Flame-retardant resin composition, layer-adding film, preparation method of layer-adding film and packaging substrate

Abstract

The invention relates to the technical field of packaging substrates, in particular to a flame-retardant resin composition, a layer-adding film, a preparation method of the layer-adding film and a packaging substrate. The flame-retardant resin composition is prepared from the following raw materials in parts by weight: 20 to 50 parts of flame-retardant prepolymer, 10 to 50 parts of functional resin, 20 to 60 parts of curing agent, 1 to 10 parts of curing accelerator, 100 to 300 parts of inorganic filler and 10 to 40 parts of organic filler, wherein the flame-retardant prepolymer is prepared from the following raw materials: acrylate type polyphenyl ether resin and an allyl type phosphorus-containing compound. The flame-retardant resin composition provided by the invention is prepared into a layer-adding film, the flame-retardant grade of the layer-adding film can reach UL94V0, and the layer-adding film is high in glass-transition temperature, good in heat resistance, low in water absorption rate, extremely high in dielectric property and suitable for preparing a high-performance packaging carrier plate.

Description

Technical Field

[0001] The present application relates to the technical field of packaging carrier boards, and in particular to a flame retardant resin composition, a build-up film and a preparation method thereof, and a packaging carrier board. Background Art

[0002] As electronic products develop towards miniaturization, lightness, high functionality and high safety, electronic circuits are also developing towards multi-layer and high wiring density. Among them, Flip Chip Ball Grid Array (FCBGA) technology is an advanced packaging process that flips the chip upside down and attaches it to the carrier, and connects the chip and the carrier through solder balls to achieve electrical connection and signal transmission. FCBGA technology performs well in high speed, high density and high reliability, and is widely used in computer, communication, medical, consumer electronics and industrial control.

[0003] Compared with other packaging substrate technologies, FCBGA technology has higher integration, smaller packaging volume, higher reliability and lower power consumption, so it puts forward higher requirements on the performance of its main raw material, the build-up film, such as excellent heat resistance, flame resistance and dielectric properties. Among them, the heat resistance and flame resistance of the build-up film will affect the reliability of the product, and the dielectric properties will affect the signal transmission speed of the product. However, traditional resin compositions cannot have high heat resistance, high flame retardancy and excellent dielectric properties, and are difficult to be used in the production of build-up films for FCBGA technology. Summary of the invention

[0004] Based on this, it is necessary to provide a flame retardant resin composition, a build-up film and its preparation method and a packaging carrier to solve the problem that traditional resin compositions cannot have high heat resistance, high flame retardancy and excellent dielectric properties and are difficult to be applied to the preparation of build-up films for FCBGA technology.

[0005] The above-mentioned purpose of the present application is achieved through the following technical solutions:

[0006] In a first aspect of the present application, a flame retardant resin composition is provided, comprising the following raw materials in parts by weight:

[0007] ;

[0008] The raw materials of the flame retardant prepolymer include acrylate polyphenylene ether resin and an allyl phosphorus-containing compound, and the allyl phosphorus-containing compound has a structure as shown in the general formula (I):

[0009] (I).

[0010] In some embodiments, the acrylate polyphenylene ether resin has a structure as shown in the general formula (III):

[0011] (III);

[0012] Wherein, m and n are each independently selected from positive integers, and the sum of m and n is 5 to 60;

[0013] Y is absent or selected from C1-C3 alkylene.

[0014] In some embodiments, the mass ratio of the acrylate polyphenylene ether resin to the allyl phosphorus-containing compound is 100:(40-80).

[0015] In some embodiments, the method for preparing the flame retardant prepolymer comprises the following steps:

[0016] The acrylate polyphenylene ether resin and the allyl phosphorus-containing compound are mixed and prepolymerized at 100° C. to 150° C. for 60 min to 180 min to obtain the flame retardant prepolymer.

[0017] In some embodiments, the functional resin includes one or more of an epoxy resin, a benzoxazine resin, and a hydrocarbon resin.

[0018] In some embodiments, the epoxy resin includes one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, naphthalene epoxy resin, phosphorus-containing epoxy resin, unsaturated epoxy resin, phenolic epoxy resin, o-cresol 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.

[0019] In some embodiments, the benzoxazine resin includes one or more of bisphenol A-type benzoxazine resin, bisphenol F-type benzoxazine resin, bisphenol S-type benzoxazine resin, main chain benzoxazine resin, phosphorus-containing benzoxazine resin, dicyclopentadiene benzoxazine resin, biphenyl-type benzoxazine resin, tetraphenol ethane benzoxazine resin and naphthalene-type benzoxazine resin.

[0020] In some embodiments, the hydrocarbon resin includes one or more of polybutadiene and styrene-butadiene copolymer.

[0021] 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, an active ester curing agent, and an olefin curing agent.

[0022] 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.

[0023] In some embodiments, the inorganic filler includes one or more of modified silica and modified alumina.

[0024] In some embodiments, the organic filler includes one or more of silicone particles, core-shell rubber particles, and olefin elastomer particles.

[0025] In some embodiments, the flame retardant resin composition further comprises an auxiliary agent and a solvent, wherein the auxiliary agent comprises one or more of a dispersant, a leveling agent, a defoaming agent and a coupling agent.

[0026] In a second aspect of the present application, a build-up film is provided, comprising the flame retardant resin composition as described above.

[0027] In a third aspect of the present application, a method for preparing a build-up film is provided, comprising the following steps:

[0028] Covering the flame retardant resin composition as described above on a support to obtain a liquid film;

[0029] The liquid film is dried to obtain the build-up layer film.

[0030] In some embodiments, the drying process comprises the following steps: constant temperature drying at 100° C. to 200° C. for 5 min to 15 min.

[0031] In some embodiments, the support includes one or more of a polymer film and a metal foil.

[0032] In some embodiments, the thickness of the support body is 3 μm to 105 μm.

[0033] In some embodiments, the thickness of the liquid film is 5 μm to 150 μm.

[0034] In a fourth aspect of the present application, a packaging carrier is provided, comprising the flame retardant resin composition as described above, or comprising the build-up film as described above, or comprising a build-up film prepared by the method for preparing the build-up film as described above.

[0035] This application has at least the following beneficial effects:

[0036] In the flame retardant resin composition provided by the present application, the flame retardant prepolymer is prepolymerized by an acrylate polyphenylene ether resin and an allyl type phosphorus-containing compound, and its molecular structure contains a polyphenylene ether structure, a DOPO group and an imino group, so that its cured product exhibits excellent heat resistance and halogen-free flame retardancy while maintaining good dielectric properties, and the nitrogen and phosphorus elements in the flame retardant prepolymer synergize to make its flame retardant properties more stable and durable. At the same time, by reasonably matching the flame retardant prepolymer, functional resin, curing agent, curing accelerator and filler in a specific ratio, the number of polar groups in the composition is greatly reduced, thereby effectively improving the dielectric properties. Therefore, the flame retardant resin composition provided by the present application is made into a layered film, and its flame retardant grade can reach UL94V0, with a high glass transition temperature, good heat resistance, low water absorption and extremely strong dielectric properties, which is suitable for preparing high-performance packaging substrates. DETAILED DESCRIPTION

[0037] In order to facilitate the understanding of the present application, the present application is further described in detail below in conjunction with specific embodiments. 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.

[0038] 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.

[0039] In the present application, the meaning of "and / or" includes any and all combinations of one or more related listed items. "At least one" means more than one, such as one, two and more than two. "Multiple" or "several" means at least two, such as two, three, etc., and "multi-layer" means at least two layers, such as two layers, three layers, etc., unless otherwise clearly and specifically defined. In the description of the present application, "several" means at least one, such as one, two, etc., unless otherwise clearly and specifically defined.

[0040] When a numerical range is disclosed in this application, the above range is considered to be continuous and includes 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 combined. In other words, unless otherwise indicated, all ranges disclosed in this application should be understood to include any and all subranges included therein.

[0041] Unless otherwise specified, all steps of the present application may be performed sequentially or randomly. For example, the method includes steps (a) and (b), which means that the method may include steps (a) and (b) performed sequentially, or may include steps (b) and (a) performed sequentially. For example, the method may also include step (c), which means that step (c) may be added to the method in any order. For example, the method may include steps (a), (b) and (c), or may include steps (a), (c) and (b), or may include steps (c), (a) and (b), etc.

[0042] In this application, "above" or "below" includes the number itself. For example, "1 below" includes 1.

[0043] The temperature parameters in this application, unless otherwise specified, are allowed to be either constant temperature treatment or to vary within a certain temperature range. It should be understood that the constant temperature treatment allows the temperature to fluctuate within the accuracy range controlled by the instrument. Fluctuations within the range of ±5°C, ±4°C, ±3°C, ±2°C, and ±1°C are allowed.

[0044] In the present application, room temperature refers to indoor temperature, normal temperature or general temperature. Generally speaking, the range of room temperature can be any one of the following temperature intervals: 23°C ± 2°C, 25°C ± 5°C or 20°C ± 5°C.

[0045] the term

[0046] Unless otherwise specified or there is a contradiction, the terms and phrases used in this application have the following meanings:

[0047] In the present application, when a substituent with the same symbol appears multiple times, each substituent may be the same or different from each other. For example, when a general formula contains multiple R, R may be the same or different from each other.

[0048] "Alkyl" refers to a monovalent residue formed by the loss of a hydrogen atom from a saturated hydrocarbon containing a primary (normal) carbon atom, a secondary carbon atom, a tertiary carbon atom, a quaternary carbon atom, or a combination thereof. Alkyl can represent a straight chain, branched and / or cyclic alkyl group. The carbon number of the alkyl group can be 1 to 50, 1 to 30, 1 to 20, 1 to 10 or 1 to 6. Phrases containing this term, for example, "C1 to C9 alkyl" refers to an alkyl group containing 1 to 9 carbon atoms, and each occurrence can be independently C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, C7 alkyl, C8 alkyl or C9 alkyl. Suitable examples include, but are not limited to, methyl (Me, -CH3), ethyl (Et, -CH2CH3), 1-propyl (n-Pr, n-propyl, -CH2CH2CH3), 2-propyl (i-Pr, i-propyl, -CH(CH3)2), 1-butyl (n-Bu, n-butyl, -CH2CH2CH2CH3), 2-methyl-1-propyl (i-Bu, i-butyl, -CH2CH(CH3)2), 2-butyl (s-Bu, s-butyl, -CH(C H3)CH2CH3), 2-methyl-2-propyl (t-Bu, t-butyl, -C(CH3)3), 1-pentyl (n-pentyl, -CH2CH2CH2CH2CH3), 2-pentyl (-CH(CH3)CH2CH2CH3), 3-pentyl (-CH(CH2CH3)2), 2-methyl-2-butyl (-C(CH3)2CH2CH3), 3-methyl-2-butyl (-CH(CH3)CH(CH3)2), 3-methyl-1-butyl (- CH2CH2CH(CH3)2), 2-methyl-1-butyl (-CH2CH(CH3)CH2CH3), 1-hexyl (-CH2CH2CH2CH2CH2CH3), 2-hexyl (-CH(CH3)CH2CH2CH2CH3), 3-hexyl (-CH(CH2CH3)(CH2CH2CH3)), 2-methyl-2-pentyl (-C(CH3)2CH2CH2CH3), 3-methyl-2-pentyl (-CH(CH3)CH( CH3)CH2CH3), 4-methyl-2-pentyl (-CH(CH3)CH2CH(CH3)2), 3-methyl-3-pentyl (-C(CH3)(CH2CH3)2), 2-methyl-3-pentyl (-CH(CH2CH3)CH(CH3)2), 2,3-dimethyl-2-butyl (-C(CH3)2CH(CH3)2), 3,3-dimethyl-2-butyl (-CH(CH3)C(CH3)3, octyl (-(CH2)7CH3).

[0049] "Alkylene" refers to a hydrocarbon group with two monovalent radical centers derived from an alkyl group by removing a hydrogen atom, which can be a saturated branched alkyl group or a saturated straight-chain alkyl group. For example, "C1-C9 alkylene" means that the alkyl portion contains 1 to 9 carbon atoms, and each occurrence can be independently C1 alkylene, C4 alkylene, C5 alkylene, C6 alkylene, C7 alkylene, C8 alkylene or C9 alkylene. Suitable examples include, but are not limited to, methylene (-CH2-), 1,1-ethyl (-CH(CH3)-), 1,2-ethyl (-CH2CH2-), 1,1-propyl (-CH(CH2CH3)-), 1,2-propyl (-CH2CH(CH3)-), 1,3-propyl (-CH2CH2CH2-) and 1,4-butyl (-CH2CH2CH2CH2-).

[0050] In a first aspect of the present application, a flame retardant resin composition is provided to solve the problem that traditional resin compositions cannot have high heat resistance, high flame retardancy and excellent dielectric properties and are difficult to be applied to the preparation of build-up films of FCBGA technology.

[0051] In some embodiments, the flame retardant resin composition includes the following raw materials in parts by weight:

[0052] ;

[0053] The raw materials of the flame retardant prepolymer include acrylate polyphenylene ether resin and allyl phosphorus-containing compound, and the allyl phosphorus-containing compound has a structure as shown in the general formula (I):

[0054] (I).

[0055] It can be understood that 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, referred to as DOPO, has a structure as shown in the general formula (II):

[0056] (II);

[0057] The molecular structure of DOPO contains biphenyl rings and cyclic O=PO bonds, and compared with traditional non-annulated organic phosphates, it has very excellent thermal stability, chemical stability and halogen-free flame retardancy. The allyl-type phosphorus-containing compound in the present application contains two DOPO groups, two imino groups and two allyl groups, which give it excellent heat resistance and long-lasting flame retardancy, and the imino groups and allyl groups can combine with the acrylate groups in the acrylate-type polyphenylene ether resin to form a flame-retardant prepolymer.

[0058] In the flame retardant resin composition provided by the present application, the flame retardant prepolymer is prepolymerized by an acrylate polyphenylene ether resin and an allyl type phosphorus-containing compound, and its molecular structure contains a polyphenylene ether structure, a DOPO group and an imino group, so that its cured product exhibits excellent heat resistance and halogen-free flame retardancy while maintaining good dielectric properties, and the nitrogen and phosphorus elements in the flame retardant prepolymer synergize to make its flame retardant properties more stable and durable. At the same time, by reasonably matching the flame retardant prepolymer, functional resin, curing agent, curing accelerator and filler in a specific ratio, the number of polar groups in the composition is greatly reduced, thereby effectively improving the dielectric properties. Therefore, the flame retardant resin composition provided by the present application is made into a layered film, and its flame retardant grade can reach UL94V0, with a high glass transition temperature, good heat resistance, low water absorption and extremely strong dielectric properties, which is suitable for preparing high-performance packaging substrates.

[0059] As an example, in the flame retardant resin composition, the weight parts of the flame retardant prepolymer include but are not limited to 20 parts, 22 parts, 25 parts, 28 parts, 30 parts, 32 parts, 35 parts, 38 parts, 40 parts, 42 parts, 45 parts, 48 ​​parts or 50 parts, and can be further selected as 20 parts to 40 parts.

[0060] As an example, in the flame retardant resin composition, the weight of the functional resin includes but is not limited to 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, 28 parts, 30 parts, 32 parts, 35 parts, 38 parts, 40 parts, 42 parts, 45 parts, 48 ​​parts or 50 parts, and can be further selected as 10 parts to 30 parts.

[0061] As an example, in the flame retardant resin composition, the weight of the curing agent includes but is not limited to 20 parts, 22 parts, 25 parts, 28 parts, 30 parts, 32 parts, 35 parts, 38 parts, 40 parts, 42 parts, 45 parts, 48 ​​parts, 50 parts, 52 parts, 55 parts, 58 parts or 60 parts, and can be further selected as 20 parts to 40 parts.

[0062] As an example, in the flame retardant resin composition, the weight of the curing accelerator includes but is not limited to 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts or 10 parts, and can be further selected as 1 part to 5 parts.

[0063] As an example, in the flame retardant resin composition, the weight of the inorganic filler includes but is not limited to 100 parts, 120 parts, 140 parts, 160 parts, 180 parts, 200 parts, 220 parts, 240 parts, 260 parts, 280 parts or 300 parts, and can be further selected as 100 parts to 200 parts.

[0064] As an example, in the flame retardant resin composition, the weight of the organic filler includes but is not limited to 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, 28 parts, 30 parts, 32 parts, 35 parts, 38 parts or 40 parts, and can be further selected as 10 parts to 30 parts.

[0065] In some embodiments, the flame retardant resin composition includes the following raw materials in parts by weight:

[0066] .

[0067] In some embodiments, the flame retardant resin composition includes the following raw materials in parts by weight:

[0068] .

[0069] In some embodiments, the acrylate polyphenylene ether resin has a structure as shown in the general formula (III):

[0070] (III);

[0071] Wherein, m and n are each independently selected from positive integers, and the sum of m and n is 5 to 60;

[0072] Y is absent or selected from C1~C3 alkylene;

[0073] The molecular structure of polyphenylene oxide (PPO) resin contains a large number of benzene rings and does not contain strong polar groups, which gives it excellent properties such as high glass transition temperature (glass transition temperature, Tg), low coefficient of thermal expansion (coefficient of thermal expansion, CTE), low dielectric constant (dielectric constant, Dk) and low dielectric loss (dissipation factor, Df). Modification of polyphenylene oxide resin and introduction of unsaturated groups such as olefinic, alkynyl or acrylate groups can improve compatibility and reduce melt viscosity.

[0074] As an example, in the acrylate polyphenylene ether resin, m and n are each independently selected from a positive integer, and the sum of m and n includes but is not limited to 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55 or 60; Y is not present, or Y is selected from a C1 alkylene, a C2 alkylene or a C3 alkylene, suitable examples of which include: -CH2-, -CH(CH3)-, -CH2CH2-, -CH(CH2CH3)-, -CH2CH(CH3)-, -CH2CH2CH2-.

[0075] In some embodiments, the mass ratio of the acrylate polyphenylene ether resin to the allyl phosphorus-containing compound is 100:(40-80). As an example, the mass ratio of the acrylate polyphenylene ether resin to the allyl phosphorus-containing compound includes but is not limited to 100:40, 100:45, 100:50, 100:55, 100:60, 100:65, 100:70, 100:75 or 100:80.

[0076] By controlling the mass ratio of acrylate polyphenylene ether resin and allyl phosphorus-containing compound, the content of polyphenylene ether structure, DOPO group and imino group in the flame retardant prepolymer can be regulated, thereby improving its compatibility, thermal expansion coefficient, glass transition temperature, flame retardancy and dielectric properties.

[0077] In some embodiments, the method for preparing a flame retardant prepolymer comprises the following steps: mixing an acrylate polyphenylene ether resin and an allyl phosphorus-containing compound, and performing a prepolymerization reaction at 100° C. to 150° C. for 60 min to 180 min to obtain a flame retardant prepolymer.

[0078] As an example, the reaction temperature of the prepolymerization reaction includes but is not limited to 100°C, 105°C, 110°C, 115°C, 120°C, 125°C, 130°C, 135°C, 140°C, 145°C or 150°C, and may further be 130°C to 140°C; the reaction time of the prepolymerization reaction includes but is not limited to 60min, 70min, 80min, 90min, 100min, 110min, 120min, 130min, 140min, 150min, 160min, 170min or 180min, and may further be 120min to 150min.

[0079] In some embodiments, the method of mixing the acrylate polyphenylene ether resin and the allyl phosphorus-containing compound comprises the following steps: heating at 100° C. to 150° C. to melt the allyl phosphorus-containing compound, and adding the acrylate polyphenylene ether resin.

[0080] As an example, the temperature of the heating treatment includes but is not limited to 100°C, 105°C, 110°C, 115°C, 120°C, 125°C, 130°C, 135°C, 140°C, 145°C or 150°C, and can further be 125°C~135°C.

[0081] In some embodiments, after the prepolymerization reaction, a step of cooling to room temperature is further included.

[0082] In some embodiments, the functional resin includes one or more of an epoxy resin, a benzoxazine resin, and a hydrocarbon resin.

[0083] It can be understood that the functional resin can be selected from any one of epoxy resin, benzoxazine resin and hydrocarbon resin, or can be selected from at least two of epoxy resin, benzoxazine resin and hydrocarbon resin, such as epoxy resin and benzoxazine resin, epoxy resin and hydrocarbon resin, benzoxazine resin and hydrocarbon resin.

[0084] Among the above functional resins, there are benzene rings and six-membered oxazine rings in the molecular structure of benzoxazine resin, and the molecular polarity is low, so that the dielectric constant is relatively low and the dielectric loss is small, and it has excellent dielectric properties, high heat resistance, glass transition temperature above 150°C, curing shrinkage is almost 0, halogen-free flame retardancy is good, water absorption is low, and elastic modulus is good. The molecular structure of hydrocarbon resin contains only two elements, carbon and hydrogen, does not contain heteroatoms, has very few polar groups, and has good dielectric properties. Epoxy resin can be cured and cross-linked to form a network structure, with excellent physical and mechanical properties, electrical insulation properties, bonding properties and processing properties, but its molecular structure contains polar groups such as epoxy groups and hydroxyl groups, which makes its dielectric constant and dielectric loss relatively high. Through the reasonable combination of functional resins of different components, the number of polar groups in the cured product of the flame retardant resin composition can be greatly reduced, and its dielectric properties can be further improved, and its cured product can maintain excellent heat resistance, high temperature modulus retention and halogen-free flame retardancy.

[0085] In some embodiments, the epoxy resin includes one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, naphthalene epoxy resin, phosphorus-containing epoxy resin, unsaturated epoxy resin, phenolic epoxy resin, o-cresol 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, and further selected from one or more of naphthalene epoxy resin, phosphorus-containing epoxy resin, biphenyl epoxy resin and dicyclopentadiene epoxy resin.

[0086] In some embodiments, the benzoxazine resin includes one or more of bisphenol A-type benzoxazine resin, bisphenol F-type benzoxazine resin, bisphenol S-type benzoxazine resin, main chain benzoxazine resin, phosphorus-containing benzoxazine resin, dicyclopentadiene benzoxazine resin, biphenyl benzoxazine resin, tetraphenol ethane benzoxazine resin and naphthalene benzoxazine resin, and can further be selected from one or more of phosphorus-containing benzoxazine resin, dicyclopentadiene benzoxazine resin, biphenyl benzoxazine resin and naphthalene benzoxazine resin.

[0087] In some embodiments, the hydrocarbon resin includes one or more of polybutadiene and styrene-butadiene copolymer, and may further be polybutadiene.

[0088] 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, an active ester curing agent, and an olefin curing agent.

[0089] In some embodiments, the amine curing agent includes one or more of ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenyl sulfone, dicyandiamide, polyetheramine, and polyamide.

[0090] In some embodiments, the phenolic curing agent includes one or more of linear phenol formaldehyde resin, linear bisphenol A formaldehyde resin, linear o-cresol formaldehyde resin, neophenol resin, biphenyl aralkylphenol resin, halogen-free flame retardant nitrogen-containing phenolic resin and halogen-free flame retardant phosphorus-containing phenolic resin.

[0091] In some embodiments, the anhydride curing agent includes one or more of phthalic anhydride, styrene maleic anhydride copolymer, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, maleic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, benzophenonetetracarboxylic anhydride, glutaric anhydride, polyazetaic anhydride, dichloromaleic anhydride, trimellitic anhydride, pyromellitic anhydride, pyromellitic anhydride, dibenzophenonetetracarboxylic anhydride, dodecylmaleic anhydride, succinic anhydride, hexahydrophthalic anhydride and cyclopentanetetracarboxylic anhydride.

[0092] In some embodiments, the cyanate ester curing agent includes one or more of bisphenol A cyanate ester resin, bisphenol F cyanate ester resin, bisphenol S cyanate ester resin, bisphenol M cyanate ester resin, bisphenol E cyanate ester resin, phenolic cyanate ester resin, biphenyl cyanate ester resin, naphthalene cyanate ester resin, multifunctional cyanate ester resin and dicyclopentadiene bisphenol cyanate ester resin.

[0093] In some embodiments, the active ester curing agent includes one or more of bis(2-methacryloyloxyethyl)-3,3′-dithiodipropionate active ester and pentaerythritol tetrakis(3-mercaptopropionate) active ester.

[0094] In some embodiments, the olefin curing agent includes one or more of pentaerythritol triacrylate, triallyl cyanurate (TAC), trimethylolpropane trimethacrylate, tripropylene glycol diacrylate, and triallyl isocyanurate (TAIC).

[0095] 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.

[0096] In some embodiments, the tertiary amine accelerator includes one or more of triethylamine, benzyldimethylamine, tris(dimethylaminomethyl)phenol, triethylenediamine, and dimethylaniline.

[0097] In some embodiments, the imidazole accelerator includes one or more of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and 1-cyano-2-methylimidazole.

[0098] In some embodiments, the peroxide-based accelerator includes one or more of benzoyl peroxide, di-tert-butyl peroxide, dicumyl peroxide (DCP), tert-butyl perbenzoate, and tert-butyl peroxyoctanoate.

[0099] In some embodiments, the organophosphorus accelerator includes one or more of triphenylphosphine and tributyl phosphate.

[0100] In some embodiments, the transition metal carboxylate promoter includes one or more of manganese acetate, zinc octoate, zinc isooctanoate, zinc naphthenate, zinc acetylacetonate, stannous octoate, dibutyltin dilaurate, cobalt octoate, cobalt naphthenate, cobalt acetylacetonate, aluminum acetylacetonate, copper acetylacetonate, and nickel acetylacetonate.

[0101] In some embodiments, the inorganic filler includes one or more of modified silica and modified alumina.

[0102] Adding a suitable inorganic filler into the flame retardant resin composition can play a synergistic role with the flame retardant prepolymer and the functional resin, and significantly reduce the thermal expansion coefficient of the resin composition.

[0103] In some embodiments, the modified silica includes one or more of epoxy-modified silica, aniline-modified silica, vinyl-modified silica, hollow silica, acrylic (polymethyl methacrylate, PMMA)-modified silica, fluoroalkyl-modified silica, and molybdate-modified silica.

[0104] In some embodiments, the modified alumina includes one or more of epoxy-modified alumina, aniline-modified alumina, vinyl-modified alumina, hollow alumina, acrylic (polymethyl methacrylate, PMMA)-modified alumina, fluoroalkyl-modified alumina, and molybdate-modified alumina.

[0105] In some embodiments, the shape of the modified silicon dioxide and the shape of the modified aluminum oxide are each independently selected from one or more of sphere, ellipsoid, strip, and amorphous, and can further be selected to be spherical.

[0106] It is understood that the average particle size of the inorganic filler is not particularly limited. In some embodiments, the average particle size of the inorganic filler is ≤10 μm, including but not limited to 10 μm, 5 μm, 3 μm, 1 μm, 0.5 μm, 0.1 μm, 0.05 μm or 0.01 μm.

[0107] In some embodiments, the organic filler includes one or more of silicone particles, core-shell rubber particles, and olefin elastomer particles, and may further include core-shell rubber particles.

[0108] Adding suitable organic fillers to the flame retardant resin composition can play the role of reinforcement, reducing curing shrinkage and improving dimensional stability.

[0109] It is understood that the average particle size of the organic filler is not particularly limited. In some embodiments, the average particle size of the organic filler is ≤1000 nm, including but not limited to 10 nm, 50 nm, 100 nm, 200 nm, 300 nm, 500 nm or 1000 nm.

[0110] In some embodiments, the flame retardant resin composition further comprises an additive and a solvent, wherein the additive comprises one or more of a dispersant, a leveling agent, a defoaming agent and a coupling agent.

[0111] Adding appropriate additives to the flame retardant resin composition can improve the dispersibility, fluidity, uniformity and bonding ability between different components of the flame retardant resin composition, improve the curing ability of the flame retardant resin composition, and enhance the various properties of its cured product. Adding solvents can improve the compatibility between multiple components and avoid the undesirable phenomenon of stratification or precipitation.

[0112] In some embodiments, the solvent includes one or more of ethanol, acetone, cyclohexanone, butanone, toluene, xylene, N,N-dimethylformamide, N,N-dimethylacetamide and propylene glycol methyl ether. Further optionally, the solvent includes one or more of butanone, toluene and propylene glycol methyl ether. Further optionally, in the solvent, the mass ratio of butanone, toluene and propylene glycol methyl ether is 1:1:1.

[0113] In some embodiments, in the auxiliary agent, the coupling agent includes one or more of a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, and a zirconate coupling agent, and may further be a silane coupling agent.

[0114] In some embodiments, among the auxiliary agents, the defoaming agent includes one or more of alcohol defoaming agents, fatty acid defoaming agents, fatty acid ester defoaming agents, phosphate defoaming agents, mineral oil defoaming agents, amide defoaming agents, polyether defoaming agents, silicone defoaming agents and polyether-modified silicone defoaming agents, and silicone defoaming agents can be further selected.

[0115] In some embodiments, the flame retardant resin composition further comprises the following raw materials in parts by weight: 80 to 200 parts of a solvent and 1 to 5 parts of an auxiliary agent.

[0116] As an example, in the resin composition, the weight parts of the solvent include but are not limited to 80 parts, 90 parts, 100 parts, 110 parts, 120 parts, 130 parts, 140 parts, 150 parts, 160 parts, 170 parts, 180 parts, 190 parts or 200 parts, and can further be selected as 80 parts to 120 parts.

[0117] As an example, in the resin composition, the weight of the auxiliary agent includes but is not limited to 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts or 5 parts, and can further be 2 parts to 4 parts.

[0118] In a second aspect of the present application, a build-up film is provided, comprising the flame retardant resin composition as described above.

[0119] In a third aspect of the present application, a method for preparing a build-up film is provided, which uses the flame retardant resin composition as described above.

[0120] In some embodiments, the method for preparing the build-up film comprises the following steps:

[0121] Covering the flame retardant resin composition as described above on a support to obtain a liquid film;

[0122] The liquid film is dried to obtain a build-up film.

[0123] In some embodiments, the method of coating the flame retardant resin composition on the support includes one or more of a coating method and a screen printing method, wherein the coating method includes one or more of a brushing method, a spin coating method, a spray coating method, a blade coating method, and a dip coating method.

[0124] In some embodiments, the drying process comprises the following steps: constant temperature drying at 100° C. to 200° C. for 5 min to 15 min.

[0125] As an example, the temperature of the drying process includes, but is not limited to, 100° C., 110° C., 120° C., 130° C., 140° C., 150° C., 160° C., 170° C., 180° C., 190° C., or 200° C., and may further be 130° C. to 150° C. The time of the drying process includes, but is not limited to, 5 min, 6 min, 7 min, 8 min, 9 min, 10 min, 11 min, 12 min, 13 min, 14 min, or 15 min, and may further be 10 min to 15 min.

[0126] In some embodiments, the thickness of the liquid film is 5 μm to 150 μm, including but not limited to 5 μm, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 110 μm, 120 μm, 130 μm, 140 μm or 150 μm.

[0127] In some embodiments, the thickness of the support is 3 μm to 105 μm, including but not limited to 3 μm, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm or 105 μm.

[0128] In some embodiments, the support includes one or more of a polymer film and a metal foil. Optionally, the polymer film includes one or more of a polyethylene terephthalate (PET) film, a polycarbonate (PC) film, and a polymethyl methacrylate (PMMA) film; and the metal foil includes one or more of a copper foil and an aluminum foil.

[0129] It can be understood that the build-up film refers to a semi-cured product and / or cured product of the flame retardant resin composition. Generally, the support body only plays a supporting role in the preparation process of the build-up film, and the support body needs to be removed in the process of using the build-up film to make a packaging carrier. In addition, when the support body is a metal foil, it is also possible to choose not to remove the support body, but to directly make the package carrier from the combination formed by stacking the build-up film and the support body.

[0130] In a fourth aspect of the present application, a packaging carrier is provided, comprising the flame retardant resin composition as described above, or comprising the build-up film as described above, or comprising a build-up film prepared by the method for preparing the build-up film as described above.

[0131] In some embodiments, the number of the build-up films in the package carrier is one or more layers.

[0132] In some embodiments, one or both sides of each build-up layer film are coated with metal foil.

[0133] In some embodiments, the metal foil includes one or more of copper foil and aluminum foil.

[0134] In some embodiments, the thickness of the metal foil is 3 μm to 105 μm, including but not limited to 3 μm, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm or 105 μm.

[0135] In some embodiments, the method for preparing the package carrier includes vacuum hot pressing.

[0136] The following is further described in conjunction with specific examples and comparative examples. The raw materials involved in the following specific examples and comparative examples, unless otherwise specified, can all be sourced from commercial sources, the instruments used, unless otherwise specified, can all be sourced from commercial sources, and the processes involved, unless otherwise specified, are all routinely selected by those skilled in the art. Among them, the sources of some raw materials are as follows:

[0137] Phosphazene compound: Otsuka Chemical SPB100;

[0138] Acrylate polyphenylene ether resin: Sabic SA9000, the structure is shown in the general formula (III), the glass transition temperature is 160°C, the specific gravity is 1.02, the intrinsic viscosity is 0.09 dL / g, the number average molecular weight (Mn) is 2300, the vinyl functionality is 1.9, the dielectric constant (Dk, 1MHz) is 2.54, and the dielectric loss (Df, 1MHz) is 0.0007;

[0139] Dicyclopentadiene (DCPD) benzoxazine resin: Cologne KZH-5031MP70;

[0140] Olefin curing agent: TAIC from Zhisheng Technology;

[0141] Peroxide curing accelerator: Nouryon DCP;

[0142] Vinyl modified spherical silica: Yaduma, model SO-C1, average particle size 0.4μm;

[0143] Core-shell rubber particles: UMG Co., Ltd., model B0603;

[0144] Additive: BYK-1650, a silicone defoamer.

[0145] Example 1

[0146] The method for preparing the packaging substrate provided in this embodiment is specifically as follows:

[0147] (1) Preparation of allyl phosphorus-containing compounds:

[0148] Step S110: 1 mol of 2-methylallylamine and 100 mL of acetone solvent are mixed, the temperature is raised to 80° C. to 120° C., 0.5 mol of terephthalaldehyde is added, and the mixture is reacted for 3 h to 8 h under a nitrogen atmosphere to obtain a first mixed solution;

[0149] Step S120: Cool the first mixed solution to room temperature, filter it with suction to obtain a crude product, and then recrystallize it with water for 4 to 7 times, and then dry the recrystallized product at 60° C. to 90° C. for 24 hours to obtain an intermediate;

[0150] Step S130: 0.5 mol of the intermediate, 1 mol of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and 80 mL of dimethylformamide solvent are mixed, the temperature is raised to 100° C. to 150° C., and the mixture is reacted for 5 h to 7 h under a nitrogen atmosphere to obtain a second mixed solution;

[0151] Step S140: Cool the second mixed solution to room temperature, and then recrystallize it with water for 4 to 7 times, and then dry the recrystallized product at 60° C. to 90° C. for 24 hours to obtain an allyl-type phosphorus-containing compound.

[0152] (2) Preparation of flame retardant prepolymer:

[0153] Please refer to Table 1. By weight, 40 parts of allyl phosphorus-containing compound were taken and heated to a molten state at 130°C. Then, 100 parts of acrylate polyphenylene ether resin were added and prepolymerized at 130°C. After 120 minutes, the mixture was cooled to room temperature to obtain flame retardant prepolymer A.

[0154] (3) Preparation of flame retardant resin composition:

[0155] Please refer to Table 2. According to parts by weight, 20 parts of flame retardant prepolymer A, 10 parts of dicyclopentadiene (DCPD) benzoxazine resin, 20 parts of olefin curing agent, 3 parts of peroxide curing accelerator, 100 parts of vinyl modified spherical silica, 10 parts of core-shell rubber particles and 1 part of auxiliary agent are dissolved in 100 parts of solvent (mixed by butanone, toluene and propylene glycol methyl ether in a mass ratio of 1:1:1), and the mixture is fully stirred to obtain a flame retardant resin composition in a colloidal liquid state.

[0156] (4) Preparation of a build-up film: spray the flame retardant resin composition onto one surface of a PET film, bake it at 140° C. for 10 min to obtain a build-up film, and stack the build-up film and the PET film to form a composite body.

[0157] (5) Preparation of packaging substrate: Use a laminating machine to laminate the build-up film in the assembly onto a 12 μm thick copper foil, remove the PET film, and then cover the build-up film with another 12 μm thick copper foil. Place the assembly in a programmable temperature and pressure controlled vacuum press and press the assembly under a vacuum of ≤10 mBar and 10 kgf / cm 2 The build-up layer film was completely cured under vacuum hot pressing at 100°C for 30 min, vacuum hot pressing at 150°C for 30 min, and vacuum hot pressing at 190°C for 120 min to obtain a packaging carrier.

[0158] Example 2

[0159] The method for preparing the packaging substrate provided in this embodiment is specifically as follows:

[0160] (1) Preparation of allyl phosphorus-containing compound: Same as Example 1.

[0161] (2) Preparation of flame retardant prepolymer: same as in Example 1.

[0162] (3) Preparation of flame retardant resin composition:

[0163] Please refer to Table 2. According to parts by weight, 30 parts of flame retardant prepolymer A, 30 parts of dicyclopentadiene (DCPD) benzoxazine resin, 30 parts of olefin curing agent, 5 parts of peroxide curing accelerator, 200 parts of vinyl modified spherical silica, 20 parts of core-shell rubber particles and 3 parts of additives are dissolved in 130 parts of solvent (mixed by butanone, toluene and propylene glycol methyl ether in a mass ratio of 1:1:1), and the mixture is fully stirred to obtain a flame retardant resin composition in a colloidal liquid state.

[0164] (4) Preparation of a build-up film: spray the flame retardant resin composition onto one surface of a PET film, bake it at 140° C. for 14 min to obtain a build-up film, and stack the build-up film and the PET film to form a composite body.

[0165] (5) Preparation of packaging substrate: same as in Example 1.

[0166] Example 3

[0167] (1) Preparation of allyl phosphorus-containing compound: Same as Example 1.

[0168] (2) Preparation of flame retardant prepolymer: same as in Example 1.

[0169] (3) Preparation of flame retardant resin composition:

[0170] Please refer to Table 2. According to parts by weight, 40 parts of flame retardant prepolymer A, 20 parts of dicyclopentadiene (DCPD) benzoxazine resin, 40 parts of olefin curing agent, 1 part of peroxide curing accelerator, 150 parts of vinyl modified spherical silica, 30 parts of core-shell rubber particles and 5 parts of additives are dissolved in 120 parts of solvent (mixed by butanone, toluene and propylene glycol methyl ether in a mass ratio of 1:1:1), and the mixture is fully stirred to obtain a flame retardant resin composition in a colloidal liquid state.

[0171] (4) Preparation of a build-up film: spray the flame retardant resin composition onto one surface of a PET film, bake it at 130° C. for 13 min to obtain a build-up film, and stack the build-up film and the PET film to form a composite body.

[0172] (5) Preparation of packaging substrate: same as in Example 1.

[0173] Example 4

[0174] The method for preparing the packaging substrate provided in this embodiment is specifically as follows:

[0175] (1) Preparation of allyl phosphorus-containing compound: Same as Example 1.

[0176] (2) Preparation of flame retardant prepolymer:

[0177] Please refer to Table 1. By weight, 60 parts of allyl phosphorus-containing compound were taken and heated to a molten state at 130°C. Then, 100 parts of acrylate polyphenylene ether resin were added and prepolymerized at 130°C. After 150 minutes, the prepolymer was cooled to room temperature to obtain flame retardant prepolymer B.

[0178] (3) Preparation of flame retardant resin composition:

[0179] Please refer to Table 2. According to parts by weight, 30 parts of flame retardant prepolymer B, 30 parts of dicyclopentadiene (DCPD) benzoxazine resin, 30 parts of olefin curing agent, 5 parts of peroxide curing accelerator, 200 parts of vinyl modified spherical silica, 20 parts of core-shell rubber particles and 3 parts of additives are dissolved in 130 parts of solvent (mixed by butanone, toluene and propylene glycol methyl ether in a mass ratio of 1:1:1), and the mixture is fully stirred to obtain a flame retardant resin composition in a colloidal liquid state.

[0180] (4) Preparation of a build-up film: spray the flame retardant resin composition onto one surface of a PET film, bake it at 145° C. for 14 min to obtain a build-up film, and stack the build-up film and the PET film to form a composite.

[0181] (5) Preparation of packaging substrate: same as in Example 1.

[0182] Example 5

[0183] The method for preparing the packaging substrate provided in this embodiment is specifically as follows:

[0184] (1) Preparation of allyl phosphorus-containing compound: Same as Example 1.

[0185] (2) Preparation of flame retardant prepolymer:

[0186] Please refer to Table 1. By weight, 80 parts of allyl phosphorus-containing compound were taken and heated to a molten state at 130°C. Then, 100 parts of acrylate polyphenylene ether resin were added and prepolymerized at 140°C. After 140 minutes, the mixture was cooled to room temperature to obtain flame retardant prepolymer C.

[0187] (3) Preparation of flame retardant resin composition:

[0188] Please refer to Table 2. According to parts by weight, 30 parts of flame retardant prepolymer C, 30 parts of dicyclopentadiene (DCPD) benzoxazine resin, 30 parts of olefin curing agent, 5 parts of peroxide curing accelerator, 200 parts of vinyl modified spherical silica, 20 parts of core-shell rubber particles and 3 parts of additives are dissolved in 130 parts of solvent (mixed by butanone, toluene and propylene glycol methyl ether in a mass ratio of 1:1:1), and the mixture is fully stirred to obtain a flame retardant resin composition in a colloidal liquid state.

[0189] (4) Preparation of a build-up film: spray the flame retardant resin composition onto one surface of a PET film, bake it at 150° C. for 14 min to obtain a build-up film, and stack the build-up film and the PET film to form a composite body.

[0190] (5) Preparation of packaging substrate: same as in Example 1.

[0191] Comparative Example 1

[0192] The preparation method of the packaging substrate provided in this comparative example is as follows:

[0193] (1) Preparation of flame retardant resin composition:

[0194] Please refer to Table 2. According to parts by weight, 30 parts of acrylate polyphenylene ether resin, 30 parts of dicyclopentadiene (DCPD) benzoxazine resin, 30 parts of olefin curing agent, 5 parts of peroxide curing accelerator, 200 parts of vinyl modified spherical silica, 20 parts of core-shell rubber particles and 3 parts of additives are dissolved in 130 parts of solvent (mixed by butanone, toluene and propylene glycol methyl ether in a mass ratio of 1:1:1), and the mixture is fully stirred to obtain a flame retardant resin composition in a colloidal liquid state.

[0195] (2) Preparation of a build-up film: The flame retardant resin composition was sprayed on one surface of a PET film and baked at 130° C. for 14 min to obtain a build-up film, and the build-up film and the PET film were stacked to form a composite body.

[0196] (3) Preparation of packaging substrate: the same as step (5) of Example 1.

[0197] Comparative Example 2

[0198] The preparation method of the packaging substrate provided in this comparative example is as follows:

[0199] (1) Preparation of flame retardant resin composition:

[0200] Please refer to Table 2. According to parts by weight, 60 parts of flame retardant prepolymer A, 30 parts of dicyclopentadiene (DCPD) benzoxazine resin, 30 parts of olefin curing agent, 5 parts of peroxide curing accelerator, 200 parts of vinyl modified spherical silica, 20 parts of core-shell rubber particles and 3 parts of additives are dissolved in 130 parts of solvent (mixed by butanone, toluene and propylene glycol methyl ether in a mass ratio of 1:1:1), and the mixture is fully stirred to obtain a flame retardant resin composition in a colloidal liquid state.

[0201] (2) Preparation of a build-up film: The flame retardant resin composition was sprayed on one surface of a PET film and baked at 140° C. for 11 min to obtain a build-up film, and the build-up film and the PET film were stacked to form a composite body.

[0202] (3) Preparation of packaging substrate: the same as step (5) of Example 1.

[0203] Comparative Example 3

[0204] The preparation method of the packaging substrate provided in this comparative example is as follows:

[0205] (1) Preparation of flame retardant resin composition:

[0206] Please refer to Table 2. According to parts by weight, 30 parts of phosphazene compound, 30 parts of dicyclopentadiene (DCPD) benzoxazine resin, 30 parts of olefin curing agent, 5 parts of peroxide curing accelerator, 200 parts of vinyl modified spherical silica, 20 parts of core-shell rubber particles and 3 parts of auxiliary agents are dissolved in 130 parts of solvent (mixed by butanone, toluene and propylene glycol methyl ether in a mass ratio of 1:1:1), and the mixture is fully stirred to obtain a flame retardant resin composition in a colloidal liquid state.

[0207] (2) Preparation of a build-up film: spray the flame retardant resin composition onto one surface of a PET film, bake it at 130° C. for 14 min to obtain a build-up film, and stack the build-up film and the PET film to form a composite.

[0208] (3) Preparation of packaging substrate: the same as step (5) of Example 1.

[0209] Test Case

[0210] 1. Test items:

[0211] 1. Thermomechanical analysis (TMA) test: According to IPC-TM-650 2.4.24.5 test, to obtain the glass transition temperature (Tg) of the package substrate.

[0212] 2. Heat resistance test: Test according to IPC-TM-650 2.4.13 to obtain the time that the package substrate can maintain stable performance under high temperature conditions. If the package substrate cannot maintain stable performance under high temperature conditions, it is easy to cause problems such as circuit short circuit and component damage, thereby affecting the normal operation of electronic equipment. The longer the package substrate maintains stable performance under high temperature conditions, the better its heat resistance.

[0213] 3. Dielectric performance test: According to IPC-TM-650 2.5.5.2 test, the dielectric constant (Dk) and dielectric loss factor (Df) of the package substrate are obtained;

[0214] 4. Water absorption: Tested according to IPC-TM650 2.6.2.1.

[0215] 5. Flame retardancy test: Tested according to IPC-TM-650 2.3.10.

[0216] (II) Results analysis:

[0217] As shown in Table 3, the packaging substrates of Examples 1 to 5 have Tg≥168°C, the time for maintaining stable performance under high temperature conditions is>1000s, Dk≤3.64, Df≤0.0083, water absorption≤0.10%, and the flame retardancy level can reach UL94V0. This shows that adding an appropriate amount of flame retardant prepolymer obtained by reacting acrylate polyphenylene ether resin and allyl phosphorus-containing compound can significantly improve the heat resistance, flame retardancy and dielectric properties of the flame retardant resin composition, so that the packaging substrate exhibits extremely high heat resistance, extremely low dielectric constant and dielectric loss, and more stable and lasting flame retardancy, and is very suitable for preparing high-performance FCBGA substrates.

[0218] The difference between Comparative Example 1 and Example 2 is that the flame retardant prepolymer A is replaced with an equal mass of acrylic ester polyphenylene ether resin, resulting in a significant deterioration in the glass transition temperature, heat resistance, flame retardancy, dielectric properties and water absorption of the packaging carrier.

[0219] In Comparative Example 2, the amount of flame retardant prepolymer A is increased, and the glass transition temperature, heat resistance, flame retardancy, dielectric properties and water absorption of the packaging substrate are slightly improved compared with those of Comparative Example 1, but each performance is significantly lower than that of the packaging substrates of Examples 1 to 5, indicating that the amount of flame retardant prepolymer has a crucial influence on the heat resistance, flame retardancy and dielectric properties of the packaging substrate.

[0220] The difference between Comparative Example 3 and Example 2 is that the flame retardant prepolymer A is replaced with an equal mass of a phosphazene compound, which also leads to significant deterioration of the glass transition temperature, heat resistance, flame retardancy, dielectric properties and water absorption of the packaging carrier.

[0221] Table 1. Prepolymer formulation

[0222]

[0223] Table 2. Formula of flame retardant resin composition

[0224]

[0225] Note: “-” means no addition.

[0226] Table 3. Test results of package substrate

[0227]

[0228] 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.

[0229] The above-described 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 protection of the present application. 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 scope of protection of the present application. Therefore, the scope of protection of the present application shall be subject to the attached claims.

Claims

1. A flame retardant resin composition, characterized in that: The invention comprises the following raw materials in parts by weight: ； The raw materials of the flame retardant prepolymer include acrylate polyphenylene ether resin and an allyl phosphorus-containing compound, and the allyl phosphorus-containing compound has a structure as shown in the general formula (I): （Ⅰ）。 2. The flame retardant resin composition according to claim 1, characterized in that The acrylate polyphenylene ether resin has a structure as shown in the general formula (III): （Ⅲ）； Wherein, m and n are each independently selected from positive integers, and the sum of m and n is 5 to 60; Y is absent or selected from C1-C3 alkylene.

3. The flame retardant resin composition according to claim 2, characterized in that The mass ratio of the acrylic ester polyphenylene ether resin to the allyl phosphorus-containing compound is 100:(40-80).

4. The flame retardant resin composition according to any one of claims 1 to 3, characterized in that The method for preparing the flame retardant prepolymer comprises the following steps: The acrylate polyphenylene ether resin and the allyl phosphorus-containing compound are mixed and prepolymerized at 100° C. to 150° C. for 60 min to 180 min to obtain the flame retardant prepolymer.

5. The flame retardant resin composition according to any one of claims 1 to 3, characterized in that The functional resin includes one or more of epoxy resin, benzoxazine resin and hydrocarbon resin.

6. The flame retardant resin composition according to claim 5, characterized in that One or more of the following conditions are met: (1) The epoxy resin includes one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, naphthalene epoxy resin, phosphorus-containing epoxy resin, unsaturated epoxy resin, novolac epoxy resin, o-cresol novolac 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; (2) The benzoxazine resin includes one or more of bisphenol A type benzoxazine resin, bisphenol F type benzoxazine resin, bisphenol S type benzoxazine resin, main chain type benzoxazine resin, phosphorus-containing benzoxazine resin, dicyclopentadiene benzoxazine resin, biphenyl type benzoxazine resin, tetraphenol ethane benzoxazine resin and naphthalene type benzoxazine resin; (3) The hydrocarbon resin includes one or more of polybutadiene and styrene-butadiene copolymer.

7. The flame retardant resin composition according to any one of claims 1 to 3, characterized in that One or more of the following conditions are met: (1) The curing agent includes one or more of an amine curing agent, a phenolic curing agent, an anhydride curing agent, a cyanate curing agent, an active ester curing agent and an olefin curing agent; (2) 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; (3) The inorganic filler includes one or more of modified silica and modified alumina; (4) The organic filler includes one or more of silicone particles, core-shell rubber particles and olefin elastomer particles.

8. The flame retardant resin composition according to any one of claims 1 to 3, characterized in that The flame retardant resin composition further comprises an auxiliary agent and a solvent, wherein the auxiliary agent comprises one or more of a dispersant, a leveling agent, a defoaming agent and a coupling agent.

9. A build-up film, characterized in that: The invention comprises the flame retardant resin composition as claimed in any one of claims 1 to 8.

10. A method for preparing a build-up film, characterized in that: The following steps are involved: Covering the flame retardant resin composition according to any one of claims 1 to 8 on a support to obtain a liquid film; The liquid film is dried to obtain the build-up layer film.

11. The method for preparing a build-up film according to claim 10, characterized in that: The drying process comprises the following steps: constant temperature drying at 100° C. to 200° C. for 5 min to 15 min.

12. The method for preparing a build-up film according to claim 10, characterized in that: One or more of the following conditions are met: (1) The support comprises one or more of a polymer film and a metal foil; (2) The thickness of the support is 3 μm to 105 μm; (3) The thickness of the liquid film is 5 μm to 150 μm.

13. A packaging carrier, characterized in that: It comprises the flame retardant resin composition as described in any one of claims 1 to 8, or comprises the build-up film as described in claim 9, or comprises the build-up film prepared by the preparation method of the build-up film as described in any one of claims 10 to 12.

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