of the present application is to provide a modified allylbenzoxazine resin composition with low dielectric constant, low dielectric loss and low water absorption to meet the application requirements of the film build-up layer.

[0008] In a first aspect of the present application, a modified allylbenzoxazine resin composition is provided, which comprises the following components in parts by weight:

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

[0010] Functional resin 10-60 parts;

[0011] 10-40 parts of curing agent;

[0012] 1-10 parts of curing accelerator;

[0013] 50-300 parts of inorganic filler;

[0014] Additives 0-5 parts;

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

[0016] The modifier includes a first modifier; the first modifier is an amine fluorine-containing compound;

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

[0018] In some embodiments, the method for preparing the modified allylbenzoxazine resin comprises the following steps:

[0019] The modifier is mixed with the allyl benzoxazine resin and reacted at 120-180° C. to prepare the modified allyl benzoxazine resin.

[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] Wherein, 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 bisallyl 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; alternatively, 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 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 bisphenol A-type benzoxazine resin, bisphenol F-type benzoxazine resin, main chain 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 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 inorganic filler includes 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 auxiliary agent includes one or more of a dispersant, a leveling agent, a defoaming agent, a treating agent, and a coupling agent.

[0036] The second aspect of the present application provides a build-up film, comprising the aforementioned modified allyl benzoxazine resin composition.

[0037] The third aspect of the present application provides a method for preparing the aforementioned build-up film, comprising the following steps:

[0038] The modified allylbenzoxazine resin composition is coated on a substrate to form a resin composition coating, which is then heated and dried to prepare a build-up film.

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

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

[0041] The fourth aspect of the present application provides the use of the modified allylbenzoxazine resin composition and the build-up layer film in a packaging substrate of a flip chip ball grid array.

[0042] In a fifth aspect of the present application, a flip chip ball grid array packaging substrate is provided, comprising the aforementioned modified allyl benzoxazine resin composition and the aforementioned build-up layer film.

[0043] The beneficial effects of this application are:

[0044] The present application adopts amine fluorine-containing compounds to modify allyl benzoxazine resin, and prepares modified allyl benzoxazine resin through addition reaction of amino group and carbon-carbon double bond. The selected amine fluorine-containing compounds have multiple rigid benzene rings and fluorine atoms. Due to the special molecular structure and chemical properties of the rigid benzene rings, it is difficult for them to form hydrogen bonds with water molecules. The presence of multiple rigid benzene rings can effectively reduce the water absorption rate of the resin; and the fluorine atoms have extremely high electronegativity, which can effectively shield the charge and reduce the dielectric constant and dielectric loss of the resin, thereby preparing a modified allyl benzoxazine resin composition with low dielectric constant, low dielectric loss and low water absorption, which meets the application requirements of the film-building layer. DETAILED DESCRIPTION

[0045] 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.

[0046] 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.

[0047] 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.

[0048] 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.

[0049] In the description herein, "plurality" means more than two, for example, two, three, etc., unless otherwise clearly and specifically defined.

[0050] 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.

[0051] 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).

[0052] The temperature parameters herein, if not specifically limited, 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.

[0053] 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.

[0054] In one aspect of the present application, a modified allylbenzoxazine resin composition is provided, which comprises the following components in parts by weight:

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

[0056] Functional resin 10-60 parts;

[0057] 10-40 parts of curing agent;

[0058] 1-10 parts of curing accelerator;

[0059] 50-300 parts of inorganic filler;

[0060] Additives 0-5 parts;

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

[0062] The modifier includes a first modifier; the first modifier is an amine fluorine-containing compound;

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

[0064] Among them, the structure of 2,2-bis(4-allyloxyphenyl)hexafluoropropane is as follows:

[0065] .

[0066] The present application adopts amine fluorine-containing compounds to modify allyl benzoxazine resin, and prepares modified allyl benzoxazine resin through addition reaction of amino group and carbon-carbon double bond. The selected amine fluorine-containing compounds have multiple rigid benzene rings and fluorine atoms. Due to the special molecular structure and chemical properties of the rigid benzene rings, it is difficult for them to form hydrogen bonds with water molecules. The presence of multiple rigid benzene rings can effectively reduce the water absorption rate of the resin; and the fluorine atoms have extremely high electronegativity, which can effectively shield the charge and reduce the dielectric constant and dielectric loss of the resin, thereby preparing a modified allyl benzoxazine resin composition with low dielectric constant, low dielectric loss and low water absorption, which meets the application requirements of the film-building layer.

[0067] In some embodiments, the method for preparing the modified allylbenzoxazine resin comprises the following steps:

[0068] The modifier is mixed with the allyl benzoxazine resin and reacted at 120-180° C. to prepare the modified allyl benzoxazine resin.

[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, and more preferably, the mass ratio of the modifier to the allyl benzoxazine resin is (80-120):100.

[0070] It is understandable that in the present application, the modifier reacts with the double bond in the allyl benzoxazine resin via the amino group to achieve the modification of the allyl benzoxazine resin. The reaction temperature, reaction time and the ratio of the two can be adjusted according to actual needs. For example, increasing the reaction temperature is conducive to accelerating the reaction, extending the reaction time is conducive to increasing the degree of reaction, and increasing the proportion of the modifier is conducive to increasing the degree of modification. Specifically, the reaction temperature may be 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, etc., the reaction time may be 1h, 1.5h, 2h, 2.5h, 3h, etc., and the mass ratio of the modifier to the allyl benzoxazine resin may 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 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:

[0072]

[0073]

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

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

[0076] Understandable, It refers to a disubstituted naphthalene ring, and the substitution site is not limited.

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

[0078] It is understandable that in the present 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 bisallyl 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 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 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.

[0083] The curing agent is not limited to a specific type. In some embodiments, the curing agent includes 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.

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

[0085] In some embodiments, the inorganic filler includes 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] It is understandable that the average particle size of the inorganic filler is not particularly limited, and may be 0.01 μm-100 μm, specifically 100 μm, 50 μm, 10 μm, 5 μm, 3 μm, 1 μm, 0.5 μm, 0.1 μm, 0.05 μm, 0.01 μm, etc.

[0088] In some embodiments, the auxiliary agent includes one or more of a dispersant, a leveling agent, a defoaming agent, a treating agent, and a coupling agent.

[0089] In some embodiments, the modified allylbenzoxazine 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] 1-5 parts of additives.

[0096] The second aspect of the present application provides a build-up film, comprising the aforementioned modified allyl benzoxazine resin composition.

[0097] The third aspect of the present application provides a method for preparing the aforementioned build-up film, comprising the following steps:

[0098] The modified allylbenzoxazine resin composition is coated on a substrate to form a resin composition coating, which is then heated and dried to prepare a build-up film.

[0099] It is understandable that the step of coating the modified allylbenzoxazine resin composition on the support to form a resin composition coating may be: dispersing the modified allylbenzoxazine resin composition in a solvent to prepare a dispersion, and then coating the dispersion on the support to form a 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; the mass ratio of the solvent to the modified allylbenzoxazine resin composition may be 1:1-5.

[0100] It is understandable that during heating and drying, volatilization of the solvent can be achieved.

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

[0102] It is understandable that there is no special limitation on the substrate, and 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 can be copper foil or aluminum foil, etc.

[0103] It is understandable that there is no special requirement for the thickness of the resin composition coating and the thickness of the substrate. For example, the thickness of the resin composition coating may be 5-150 μm, and the thickness of the substrate may be 3-105 μm.

[0104] The fourth aspect of the present application provides the use of the modified allylbenzoxazine resin composition and the build-up layer film in a packaging substrate of a flip chip ball grid array.

[0105] In a fifth aspect of the present application, a flip chip ball grid array packaging substrate is provided, comprising the aforementioned modified allyl benzoxazine resin composition and the aforementioned build-up layer 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, 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 examples of the present application are all common commercially available products, and their sources are not specifically limited.

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

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

[0110] Allyl benzoxazine resin: Dongcai Technology D148;

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

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

[0113] Imidazole accelerator: Shikoku Chemical 2MI;

[0114] Spherical silica: Yaduma SO-C1;

[0115] Additive: BYK-1650.

[0116] The following are specific embodiments.

[0117] Synthesis Example 1 of Modified Allylbenzoxazine 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, and the mixture was prepolymerized at 150° C. for 120 minutes and then cooled to room temperature to obtain modified allylbenzoxazine resin A.

[0119] Synthesis Example 2 of Modified Allylbenzoxazine 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, and the mixture was prepolymerized at 160° C. for 140 minutes and then cooled to room temperature to obtain modified allylbenzoxazine resin B.

[0121] Synthesis Example 3 of Modified Allylbenzoxazine 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, and the mixture was prepolymerized at 150° C. for 130 minutes and then cooled to room temperature to obtain modified allylbenzoxazine resin C.

[0123] Synthesis Example 4 of Modified Allylbenzoxazine 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, 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 modified allyl benzoxazine resin D.

[0125] Synthesis Example 5 of Modified Allylbenzoxazine 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, and the mixture was prepolymerized at 160° C. for 130 minutes and then cooled to room temperature to obtain modified allyl benzoxazine resin E.

[0127] Example 1

[0128] Calculated by weight, 10 parts of modified allyl benzoxazine resin A, 50 parts of DCPD epoxy resin, 30 parts of active ester curing agent, 5 parts of imidazole accelerator, 250 parts of spherical silica and 5 parts of auxiliary agent 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 8 minutes to obtain a build-up film (PET film 38 μm, coating thickness of 100 μm, other embodiments and comparative examples have the same thickness).

[0129] Example 2

[0130] Calculated by weight, 20 parts of modified allyl benzoxazine resin A, 30 parts of DCPD epoxy resin, 20 parts of active ester curing agent, 3 parts of imidazole accelerator, 150 parts of spherical silica and 3 parts 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 120°C for 8 minutes to obtain a build-up layer film.

[0131] Example 3

[0132] Calculated by weight, 30 parts of modified allyl benzoxazine resin A, 10 parts of DCPD epoxy resin, 10 parts of active ester curing agent, 1 part of imidazole accelerator, 50 parts of spherical silica and 1 part of auxiliary agent are dissolved in 80 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 120°C for 8 minutes to obtain a build-up layer film.

[0133] Example 4

[0134] Calculated by weight, 40 parts of modified allyl benzoxazine resin A, 60 parts of DCPD epoxy resin, 40 parts of active ester curing agent, 10 parts of imidazole accelerator, 300 parts of spherical silica and 5 parts of additives are dissolved in 150 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 130°C for 10 minutes to obtain a build-up layer film.

[0135] Example 5

[0136] Calculated by weight, 20 parts of modified allyl benzoxazine resin B, 30 parts of DCPD epoxy resin, 20 parts of active ester curing agent, 3 parts of imidazole accelerator, 150 parts of spherical silica and 3 parts 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 well and sprayed on the surface of the PET film, and then baked at 120°C for 8 minutes to obtain a build-up layer film.

[0137] Example 6

[0138] Calculated by weight, 20 parts of modified allyl benzoxazine resin C, 30 parts of DCPD epoxy resin, 20 parts of active ester curing agent, 3 parts of imidazole accelerator, 150 parts of spherical silica and 3 parts 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 well and sprayed on the surface of the PET film, and then baked at 120°C for 8 minutes to obtain a build-up layer film.

[0139] Example 7

[0140] Calculated by weight, 20 parts of modified allyl benzoxazine resin D, 30 parts of DCPD epoxy resin, 20 parts of active ester curing agent, 3 parts of imidazole accelerator, 150 parts of spherical silica and 3 parts 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 well and sprayed on the surface of the PET film, and then baked at 120°C for 8 minutes to obtain a build-up layer film.

[0141] Comparative Example 1

[0142] Calculated by weight, 20 parts of modified allyl benzoxazine resin E, 30 parts of DCPD epoxy resin, 20 parts of active ester curing agent, 3 parts of imidazole accelerator, 150 parts of spherical silica and 3 parts 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 120°C for 8 minutes to obtain a build-up layer film.

[0143] Comparative Example 2

[0144] Calculated by weight, 20 parts of allyl benzoxazine, 30 parts of DCPD epoxy resin, 20 parts of active ester curing agent, 3 parts of imidazole accelerator, 150 parts of spherical silica and 3 parts 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 120°C for 8 minutes to obtain a build-up layer film.

[0145] Comparative Example 3

[0146] Calculated by weight, 50 parts of modified allyl benzoxazine resin A, 30 parts of DCPD epoxy resin, 20 parts of active ester curing agent, 3 parts of imidazole accelerator, 150 parts of spherical silica and 3 parts of auxiliary agents 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 120°C for 8 minutes to obtain a build-up layer film.

[0147] The components of the resin compositions in the above examples and comparative examples are shown in Table 1.

[0148] Table 1 Compositions of Examples and Comparative Examples

[0149]

[0150] The build-up films obtained in Examples 1-7 and Comparative Examples 1-3 were tested, and the testing method was as follows:

[0151] The build-up films obtained in Examples 1-7 and Comparative Examples 1-3 (without the PET film on the side) were respectively bonded to a copper foil with a thickness of 12 μm by a bonding machine, and then the PET film was removed and then covered with a copper foil with a thickness of 12 μm, and placed in a vacuum press with programmable temperature and pressure control, and cured completely at 100°C×30min+150°C×30min+190°C×120min under a vacuum state (vacuum parameters are <10 mBar) and a pressure of 10kgf / cm² to obtain a packaging substrate, which was then subjected to performance testing according to the following test standards. 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, where CTE includes CTE below Tg (Before TG) and CTE above Tg (After TG);

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

[0154] 3. Water absorption: 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] It can be seen from Table 2 that the packaging substrates prepared by the build-up films prepared in Examples 1-7 all have relatively high Tg (≥168°C), as well as relatively low thermal expansion coefficient (CTE≤46 ppm / °C below Tg, CTE≤125 ppm / °C above Tg), dielectric constant (≤3.71), dielectric loss (≤0.0114) and water absorption (≤0.10%), that is, they have relatively ideal heat resistance, thermal expansion coefficient, dielectric properties and water absorption.

[0158] By comparing Example 2 with Comparative Example 1, it can be seen that the use of amine fluorine-containing compounds as modifiers is more beneficial to reducing the thermal expansion coefficient, dielectric properties and water absorption rate, while improving heat resistance, compared with the use of allyl bisphenol A as a modifier; By comparing Example 2 with Comparative Example 2, it can be seen that the use of modified allyl benzoxazine resin in Example 2 can significantly improve the heat resistance of the build-up film, and significantly reduce its thermal expansion coefficient, dielectric properties and water absorption rate, compared with the use of allyl benzoxazine resin in Comparative Example 2; By comparing Example 2 with Comparative Example 3, it can be seen that when the amount of modified allyl benzoxazine resin used is too much, it will lead to degradation of the overall performance, and the amount of modified allyl benzoxazine resin used is preferably 10-40 parts.

[0159] 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.

[0160] The above-mentioned embodiments only express various 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 allylbenzoxazine resin composition, characterized in that: The composition comprises the following components in parts by weight: 10-40 parts of modified allyl benzoxazine resin; Functional resin 10-60 parts; 10-40 parts of curing agent; 1-10 parts of curing accelerator; 50-300 parts of inorganic filler; Additives 0-5 parts; The raw materials for preparing the modified allylbenzoxazine resin include: a modifier and an allylbenzoxazine resin; The modifier includes a first modifier; the first modifier is an amine fluorine-containing compound; The amine fluorine-containing compound is 2,2-bis(4-allyloxyphenyl)hexafluoropropane.

2. The modified allylbenzoxazine 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; further optionally, 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 bisallyl ether; Optionally, the mass ratio of the first modifier to the second modifier is (3-6):

1.

3. The modified allylbenzoxazine resin composition according to claim 1, characterized in that: The preparation method of the modified allylbenzoxazine resin comprises 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 1-3h.

4. The modified allylbenzoxazine 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, and R3 are each independently selected from -H or -CH3.

5. The modified allylbenzoxazine resin composition according to any one of claims 1 to 4, characterized in that: The functional resin includes epoxy resin and / or benzoxazine resin; Optionally, the epoxy resin includes one or more of naphthalene epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, phosphorus-containing epoxy resin, unsaturated epoxy resin, phenolic epoxy resin, o-cresol epoxy resin, bisphenol A novolac epoxy resin, multifunctional epoxy resin, alicyclic epoxy resin, resorcinol epoxy resin, rubber-modified epoxy resin, biphenyl epoxy resin and dicyclopentadiene epoxy resin; Optionally, the benzoxazine resin includes one or more of 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 allylbenzoxazine resin composition according to any one of claims 1 to 4, characterized in that: The curing agent includes 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 comprises modified spherical silica and / or modified spherical alumina; And / or the auxiliary agent includes one or more of a dispersant, a leveling agent, a defoaming agent, a treating agent and a coupling agent.

7. The modified allylbenzoxazine 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 build-up film, characterized in that: The invention comprises the modified allylbenzoxazine resin composition according to any one of claims 1 to 7.

9. The method for preparing a build-up film according to claim 8, characterized in that: The steps include: The modified allylbenzoxazine resin composition is coated on a substrate to form a resin composition coating, and then heated and dried to prepare a build-up film; Optionally, the heating and drying temperature is 70°C-160°C, and the heating and drying time is 2min-15min; Optionally, the substrate includes a plastic film and / or a metal film.

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

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