A resin composition, and a prepreg, a metal-clad laminate, a printed circuit board comprising the same

Abstract

This invention provides a resin composition and prepregs, metal foil laminates, and printed circuit boards containing the same. The resin composition comprises the following components: (A) modified maleimide: 80-100 parts; (B) filler with an average coefficient of thermal expansion of less than 0 ppm / ℃ at 30-150℃: 50-300 parts; (C) other inorganic fillers besides component (B): 5-300 parts. The raw materials for preparing the modified maleimide, by weight, include: maleimide compound a1 containing at least two N-substituted maleimide groups per molecule: 45-80 parts; and siloxane compound a2 containing at least two primary amino groups per molecule: 10-35 parts. The resin composition provided by this invention has an extremely low planar coefficient of thermal expansion, good flowability, high glass transition temperature, and high peel strength, which can meet the more stringent requirements of large-size chip packaging for substrate material warpage.

Description

Technical Field

[0001] This invention belongs to the field of printed circuit board technology, specifically relating to a resin composition and a prepreg containing the same, a metal foil laminate, and a printed circuit board. Background Technology

[0002] In recent years, with the development of technologies such as AI (Artificial Intelligence), 5G communication, and big data, the demand for high-performance central processing units (CPUs), graphics processing units (GPUs), and field-programmable gate arrays (FPGAs) has surged. Large-size chips, due to their ultra-high-speed computing capabilities, have experienced explosive growth. Large-size chip packaging places demands on large-size packaging substrates, with the biggest technical challenge stemming from controlling substrate warpage. Substrate warpage is primarily caused by a significant difference in the coefficient of thermal expansion (CTE) between the chip and the substrate. To meet the increasingly stringent requirements for substrate warpage, the CTE requirements for the packaging substrate are further strengthened.

[0003] To further reduce the CTE of the packaging substrate, previous methods have involved increasing the amount of inorganic fillers, introducing resins containing rigid segments (such as biphenyl and naphthyl groups), and / or increasing the crosslinking density of the resin. However, these techniques are clearly insufficient when facing more stringent CTE requirements (CTE close to that of silicon wafers, which have a CTE of approximately 2.6 ppm / °C), and they also introduce other problems, such as decreased drillability and reduced flowability. For example, TWI228388B, by adding a large amount of inorganic fillers to the resin composition, leads to decreased hole position accuracy and accelerated drill wear, resulting in decreased drillability. CN102656234A addresses the decreased drillability issue by adding molybdenum compounds such as zinc molybdate, but it still cannot solve the problem of insufficient CTE. Summary of the Invention

[0004] To address the shortcomings of existing technologies, the present invention aims to provide a resin composition and prepregs, metal foil laminates, and printed circuit boards containing the same. The resin composition provided by the present invention has an extremely low coefficient of planar thermal expansion, good flowability, high glass transition temperature, and high peel strength, which can meet the more stringent requirements of large-size chip packaging for substrate material warpage.

[0005] To achieve this objective, the present invention adopts the following technical solution:

[0006] In a first aspect, the present invention provides a resin composition comprising, by weight parts, the following components:

[0007] (A) Modified maleimide: 80-100 parts;

[0008] (B) Fillers with an average thermal expansion coefficient of less than 0 ppm / ℃ at 30-150℃: 50-300 parts;

[0009] (C) Other inorganic fillers besides component (B): 5 to 300 parts;

[0010] The raw materials for preparing the modified maleimide, by weight, include: maleimide compound a1 containing at least two (e.g., two, three, four, etc.) N-substituted maleimide groups in one molecule: 45-80 parts; and siloxane compound a2 containing at least two (e.g., two, three, four, etc.) primary amino groups in one molecule: 10-35 parts.

[0011] The resin composition provided by this invention includes modified maleimide, a filler with an average thermal expansion coefficient of less than 0 ppm / ℃ at 30–150°C, and other inorganic fillers. These three components work synergistically in specific amounts to impart an extremely low planar thermal expansion coefficient to the resin composition, increasing the fluidity of the resin system, and providing a high glass transition temperature and high peel strength. This meets the more stringent requirements of large-size chip packaging for substrate material warpage. The filler with an average thermal expansion coefficient of less than 0 ppm / ℃ at 30–150°C in this invention has poor fluidity; by adding siloxane-modified maleimide and other inorganic fillers, the fluidity of the resin composition can be improved.

[0012] In this invention, the method for determining the average thermal expansion coefficient of the filler at 30–150°C can be, for example, by using a thermal expansion meter that detects the elongation of the sample using a laser interferometer or by known methods such as X-ray diffraction.

[0013] In this invention, the amount of modified maleimide in the resin composition, by weight, can be, for example, 80 parts, 82 parts, 84 parts, 86 parts, 88 parts, 90 parts, 92 parts, 94 parts, 96 parts, 98 parts, or 100 parts, as well as specific values ​​between the above points. Due to space limitations and for the sake of brevity, this invention will not exhaustively list the specific values ​​included in the range.

[0014] In this invention, the amount of filler (B) with an average thermal expansion coefficient of less than 0 ppm / ℃ at 30-150℃ in the resin composition, based on the weight percentage, can be, for example, 50 parts, 60 parts, 80 parts, 90 parts, 100 parts, 130 parts, 150 parts, 180 parts, 200 parts, 230 parts, 250 parts, 280 parts, or 300 parts, as well as specific values ​​between the above-mentioned values. Due to space limitations and for the sake of brevity, this invention will not exhaustively list the specific values ​​included in the range.

[0015] In this invention, the amount of other inorganic fillers (C) besides component (B) in the resin composition, based on weight parts, can be, for example, 5 parts, 8 parts, 10 parts, 30 parts, 50 parts, 60 parts, 80 parts, 90 parts, 100 parts, 130 parts, 150 parts, 180 parts, 200 parts, 230 parts, 250 parts, 280 parts, or 300 parts, as well as specific values ​​between the above points. Due to space limitations and for the sake of brevity, this invention will not exhaustively list the specific values ​​included in the range.

[0016] In this invention, the amount of maleimide compound a1 containing at least two N-substituted maleimide groups in one molecule, based on the raw materials for preparing the modified maleimide, can be, for example, 45 parts, 46 parts, 47 parts, 48 ​​parts, 49 parts, 50 parts, 52 parts, 54 parts, 56 parts, 58 parts, 60 parts, 62 parts, 64 parts, 66 parts, 68 parts, 70 parts, 72 parts, 74 parts, 76 parts, 78 parts, or 80 parts by weight, as well as specific values ​​between the above-mentioned values. Due to space limitations and for the sake of brevity, this invention will not exhaustively list the specific values ​​included in the range.

[0017] In this invention, the amount of the raw material for preparing the modified maleimide, based on weight, of the siloxane compound a2 containing at least two primary amino groups in one molecule, can be, for example, 10 parts, 12 parts, 14 parts, 15 parts, 16 parts, 18 parts, 20 parts, 22 parts, 24 parts, 26 parts, 28 parts, 30 parts, 32 parts, 34 parts, or 35 parts, as well as specific values ​​between the above-mentioned values. Due to space limitations and for the sake of brevity, this invention will not exhaustively list the specific values ​​included in the range.

[0018] In this invention, a maleimide compound a1 containing at least two N-substituted maleimide groups in one molecule is reacted with a siloxane compound a2 containing at least two primary amino groups in one molecule to prepare (A) modified maleimide.

[0019] The present invention does not particularly limit the maleimide compound a1, as long as it is a maleimide compound containing at least two N-substituted maleimide groups in one molecule. Preferably, the maleimide compound a1 containing at least two N-substituted maleimide groups in one molecule has the structure shown in formula (I-1):

[0020]

[0021] In formula (I-1), A1 is a divalent organic group;

[0022] Preferably, A1 is selected from groups with the structures shown in formula (1), formula (2), formula (3) or formula (4);

[0023]

[0024]

[0025] In formula (1), R1 is independently selected from aliphatic hydrocarbon groups or halogen atoms with 1 to 5 carbon atoms, and a is selected from integers from 0 to 4, such as 0, 1, 2, 3, 4;

[0026] As an aliphatic hydrocarbon group having 1 to 5 carbon atoms, it can be selected, for example, from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, etc., preferably from aliphatic hydrocarbon groups having 1 to 3 carbon atoms, and more preferably from methyl or ethyl.

[0027] From the perspective of lower CTE, a is preferably an integer from 0 to 2, more preferably 0; when a is an integer greater than 2, multiple R1s can be the same or different from each other.

[0028] In equation (2), R 2a R 2b R 3a R 3b Each of the following groups is independently selected from aliphatic hydrocarbon groups or halogen atoms having 1 to 5 carbon atoms. A2 is selected from straight-chain or branched alkylene groups having 1 to 5 carbon atoms, straight-chain or branched alkylidene groups having 2 to 5 carbon atoms, ether groups, thioether groups, sulfonyl groups, carbonyl groups, ketone groups, single bonds, or groups with the structure shown in formula (2-1) or formula (2-2) below. pa, pb, qa, and qb are each independently selected from integers from 0 to 4, while pa+pb≤4 and qa+qb≤4.

[0029] As an aliphatic hydrocarbon group having 1 to 5 carbon atoms, it can be selected, for example, from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, etc., preferably from aliphatic hydrocarbon groups having 1 to 3 carbon atoms, and more preferably from methyl or ethyl.

[0030] As the straight-chain or branched alkylene group having 1 to 5 carbon atoms, it can be selected, by example, from methylene, 1,2-ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene, etc., preferably from alkylene groups having 1 to 3 carbon atoms, and more preferably from methylene.

[0031] As a straight-chain or branched alkylidene group having 2 to 5 carbon atoms, it can be selected, by example, from ethoxyl, propionyl, isopropionyl, butylidene, isobutylidene, pentylidene, isopentyl, and preferably isopropionyl.

[0032] From the perspective of lower CTE, pa, pb, qa, and qb are each preferably integers from 0 to 2, more preferably 0; from the perspective of simultaneously possessing low CTE and good dielectric properties, pa, pb, qa, and qb are each preferably integers from 1 to 2, more preferably 1; when pa, pb, qa, and qb are each integers greater than 2, multiple R 2a R 2b R 3a Or R 3b They are the same or different from each other.

[0033]

[0034] In equation (2-1), R 4a R 4b R 5a R 5b Each of the following is independently selected from aliphatic hydrocarbon groups or halogen atoms having 1 to 5 carbon atoms. A3 is selected from straight-chain or branched alkylene groups having 1 to 5 carbon atoms, straight-chain or branched alkylidene groups having 2 to 5 carbon atoms, ether groups, thioether groups, sulfonyl groups, carbonyl groups, ketone groups, and single bonds. ka, kb, la, and lb are each independently selected from integers from 0 to 4, while ka+kb≤4 and la+lb≤4.

[0035] As an aliphatic hydrocarbon group having 1 to 5 carbon atoms, it can be selected, for example, from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, etc., preferably from aliphatic hydrocarbon groups having 1 to 3 carbon atoms, and more preferably from methyl or ethyl.

[0036] As the straight-chain or branched alkylene group having 1 to 5 carbon atoms, it can be selected, by example, from methylene, 1,2-ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene, etc., preferably from alkylene groups having 1 to 3 carbon atoms, and more preferably from methylene.

[0037] As a straight-chain or branched alkylidene group having 2 to 5 carbon atoms, it can be selected, by example, from ethoxyl, propionyl, isopropionyl, butylidene, isobutylidene, pentylidene, isopentyl, and preferably isopropionyl.

[0038] From the perspective of lower CTE, ka, kb, la, and lb are each independently preferably integers from 0 to 2, more preferably 0; from the perspective of simultaneously possessing low CTE and good dielectric properties, ka, kb, la, and lb are each independently preferably integers from 1 to 2, more preferably 1; when ka, kb, la, and lb are each independently integers greater than 2, multiple R 4a R 4b R 5a Or R 5bThey are the same or different from each other.

[0039] In formula (2-2), R8 is independently selected from aliphatic hydrocarbon groups or halogen atoms with 1 to 5 carbon atoms, and o is selected from integers from 0 to 4.

[0040] As an aliphatic hydrocarbon group having 1 to 5 carbon atoms, it can be selected, for example, from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, etc., preferably from aliphatic hydrocarbon groups having 1 to 3 carbon atoms, and more preferably from methyl or ethyl.

[0041] From the perspective of lower CTE, o is preferably an integer from 0 to 2, more preferably 0; when o is an integer greater than 2, multiple R8s can be the same or different from each other.

[0042] In formula (3), m is selected from an integer from 1 to 10, preferably an integer from 1 to 5, and more preferably an integer from 1 to 3.

[0043] In formula (4), R6 and R7 are each independently selected from aliphatic hydrocarbon groups with 1 to 5 hydrogen atoms or carbon atoms, and n is selected from integers from 1 to 10.

[0044] As an aliphatic hydrocarbon group having 1 to 5 carbon atoms, it can be selected, for example, from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, etc., preferably from aliphatic hydrocarbon groups having 1 to 3 carbon atoms, and more preferably from methyl or ethyl.

[0045] From the perspective of lower CTE, n is preferably an integer from 1 to 8, more preferably an integer from 1 to 3, and even more preferably 1; when n is an integer of 2 or more, the multiple R6s or the multiple R7s can be the same or different from each other.

[0046] In formulas (1), (2), (2-1), (2-2), (3), and (4), the short straight lines on both sides of the group represent the bond attached to the group, not the methyl group.

[0047] Preferably, the maleimide compound a1 contains two N-substituted maleimide groups in one molecule, which can impart better solubility to the (A) modified maleimide.

[0048] From the perspective of better processability and lower CTE, the maleimide compound a1 containing at least two N-substituted maleimide groups in one molecule includes any one or a combination of at least two of the following: bis(4-maleimidephenyl)methane, bis(3-methyl-4-maleimidephenyl)methane, bis(3,5-dimethyl-4-maleimidephenyl)methane, bis(3-ethyl-5-methyl-4-maleimidephenyl)methane, bis(3-ethyl-4-maleimidephenyl)methane, bis(3,5-diethyl-4-maleimidephenyl)methane, or 2,2-bis(4-(4-maleimidephenoxy)phenyl)propane. The maleimide compound a1 can be used alone or in combination of at least two.

[0049] This invention does not particularly limit the siloxane compound a2 containing at least two primary amino groups in one molecule, as long as it contains at least two primary amino groups in one molecule and has a siloxane segment in its molecular structure. Preferably, the siloxane compound a2 containing at least two primary amino groups in one molecule has a divalent organic group in its molecular structure as shown in formula (I-2):

[0050]

[0051] In equation (I-2), R9, R 10 R 11 R 12 Each group is independently selected from aliphatic hydrocarbon groups, aryl groups, or substituted aryl groups with 1 to 5 carbon atoms. A4 and A5 are each independently selected from divalent organic groups. r is selected from integers from 2 to 100, such as 2, 4, 6, 8, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, etc.

[0052] As an aliphatic hydrocarbon group having 1 to 5 carbon atoms, it can be selected, for example, from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, etc., preferably from aliphatic hydrocarbon groups having 1 to 3 carbon atoms, and more preferably from methyl.

[0053] The aryl group can be selected, by example, from phenyl, biphenyl, naphthyl, etc., with phenyl being preferred;

[0054] As the substituted aryl group, it can be selected, for example, from substituted phenyl, substituted biphenyl, substituted naphthyl, etc., preferably substituted phenyl; as the substituent of the aryl group, it can be selected, for example, from aliphatic hydrocarbon groups having 1 to 5 carbon atoms, alkenyl groups having 2 to 5 carbon atoms, alkynyl groups having 2 to 5 carbon atoms, etc.; as the aliphatic hydrocarbon group having 1 to 5 carbon atoms, it can be selected, for example, from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, etc.; as the alkenyl group having 2 to 5 carbon atoms, it can be selected, for example, from vinyl, allyl, etc.; as the alkynyl group having 2 to 5 carbon atoms, it can be selected, for example, from ethynyl, propynyl, etc.

[0055] As the divalent organic groups independently selected from A4 and A5, exemplaryly, they may be selected from alkylene, alkenylene, ynylene, arylene, -O-, or divalent linking groups formed by combining them; as the alkylene, exemplaryly, they may be selected from alkylene with 1 to 10 carbon atoms, such as methylene, ethylene, or propylene; as the alkenylene, exemplaryly, they may be selected from alkenylene with 2 to 10 carbon atoms; as the ynylene, exemplaryly, they may be selected from ynylene with 2 to 10 carbon atoms; as the arylene, exemplaryly, they may be selected from arylene with 6 to 20 carbon atoms, such as phenylene or naphthylene; the divalent organic groups independently selected from A4 and A5 are preferably alkylene or arylene, and more preferably alkylene;

[0056] r is preferably an integer from 2 to 50, more preferably an integer from 3 to 40, and even more preferably an integer from 5 to 30. When r is an integer of 2 or more, multiple R9s or multiple R... 10 They can be the same or different.

[0057] The present invention does not particularly limit the functional group equivalent of the siloxane compound a2 containing at least two primary amino groups in one molecule. Preferably, the functional group equivalent of the siloxane compound a2 containing at least two primary amino groups in one molecule is 100 to 6000 g / mol, for example, 100 g / mol, 300 g / mol, 500 g / mol, 800 g / mol, 1000 g / mol, 1500 g / mol, 2000 g / mol, 2500 g / mol, 3000 g / mol, 3500 g / mol, 4000 g / mol, 4500 g / mol, 5000 g / mol, 5500 g / mol, 6000 g / mol, etc., more preferably 300 to 3000 g / mol, and more preferably 600 to 2000 g / mol.

[0058] Preferably, the raw materials for preparing the modified maleimide also include amine compounds other than siloxane compounds a3 that contain at least two (e.g., two, three, four, etc.) primary amino groups in one molecule.

[0059] Preferably, the other amine compound a3 is selected from any one or a combination of at least two of 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-5,5'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-5,5'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diaminodiphenylmethane, or 2,2-bis(4-(4-aminophenoxy)phenyl)propane.

[0060] Preferably, the amount of the other amine compound a3 is 0.5 to 10 parts, for example, 0.5 parts, 0.8 parts, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts or 10 parts, and specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0061] Preferably, the filler with an average thermal expansion coefficient of less than 0 ppm / ℃ at 30–150℃ has a particle size (D) 50 The value can be 0.1 to 10 μm, for example, 0.1 μm, 0.5 μm, 1 μm, 3 μm, 5 μm, 8 μm or 10 μm, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, this invention will not exhaustively list the specific values ​​included in the range.

[0062] In this invention, the particle size was obtained using an MS3000 Malvern laser particle size analyzer.

[0063] Preferably, the filler with an average thermal expansion coefficient of less than 0 ppm / ℃ at 30-150℃ includes any one or a combination of at least two of zirconium phosphate fillers, cordierite fillers, rare earth tungstate fillers, and manganese nitride fillers, with rare earth tungstate fillers being the most preferred.

[0064] Preferably, the rare earth tungstate packing includes zirconium tungstate packing.

[0065] Preferably, the zirconium tungstate-based filler includes zirconium tungstate and / or zirconium tungstate phosphate.

[0066] The present invention does not limit the type of inorganic filler (C). Preferably, the inorganic filler (C) includes any one or a combination of at least two of silicon dioxide, magnesium oxide, aluminum oxide, aluminum nitride, boron nitride, boehmite, and aluminum hydroxide. It is more preferably silicon dioxide, and more preferably spherical silicon dioxide.

[0067] Preferably, the inorganic filler (C) comprises a surface-treated inorganic filler.

[0068] Preferably, the composition further includes a compound (D) that can undergo a crosslinking reaction with (A).

[0069] The present invention does not limit the type of compound (D) that can undergo cross-linking reaction with (A), as long as it can react with the maleimide modified by (A). Preferably, the compound (D) that can undergo cross-linking reaction with (A) includes any one or a combination of at least two of epoxy resin, compound having carbon-carbon unsaturated double bonds in the molecule, acid anhydride compound, active ester compound or cyanate ester resin.

[0070] From the perspective of lower CTE, the compound (D) that can undergo crosslinking reaction with (A) is preferably an epoxy resin, a compound having carbon-carbon unsaturated double bonds in its molecule, or a combination of any two of these compounds. The compound having carbon-carbon unsaturated double bonds in its molecule includes any one or a combination of at least two of unsaturated polyphenylene ether compounds, polyfunctional vinyl compounds, allyl compounds, acrylate compounds, methacrylate compounds, acenaphthene compounds, or polybutadiene compounds. More preferably, it is a combination of any one or a combination of at least two of unsaturated polyphenylene ether compounds, polyfunctional vinyl compounds, allyl compounds, or acenaphthene compounds.

[0071] Preferably, the amount of compound (D) that can undergo crosslinking reaction with (A) is 0.1 to 20 parts, for example, 0.1 parts, 0.3 parts, 0.5 parts, 0.8 parts, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 12 parts, 14 parts, 16 parts, 18 parts or 20 parts, and specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0072] Preferably, the resin composition further includes an elastomer, preferably a styrene-based elastomer.

[0073] Preferably, the resin composition further includes a curing accelerator.

[0074] Preferably, the curing accelerator includes any one or a combination of at least two of the following: acidic curing accelerators, organophosphorus curing accelerators, imidazole curing accelerators, pyridine curing accelerators, amine curing accelerators, peroxides, or organometallic salts.

[0075] Preferably, the amount of the curing accelerator is 0.01 to 5 parts, for example, 0.01 parts, 0.03 parts, 0.05 parts, 0.08 parts, 0.1 parts, 0.3 parts, 0.5 parts, 0.8 parts, 1 part, 2 parts, 3 parts, 4 parts or 5 parts, and specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0076] Preferably, the resin composition further includes a coupling agent.

[0077] Preferably, the coupling agent comprises a silane coupling agent.

[0078] Preferably, the amount of the coupling agent is 0.01 to 10 parts, for example, 0.01 parts, 0.03 parts, 0.05 parts, 0.08 parts, 0.1 parts, 0.3 parts, 0.5 parts, 0.8 parts, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, or 10 parts, as well as specific values ​​between the above-mentioned values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0079] The "parts" and "parts by weight" used in this invention are calculated based on solid content and do not include solvents, dispersants, etc.

[0080] Solvents may also be added to the above-mentioned resin composition. The amount of solvent added is selected by those skilled in the art based on experience and process requirements, so that the resin composition reaches a suitable viscosity for use, facilitating coating and other processes. During subsequent drying, semi-curing, or full curing stages, the solvent in the resin composition will partially or completely evaporate.

[0081] The solvent used in this invention is not particularly limited, and generally can be ketones such as acetone, butanone, and cyclohexanone; aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and butyl acetate; alcohols such as methanol, ethanol, or butanol; alcohols such as ethyl cellosolve, butyl cellosolve, ethylene glycol monomethyl ether, carbitol, or butyl carbitol; and nitrogen-containing solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, or N-methyl-2-pyrrolidone. The solvent can be used alone or in mixtures of two or more. Preferably, ketones such as acetone, butanone, and cyclohexanone, and aromatic hydrocarbons such as toluene and xylene are used.

[0082] The resin composition provided by the present invention is prepared by the following method, the preparation method comprising: mixing and dispersing the components in the resin composition evenly to obtain the resin composition.

[0083] In a second aspect, the present invention provides a prepreg comprising a substrate and a resin composition as described in the first aspect, which is attached to the substrate by impregnation and drying.

[0084] Preferably, the substrate comprises any one of glass fiber cloth, organic fiber cloth, or glass fiber paper.

[0085] Thirdly, the present invention provides a metal foil laminate, the metal foil laminate comprising at least one prepreg as described in the second aspect, and metal foil disposed on one or both sides of the prepreg.

[0086] Preferably, the metal foil is a copper foil.

[0087] Fourthly, the present invention provides a printed circuit board comprising at least one prepreg as described in the second aspect or a metal foil laminate as described in the third aspect.

[0088] Compared with the prior art, the present invention has at least the following beneficial effects:

[0089] The resin composition provided by the present invention includes modified maleimide, filler with an average thermal expansion coefficient of less than 0 ppm / ℃ at 30-150℃, and other inorganic fillers. These three components are synergistically combined in specific amounts to give the resin composition an extremely low planar thermal expansion coefficient, increase the fluidity of the resin system, and have a high glass transition temperature and high peel strength, which can meet the more stringent requirements of large-size chip packaging for substrate material warpage. Detailed Implementation

[0090] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.

[0091] Preparation Example 1

[0092] A modified maleimide (hereinafter referred to as A1) is prepared by the following steps:

[0093] In a three-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, add 16 parts by weight of a siloxane compound containing two primary amino groups in one molecule (X-22-161B from Shin-Etsu Chemical Industry Co., Ltd.), 1 part by weight of an amine compound containing two primary amino groups in one molecule (Kayahard AA from Nippon Kayaku Kogyo Co., Ltd., 3,3'-diethyl-4,4'-diaminodiphenylmethane), 63 parts by weight of a maleimide compound (BMI-4000 from Daiwa Chemical Industry Co., Ltd., 2,2-bis(4-(4-maleiminophenoxy)phenyl)propane), and 80 parts by weight of propylene glycol monomethyl ether. The mixture is stirred and heated to 115°C and then kept at that temperature for 360 min.

[0094] Preparation Example 2

[0095] A modified maleimide (hereinafter referred to as A2) is prepared by the following steps:

[0096] In a three-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, 32 parts by weight of a siloxane compound containing two primary amino groups in one molecule (X-22-161B from Shin-Etsu Chemical Industry Co., Ltd.), 1 part by weight of an amine compound containing two primary amino groups in one molecule (Kayahard AA from Nippon Kayaku Kogyo Co., Ltd., 3,3'-diethyl-4,4'-diaminodiphenylmethane), 47 parts by weight of a maleimide compound (BMI-4000 from Daiwa Chemical Industry Co., Ltd., 2,2-bis(4-(4-maleiminophenoxy)phenyl)propane), and 80 parts by weight of propylene glycol monomethyl ether were added. The mixture was stirred and heated to 120°C, and then kept at that temperature for 480 min.

[0097] Preparation Example 3

[0098] A modified maleimide (hereinafter referred to as A3) is prepared by the following steps:

[0099] In a three-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, add 12 parts by weight of a siloxane compound containing two primary amino groups in one molecule (X-22-161B from Shin-Etsu Chemical Industry Co., Ltd.), 4 parts by weight of an amine compound containing two primary amino groups in one molecule (Kayahard AA from Nippon Kayaku Kogyo Co., Ltd., 3,3'-diethyl-4,4'-diaminodiphenylmethane), 64 parts by weight of a maleimide compound (BMI-4000 from Daiwa Chemical Industry Co., Ltd., 2,2-bis(4-(4-maleiminophenoxy)phenyl)propane), and 80 parts by weight of propylene glycol monomethyl ether. The mixture is stirred and heated to 110°C and then kept at that temperature for 300 min.

[0100] Preparation Example 4

[0101] A modified maleimide (hereinafter referred to as A4) is prepared by the following steps:

[0102] In a three-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, add 16 parts by weight of a siloxane compound containing two primary amino groups in one molecule (X-22-161A from Shin-Etsu Chemical Industry Co., Ltd.), 1 part by weight of an amine compound containing two primary amino groups in one molecule (Kayahard AA from Nippon Kayaku Kogyo Co., Ltd., 3,3'-diethyl-4,4'-diaminodiphenylmethane), 63 parts by weight of a maleimide compound (BMI-1000 from Daiwa Chemical Industry Co., Ltd., bis(4-maleimide-phenyl)methane), and 80 parts by weight of propylene glycol monomethyl ether. The mixture is stirred and heated to 110°C and then kept at that temperature for 300 min.

[0103] Comparative Preparation Example 1

[0104] A modified maleimide (hereinafter referred to as Z1) is prepared as follows:

[0105] In a three-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, add 5 parts by weight of a siloxane compound containing two primary amino groups in one molecule (X-22-161B from Shin-Etsu Chemical Industry Co., Ltd.), 4 parts by weight of an amine compound containing two primary amino groups in one molecule (Kayahard AA from Nippon Kayaku Kogyo Co., Ltd., 3,3'-diethyl-4,4'-diaminodiphenylmethane), 71 parts by weight of a maleimide compound (BMI-4000 from Daiwa Chemical Industry Co., Ltd., 2,2-bis(4-(4-maleiminophenoxy)phenyl)propane), and 80 parts by weight of propylene glycol monomethyl ether. The mixture is stirred and heated to 110°C, and then kept at this temperature for 300 min.

[0106] Comparative Preparation Example 2

[0107] A modified maleimide (hereinafter referred to as Z2) is prepared as follows:

[0108] In a three-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, add 36 parts by weight of a siloxane compound containing two primary amino groups in one molecule (X-22-161B from Shin-Etsu Chemical Industry Co., Ltd.), 1 part by weight of an amine compound containing two primary amino groups in one molecule (Kayahard AA from Nippon Kayaku Kogyo Co., Ltd., 3,3'-diethyl-4,4'-diaminodiphenylmethane), 43 parts by weight of a maleimide compound (BMI-4000 from Daiwa Chemical Industry Co., Ltd., 2,2-bis(4-(4-maleiminophenoxy)phenyl)propane), and 80 parts by weight of propylene glycol monomethyl ether. The mixture is stirred and heated to 115°C and then kept at that temperature for 360 min.

[0109] The raw materials used in the following embodiments and comparative examples are as follows:

[0110] (A) Modified maleimide

[0111] A1 to A4: provided by preparation examples 1 to 4 respectively;

[0112] Z1 and Z2 were provided by Comparative Preparation Example 1 and Comparative Preparation Example 2, respectively.

[0113] (B) Filler with an average thermal expansion coefficient of less than 0 ppm / ℃ at temperatures ranging from 30 to 150℃

[0114] B1: CERAFIT, zirconium tungstate phosphate, with a particle size D50 of 1.4 μm, Nippon Steel Chemical Co., Ltd., Japan;

[0115] B2: WZ-501, zirconium tungstate, particle size D50 is 1.1μm, Shanghai Dianyang Industrial Co., Ltd.

[0116] (C) Inorganic packing

[0117] C1: SC2050-MTX, spherical silica surface-treated with aniline silane coupling agent, median particle size D50 of 0.5μm, Admatechs Corporation, Japan.

[0118] (D) Compounds that can undergo cross-linking reactions with (A)

[0119] D1: NC-3000-H, biphenyl aryl epoxy resin, Nippon Kayaku Co., Ltd.;

[0120] D2: OPE-2st 1200, a polyphenylene ether with a vinyl benzyl end, Mitsubishi Chemical Corporation, Japan.

[0121] (E) Coupling agent

[0122] KBM-573, N-phenyl-3-aminopropyltrimethoxysilane, Shin-Etsu Corporation, Japan.

[0123] (F) Unmodified maleimide

[0124] Phenylaralkyl polymaleimide compound, MIR-5000-60T, Nippon Kayaku Kogyo Co., Ltd.

[0125] Example 1

[0126] This embodiment provides a resin composition, the specific components and amounts (parts by weight) of which are shown in Table 1.

[0127] This embodiment also provides a metal foil-coated laminate, the specific preparation method of which is as follows:

[0128] (1) The resin composition provided in this embodiment, toluene and methyl ethyl ketone are mixed, fully dissolved and evenly dispersed to obtain a resin solution with a solid content of 68%;

[0129] (2) Impregnate the glass fiber cloth (Nittobo 2118T) with the resin solution obtained in step (1), and heat and dry it in a forced-air oven at 165°C for 5 minutes to transform the resin composition in the varnish state into a semi-cured resin composition to obtain a prepreg with a thickness controlled at 0.10 mm.

[0130] (3) Stack two (or eight) sheets of prepreg obtained in step (2) together, and press an electrolytic copper foil with a thickness of 12 μm onto the top and bottom sides of the stack. 240℃, 45 kg / cm 2 After curing for 2 hours, a copper-clad laminate with a core thickness of 0.20 mm (or 0.80 mm) is obtained.

[0131] After etching the copper foil of the above copper-clad laminate, a laminate with a thickness of 0.20 mm (or 0.80 mm) is obtained.

[0132] The performance of the above-mentioned metal foil-coated laminate or laminate was tested using the following specific methods:

[0133] (1) Glass transition temperature T g A laminate with a length of 60 mm, a width of 10 mm, and a thickness of 0.80 mm was used as a sample. Dynamic mechanical thermal analyzer (DMA) was used for measurement, with a heating rate of 10 °C / min. The result was taken as the tanδ transition peak temperature, in °C.

[0134] (2) Coefficient of thermal expansion in the plane (XY-CTE, tensile method): A laminate with a length of 60 mm, a width of 4 mm, and a thickness of 0.20 mm was used as the sample. The warp direction of the glass fiber was Y-direction, and the weft direction of the glass fiber was X-direction. The sample was dried in an oven at 105℃ for 1 h and then cooled to room temperature in a desiccator. The mechanical thermal analysis (TMA) method was used for measurement. The heating rate was 10℃ / min. The temperature was increased from room temperature to 300℃ twice. After the first heating was completed and the sample was cooled to room temperature, it was placed again for the second heating. The result was the coefficient of thermal expansion in the plane at the second heating from 50℃ to 130℃, and the unit was ppm / ℃.

[0135] (3) Coefficient of thermal expansion in the plane (XY-CTE, compression method): A laminate with a length of 80 mm, a width of 80 mm, and a thickness of 0.80 mm was used as the sample. The warp direction of the glass fiber was Y-direction, and the weft direction of the glass fiber was X-direction. The sample was dried in an oven at 105℃ for 1 h and then cooled to room temperature in a desiccator. The mechanical thermal analysis (TMA) method was used for measurement. The heating rate was 10℃ / min. The temperature was increased from room temperature to 300℃ twice. After the first heating was completed and the sample was cooled to room temperature, it was placed again for the second heating. The result was the coefficient of thermal expansion in the plane at the second heating from 50℃ to 130℃, and the unit was ppm / ℃.

[0136] (4) Peel strength (PS): A metal foil laminate with a length of 50 mm and a width of 50 mm was used as a sample. A metal foil strip with a width of 3.0 mm was prepared on the sample by applying adhesive tape and etching. A peel tester was used to apply pressure in the vertical direction at a speed of 50 mm / min to peel the metal foil off the laminate. The peel strength of the metal foil laminate can be obtained, and the unit is N / mm.

[0137] (5) Liquidity: Tested according to the method of IPC-TM-650 2.3.17. If the liquidity test result is >1%, it is recorded as "good"; otherwise, it is recorded as "poor".

[0138] The test results are shown in Table 1.

[0139] Examples 2-10, Comparative Examples 1-7

[0140] A resin composition and a prepreg and laminate containing the same are different from those in Example 1 in that the formulation of the resin composition is different, as shown in Tables 1 and 2; wherein, the amount of each component is in "parts by weight"; the preparation method and performance testing method of the prepreg and laminate are the same as those in Example 1.

[0141] Table 1

[0142]

[0143]

[0144] Table 2

[0145]

[0146] As can be seen from Table 1, the laminate prepared by the resin composition provided in the embodiments of the present invention has a low planar thermal expansion coefficient (XY-CTE-compression method: 3.6~5.3ppm / ℃, XY-CTE-tensile method: both <1ppm / ℃), good peel strength (PS: 0.46~0.63N / mm), good flowability and high glass transition temperature.

[0147] Compared to Example 1, the resin compositions provided by Comparative Examples 1 and 5 have a higher coefficient of planar thermal expansion because the filler content with an average coefficient of thermal expansion of less than 0 ppm / ℃ at 30–150°C is less than 50 parts; the resin compositions provided by Comparative Examples 2 and 4 have a higher coefficient of planar thermal expansion because the siloxane compound containing at least two primary amino groups per molecule is less than 15 parts; the resin composition provided by Comparative Example 3 has a lower coefficient of planar thermal expansion because the siloxane compound containing at least two primary amino groups per molecule is more than 35 parts, but the excessive siloxane compound leads to deterioration in peel strength and flowability; the resin composition provided by Comparative Example 6 has deteriorated flowability because it does not contain inorganic filler (spherical silica); and the resin composition provided by Comparative Example 7 has a deteriorated coefficient of planar thermal expansion because the content of modified maleimide is less than 80 parts.

[0148] The applicant declares that the above embodiments illustrate the resin composition of the present invention and the prepreg containing it, the metal foil laminate, and the printed circuit board, but the present invention is not limited to the above embodiments, that is, it does not mean that the present invention must rely on the above embodiments to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent substitutions of the raw materials of the products of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A resin composition, characterized in that, The resin composition comprises the following components in parts by weight: (A) Modified maleimide: 80-100 parts; (B) Fillers with an average thermal expansion coefficient of less than 0 ppm / ℃ at 30-150℃: 50-300 parts; (C) Other inorganic fillers besides component (B): 5 to 300 parts; The raw materials for preparing the modified maleimide, by weight, include: maleimide compound a1 containing at least two N-substituted maleimide groups in one molecule: 45-80 parts; and siloxane compound a2 containing at least two primary amino groups in one molecule: 10-35 parts.

2. The resin composition according to claim 1, characterized in that, The maleimide compound a1 containing at least two N-substituted maleimide groups in one molecule has the structure shown in formula (I-1): In formula (I-1), A1 is a divalent organic group; Preferably, A1 is selected from groups with the structures shown in formula (1), formula (2), formula (3) or formula (4); In formula (1), R1 is independently selected from aliphatic hydrocarbon groups or halogen atoms with 1 to 5 carbon atoms, and a is selected from integers from 0 to 4. In equation (2), R 2a R 2b R 3a R 3b Each of the following groups is independently selected from aliphatic hydrocarbon groups or halogen atoms having 1 to 5 carbon atoms. A2 is selected from straight-chain or branched alkylene groups having 1 to 5 carbon atoms, straight-chain or branched alkylidene groups having 2 to 5 carbon atoms, ether groups, thioether groups, sulfonyl groups, carbonyl groups, ketone groups, single bonds, or groups with the structure shown in formula (2-1) or formula (2-2) below. pa, pb, qa, and qb are each independently selected from integers from 0 to 4, while pa+pb≤4 and qa+qb≤4. In equation (2-1), R 4a R 4b R 5a R 5b Each of the following is independently selected from aliphatic hydrocarbon groups or halogen atoms having 1 to 5 carbon atoms. A3 is selected from straight-chain or branched alkylene groups having 1 to 5 carbon atoms, straight-chain or branched alkylidene groups having 2 to 5 carbon atoms, ether groups, thioether groups, sulfonyl groups, carbonyl groups, ketone groups, and single bonds. ka, kb, la, and lb are each independently selected from integers from 0 to 4, while ka+kb≤4 and la+lb≤4. In formula (2-2), R8 is independently selected from aliphatic hydrocarbon groups or halogen atoms with 1 to 5 carbon atoms, and o is selected from integers from 0 to 4. In formula (3), m is selected from an integer from 1 to 10, preferably an integer from 1 to 5, and more preferably an integer from 1 to 3; In formula (4), R6 and R7 are each independently selected from aliphatic hydrocarbon groups with 1 to 5 hydrogen atoms or carbon atoms, and n is selected from integers from 1 to 10. In formulas (1), (2), (2-1), (2-2), (3), and (4), the short straight lines on both sides of the group represent the bond attached to the group, not the methyl group.

3. The resin composition according to claim 1 or 2, characterized in that, The maleimide compound a1 containing at least two N-substituted maleimide groups in one molecule includes any one or a combination of at least two of bis(4-maleimidephenyl)methane, bis(3-methyl-4-maleimidephenyl)methane, bis(3,5-dimethyl-4-maleimidephenyl)methane, bis(3-ethyl-5-methyl-4-maleimidephenyl)methane, bis(3-ethyl-4-maleimidephenyl)methane, bis(3,5-diethyl-4-maleimidephenyl)methane, or 2,2-bis(4-(4-maleimidephenyl)propane).

4. The resin composition according to any one of claims 1-3, characterized in that, The siloxane compound a2 containing at least two primary amino groups in one molecule has a divalent organic group in its molecular structure as shown in formula (I-2): In equation (I-2), R9, R 10 R 11 R 12 Each group is independently selected from aliphatic hydrocarbon groups, aryl groups, or substituted aryl groups having 1 to 5 carbon atoms; A4 and A5 are independently selected from divalent organic groups; and r is selected from integers from 2 to 100. Preferably, the functional group equivalent of the siloxane compound a2 containing at least two primary amino groups in one molecule is 100-6000 g / mol, more preferably 300-3000 g / mol, and even more preferably 600-2000 g / mol.

5. The resin composition according to any one of claims 1-4, characterized in that, The raw materials for preparing the modified maleimide also include amine compounds other than siloxane compounds, which contain at least two primary amino groups in one molecule; Preferably, the other amine compound a3 is selected from any one or a combination of at least two of 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-5,5'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-5,5'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diaminodiphenylmethane, or 2,2-bis(4-(4-aminophenoxy)phenyl)propane; Preferably, the amount of the other amine compound a3 is 0.5 to 10 parts.

6. The resin composition according to any one of claims 1-5, characterized in that, The filler with an average thermal expansion coefficient of less than 0 ppm / ℃ at 30–150℃ has a particle size of 0.1–10 μm; Preferably, the filler with an average thermal expansion coefficient of less than 0 ppm / ℃ at 30-150℃ includes any one or a combination of at least two of zirconium phosphate fillers, cordierite fillers, rare earth tungstate fillers, and manganese nitride fillers, with rare earth tungstate fillers being preferred. Preferably, the rare earth tungstate packing includes zirconium tungstate packing; Preferably, the zirconium tungstate-based filler includes zirconium tungstate and / or zirconium tungstate phosphate; Preferably, the inorganic filler (C) comprises any one or a combination of at least two of silicon dioxide, magnesium oxide, aluminum oxide, aluminum nitride, boron nitride, boehmite, and aluminum hydroxide, preferably silicon dioxide, and more preferably spherical silicon dioxide; Preferably, the inorganic filler (C) comprises a surface-treated inorganic filler.

7. The resin composition according to any one of claims 1-6, characterized in that, The composition also includes a compound (D) that can undergo a crosslinking reaction with (A); Preferably, the compound (D) that can undergo a crosslinking reaction with (A) includes any one or a combination of at least two of epoxy resin, compound having carbon-carbon unsaturated double bonds in the molecule, acid anhydride compound, active ester compound or cyanate ester resin; Preferably, the amount of compound (D) that can undergo a cross-linking reaction with (A) is 0.1 to 20 parts; Preferably, the resin composition further includes an elastomer, preferably a styrene-based elastomer; Preferably, the resin composition further includes a coupling agent; Preferably, the coupling agent comprises a silane coupling agent; Preferably, the amount of the coupling agent is 0.01 to 10 parts.

8. A prepreg, characterized in that, The prepreg includes a substrate and a resin composition as described in any one of claims 1 to 7, which is attached to the substrate by impregnation and drying. Preferably, the substrate comprises any one of glass fiber cloth, organic fiber cloth, or glass fiber paper.

9. A metal foil-coated laminate, characterized in that, The metal foil laminate includes at least one prepreg as described in claim 8, and metal foil disposed on one or both sides of the prepreg; Preferably, the metal foil is a copper foil.

10. A printed circuit board, characterized in that, The printed circuit board includes at least one prepreg as described in claim 8 or a metal foil laminate as described in claim 9.

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