Organosilicon modified bismaleimide resin and preparation method and application thereof

Abstract

The invention discloses organic silicon modified bismaleimide resin as well as a preparation method and application thereof, and belongs to the technical field of composite materials. The organosilicone modified bismaleimide resin disclosed by the invention contains a siloxane (Si-O-Si) skeleton and an aromatic ring structure, so that the organosilicone modified bismaleimide resin has relatively low polarization capability, and the dielectric constant (Dk), dielectric loss (Df) and water absorption of the material are reduced; meanwhile, an aromatic ring structure has relatively large steric hindrance and rigidity, and further cross-linking of C = C double bonds improves the cross-linking density and rigidity of the material and limits rotation and movement of molecular chains, so that the glass-transition temperature and heat resistance of the material are further improved, and while the compatibility of bismaleimide and other resins is improved, the service life of the bismaleimide resin is prolonged. The excellent heat resistance, high modulus, low dielectric constant and dielectric loss value and low water absorption rate of the material can be maintained, and the requirement of high-performance application is met.

Description

Technical Field

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

[0002] With the rapid development of autonomous driving technology, Internet of Things (IoT) technology, and augmented reality / virtual reality (AR / VR) technology, electronic components in the fields of consumer electronics, computers, and communication electronic equipment are gradually evolving towards high speed, miniaturization, and high integration. Correspondingly, the performance requirements of PCB substrates are also increasing, requiring not only excellent heat resistance and mechanical properties, but also lower water absorption, dielectric constant, and dielectric loss to meet the needs of high-speed signal transmission and high-frequency applications.

[0003] Researchers have used bismaleimide in the preparation of high-frequency and high-speed copper-clad laminates. Although bismaleimide has high thermal stability and excellent dielectric properties, it has poor compatibility with other resins and is easily precipitated in the resin composition. In order to improve the compatibility of bismaleimide, it is usually necessary to blend bismaleimide with other polymers such as styrene-butadiene-styrene (SBS), styrene-ethylene-butadiene-styrene (SEBS), etc. However, while such blended materials improve compatibility, they usually lead to a decrease in the crosslinking density of the original polymer matrix, which in turn adversely affects its dielectric properties and thermal stability.

[0004] Therefore, how to improve the compatibility of bismaleimide with other resins while making the material have excellent heat resistance, high modulus, low dielectric constant and dielectric loss value, and low water absorption to meet the requirements of high-performance applications is a difficult problem that is difficult to overcome in the industry. Summary of the invention

[0005] Based on this, the main purpose of this application is to provide a silicone modified bismaleimide resin, which can improve the compatibility of bismaleimide with other resins while maintaining the material's excellent heat resistance, high modulus, low dielectric constant and dielectric loss value, and low water absorption to meet the requirements of high-performance applications.

[0006] In a first aspect of the present application, a silicone-modified bismaleimide resin is provided, wherein the raw materials for preparation include silicone resin and bismaleimide resin;

[0007] The structural unit of the organic silicone resin includes a structural unit shown in Formula I and a structural unit shown in Formula II:

[0008] ;

[0009] Wherein, the structural unit represented by the formula I and the structural unit represented by the formula II are connected by forming a Si-O-Si bond;

[0010] R1 is a C2-C10 olefin or -O-R8; R2 is a C1-C8 alkyl; R3 and R4 are each independently selected from -O-R5, aryl, -R6-R7;

[0011] R5 is an aryl group; R6 is a C1-C3 alkylene group; R7 is an aryl group; R8 is a C2-C10 alkene group;

[0012] The molar ratio of the structural unit represented by formula I to the structural unit represented by formula II is 1:1-2;

[0013] The average molecular weight of the silicone resin is 500-5000.

[0014] The second aspect of the present application provides an organosilicon-modified bismaleimide resin, wherein the raw materials for preparation include an organosilicon resin and a bismaleimide resin;

[0015] The organosilicon resin is formed by polymerization of a monomer represented by formula III and a monomer represented by formula IV:

[0016] ;

[0017] Wherein, R1 is a C2-C10 olefin or -O-R8; R2 is a C1-C8 alkyl; R3 and R4 are each independently selected from -O-R5, aryl, -R6-R7;

[0018] R5 is an aryl group; R6 is a C1-C3 alkylene group; R7 is an aryl group; R8 is a C2-C10 alkene group; R9 is a C1-C4 alkyl group;

[0019] The molar ratio of the monomer represented by formula III to the monomer represented by formula IV is 1:1-2.

[0020] In some embodiments, R1 is selected from -CH=CH2, -CH2CH=CH2 or -OCH=CH2;

[0021] R2 is a C1-C8 alkyl group; R3 and R4 are each independently selected from phenyl, benzyl, phenoxy or naphthyl.

[0022] In some embodiments, R1 is -CH=CH2; R2 is methyl, ethyl or propyl; and R3 and R4 are the same.

[0023] In some embodiments, the mass ratio of the bismaleimide resin to the silicone resin is 100:40-100;

[0024] And / or the bismaleimide resin includes at least one of N-phenylmaleimide, N-(2-methylphenyl)maleimide, N-(4-methylphenyl)maleimide, N-(2,6-dimethylphenyl)maleimide, di(4-maleimidophenyl)methane, 2,2-di(4-(4-maleimidophenoxy)-phenyl)propane, di(3,5-dimethyl-4-maleimidophenyl)methane, di(3-ethyl-5-methyl-4-maleimidophenyl)methane, di(3,5-diethyl-4-maleimidophenyl)methane, polyphenylmethane bismaleimide and maleimide containing biphenyl structure.

[0025] The third aspect of the present application provides a method for preparing the aforementioned organosilicon-modified bismaleimide resin, comprising the following steps:

[0026] The organosilicon resin and the bismaleimide resin are mixed and reacted at 120-180° C. to prepare the organosilicon-modified bismaleimide resin.

[0027] In some embodiments, the reaction time is 30-90 min.

[0028] The fourth aspect of the present application provides a resin composition comprising the following raw materials: the aforementioned organosilicon-modified bismaleimide resin, a cyanate resin, a flame retardant, an inorganic filler and a curing accelerator.

[0029] In some embodiments, the resin composition comprises the following raw materials by weight:

[0030] 50-80 parts of silicone modified bismaleimide resin;

[0031] 30-80 parts of cyanate resin;

[0032] Flame retardant 5-20 parts;

[0033] 10-40 parts of inorganic filler;

[0034] 1-5 parts of curing accelerator.

[0035] In some embodiments, the cyanate ester resin includes at least one of bisphenol A cyanate ester resin, novolac cyanate ester resin, bisphenol F cyanate ester resin, multifunctional cyanate ester resin, bisphenol M cyanate ester resin, bisphenol E cyanate ester resin and dicyclopentadiene bisphenol cyanate ester resin;

[0036] and / or the flame retardant is a halogen-free flame retardant;

[0037] and / or the inorganic filler is selected from at least one of zirconium vanadate, zirconium tungstate, hafnium tungstate, glass-ceramics, eucryptite, silicon dioxide, quartz, mica powder, titanium dioxide, magnesium oxide, magnesium hydroxide, talc, aluminum oxide, silicon carbide, boron nitride, aluminum nitride, molybdenum oxide, barium sulfate, zinc molybdate, zinc borate, zinc stannate, zinc oxide, strontium titanate, barium titanate, calcium titanate, clay and kaolin;

[0038] And / or the curing accelerator includes an imidazole curing accelerator and / or an organic metal salt curing accelerator.

[0039] The fifth aspect of the present application provides the use of the aforementioned organosilicon-modified bismaleimide resin or the aforementioned resin composition in an electronic substrate.

[0040] The sixth aspect of the present application provides a prepreg, the raw materials of which include the aforementioned resin composition and a reinforcing material.

[0041] The seventh aspect of the present application provides a laminate, the raw materials for preparing which include the aforementioned prepreg.

[0042] An eighth aspect of the present application provides a printed circuit board comprising the aforementioned laminate.

[0043] The beneficial effects of this application are:

[0044] The organosilicon-modified bismaleimide resin of the present application contains a siloxane (Si-O-Si) skeleton and an aromatic ring structure, has a low polarization ability, and reduces the dielectric constant (Dk), dielectric loss (Df) and water absorption of the material; at the same time, the aromatic ring structure has greater steric hindrance and rigidity, and the further cross-linking of the C=C double bond increases the cross-linking density and rigidity of the material, restricts the rotation and movement of the molecular chain, and thus increases the glass transition temperature and heat resistance of the material. The organosilicon-modified bismaleimide resin is used in a resin composition, showing excellent compatibility, and has excellent heat resistance, low water absorption, high modulus and excellent dielectric properties. It can be used in integrated circuit packaging, high-frequency and high-speed fields, and other high-performance printed circuit board manufacturing, thereby promoting the development of high-end integrated circuits. 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, "at least one" means more than one, including one, two, three, etc.; "plurality" means more than two, such as 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, unless otherwise specified, allow for both constant temperature treatment and treatment within a certain temperature range. The constant temperature treatment allows for temperature fluctuations within the precision range of instrument control.

[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 the present application, when it comes to a numerical interval (i.e., a numerical range), unless otherwise specified, the distribution of the optional numerical values ​​in the numerical interval is considered to be continuous, and includes the two numerical endpoints (i.e., the minimum value and the maximum value) of the numerical interval, and each numerical value between the two numerical endpoints. Unless otherwise specified, when the numerical interval only refers to the integers in the numerical interval, it includes the two endpoint integers of the numerical range, and each integer between the two endpoints, which is equivalent to directly listing each integer. When multiple numerical ranges are provided to describe features or characteristics, these numerical ranges can be combined. In other words, unless otherwise specified, the numerical range disclosed herein should be understood to include any and all sub-ranges included therein. The "numerical value" in the numerical interval can be any quantitative value, such as a number, a percentage, a ratio, etc. "Numerical interval" allows broadly including numerical interval types such as percentage intervals, ratio intervals, and ratio intervals.

[0055] In the present application, in expressions about the number of carbons, i.e., the number following the capital letter "C", such as "C1-C8", "C1-C4", etc., the number following "C", such as "1", "4", or "8", indicates the number of carbons in a specific functional group. That is, the functional group may include 1-8 carbon atoms and 1-4 carbon atoms, respectively. For example, "C1-C8 alkyl" refers to an alkyl group having 1, 2, 3, 4, 5, 6, 7, or 8 carbon atoms. 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, -C H(CH3)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) and 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.

[0056] In the present application, "C1-C8 alkyl" is expected to be a straight chain saturated hydrocarbon structure with 1-8 carbon atoms or a branched or cyclic hydrocarbon structure with 3-8 carbon atoms. When specifying an alkyl with a specific carbon number, it is expected to cover all geometric isomers with this carbon number. Therefore, for example, "butyl" means to include normal-butyl, sec-butyl, isobutyl, the tert-butyl and cyclobutyl. "propyl" means to include normal-propyl, isopropyl and cyclopropyl. C1-C8 alkyl includes, but is not limited to methyl, ethyl, normal-propyl, isopropyl, cyclopropyl, normal-butyl, isobutyl, sec-butyl, the tert-butyl, cyclobutyl, normal-pentyl, isopentyl, neopentyl, cyclopentyl, methylcyclopentyl, ethylcyclopentyl, normal-hexyl, isohexyl, cyclohexyl, normal-heptyl, octyl, cyclopropyl, cyclobutyl, norbornyl etc. In addition, alkyl can be optionally substituted.

[0057] In a first aspect of the present application, a silicone-modified bismaleimide resin is provided, wherein the raw materials for preparation include silicone resin and bismaleimide resin;

[0058] The structural unit of the organic silicone resin includes a structural unit shown in Formula I and a structural unit shown in Formula II:

[0059] ;

[0060] Wherein, the structural unit represented by the formula I and the structural unit represented by the formula II are connected by forming a Si-O-Si bond;

[0061] R1 is a C2-C10 olefin or -O-R8; R2 is a C1-C8 alkyl; R3 and R4 are each independently selected from -O-R5, aryl, -R6-R7;

[0062] R5 is an aryl group; R6 is a C1-C3 alkylene group; R7 is an aryl group; R8 is a C2-C10 alkene group;

[0063] The molar ratio of the structural unit represented by formula I to the structural unit represented by formula II is 1:1-2;

[0064] The average molecular weight of the silicone resin is 500-5000.

[0065] It should be noted that the structural unit shown in formula I and the structural unit shown in formula II are connected to form a Si-O-Si bond. The connection can occur between different structural units shown in formula I, between different structural units shown in formula II, or between the structural unit shown in formula I and the structural unit shown in formula II.

[0066] The organosilicon-modified bismaleimide resin of the present application contains a siloxane (Si-O-Si) skeleton and an aromatic ring structure, has a low polarization ability, and reduces the dielectric constant (Dk), dielectric loss (Df) and water absorption of the material; at the same time, the aromatic ring structure has greater steric hindrance and rigidity, and the further cross-linking of the C=C double bond increases the cross-linking density and rigidity of the material, restricts the rotation and movement of the molecular chain, and thereby increases the glass transition temperature and heat resistance of the material.

[0067] The second aspect of the present application provides an organosilicon-modified bismaleimide resin, wherein the raw materials for preparation include an organosilicon resin and a bismaleimide resin;

[0068] The organosilicon resin is formed by polymerization of a monomer represented by formula III and a monomer represented by formula IV:

[0069] ;

[0070] Wherein, R1 is a C2-C10 olefin or -O-R8; R2 is a C1-C8 alkyl; R3 and R4 are each independently selected from -O-R5, aryl, -R6-R7;

[0071] R5 is an aryl group; R6 is a C1-C3 alkylene group; R7 is an aryl group; R8 is a C2-C10 alkene group; R9 is a C1-C4 alkyl group;

[0072] The molar ratio of the monomer represented by formula III to the monomer represented by formula IV is 1:1-2.

[0073] The present application adopts the monomer shown in formula III and the monomer shown in formula IV to form an organosilicon and a bismaleimide resin to react to prepare an organosilicon-modified bismaleimide resin, which contains a siloxane (Si-O-Si) skeleton and an aromatic ring structure, has a low polarization ability, and reduces the dielectric constant (Dk), dielectric loss (Df) and water absorption of the material; at the same time, the aromatic ring structure has greater steric hindrance and rigidity, and the further cross-linking of the C=C double bond increases the cross-linking density and rigidity of the material, restricts the rotation and movement of the molecular chain, and thereby increases the glass transition temperature and heat resistance of the material.

[0074] In a specific example, the preparation process of the silicone resin includes:

[0075] The monomer represented by the formula III and the monomer represented by the formula IV are mixed with an alkaline catalyst, reacted at 70-100° C. for 8-20 hours, and the pH is adjusted to neutral to terminate the reaction.

[0076] In a specific example, the amount of the alkaline catalyst added is 0.05-0.5 mol%, for example, 0.05 mol%, 0.1 mol%, 0.15 mol%, 0.2 mol%, 0.25 mol%, 0.3 mol%, 0.35 mol%, 0.4 mol%, 0.45 mol%, 0.5 mol%, etc.; the reaction temperature can be 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, 100°C, etc.; the reaction time can be 8h, 10h, 12h, 14h, 16h, 18h, 20h, etc.

[0077] In a specific example, the C1-C8 alkyl group is an alkyl group containing 1, 2, 3, 4, 5, 6, 7 or 8 carbon atoms, including but not limited to methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, n-pentyl, isopentyl, neopentyl, cyclopentyl, methylcyclopentyl, ethylcyclopentyl, n-hexyl, isohexyl, cyclohexyl, n-heptyl, octyl, cyclopropyl, cyclobutyl, norbornyl, 2-ethylhexyl, etc.; the C1-C4 alkyl group is an alkyl group containing 1, 2, 3 or 4 carbon atoms, including but not limited to methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl.

[0078] In a specific example, the C2-C10 alkenyl group is an alkenyl group containing 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms, including but not limited to ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, isopentenyl and the like.

[0079] In a specific example, the aryl group is phenyl, naphthyl or biphenyl;

[0080] In a specific example, the C1-C3 alkylene group is a methylene group, an ethylene group or a propylene group.

[0081] In a specific example, the molar ratio of the structural unit represented by Formula I to the structural unit represented by Formula II can be 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9, or 1:2.

[0082] In a specific example, the average molecular weight of the silicone resin can be 500, 1000, 1500, 2000, 2500, 3000, 3500, 4000, 4500, 5000, etc.

[0083] In a specific example, R1 is selected from -CH=CH2, -CH2CH=CH2 or -OCH=CH2;

[0084] R2 is a C1-C8 alkyl group; R3 and R4 are each independently selected from phenyl, benzyl, phenoxy or naphthyl.

[0085] In a specific example, R1 is -CH=CH2; R2 is methyl, ethyl or propyl; and R3 and R4 are the same.

[0086] It is understandable that the mass ratio of the silicone resin to the bismaleimide resin mainly affects the degree of modification, and can be adjusted according to actual needs, and there is no special limitation in this application. In a specific example, the mass ratio of the bismaleimide resin to the silicone resin is 100:40-100, such as 100:40, 100:50, 100:60, 100:70, 100:80, 100:90, 100:100, etc.

[0087] Specifically, the present application has no particular restrictions on bismaleimide resins, and an organic compound containing two or more maleimide structures in the molecular structure can be used. In a specific example, the bismaleimide resin includes N-phenylmaleimide, N-(2-methylphenyl)maleimide, N-(4-methylphenyl)maleimide, N-(2,6-dimethylphenyl)maleimide, di(4-maleimidophenyl)methane, 2,2-bis(4-(4-maleimidophenoxy)-phenyl)propane, di(3,5-dimethyl-4-maleimidophenyl)methane, di(3-ethyl-5-methyl-4-maleimidophenyl)methane, di(3,5-diethyl-4-maleimidophenyl)methane, polyphenylmethane bismaleimide and at least one of maleimide containing biphenyl structure.

[0088] The third aspect of the present application provides a method for preparing the aforementioned organosilicon-modified bismaleimide resin, comprising the following steps:

[0089] The organosilicon resin and the bismaleimide resin are mixed and reacted at 120-180° C. to prepare the organosilicon-modified bismaleimide resin.

[0090] In a specific example, the reaction temperature can be 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, etc.; the reaction time can be 30-90 min, for example, 30 min, 40 min, 50 min, 60 min, 70 min, 80 min, 90 min, etc.

[0091] The fourth aspect of the present application provides a resin composition comprising the following raw materials: the aforementioned organosilicon-modified bismaleimide resin, a cyanate resin, a flame retardant, an inorganic filler and a curing accelerator.

[0092] The organosilicon-modified bismaleimide resin of the present application contains a siloxane (Si-O-Si) skeleton and an aromatic ring structure, has a low polarization ability, and reduces the dielectric constant (Dk), dielectric loss (Df) and water absorption of the material; at the same time, the aromatic ring structure has greater steric hindrance and rigidity, and the further cross-linking of the C=C double bond increases the cross-linking density and rigidity of the material, restricts the rotation and movement of the molecular chain, and thus increases the glass transition temperature and heat resistance of the material. The organosilicon-modified bismaleimide resin is used in a resin composition, showing excellent compatibility, and has excellent heat resistance, low water absorption, high modulus and excellent dielectric properties. It can be used in integrated circuit packaging, high-frequency and high-speed fields, and other high-performance printed circuit board manufacturing, thereby promoting the development of high-end integrated circuits.

[0093] In a specific example, the resin composition comprises the following raw materials by weight:

[0094] 50-80 parts of silicone modified bismaleimide resin;

[0095] 30-80 parts of cyanate resin;

[0096] Flame retardant 5-20 parts;

[0097] 10-40 parts of inorganic filler;

[0098] 1-5 parts of curing accelerator.

[0099] Specifically, the specific type of cyanate resin is not particularly limited. In a specific example, the cyanate resin includes at least one of bisphenol A cyanate resin, phenolic cyanate resin, bisphenol F cyanate resin, multifunctional cyanate resin, bisphenol M cyanate resin, bisphenol E cyanate resin and dicyclopentadiene bisphenol cyanate resin.

[0100] Specifically, the type of flame retardant is not particularly limited, among which halogen-free flame retardants are environmentally friendly and more preferred. In a specific example, the halogen-free flame retardant includes a phosphorus-containing flame retardant and / or a silicon-containing flame retardant; optionally, the phosphorus-containing flame retardant includes at least one of a phosphorus-containing epoxy resin, a phosphorus-containing phenolic resin, a phosphazene compound, and a phosphate ester compound; and the silicon-containing flame retardant includes a silicone polymer.

[0101] Specifically, the inorganic filler has a filling effect, and the type is not particularly limited. In a specific example, the inorganic filler is selected from at least one of zirconium vanadate, zirconium tungstate, hafnium tungstate, microcrystalline glass, eucryptite, silicon dioxide, quartz, mica powder, titanium dioxide, magnesium oxide, magnesium hydroxide, talc, aluminum oxide, silicon carbide, boron nitride, aluminum nitride, molybdenum oxide, barium sulfate, zinc molybdate, zinc borate, zinc stannate, zinc oxide, strontium titanate, barium titanate, calcium titanate, clay and kaolin; among which spherical silicon dioxide is more preferred.

[0102] Specifically, the curing accelerator can be a curing accelerator commonly used in the art, and the specific type is not particularly limited. In a specific example, the curing accelerator includes an imidazole curing accelerator and / or an organic metal salt curing accelerator; wherein the imidazole curing accelerator includes at least one of 2-methylimidazole, 2-phenylimidazole and 2-ethyl-4-methylimidazole; the organic metal salt includes at least one of zinc octanoate, zinc isooctanoate, stannous octanoate, dibutyltin dilaurate, zinc naphthenate, cobalt naphthenate, aluminum acetylacetonate, cobalt acetylacetonate and copper acetylacetonate.

[0103] It is understandable that the resin composition may further include other resins and additives, wherein the other resins include at least one of epoxy resin, benzoxazine, polyphenylene ether and hydrocarbon resin; and the other additives include coupling agents and toughening agents.

[0104] The fifth aspect of the present application provides the use of the aforementioned organosilicon-modified bismaleimide resin or the aforementioned resin composition in an electronic substrate.

[0105] The resin composition of the present application exhibits excellent compatibility, and has excellent heat resistance, low water absorption, high modulus and excellent dielectric properties. It can be applied to integrated circuit packaging, high frequency and high speed fields, and the manufacture of other high-performance printed circuit boards, thereby promoting the development of high-end integrated circuits.

[0106] The sixth aspect of the present application provides a prepreg, the raw materials of which include the aforementioned resin composition and a reinforcing material.

[0107] Specifically, the reinforcing material is selected from inorganic fiber materials and / or organic fiber materials. In a specific example, the inorganic fiber material includes at least one of glass fiber, carbon fiber, silicon carbide fiber and asbestos fiber; the organic fiber material includes at least one of nylon, ultra-high molecular weight polyethylene fiber, aramid fiber, polyimide fiber, polyester fiber and cotton fiber; wherein the glass fiber includes different types of glass fibers such as E, NE, D, S, T, etc.

[0108] In a specific example, the method for preparing the prepreg comprises the following steps:

[0109] The resin composition is impregnated into a reinforcing material and heated to prepare a prepreg.

[0110] In a specific example, the heating condition is: heating at 130° C.-250° C. for 2 min-10 min.

[0111] In a specific example, the step of infiltrating the resin composition into the reinforcing material comprises:

[0112] The resin composition is made into glue solution, and the reinforcing material is immersed in the glue solution.

[0113] In a specific example, the step of preparing the resin composition into a glue solution comprises:

[0114] Mixing the organosilicon-modified bismaleimide resin and the cyanate ester resin with an organic solvent to form a mixture;

[0115] The mixture is mixed with inorganic fillers and other additives to form a glue solution.

[0116] It is understood that if the above resin composition also contains other functional resins, the organosilicon-modified bismaleimide resin, cyanate resin and other functional resins are mixed with an organic solvent. In a specific example, the organic solvent is selected from at least one of butanone, toluene and propylene glycol methyl ether; further, the organic solvent is selected from a mixed solvent of butanone, toluene and propylene glycol methyl ether, wherein the mass ratio of butanone, toluene and propylene glycol methyl ether is 1:0.5-2:0.5-2, for example, 1:1:1.

[0117] The seventh aspect of the present application provides a laminate, the raw materials for preparing which include the aforementioned prepreg.

[0118] In one specific example, the laminate comprises a metal foil laminate.

[0119] It is understood that the amount of the prepreg in the raw materials for preparing the laminate can be adjusted according to the actual application. For the metal foil laminate, the laminate is coated with metal foil on one side or both sides. It is understood that the metal foil can be copper foil or aluminum foil, and their thickness is not particularly limited and can be adaptively adjusted according to the actual application, for example, 3μm-70μm.

[0120] In a specific example, the process for preparing the laminate includes: hot pressing the prepreg under vacuum conditions to form a laminate.

[0121] In a specific example, the process parameters of hot pressing are: vacuum degree <2kPa, temperature 150℃-300℃, pressure 10kgf / cm 2 -30kgf / cm 2And the time is 200min-400min.

[0122] It can be understood that when the raw materials for preparing the laminate include two or more prepregs, the prepregs are stacked and hot-pressed.

[0123] An eighth aspect of the present application provides a printed circuit board comprising the aforementioned laminate.

[0124] The printed circuit board has excellent heat resistance, low water absorption, high modulus, low dielectric constant and dielectric loss value, and is suitable for preparing high-performance printed circuit boards such as high temperature resistance and anti-aging, integrated circuit packaging, high frequency and high speed, thereby promoting the development of high-end integrated circuits.

[0125] 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.

[0126] The sources of some components in the embodiments and comparative examples are as follows:

[0127] Bismaleimide resin: purchased from Yamato Chemical, model number BMI-5100;

[0128] Cyanate resin: bisphenol A cyanate resin, purchased from Tianqi New Materials, model C01MO;

[0129] Spherical silica: purchased from Yaduma, model number is SO-C4;

[0130] 2-Methylimidazole: purchased from Shikoku Chemical;

[0131] Styrene-butadiene-styrene (SBS): purchased from Cray Valley, model R100;

[0132] Flame retardant: phosphazene flame retardant, purchased from Otsuka Chemical, model number SP100;

[0133] Other raw materials are commercially available.

[0134] The following are specific embodiments.

[0135] Synthesis example 1

[0136] Preparation of silicone resin A

[0137] The specific preparation steps are as follows:

[0138] 1) Under nitrogen atmosphere, add 1 mol of vinylmethyldimethoxysilane (precursor 1) and 1.5 mol of diphenylsilanediol (precursor 2) in the required molar ratio into a 500 ml three-necked flask. According to the total molar amount of the silane precursor, weigh 0.1 mol% of Ba(OH)2·H2O (alkaline catalyst) and add it to the flask. Insert a stir bar into the flask and set the reaction temperature to 80°C via an oil bath. Connect the flask to a condensing reflux device to avoid loss of solvent or volatile reactants.

[0139] 2) Stir the reaction system at 80°C and maintain a nitrogen atmosphere. After the reaction continues for 12 hours, adjust the pH to 7 to ensure that the silane precursor forms a silicone resin through a non-hydrolytic sol-gel condensation reaction. During the reaction, the solution can be observed to gradually become viscous, which is a sign of the gradual formation of the resin. After the reaction is completed, remove the flask from the oil bath, turn off the heating, continue stirring and cool to room temperature.

[0140] 3) Use a rotary evaporator to remove low-boiling byproducts and unreacted precursors produced during the reaction under reduced pressure. The temperature can be controlled at around 50-60°C to ensure that volatile substances are fully removed.

[0141] 4) Transfer the cooled reaction mixture to a large beaker and slowly add tetrahydrofuran to precipitate the vinylphenylsiloxane resin while stirring continuously. Filter the precipitate using a Buchner funnel and vacuum pump to collect the solid resin. Unreacted materials in the solution will be filtered out. Wash the precipitate several times with tetrahydrofuran to remove residual catalyst and by-products. After each wash, separate the resin again through the filter, and its average molecular weight is 1300.

[0142] Synthesis example 2

[0143] Preparation of silicone resin B

[0144] The specific preparation steps are as follows:

[0145] 1) Under nitrogen atmosphere, add 1 mol of vinylmethyldimethoxysilane (precursor 1) and 1.5 mol of dibenzylsilanediol (precursor 2) in the required molar ratio into a 500 ml three-necked flask. According to the total molar amount of the silane precursor, weigh 0.1 mol% of Ba(OH)2·H2O (alkaline catalyst) and add it to the flask. Insert a stir bar into the flask and set the reaction temperature to 80 °C via an oil bath. Connect the flask to a condensing reflux device to avoid loss of solvent or volatile reactants.

[0146] 2) Stir the reaction system at 80°C and maintain a nitrogen atmosphere. After the reaction continues for 12 hours, adjust the pH to 7 to ensure that the silane precursor forms a silicone resin through a non-hydrolytic sol-gel condensation reaction. During the reaction, the solution can be observed to gradually become viscous, which is a sign of the gradual formation of the resin. After the reaction is completed, remove the flask from the oil bath, turn off the heating, continue stirring and cool to room temperature.

[0147] 3) Use a rotary evaporator to remove low-boiling byproducts and unreacted precursors produced during the reaction under reduced pressure. The temperature can be controlled at around 50-60 °C to ensure that volatile substances are fully removed.

[0148] 4) Transfer the cooled reaction mixture to a large beaker and slowly add tetrahydrofuran to precipitate the vinylbenzylsiloxane resin while stirring continuously. Filter the precipitate using a Buchner funnel and vacuum pump to collect the solid resin. Unreacted materials in the solution will be filtered out. Wash the precipitate several times with tetrahydrofuran to remove residual catalyst and by-products. After each wash, separate the resin again through the filter, and its average molecular weight is 1700.

[0149] Synthesis example 3

[0150] Preparation of silicone resin C

[0151] The specific preparation steps are as follows:

[0152] 1) Under nitrogen atmosphere, add 1 mol of vinylmethyldimethoxysilane (precursor 1) and 1.5 mol of diphenoxysilanediol (precursor 2) in the required molar ratio into a 500 ml three-necked flask. According to the total molar amount of the silane precursor, weigh 0.1 mol% of Ba(OH)2·H2O (alkaline catalyst) and add it to the flask. Insert a stir bar into the flask and set the reaction temperature to 80 °C via an oil bath. Connect the flask to a condensing reflux device to avoid loss of solvent or volatile reactants.

[0153] 2) Stir the reaction system at 80°C and maintain a nitrogen atmosphere. After the reaction continues for 12 hours, adjust the pH to 7 to ensure that the silane precursor forms a silicone resin through a non-hydrolytic sol-gel condensation reaction. During the reaction, the solution can be observed to gradually become viscous, which is a sign of the gradual formation of the resin. After the reaction is completed, remove the flask from the oil bath, turn off the heating, continue stirring and cool to room temperature.

[0154] 3) Use a rotary evaporator to remove low-boiling byproducts and unreacted precursors produced during the reaction under reduced pressure. The temperature can be controlled at around 50-60°C to ensure that volatile substances are fully removed.

[0155] 4) Transfer the cooled reaction mixture to a large beaker and slowly add tetrahydrofuran to precipitate the vinylphenoxysiloxane resin while stirring continuously. Filter the precipitate using a Buchner funnel and vacuum pump to collect the solid resin. Unreacted materials in the solution will be filtered out. Wash the precipitate several times with tetrahydrofuran to remove residual catalyst and by-products. After each wash, separate the resin again through the filter, and its average molecular weight is 1600.

[0156] Synthesis example 4

[0157] Preparation of silicone resin D

[0158] The specific preparation steps are as follows:

[0159] 1) Under nitrogen atmosphere, add 1 mol of vinylmethyldimethoxysilane (precursor 1) and 1.5 mol of dinaphthylsilanediol (precursor 2) in the required molar ratio into a 500 ml three-necked flask. According to the total molar amount of the silane precursor, weigh 0.1 mol% of Ba(OH)2·H2O (alkaline catalyst) and add it to the flask. Insert a stir bar into the flask and set the reaction temperature to 80 °C via an oil bath. Connect the flask to a condensing reflux device to avoid loss of solvent or volatile reactants.

[0160] 2) Stir the reaction system at 80°C and maintain a nitrogen atmosphere. After the reaction continues for 12 hours, adjust the pH to 7 to ensure that the silane precursor forms a silicone resin through a non-hydrolytic sol-gel condensation reaction. During the reaction, the solution can be observed to gradually become viscous, which is a sign of the gradual formation of the resin. After the reaction is completed, remove the flask from the oil bath, turn off the heating, continue stirring and cool to room temperature.

[0161] 3) Use a rotary evaporator to remove low-boiling byproducts and unreacted precursors produced during the reaction under reduced pressure. The temperature can be controlled at around 50-60°C to ensure that volatile substances are fully removed.

[0162] 4) Transfer the cooled reaction mixture to a large beaker and slowly add tetrahydrofuran to precipitate the vinyl naphthyl siloxane resin while stirring continuously. Filter the precipitate using a Buchner funnel and vacuum pump to collect the solid resin. Unreacted materials in the solution will be filtered out. Wash the precipitate several times with tetrahydrofuran to remove residual catalyst and by-products. After each wash, separate the resin again through the filter, and its average molecular weight is 2000.

[0163] Synthesis example 5

[0164] The same procedures as in Example 1 were followed except that dimethylsilanediol was used instead of diphenylsilanediol to prepare the organosilicon resin E (average molecular weight of 800).

[0165] Next, silicone resin is applied to the examples.

[0166] Example 1

[0167] 1) 80 parts of silicone resin A are heated to a molten state, 100 parts of bismaleimide resin are added, and prepolymerized at 150° C. for 60 min and then cooled to room temperature to obtain silicone-modified bismaleimide resin A.

[0168] 2) 50 parts of the above-mentioned organosilicon-modified bismaleimide resin A, 30 parts of cyanate resin and 5 parts of flame retardant are dissolved in a mixed solvent of butanone, toluene and propylene glycol methyl ether, wherein the mass ratio of butanone, toluene and propylene glycol methyl ether is 1:1:1. Under stirring conditions, 10 parts of spherical silica and 1 part of 2-methylimidazole are added, and stirring is continued to obtain a uniform resin composition glue.

[0169] 3) 2116 glass fiber cloth (basic weight 105g / m 2 ) was immersed in the above-mentioned resin composition glue solution and then placed in a hot air circulation oven and baked at 180°C for 3 min to obtain a semi-cured sheet with a resin content of 50wt%.

[0170] 4) Stack 6 prepregs, cover the upper and lower sides of the stack with a 12 μm thick electrolytic copper foil, and place them in a programmable temperature and pressure controlled vacuum press. 2 Under the pressure of , after hot pressing and curing according to the procedure of 180℃×1h+200℃×2h+240℃×2h, a 0.6mm thick copper-clad laminate was made.

[0171] Example 2

[0172] 1) 80 parts of silicone resin A are heated to a molten state, 100 parts of bismaleimide resin are added, and the mixture is prepolymerized at 150° C. for 60 minutes and then cooled to room temperature to obtain silicone-modified bismaleimide resin A.

[0173] 2) 80 parts of the above-mentioned organosilicon-modified bismaleimide resin A, 60 parts of cyanate resin and 10 parts of flame retardant are dissolved in a mixed solvent of butanone, toluene and propylene glycol methyl ether, wherein the mass ratio of butanone, toluene and propylene glycol methyl ether is 1:1:1. Under stirring conditions, 30 parts of spherical silica and 5 parts of 2-methylimidazole are added, and stirring is continued to obtain a uniform resin composition glue.

[0174] 3) 2116 glass fiber cloth (basic weight 105g / m 2 ) was immersed in the above-mentioned resin composition glue solution and then placed in a hot air circulation oven and baked at 180°C for 3 minutes to obtain a semi-cured sheet with a resin content of 50wt%.

[0175] 4) Stack 6 prepregs, cover the upper and lower sides of the stack with a 12 μm thick electrolytic copper foil, and place them in a programmable temperature and pressure controlled vacuum press. 2 Under the pressure of , after hot pressing and curing according to the procedure of 180℃×1h+200℃×2h+240℃×2h, a 0.6mm thick copper-clad laminate was made.

[0176] Example 3

[0177] 1) 80 parts of silicone resin B are heated to a molten state, 100 parts of bismaleimide resin are added, and the mixture is prepolymerized at 150° C. for 60 minutes and then cooled to room temperature to obtain silicone-modified bismaleimide resin B.

[0178] 2) 70 parts of the above-mentioned organosilicon-modified bismaleimide resin B, 45 parts of cyanate resin and 5 parts of flame retardant are dissolved in a mixed solvent of butanone, toluene and propylene glycol methyl ether, wherein the mass ratio of butanone, toluene and propylene glycol methyl ether is 1:1:1. Under stirring conditions, 20 parts of spherical silica and 3 parts of 2-methylimidazole are added, and stirring is continued to obtain a uniform resin composition glue.

[0179] 3) 2116 glass fiber cloth (basic weight 105g / m 2 ) was immersed in the above-mentioned resin composition glue solution and then placed in a hot air circulation oven and baked at 180°C for 3 minutes to obtain a semi-cured sheet with a resin content of 50wt%.

[0180] 4) Stack 6 prepregs, cover the upper and lower sides of the stack with a 12 μm thick electrolytic copper foil, and place them in a programmable temperature and pressure controlled vacuum press. 2 Under the pressure of , after hot pressing and curing according to the procedure of 180℃×1h+200℃×2h+240℃×2h, a 0.6mm thick copper-clad laminate was made.

[0181] Example 4

[0182] 1) 80 parts of silicone resin C are heated to a molten state, 100 parts of bismaleimide resin are added, and the mixture is prepolymerized at 150° C. for 60 minutes and then cooled to room temperature to obtain silicone-modified bismaleimide resin C.

[0183] 2) 70 parts of the above-mentioned organosilicon-modified bismaleimide resin C, 70 parts of cyanate resin and 5 parts of flame retardant are dissolved in a mixed solvent of butanone, toluene and propylene glycol methyl ether, wherein the mass ratio of butanone, toluene and propylene glycol methyl ether is 1:1:1. Under stirring conditions, 40 parts of spherical silica and 8 parts of 2-methylimidazole are added, and stirring is continued to obtain a uniform resin composition glue.

[0184] 3) 2116 glass fiber cloth (basic weight 105g / m 2 ) was immersed in the above-mentioned resin composition glue solution and then placed in a hot air circulation oven and baked at 180°C for 3 minutes to obtain a semi-cured sheet with a resin content of 50wt%.

[0185] 4) Stack 6 prepregs, cover the upper and lower sides of the stack with a 12 μm thick electrolytic copper foil, and place them in a programmable temperature and pressure controlled vacuum press. 2 Under the pressure of , after hot pressing and curing according to the procedure of 180℃×1h+200℃×2h+240℃×2h, a 0.6mm thick copper-clad laminate was made.

[0186] Example 5

[0187] 1) 80 parts of silicone resin D are heated to a molten state, 100 parts of bismaleimide resin are added, and the mixture is prepolymerized at 150° C. for 60 minutes and then cooled to room temperature to obtain silicone-modified bismaleimide resin D.

[0188] 2) 70 parts of the above-mentioned organosilicon-modified bismaleimide resin D, 60 parts of cyanate resin and 10 parts of flame retardant are dissolved in a mixed solvent of butanone, toluene and propylene glycol methyl ether, wherein the mass ratio of butanone, toluene and propylene glycol methyl ether is 1:1:1. Under stirring conditions, 30 parts of spherical silica and 5 parts of 2-methylimidazole are added, and stirring is continued to obtain a uniform resin composition glue.

[0189] 3) 2116 glass fiber cloth (basic weight 105g / m 2 ) was immersed in the above-mentioned resin composition glue solution and then placed in a hot air circulation oven and baked at 180°C for 3 minutes to obtain a semi-cured sheet with a resin content of 50wt%.

[0190] 4) Stack 6 prepregs, cover the upper and lower sides of the stack with a 12 μm thick electrolytic copper foil, and place them in a programmable temperature and pressure controlled vacuum press. 2 Under the pressure of , after hot pressing and curing according to the procedure of 180℃×1h+200℃×2h+240℃×2h, a 0.6mm thick copper-clad laminate was made.

[0191] Comparative Example 1

[0192] 1) Dissolve 50 parts of bismaleimide resin, 30 parts of cyanate resin, 40 parts of styrene-butadiene-styrene and 5 parts of flame retardant in a mixed solvent of butanone, toluene and propylene glycol methyl ether, wherein the mass ratio of butanone, toluene and propylene glycol methyl ether is 1:1:1. Add 10 parts of spherical silica and 1 part of 2-methylimidazole under stirring, and continue stirring to obtain a uniform resin composition glue.

[0193] 2) 2116 glass fiber cloth (basic weight 105g / m 2 ) was immersed in the above-mentioned resin composition glue solution and then placed in a hot air circulation oven and baked at 180°C for 3 minutes to obtain a semi-cured sheet with a resin content of 50wt%.

[0194] 3) Stack 6 prepregs, cover the upper and lower sides of the stack with a 12 μm thick electrolytic copper foil, and place them in a programmable temperature and pressure controlled vacuum press. 2 Under the pressure of , after hot pressing and curing according to the procedure of 180℃×1h+200℃×2h+240℃×2h, a 0.6mm thick copper-clad laminate was made.

[0195] Comparative Example 2

[0196] 1) 50 parts of bismaleimide resin, 30 parts of cyanate resin and 5 parts of flame retardant are dissolved in a mixed solvent of butanone, toluene and propylene glycol methyl ether, wherein the mass ratio of butanone, toluene and propylene glycol methyl ether is 1:1:1. Under stirring conditions, 10 parts of spherical silica and 1 part of 2-methylimidazole are added, and stirring is continued to obtain a uniform resin composition glue.

[0197] 3) 2116 glass fiber cloth (basic weight 105g / m 2 ) was immersed in the above-mentioned resin composition glue solution and then placed in a hot air circulation oven and baked at 180°C for 3 minutes to obtain a semi-cured sheet with a resin content of 50wt%.

[0198] 4) Stack 6 prepregs, cover the upper and lower sides of the stack with a 12 μm thick electrolytic copper foil, and place them in a programmable temperature and pressure controlled vacuum press. 2 Under the pressure of , a copper-clad laminate with a thickness of 0.6 mm was made after hot pressing and curing according to the procedure of 180℃×1h+200℃×2h+240℃×2h.

[0199] Comparative Example 3

[0200] 1) 80 parts of silicone resin A are heated to a molten state, 100 parts of bismaleimide resin are added, and prepolymerized at 150° C. for 60 min and then cooled to room temperature to obtain silicone-modified bismaleimide resin A.

[0201] 2) 90 parts of the above-mentioned organosilicon-modified bismaleimide resin A, 30 parts of cyanate resin and 5 parts of flame retardant are dissolved in a mixed solvent of butanone, toluene and propylene glycol methyl ether, wherein the mass ratio of butanone, toluene and propylene glycol methyl ether is 1:1:1. Under stirring conditions, 10 parts of spherical silica and 1 part of 2-methylimidazole are added, and stirring is continued to obtain a uniform resin composition glue.

[0202] 3) 2116 glass fiber cloth (basic weight 105g / m 2 ) was immersed in the above-mentioned resin composition glue solution and then placed in a hot air circulation oven and baked at 180°C for 3 min to obtain a semi-cured sheet with a resin content of 50wt%.

[0203] 4) Stack 6 prepregs, cover the upper and lower sides of the stack with a 12 μm thick electrolytic copper foil, and place them in a programmable temperature and pressure controlled vacuum press. 2 Under the pressure of , after hot pressing and curing according to the procedure of 180℃×1h+200℃×2h+240℃×2h, a 0.6mm thick copper-clad laminate was made.

[0204] Comparative Example 4

[0205] Except that silicone resin E was used instead of silicone A to prepare silicone-modified bismaleimide resin E, the rest was the same as in Example 1.

[0206] The raw materials in Examples 1-6 and Comparative Examples 1-4 are shown in Table 1:

[0207] Table 1 Raw materials of Examples and Comparative Examples

[0208]

[0209] Test Case

[0210] The copper-clad laminates prepared in Examples 1-6 and Comparative Examples 1-4 were subjected to performance tests, and the specific test methods are as follows:

[0211] 1) Peel strength: The test method is carried out in accordance with IPC-TM-650 2.4.8;

[0212] 2) Glass transition temperature (Tg): tested according to IPC-TM650 2.4.25D;

[0213] 3) Thermal decomposition temperature (Td): tested according to IPC-TM650 2.4.24.6;

[0214] 4) Elastic modulus: tested according to GB / T 22315-2008;

[0215] 5) Water absorption: Tested according to IPC-TM650 2.6.2.1;

[0216] 6)Dk / Df: Tested according to IPC-TM650 2.5.5.2;

[0217] 7) Resin compatibility: Place the resin glue solution at room temperature and let it stand to observe whether any substance precipitates.

[0218] The results are shown in Table 2:

[0219] Table 2 Summary of performance of examples and comparative examples

[0220]

[0221] As can be seen from Table 2, Examples 1-5 use silicone-modified bismaleimide resin in the resin composition, and the copper-clad laminates prepared have good compatibility, excellent heat resistance (Tg ≥ 300°C, Td ≥ 380°C), high modulus (≥ 30 GPa), low dielectric constant and dielectric loss value (Dk < 3.65; Df < 0.01), and low water absorption (< 0.15%), which can meet the requirements of high-performance applications.

[0222] Comparative example 1 adopts unmodified bismaleimide resin, adds SBS simultaneously, although compatibility problem can be solved, but heat resistance, modulus are significantly inferior to embodiment, and dielectric constant, dielectric loss and water absorption are significantly greater than embodiment.Comparative example 2 adopts unmodified bismaleimide resin, does not add SBS, cannot solve compatibility problem, and each performance is also inferior to embodiment.In comparative example 3, organosilicon-modified bismaleimide resin addition is too much, can cause overall performance to have a certain degree of deterioration, and the addition of organosilicon-modified bismaleimide resin should not be too high, is advisable with 50-80 parts.

[0223] In Comparative Example 4, the use of a silicone resin without an aromatic ring structure to prepare a silicone-modified bismaleimide resin will result in poor compatibility, significant deterioration of heat resistance and modulus, and increased dielectric constant, dielectric loss and water absorption. It can be seen that the structure of the silicone resin has a great influence on the performance of the resin composition, and containing an aromatic ring structure is beneficial to improving the overall performance.

[0224] 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.

[0225] 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 silicone-modified bismaleimide resin, characterized in that: The preparation raw materials include silicone resin and bismaleimide resin; The structural unit of the organic silicone resin includes a structural unit shown in Formula I and a structural unit shown in Formula II: ； Wherein, the structural unit represented by the formula I and the structural unit represented by the formula II are connected by forming a Si-O-Si bond; R1 is a C2-C10 olefin or -O-R8; R2 is a C1-C8 alkyl; R3 and R4 are each independently selected from -O-R5, aryl, -R6-R7; R5 is an aryl group; R6 is a C1-C3 alkylene group; R7 is an aryl group; R8 is a C2-C10 alkene group; The molar ratio of the structural unit represented by formula I to the structural unit represented by formula II is 1:1-2; The average molecular weight of the silicone resin is 500-5000.

2. A silicone-modified bismaleimide resin, characterized in that: The preparation raw materials include silicone resin and bismaleimide resin; The organosilicon resin is formed by polymerization of a monomer represented by formula III and a monomer represented by formula IV: ； Wherein, R1 is a C2-C10 olefin or -O-R8; R2 is a C1-C8 alkyl; R3 and R4 are each independently selected from -O-R5, aryl, -R6-R7; R5 is an aryl group; R6 is a C1-C3 alkylene group; R7 is an aryl group; R8 is a C2-C10 alkene group; R9 is a C1-C4 alkyl group; The molar ratio of the monomer represented by formula III to the monomer represented by formula IV is 1:1-2.

3. The organosilicon-modified bismaleimide resin according to claim 1 or 2, characterized in that: R1 is selected from -CH=CH2, -CH2CH=CH2 or -OCH=CH2; R2 is C1-C8 alkyl; R3 and R4 are each independently selected from phenyl, benzyl, phenoxy or naphthyl; Optionally, R1 is -CH=CH2; R2 is methyl, ethyl or propyl; and R3 and R4 are the same.

4. The organosilicon-modified bismaleimide resin according to claim 1 or 2, characterized in that: The mass ratio of the bismaleimide resin to the silicone resin is 100:40-100; And / or the bismaleimide resin includes at least one of N-phenylmaleimide, N-(2-methylphenyl)maleimide, N-(4-methylphenyl)maleimide, N-(2,6-dimethylphenyl)maleimide, di(4-maleimidophenyl)methane, 2,2-di(4-(4-maleimidophenoxy)-phenyl)propane, di(3,5-dimethyl-4-maleimidophenyl)methane, di(3-ethyl-5-methyl-4-maleimidophenyl)methane, di(3,5-diethyl-4-maleimidophenyl)methane, polyphenylmethane bismaleimide and maleimide containing biphenyl structure.

5. The method for preparing the organosilicon-modified bismaleimide resin according to any one of claims 1 to 4, characterized in that: The steps include: The organosilicon resin and the bismaleimide resin are mixed and reacted at 120-180° C. to prepare the organosilicon-modified bismaleimide resin.

6. A resin composition, characterized in that The method comprises the following raw materials: the organosilicon-modified bismaleimide resin according to any one of claims 1 to 4, a cyanate resin, a flame retardant, an inorganic filler and a curing accelerator; Optionally, the resin composition comprises the following raw materials in parts by weight: 50-80 parts of silicone modified bismaleimide resin; 30-80 parts of cyanate resin; Flame retardant 5-20 parts; 10-40 parts of inorganic filler; 1-5 parts of curing accelerator; Optionally, the cyanate resin includes at least one of bisphenol A cyanate resin, phenolic cyanate resin, bisphenol F cyanate resin, multifunctional cyanate resin, bisphenol M cyanate resin, bisphenol E cyanate resin and dicyclopentadiene bisphenol cyanate resin; Optionally, the flame retardant is a halogen-free flame retardant; Optionally, the inorganic filler is selected from at least one of zirconium vanadate, zirconium tungstate, hafnium tungstate, microcrystalline glass, eucryptite, silicon dioxide, quartz, mica powder, titanium dioxide, magnesium oxide, magnesium hydroxide, talc, aluminum oxide, silicon carbide, boron nitride, aluminum nitride, molybdenum oxide, barium sulfate, zinc molybdate, zinc borate, zinc stannate, zinc oxide, strontium titanate, barium titanate, calcium titanate, clay and kaolin; Optionally, the curing accelerator includes an imidazole curing accelerator and / or an organic metal salt curing accelerator.

7. Use of the organosilicon-modified bismaleimide resin according to any one of claims 1 to 4 or the resin composition according to claim 6 in electronic substrates.

8. A prepreg, characterized in that: The raw materials include the resin composition according to claim 6 and a reinforcing material.

9. A laminated board, characterized in that: The preparation raw materials include the prepreg according to claim 8.

10. A printed circuit board, characterized in that: Comprising the laminate as claimed in claim 9.

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