Resin composition and prepreg and metal foil-clad laminated board containing same

Abstract

The invention provides a resin composition, and a prepreg and a metal foil-clad laminated board containing the same. The resin composition comprises the following components: an addition reactant (A) of a maleimide compound a1 containing at least two N-substituted maleimide groups in one molecule and a siloxane compound a2 containing at least two primary amino groups in one molecule, and thermosetting resin (B), and the total weight of the addition reactants with the weight-average molecular weight of 1100-20000 in the component (A) accounts for 10-70% of the component (A). The resin composition provided by the invention has low planar thermal expansion coefficient, low dielectric loss and low Df change after thermal oxidation treatment, and is especially suitable for high-frequency and high-speed packaging.

Description

Technical Field

[0001] The present invention belongs to the technical field of printed circuit boards, and particularly relates to a resin composition, a prepreg containing the same, and a metal-clad laminate. Background Art

[0002] In recent years, information technology has entered a stage of high-speed signal and high-frequency transmission. In order to match the increasing data processing volume, the frequency of electronic devices is getting higher and higher, which puts forward higher requirements for the electrical performance of the substrate to minimize the loss and delay of high-frequency signals as much as possible. With the advent of the 5G era, applications such as high-frequency RF (such as PA, WiGig, WiHD / 60GHz, etc.), large-size chips, and DDR5 (3.2 - 6.4Gbps) represent higher requirements for the performance of packaging substrate materials: having a low coefficient of planar thermal expansion and a lower dielectric loss tangent at the same time.

[0003] Bismaleimide (BMI) resin is a traditional resin system for packaging substrates, with high monomer activity, no molecular release during polymerization, stable product performance, and can maintain high physical and mechanical properties within a wide temperature range. CN109825081A discloses a thermosetting resin composition, and the resin composition includes the following components: a combination of bismaleimide resin and benzoxazine resin or a prepolymer of bismaleimide resin and benzoxazine resin, epoxy resin, and active ester; the metal-clad laminate prepared by this resin composition has a high glass transition temperature, a low coefficient of thermal expansion, a high high-temperature modulus, and good heat resistance; however, the cured product of the maleimide resin system is brittle, has a short storage period, and the dielectric loss tangent performance is poor, so its application in high-frequency and high-speed electronic products is limited.

[0004] In current mainstream high-speed and low-dielectric-loss tangent resin systems, polyphenylene ether resin is usually included. The molecular structure of polyphenylene ether resin contains benzene rings, which endows it with good physical and mechanical properties, and at the same time has a low dielectric constant and dielectric loss tangent. However, polyphenylene ether resin is a thermoplastic resin, and there are problems such as high melting point, poor processing performance, and poor solvent resistance. Therefore, in actual use, polyphenylene ether needs to be modified. CN109988298A discloses a modified polyphenylene ether resin, a thermosetting resin composition and its uses; the modified polyphenylene ether resin is a resin structure obtained by reacting low-molecular-weight bis-hydroxyl-terminated polyphenylene ether with diacyl halide or dicarboxylic acid containing specific structural units, monofunctional aromatic phenol or monofunctional aromatic acyl halide or monofunctional aromatic carboxylic acid; prepregs, circuit boards and laminated films made of this thermosetting resin composition have low dielectric constant, low dielectric loss tangent and good heat resistance; however, there are unreacted hydroxyl groups in the polyphenylene ether resin system containing hydroxyl ends, resulting in an increase in the water absorption rate of prepregs or circuit boards during use and a decrease in the moisture and heat resistance, affecting the reliability of the boards.

[0005] Polyolefin resin has excellent performance in terms of toughness and dielectric properties. Combining it with polyphenylene ether resin can improve the comprehensive performance. CN111154197A discloses a polyolefin resin composition, including 30-80 parts of polyolefin resin, 1-30 parts of bismaleimide resin, 30-80 parts of polyphenylene ether resin, 0.1-5 parts of initiator, 20-60 parts of inorganic filler, 10-30 parts of flame retardant and 50-120 parts of solvent; the copper-clad laminate made by impregnating glass fiber cloth with this polyolefin resin composition as the resin matrix has a low dielectric constant and dielectric loss tangent, and good peel strength, but its coefficient of thermal expansion is high and its dimensional stability is poor, making it difficult to meet the performance requirements of high-frequency devices for packaging substrates.

[0006] At the same time, with the increase in chip size and the improvement of working frequency, there is a need for a low △D f change after thermal oxidation treatment of the packaging substrate, requiring the substrate to still maintain low dielectric performance after experiencing a high-temperature environment, while existing packaging substrates are difficult to meet this requirement.

[0007] Therefore, developing a resin material with excellent dielectric properties, low △D f change after thermal oxidation treatment and low coefficient of thermal expansion is the research focus in this field. Summary of the Invention

[0008] Aiming at the deficiencies of the prior art, the purpose of the present invention is to provide a resin composition, a prepreg and a metal-clad laminate containing the same. The resin composition has a low planar coefficient of thermal expansion and low dielectric loss, and a low △D f change after thermal oxidation treatment, and is particularly suitable for high-frequency and high-speed packaging.

[0009] In order to achieve the purpose of the invention, the present invention adopts the following technical solutions:

[0010] In one aspect, the present invention provides a resin composition, comprising the following components: an addition reaction product (A) of a maleimide compound a1 containing at least two N-substituted maleimide groups in one molecule and a siloxane compound a2 containing at least two primary amino groups in one molecule, and a thermosetting resin (B);

[0011] The weight of the addition reactants having a weight average molecular weight of 1,100 to 20,000 in the component (A) accounts for 10 to 70% of the component (A).

[0012] In the present invention, the components (A) and (B) in the resin composition are matched, and the weight of the addition reactants with a weight average molecular weight of 1100 to 20000 in the component (A) accounts for 10 to 70% of the component (A), thereby solving the problems of low thermal expansion coefficient, low dielectric loss and low ΔD after thermal oxidation treatment in the prior art. f The defects that cannot coexist with each other are changed, and the resin composition is given a low plane thermal expansion coefficient, a low dielectric loss tangent and good thermal oxygen aging resistance, so that the metal foil laminate containing it has a low plane thermal expansion coefficient, excellent dielectric properties and low △ D after thermal oxygen treatment f changes, especially for high-speed packaging.

[0013] In the present invention, the total weight of the addition reactants with a weight average molecular weight of 1100 to 20000 in the component (A) of the resin composition accounts for 10 to 70% (the weight average molecular weight can be measured by GB / T 21863-2008, measured by gel permeation chromatography (GPC method) based on polystyrene calibration, and the percentage can be obtained by the aforementioned gel permeation chromatography (GPC method) test), for example, 10%, 20%, 30%, 40%, 50%, 60% or 70% of the component (A). If the total weight percentage of the addition reactants with a weight average molecular weight of 1100 to 20,000 in component (A) of the resin composition is less than 10% of the total weight of the addition reactants with a weight average molecular weight of 1100 to 20,000 in component (A) of the resin composition, the processability will deteriorate, and there will even be a tendency for resin precipitation in the resin adhesive; if the total weight percentage of the addition reactants with a weight average molecular weight of 1100 to 20,000 in component (A) of the resin composition is higher than 70% of the total weight of the addition reactants with a weight average molecular weight of 1100 to 20,000 in component (A) of the resin composition, the processability and wettability of the prepreg will deteriorate, and there will even be a tendency for the prepreg to be unable to be molded.

[0014] In the present invention, the addition reaction product of a maleimide compound a1 containing at least two N-substituted maleimide groups in one molecule and an amine compound a2 containing at least two primary amino groups in one molecule has high heat resistance, high reactivity, and a low planar thermal expansion coefficient.

[0015] Preferably, the weight of the siloxane compound a2 containing at least two primary amino groups in one molecule accounts for 2 to 30% of the addition reaction product (A), such as 2%, 3%, 5%, 8%, 10%, 13%, 15%, 18%, 20%, 23%, 25%, 28%, or 30%. In the present invention, if the percentage of the siloxane compound a2 containing at least two primary amino groups in one molecule in the addition reaction product (A) is less than 2%, it will result in a relatively large CTE and △D after thermo-oxidative treatment. f If the percentage of the siloxane compound a2 containing at least two primary amino groups in one molecule in the addition reaction product (A) is greater than 30%, it will lead to poor processability and simultaneously reduce Tg.

[0016] Preferably, the addition reaction product (A) is an addition reaction product of a maleimide compound a1 containing at least two N-substituted maleimide groups in one molecule, a siloxane compound a2 containing at least two primary amino groups in one molecule, and an amine compound a3 containing at least two primary amino groups in one molecule.

[0017] In the present invention, when an amine compound a3 containing at least two primary amino groups is added to the raw materials for preparing the addition reaction product (A), it is beneficial to adjust the processability.

[0018] Preferably, the primary amine value of the component (A) is 0.10 to 1.00 mmol / g. For example, it can be 0.15 mmol / g, 0.20 mmol / g, 0.25 mmol / g, 0.30 mmol / g, 0.35 mmol / g, 0.40 mmol / g, 0.45 mmol / g, 0.50 mmol / g, 0.55 mmol / g, 0.60 mmol / g, 0.65 mmol / g, 0.70 mmol / g, 0.75 mmol / g, 0.85 mmol / g, 0.90 mmol / g, or 0.95 mmol / g, etc. Its primary amine value can be obtained by titration test with potassium hydrogen phthalate. Due to the specific content of the primary amine value in the component (A), the resin composition prepared therefrom has a low dielectric constant and a low dielectric loss tangent. If the primary amine value is too high, the gelation time of the component (A) will rapidly become shorter during storage, thereby affecting the timeliness of the use of the component (A) in the resin composition. If the primary amine value is too low, resin will precipitate during the storage of the component (A), which will also affect the timeliness of the use of the component (A) in the resin composition.

[0019] In the present invention, the primary amine value can be measured by the following method: Prepare a 0.1 mol / L perchloric acid acetic acid solution, calibrate the concentration with potassium hydrogen phthalate and record it as C; Take M g of an addition reaction product of a maleimide compound a1 containing at least 2 N-substituted maleimide groups in one molecule and an amine compound a2 containing at least 2 primary amino groups in one molecule with a solid content of A, add 50 mL of acetic acid and 5 mL of acetone, and stir until completely and evenly mixed; Use an automatic potentiometric titrator to titrate with the calibrated perchloric acid acetic acid solution, record the volume of the solvent consumed at the end point and record it as V; The primary amine value = 10 × C × V / M / A, and the unit is mmol / g.

[0020] In the present invention, the specific examples of the maleimide compound a1 are not particularly limited, as long as it is a maleimide compound containing at least two N-substituted maleimide groups in one molecule. Exemplarily, it includes but is not limited to the following aromatic maleimide compounds and aliphatic maleimide compounds: N,N'-ethylenebismaleimide, N,N'-hexamethylenebismaleimide, N,N'-(1,3-phenylene)bismaleimide, N,N'-(1,3-(2-methylphenylene))bismaleimide, N,N'-(1,3-(4-methylphenylene))bismaleimide, N,N'-(1,4-phenylene)bismaleimide, bis(4-maleimidophenyl)methane, bis(3-methyl-4-maleimidophenyl)methane, bis(3,5-dimethyl-4-maleimidophenyl)methane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, bis(3-ethyl-4-maleimidophenyl)methane, bis(3,5-diethyl-4-maleimidophenyl)methane, bis(4-maleimidophenyl)ether, bis(4-maleimidophenyl)ketone, bis(4-maleimidophenyl)sulfone, bis(4-maleimidocyclohexyl)methane, 1,4-bis(4-maleimidophenyl)cyclohexane, 1,4-bis(maleimidomethyl)cyclohexane, 1,4-bis(maleimidomethyl)benzene, 1,3-bis(4-maleimidophenoxy)benzene, 1,3-bis(3-maleimidophenoxy)benzene, bis(4-(3-maleimidophenoxy)phenyl)methane, bis(4-(4-maleimidophenoxy)phenyl)methane, 1,1-bis(4-(3-maleimidophenoxy)phenyl)ethane, 1,1-bis(4-(4-maleimidophenoxy)phenyl)ethane, 1,2-bis(4-(3-maleimidophenoxy)phenyl)ethane, 1,2-bis(4-(4-maleimidophenoxy)phenyl)ethane, 2,2-bis(4-(3-maleimidophenoxy)phenyl)propane, 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane, 2,2-bis(4-(3-maleimidophenoxy)phenyl)butane, 2,2-bis(4-(4-maleimidophenoxy)phenyl)butane, 4,4'-bis(3-maleimidophenoxy)biphenyl, 4,4'-bis(4-maleimidophenoxy)biphenyl, bis(4-(3-maleimidophenoxy)phenyl)ketone, bis(4-(4-maleimidophenoxy)phenyl)ketone, bis(4-(3-maleimidophenoxy)phenyl)ether, bis(4-(4-maleimidophenoxy)phenyl)ether, polyphenylmethane maleimide, 1,6-bis(maleimide)-(2,2,4-trimethyl)hexane, any one or a combination of at least two of long-chain alkyl-based bismaleimides.

[0021] As a preferred technical solution of the present invention, the maleimide compound a1 of the present invention has a structure in which a maleimide group is bonded to an aromatic ring, as shown in formula (I-1):

[0022]

[0023] In formula (I-1), A1 is a divalent organic group;

[0024] Preferably, A1 is selected from the groups having the structures shown in formula (1), formula (2), formula (3) or formula (4).

[0025]

[0026] In formula (1), each R1 is independently selected from a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom, and a is an integer selected from 0 to 4 (for example, 0, 1, 2, 3 or 4);

[0027] As the aliphatic hydrocarbon group having 1 to 5 carbon atoms, exemplarily, it may be selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, etc., preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, more preferably methyl and ethyl;

[0028] From the perspective of a lower CTE, a is preferably an integer from 0 to 2, more preferably 0; when a is an integer of 2 or more, the plurality of R1s may be the same or different from each other.

[0029]

[0030] In formula (2), R 2a , R 2b , R 3a , R 3b are each independently selected from a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom, A2 is selected from a linear or branched alkylene group having 1 to 5 carbon atoms, a linear or branched alkylidene group having 2 to 5 carbon atoms, an ether group, a thioether group, a sulfonyl group, a carbonyloxy group, a keto group, a single bond, a group having the structure of formula (2-1) or a group having the structure of formula (2-2), pa, pb, qa, qb are each independently selected from integers from 0 to 4 (for example, 0, 1, 2, 3 or 4), and at the same time pa + pb ≤ 4, qa + qb ≤ 4;

[0031] As the aliphatic hydrocarbon group having 1 to 5 carbon atoms, exemplarily, it may be selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, etc., preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, more preferably methyl and ethyl;

[0032] As the straight-chain or branched-chain alkylene group having 1 to 5 carbon atoms, by way of example, it may be selected from methylene, 1,2-ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene, etc., preferably an alkylene group having 1 to 3 carbon atoms, more preferably methylene;

[0033] As the straight-chain or branched-chain alkylidene group having 2 to 5 carbon atoms, by way of example, it may be selected from ethylidene, propylidene, isopropylidene, butylidene, isobutylidene, pentylidene, isopentylidene, preferably isopropylidene;

[0034] From the perspective of lower CTE, pa, pb, qa, and qb are each independently preferably an integer of 0 to 2, more preferably 0; from the perspective of simultaneously having low CTE and good dielectric properties, pa, pb, qa, and qb are each independently preferably an integer of 1 to 2, more preferably 1; when pa, pb, qa, and qb are each independently an integer of 2 or more, multiple Rs 2a each other, Rs 2b each other, Rs 3a each other or Rs 3b each other may be the same or different;

[0035]

[0036] In formula (2-1), Rs 4a , Rs 4b , Rs 5a , Rs 5b are each independently selected from a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a halogen atom, A3 is selected from a straight-chain or branched-chain alkylene group having 1 to 5 carbon atoms, a straight-chain or branched-chain alkylidene group having 2 to 5 carbon atoms, an ether group, a thioether group, a sulfonyl group, a carbonyloxy group, a ketone group, a single bond, ka, kb, la, and lb are each independently selected from integers of 0 to 4 (for example, 0, 1, 2, 3, or 4), and at the same time ka + kb ≤ 4, la + lb ≤ 4;

[0037] As the aliphatic hydrocarbon group having 1 to 5 carbon atoms, by way of example, it may be selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, etc., preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, more preferably methyl and ethyl;

[0038] As the straight-chain or branched-chain alkylene group having 1 to 5 carbon atoms, by way of example, it may be selected from methylene, 1,2-ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene, etc., preferably an alkylene group having 1 to 3 carbon atoms, more preferably methylene;

[0039] As the straight-chain or branched-chain alkanediyl group having 2 to 5 carbon atoms, by way of example, it may be selected from ethylidene, propylidene, isopropylidene, butylidene, isobutylidene, pentylidene, isopentylidene, and isopropylidene is preferred;

[0040] From the perspective of lower CTE, ka, kb, la, and lb are each independently preferably an integer of 0 to 2, more preferably 0; from the perspective of simultaneously having low CTE and good dielectric properties, ka, kb, la, and lb are each independently preferably an integer of 1 to 2, more preferably 1; when ka, kb, la, and lb are each independently an integer of 2 or more, multiple Rs 4a each other, Rs 4b each other, Rs 5a each other or Rs 5b each other may be the same or different;

[0041]

[0042] In formula (2-2), each R8 is independently selected from a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a halogen atom, and o is an integer selected from 0 to 4;

[0043] As the aliphatic hydrocarbon group having 1 to 5 carbon atoms, by way of example, it may be selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, etc., and an aliphatic hydrocarbon group having 1 to 3 carbon atoms is preferred, and methyl and ethyl are more preferred;

[0044] From the perspective of lower CTE, o is preferably an integer of 0 to 2, more preferably 0; when o is an integer of 2 or more, multiple R8s may be the same or different from each other.

[0045]

[0046]

[0047] In formula (3), m is an integer selected from 1 to 10, and from the perspective of easy availability, m is preferably an integer of 1 to 5, more preferably an integer of 1 to 3.

[0048]

[0049] In formula (4), R6 and R7 are each independently selected from a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms, and n is an integer selected from 1 to 10;

[0050] As the aliphatic hydrocarbon group having 1 to 5 carbon atoms, by way of example, it may be selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, etc., and an aliphatic hydrocarbon group having 1 to 3 carbon atoms is preferred, and methyl and ethyl are more preferred;

[0051] From the perspective of a 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, multiple R6s or multiple R7s may be the same or different from each other.

[0052] In Formula (1), Formula (2), Formula (2-1), Formula (3), and Formula (4), the short straight lines on both sides of the group represent the bonding keys of the group, and do not represent methyl groups.

[0053] Preferably, the maleimide compound a1 contains 2 N-substituted maleimide groups in one molecule, which can impart better solubility to the addition reactant (A).

[0054] From the perspectives of better processability, CTE, and dielectric properties, the maleimide compound a1 is further preferably any one or a combination of at least two of bis(4-maleimidophenyl)methane, bis(3-methyl-4-maleimidophenyl)methane, bis(3,5-dimethyl-4-maleimidophenyl)methane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, bis(3-ethyl-4-maleimidophenyl)methane, bis(3,5-diethyl-4-maleimidophenyl)methane, or 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane.

[0055] The maleimide compound a1 can be used alone or at least two of them can be mixed and used.

[0056] In the present invention, the siloxane compound a2 containing at least 2 primary amino groups in one molecule is not particularly limited as long as it contains at least 2 primary amino groups in one molecule and contains a siloxane segment in the molecular structure. Preferably, the siloxane compound a2 containing at least 2 primary amino groups in one molecule contains a divalent organic group represented by Formula (I-2) in the molecular structure:

[0057]

[0058] In Formula (I-2), R9, R 10 , R 11 , R 12 , R 13 , R 14 are each independently selected from an aliphatic hydrocarbon group, an aryl group, or a substituted aryl group having 1 to 5 carbon atoms, A4 and A5 are each independently selected from divalent organic groups, and r is an integer from 1 to 100;

[0059] As the aliphatic hydrocarbon group having 1 to 5 carbon atoms, exemplarily, it may be selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, etc., preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, more preferably methyl;

[0060] As the aryl group, exemplarily, it may be selected from phenyl, biphenyl, naphthyl, etc., preferably phenyl;

[0061] As the substituted aryl group, exemplarily, it may be selected from substituted phenyl, substituted biphenyl, substituted naphthyl, etc., preferably substituted phenyl; As the substituent of the aryl group in the substituted aryl group, exemplarily, it may be selected from an aliphatic hydrocarbon group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkynyl group having 2 to 5 carbon atoms, etc.; As the aliphatic hydrocarbon group having 1 to 5 carbon atoms, exemplarily, it may be selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, etc.; As the alkenyl group having 2 to 5 carbon atoms, exemplarily, it may be selected from vinyl, allyl, etc.; As the alkynyl group having 2 to 5 carbon atoms, exemplarily, it may be selected from ethynyl, propargyl, etc.;

[0062] As the divalent organic group independently selected by each of A4 and A5, exemplarily, it may be selected from alkylene, alkenylene, alkynylene, arylene, -O- or a divalent linking group formed by combining them, etc.; As the alkylene, exemplarily, it may be selected from alkylene having 1 to 10 carbon atoms such as methylene, ethylene, propylene, etc.; As the alkenylene, exemplarily, it may be selected from alkenylene having 2 to 10 carbon atoms; As the alkynylene, exemplarily, it may be selected from alkynylene having 2 to 10 carbon atoms; As the arylene, exemplarily, it may be selected from arylene having 6 to 20 carbon atoms such as phenylene, naphthylene, etc.; The divalent organic group independently selected by each of A4 and A5 is preferably alkylene or arylene, more preferably alkylene;

[0063] r is preferably an integer of 1 to 50, more preferably an integer of 3 to 40, still more preferably an integer of 5 to 40. When r is an integer of 2 or more, multiple R9s or multiple Rs 10 may be the same or different from each other.

[0064] In the present invention, the functional group equivalent of the siloxane compound a2 containing at least 2 primary amino groups in one molecule is not particularly limited, preferably 100 to 6000 g / mol, more preferably 300 to 3000 g / mol, still more preferably 400 to 2000 g / mol, and most preferably 600 to 2000 g / mol.

[0065] Preferably, the siloxane compound a2 containing at least two primary amino groups in one molecule preferably includes a siloxane compound having two primary amino groups at the molecular terminals.

[0066] In the present invention, the siloxane compound a2 containing at least two primary amino groups in one molecule can be a commercially available product, and exemplary ones include but are not limited to: PAM-E (side-chain methyl type, functional group equivalent 130 g / mol), KF-8010 (side-chain methyl type, functional group equivalent 430 g / mol), X-22-161A (side-chain methyl type, functional group equivalent 800 g / mol), X-22-161B (side-chain methyl type, functional group equivalent 1500 g / mol), KF-8012 (side-chain methyl type, functional group equivalent 2200 g / mol), KF-8008 (side-chain methyl type, functional group equivalent 5700 g / mol), X-22-1660B-3 (side-chain phenyl type, functional group equivalent 2200 g / mol), or X-22-9409 (side-chain phenyl type, functional group equivalent 670 g / mol) of Shin-Etsu Chemical Co., Ltd., or any one or a combination of at least two of them.

[0067] The addition reaction between the maleimide compound a1 containing at least two N-substituted maleimide groups in one molecule and the siloxane compound a2 containing at least two primary amino groups in one molecule is preferably carried out in an organic solvent; the type of the organic solvent is not particularly limited, and propylene glycol monomethyl ether is further preferred.

[0068] In the present invention, the temperature of the addition reaction between the maleimide compound a1 containing at least two N-substituted maleimide groups in one molecule and the siloxane compound a2 containing at least two primary amino groups in one molecule is not particularly limited, as long as the maleimide compound a1 and the amine compound a2 can react. As a preferred technical solution of the present invention, from the perspectives of reaction rate and solvent boiling point, preferably, the temperature of the addition reaction is 100 - 130 °C, for example, it can be 102 °C, 105 °C, 108 °C, 110 °C, 112 °C, 115 °C, 118 °C, 120 °C, 122 °C, 125 °C, or 128 °C, etc.

[0069] In the present invention, the time of the addition reaction between the maleimide compound a1 containing at least two N-substituted maleimide groups in one molecule and the siloxane compound a2 containing at least two primary amino groups in one molecule is not particularly limited. Preferably, the time of the addition reaction is 2 - 10 h, for example, it can be 2.5 h, 3 h, 3.5 h, 4 h, 4.5 h, 5 h, 5.5 h, 6 h, 6.5 h, 7 h, 7.5 h, 8 h, 8.5 h, 9 h, 9.5 h, etc., and more preferably 3 - 8 h.

[0070] In the present invention, the amine compound a3 having at least two primary amino groups in one molecule is not particularly limited. Preferably, the amine compound a3 having at least two primary amino groups in one molecule is selected from any one or a combination of at least two of diaminobenzidine, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, diaminodiphenylmethane, 3,3'-dimethoxy-4,4'-diaminodiphenylmethane, 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, diaminodiphenyl ether, 3,3'-dimethoxy-4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminodiphenyl ether, 3,3'-dimethyl-5,5'-dimethyl-4,4'-diaminodiphenyl ether, 3,3'-diethyl-4,4'-diaminodiphenyl ether, 3,3'-diethyl-5,5'-diethyl-4,4'-diaminodiphenyl ether, 3,3'-dimethyl-5,5'-diethyl-4,4'-diaminodiphenyl ether, 1,3-bis(4-aminophenoxy)benzene, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 2,2-bis(4-(3-aminophenoxy)phenyl)propane, 4,4'-bis(4-aminophenoxy)biphenyl, 1,4-bis(4-aminophenoxy)benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl or 4,4'-diamino-3,3'-dihydroxybiphenyl; more preferably, it is 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.

[0071] In the present invention, the thermosetting resin (B) is not particularly limited. Preferably, the thermosetting resin (B) is selected from one or a combination of at least two of epoxy resins, cyanate ester resins, hydrocarbon resins, polyphenylene ether resins, crosslinking agents having carbon-carbon unsaturated double bonds in the molecule, and other maleimide compounds.

[0072] Preferably, the polyphenylene ether resin is a polyphenylene ether having an unsaturated group at the end;

[0073] Preferably, the unsaturated group includes any one or a combination of at least two of vinylbenzyl, vinylphenyl or acrylate groups.

[0074] In the present invention, the structural formula of vinylbenzyl is The dotted line represents the connection site of the group.

[0075] The structural formula of the acrylate group is The dotted line represents the connection site of the group; R3 is selected from hydrogen, C1-C20 (such as C2, C3, C4, C5, C6, C7, C8, C9, C10, C12, C14, C16, C18 or C19, etc.) straight-chain or branched-chain alkyl groups, and is further preferably hydrogen, C1-C10 straight-chain or branched-chain alkyl groups.

[0076] The acrylate group is further preferably an acrylate group or a methacrylate group.

[0077] As a preferred technical solution of the present invention, the polyphenylene ether containing an unsaturated bond in the component (B) is a polyphenylene ether having vinylbenzyl at the end, which is more helpful for improving the dielectric properties and heat resistance of the resin composition. The polyphenylene ether having vinylbenzyl at the end can be a commercially available product, and exemplary ones include, but are not limited to: OPE-2st 1200 (number average molecular weight M n is 1200) and / or OPE-2st 2200 (number average molecular weight M n is 2200), etc. The number average molecular weight can be measured by GB / T21863-2008 and determined by gel permeation chromatography (GPC method) based on polystyrene calibration.

[0078] In the resin composition of the present invention, based on parts by weight, the content of the addition reactant (A) is 10-90 parts, for example, it can be 12 parts, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, 28 parts, 30 parts, 32 parts, 35 parts, 38 parts, 40 parts, 42 parts, 45 parts, 48 parts, 50 parts, 52 parts, 55 parts, 58 parts, 60 parts, 62 parts, 65 parts, 70 parts, 75 parts, 78 parts, 80 parts, 85 parts, 88 parts, etc.; the content of the thermosetting resin (B) is 10-80 parts, for example, it can be 12 parts, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, 28 parts, 30 parts, 32 parts, 35 parts, 38 parts, 40 parts, 42 parts, 45 parts, 48 parts, 50 parts, 52 parts, 55 parts, 58 parts, 60 parts, 62 parts, 65 parts, 68 parts, 70 parts, 75 parts, 78 parts, etc.

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

[0080] Preferably, the resin composition further comprises one or a combination of at least two of polyolefin resin (C), curing accelerator (D), and inorganic filler (E).

[0081] As a preferred technical solution of the present invention, the polyolefin resin helps to improve the dielectric properties of the resin composition. However, if the content of the polyolefin resin is too high, the adhesion between the resin composition and the metal foil decreases, and at the same time, the melt fluidity of the resin composition decreases, which is not conducive to preparing a resin composition with uniform thickness.

[0082] In the present invention, the polyolefin resin (C) is not particularly limited. Preferably, the polyolefin resin (C) includes a styrene copolymer. A styrene copolymer is, for example, a copolymer including an olefin structural unit and a styrene-based structural unit. The olefin structural unit is derived from an olefin monomer, such as a structural unit from butadiene, a structural unit from isoprene, etc.; the styrene-based structural unit is derived from a styrene-based monomer, such as a structural unit from styrene, a structural unit from styrene having a substituent, etc. The styrene copolymer may contain structural units other than the olefin structural unit and the styrene-based structural unit, for example, it may also contain a structural unit from an epoxy group, a structural unit from an amino group, a structural unit from maleic anhydride, etc.

[0083] The styrene copolymer may be a random copolymer or a block copolymer. If the styrene copolymer is a random copolymer, the styrene copolymer is a copolymer in which a plurality of olefin structural units and a plurality of styrene-based structural units are randomly arranged. If the styrene copolymer is a block copolymer, the styrene copolymer is a copolymer in which one or more olefin blocks and one or more styrene-based blocks are arranged. The olefin block is composed of a plurality of olefin structural units, and the styrene-based block is composed of a plurality of styrene-based structural units.

[0084] The structural unit of the polyolefin resin derived from olefin may be hydrogenated or partially hydrogenated. Considering the dielectric properties, the polyolefin resin preferably has the structural unit derived from olefin hydrogenated.

[0085] The polyolefin resin can be a commercially available product, and exemplary ones include but are not limited to: any one or a combination of at least two of Ricon 153 (butadiene copolymer, Cray Valley), Ricon 100 (butadiene-styrene copolymer, Cray Valley), Ricon 181 (butadiene-styrene copolymer, Cray Valley), Tuftec H1051 (hydrogenated styrene-butadiene copolymer, with a mass percentage of styrene of 42%, Asahi Kasei Chemicals Corporation), or Tuftec M1913 (hydrogenated styrene-butadiene copolymer with maleic anhydride structural units, with a mass percentage of styrene of 30%, Asahi Kasei Chemicals Corporation).

[0086] Preferably, in the resin composition by weight, the content of the polyolefin resin (C) is 5 to 30 parts, for example, it can be 6 parts, 8 parts, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, or 28 parts, etc.

[0087] In the present invention, the curing accelerator (D) is not particularly limited. Preferably, the curing accelerator (D) includes any one or a combination of at least two of acidic curing accelerators, organophosphorus curing accelerators, imidazole curing accelerators, pyridine curing accelerators, amine curing accelerators, peroxides, or organic metal salts.

[0088] Exemplarily, the acidic curing accelerator includes p-toluenesulfonic acid, etc.; the organophosphorus curing accelerator includes triphenylphosphine, etc.; the imidazole curing accelerator includes imidazole or imidazole derivatives (such as 2-ethyl-4-methylimidazole); the pyridine curing accelerator includes pyridine or pyridine derivatives (such as 4-dimethylaminopyridine); the amine curing accelerator includes secondary amine compounds, tertiary amine compounds, or quaternary ammonium salts; the peroxides include dicumyl peroxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hex-3-yne, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, or α,α'-bis(tert-butylperoxy)diisopropylbenzene, etc.; the organic metal salts include zinc naphthenate, cobalt naphthenate, tin octoate, or cobalt octoate, etc. The curing accelerator can be used alone or at least two of them can be mixed and used.

[0089] Preferably, in the resin composition by weight, the content of the curing accelerator (D) is 0.01 to 5 parts, for example, 0.03 parts, 0.05 parts, 0.08 parts, 0.1 parts, 0.3 parts, 0.5 parts, 0.8 parts, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 4.8 parts, etc.

[0090] Preferably, there is no particular limitation on the type of the inorganic filler (E) in the present invention. Exemplarily, it includes any one or a combination of at least two of: silica, aluminum hydroxide, magnesium hydroxide, boehmite, molybdenum oxide, zinc oxide, zinc molybdate, zinc borate, zinc stannate, titanium dioxide, strontium titanate, barium titanate, barium sulfate, clay, kaolin, talc, mica, boron nitride, aluminum nitride, silicon carbide, aluminum oxide, composite silica powder, glass powder, short glass fiber or hollow glass. In order to endow the resin composition with higher heat resistance, heat and humidity resistance and dimensional stability, it is preferably any one or a combination of at least two of: silica, aluminum hydroxide, magnesium hydroxide, boehmite, boron nitride, aluminum nitride, silicon carbide, aluminum oxide, composite silica powder, glass powder, short glass fiber or hollow glass. Among them, the silica may be crystalline silica, fused silica, amorphous silica, spherical silica or hollow silica, etc., and spherical silica is further preferred.

[0091] There is no particular limitation on the average particle size (D 50 ) of the inorganic filler, but from the perspective of dispersibility, the average particle size (D 50 ) is preferably 0.01 - 20 μm, such as 0.02 μm, 0.05 μm, 0.1 μm, 0.2 μm, 0.8 μm, 1.5 μm, 2.1 μm, 2.6 μm, 3.5 μm, 4.5 μm, 5.2 μm, 5.5 μm, 6 μm, 6.5 μm, 7 μm, 7.5 μm, 8 μm, 8.5 μm, 9 μm, 9.5 μm, 12 μm, 13.5 μm, 15 μm, 17.5 μm, 18 μm, 19.5 μm, and more preferably 0.1 - 10 μm. Different types, different particle size distributions or different average particle sizes of inorganic fillers can be used alone or in combination as needed.

[0092] Preferably, based on parts by weight of the resin composition, the content of the inorganic filler (E) is 5 - 250 parts, such as 8 parts, 10 parts, 20 parts, 30 parts, 50 parts, 70 parts, 90 parts, 100 parts, 110 parts, 130 parts, 150 parts, 170 parts, 190 parts, 200 parts, 210 parts or 230 parts, etc. The inorganic filler helps to improve the heat resistance, heat and humidity resistance and mechanical properties of the resin composition and reduce the coefficient of thermal expansion. If the amount of the inorganic filler is too large, it will cause an increase in the dielectric loss tangent of the resin composition, which is not conducive to signal transmission.

[0093] Preferably, the resin composition further comprises 0.01 to 10 parts by weight of a coupling agent (F). For example, the coupling agent can be 0.03 parts, 0.05 parts, 0.1 parts, 0.3 parts, 0.5 parts, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts or 9 parts, etc. More preferably, it is 0.1 to 6 parts of the coupling agent; the coupling agent helps to improve the compatibility between the inorganic filler and the resin composition.

[0094] Preferably, the coupling agent comprises a silane coupling agent.

[0095] The present invention does not particularly limit the type of the silane coupling agent. Exemplarily, it can be any one or a combination of at least two of: epoxy group silane coupling agent, amino group silane coupling agent, vinyl silane coupling agent, styryl silane coupling agent, isobutenyl silane coupling agent, propenyl silane coupling agent, ureido silane coupling agent, mercapto silane coupling agent, chloropropyl silane coupling agent, sulfide group silane coupling agent or isocyanate group silane coupling agent.

[0096] Preferably, the resin composition further comprises a flame retardant (G). There is no particular limitation on the flame retardant, and it can be selected from halogen-based or non-halogen-based flame retardants that are soluble or insoluble in organic solvents. Exemplarily, the non-halogen-based flame retardants include inorganic phosphorus-based flame retardants, organic phosphorus-based flame retardants, metal hydrates, etc.

[0097] From the perspective of environmental problems and excellent dielectric properties, the flame retardant is preferably an organic phosphorus-based flame retardant. Exemplarily, the organic phosphorus-based flame retardants include aromatic phosphates, monosubstituted phosphonic acid diesters, disubstituted phosphinic acid esters, metal salts of disubstituted phosphinic acids, organic nitrogen and phosphorus-containing compounds, cyclic organic phosphorus compounds, etc.

[0098] Exemplarily, the aromatic phosphates include triphenyl phosphate, tricresyl phosphate, tris(dimethylphenyl) phosphate, tolyldiphenyl phosphate, tolyl di-2,6-xylenyl phosphate, resorcinol bis(diphenyl phosphate), 1,3-phenylene bis(di(2,6-dimethylphenyl) phosphate), 4,4'-biphenylene bis(di(2,6-dimethylphenyl) phosphate), bisphenol A-bis(di(2,6-dimethylphenyl) phosphate), bisphenol A-bis(diphenyl phosphate), 1,3-phenylene bis(diphenyl phosphate), etc.; the monosubstituted phosphonic diesters include divinyl phenylphosphonate, diallyl phenylphosphonate, bis(1-butenyl) phenylphosphonate, etc.; the disubstituted phosphinic esters include phenyl diphenylphosphinate, methyl diphenylphosphinate, etc.; the metal salts of disubstituted phosphinic acids include metal salts of dialkyl phosphinic acids, metal salts of diallyl phosphinic acids, metal salts of divinyl phosphinic acids, metal salts of diaryl phosphinic acids, etc.; the organic nitrogen-containing phosphorus compounds include phosphazene compounds, melamine phosphate, melamine polyphosphate, melamine pyrophosphate, etc.; the cyclic organic phosphorus compounds include 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-phenyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, etc.

[0099] The flame retardant can be used alone or at least two of them can be used in combination.

[0100] On the other hand, the present invention provides a resin sizing solution, which is obtained by dissolving or dispersing the resin composition as described above in a solvent.

[0101] In the present invention, the amount of the solvent is not limited, as long as each component in the resin composition can be dissolved, dispersed, and no separation occurs during mixing.

[0102] In the present invention, the type of the solvent is not particularly limited, including any one or a combination of at least two of alcohol solvents, ether solvents, aromatic hydrocarbon solvents, ester solvents, ketone solvents, or nitrogen-containing solvents, preferably any one or a combination of at least two of acetone, butanone, methyl ethyl ketone, cyclohexanone, toluene, or xylene.

[0103] On the other hand, the present invention provides a prepreg, which includes a substrate and the resin composition as described above attached to the substrate by impregnation and drying.

[0104] The present invention has no particular limitation on the substrate. Preferably, the substrate includes any one of glass fiber cloth, organic fiber cloth, or glass fiber paper.

[0105] The glass fiber cloth includes Q-glass cloth, E-glass cloth, D-glass cloth, L-glass cloth, M-glass cloth, S-glass cloth, T-glass cloth, NE-glass cloth, etc.

[0106] The organic fiber cloth includes polyimide fiber cloth, polyamide fiber cloth, polyester fiber cloth, polyphenylene ether fiber cloth, liquid crystal polymer fiber cloth, etc.

[0107] Exemplarily, the method for preparing the prepreg is as follows: impregnating a substrate with the resin solution of the resin composition, and then drying to obtain the prepreg.

[0108] Preferably, the solvent in the resin solution is not particularly limited, and further preferably any one or a combination of at least two of acetone, methyl ethyl ketone, methyl ethyl ketone, cyclohexanone, toluene, or xylene.

[0109] Preferably, the drying temperature is 100-180°C, such as 105°C, 110°C, 115°C, 120°C, 125°C, 130°C, 135°C, 140°C, 145°C, 150°C, 155°C, 160°C, 165°C, 170°C, or 175°C, etc.

[0110] Preferably, the drying time is 1-10 min, such as 2 min, 3 min, 4 min, 5 min, 6 min, 7 min, 8 min, or 9 min, etc.

[0111] On the other hand, the present invention provides a metal foil-clad laminate, which includes at least 1 sheet of the prepreg as described above, and metal foil disposed on one or both sides of the prepreg.

[0112] The metal foil can be copper foil, aluminum foil, nickel foil, or alloy foil; preferably, the metal foil is copper foil.

[0113] Preferably, the number of prepregs in the metal foil-clad laminate is 1-20 sheets, such as 1 sheet, 3 sheets, 5 sheets, 7 sheets, 9 sheets, 10 sheets, 11 sheets, 13 sheets, 15 sheets, 17 sheets, or 19 sheets, etc.

[0114] Exemplarily, the method for preparing the metal foil-clad laminate is as follows: laminating metal foil on one or both sides of 1 sheet of prepreg and curing to obtain the metal foil-clad laminate; or, laminating at least 2 sheets of prepregs, and then laminating metal foil on one or both sides of the laminated prepregs and curing to obtain the metal-clad laminate.

[0115] Preferably, the curing is carried out in a press.

[0116] Preferably, the curing temperature is 200 - 250 °C, such as 205 °C, 210 °C, 212 °C, 215 °C, 218 °C, 220 °C, 223 °C, 225 °C, 228 °C, 230 °C, 235 °C, 240 °C or 245 °C, etc.

[0117] Preferably, the curing pressure is 10 - 60 kg / cm 2 , such as 15 kg / cm 2 , 20 kg / cm 2 , 25 kg / cm 2 , 30 kg / cm 2 , 35 kg / cm 2 , 40 kg / cm 2 , 45 kg / cm 2 , 50 kg / cm 2 or 55 kg / cm 2 etc.

[0118] Preferably, the curing time is 30 - 180 min, such as 40 min, 50 min, 60 min, 70 min, 80 min, 90 min, 100 min, 110 min, 120 min, 130 min, 140 min, 150 min, 160 min, 170 min or 175 min, etc.

[0119] On the other hand, the present invention provides a printed circuit board, which includes at least 1 sheet of the prepreg or the metal foil - clad laminate as described above.

[0120] Compared with the prior art, the present invention has the following beneficial effects:

[0121] In the present invention, the combination of component (A) and component (B) in the resin composition is such that the total weight of the addition reaction products with a weight - average molecular weight of 1100 - 20000 in component (A) accounts for 10 - 70% of component (A), thereby solving the defect in the prior art that low thermal expansion coefficient, low dielectric loss and low △D after thermal - oxygen treatment cannot co - exist. It endows the resin composition with a low in - plane thermal expansion coefficient, a low dielectric loss tangent and good heat - resistant oxygen aging characteristics, making the metal foil - clad laminate containing it have both a low in - plane thermal expansion coefficient, excellent dielectric properties and low △D after thermal - oxygen treatment f , especially suitable for high - speed packaging. f change. Detailed Embodiments

[0122] The technical solutions of the present invention will be further described below through specific embodiments. Those skilled in the art should understand that the embodiments are only for helping to understand the present invention and should not be regarded as specific limitations on the present invention.

[0123] Preparation Example 1

[0124] Preparation of an addition reactant (abbreviated as BMI A1) is as follows:

[0125] Add 15 parts by weight of a siloxane compound having two primary amino groups (X-22-161A of Shin-Etsu Chemical Co., Ltd.), 5 parts by weight of an amine compound having two primary amino groups (Kayahard A-A of Nippon Kayaku Co., Ltd., 3,3'-diethyl-4,4'-diaminodiphenylmethane), 80 parts by weight of a maleimide compound (BMI-4000 of Daiwa Chemical Industry Co., Ltd., 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane) and 100 parts by weight of propylene glycol monomethyl ether into a three-necked flask equipped with a thermometer, a stirring paddle and a reflux condenser. Stir and heat up to 115°C, then keep the temperature and continue the reaction. During the reaction, monitor the weight-average molecular weight of the addition reactant (BMI A1) by gel permeation chromatography (GPC, mobile phase: tetrahydrofuran). Stop the reaction when the total weight of the addition reactants with a weight-average molecular weight of 1100 - 20000 in BMI A1 accounts for 40% of component (A).

[0126] Preparation Example 2

[0127] Preparation of an addition reactant (hereinafter abbreviated as BMI A2) is as follows:

[0128] Add 7 parts by weight of a siloxane compound having two primary amino groups (X-22-161B of Shin-Etsu Chemical Co., Ltd.), 7 parts by weight of an amine compound having two primary amino groups (Tokyo Chemical Industry Co., Ltd., 2,2-bis(4-(4-aminophenoxy)phenyl)propane), 86 parts by weight of a maleimide compound (BMI-4000 of Daiwa Chemical Industry Co., Ltd., 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane) and 100 parts by weight of propylene glycol monomethyl ether into a three-necked flask equipped with a thermometer, a stirring paddle and a reflux condenser. Stir and heat up to 115°C, then keep the temperature and continue the reaction. During the reaction, monitor the weight-average molecular weight of the addition reactant (BMI A2) by gel permeation chromatography (GPC, mobile phase: tetrahydrofuran). Stop the reaction when the total weight of the addition reactants with a weight-average molecular weight of 1100 - 20000 in BMI A2 accounts for 20% of component (A).

[0129] Preparation Example 3

[0130] Preparation of an addition reactant (hereinafter abbreviated as BMI A3) is as follows:

[0131] In a three-necked flask equipped with a thermometer, a stirring paddle and a reflux condenser, 25 parts by weight of a siloxane compound having two primary amino groups (X-22-161A of Shin-Etsu Chemical Co., Ltd.), 5 parts by weight of an amine compound having two primary amino groups (Kayahard A-A of Nippon Kayaku Co., Ltd., 3,3'-diethyl-4,4'-diaminodiphenylmethane), 10 parts by weight of a maleimide compound (BMI-1000 of Daiwa Chemical Industry Co., Ltd., bis(4-maleimidophenyl)methane), 60 parts by weight of a maleimide compound (BMI-4000 of Daiwa Chemical Industry Co., Ltd., 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane) and 100 parts by weight of propylene glycol monomethyl ether were added. After stirring and heating to 115 °C, the mixture was kept warm and continuously reacted. During the reaction, the weight-average molecular weight of the addition reactant (BMI A3) was monitored by gel permeation chromatography (GPC, mobile phase: tetrahydrofuran). The reaction was stopped when the total weight of the addition reactants with a weight-average molecular weight of 1100 - 20000 in BMI A3 accounted for 40% of the component (A).

[0132] Preparation Example 4

[0133] Preparation of an addition reactant (hereinafter simply referred to as BMI A4), the preparation method is as follows:

[0134] In a three-necked flask equipped with a thermometer, a stirring paddle and a reflux condenser, 20 parts by weight of a siloxane compound having two primary amino groups (KF-8010 of Shin-Etsu Chemical Co., Ltd.), 80 parts by weight of a maleimide compound (BMI-1000 of Daiwa Chemical Industry Co., Ltd., bis(4-maleimidophenyl)methane) and 100 parts by weight of propylene glycol monomethyl ether were added. After stirring and heating to 115 °C, the mixture was kept warm and continuously reacted. During the reaction, the weight-average molecular weight of the addition reactant (BMI A4) was monitored by gel permeation chromatography (GPC, mobile phase: tetrahydrofuran). The reaction was stopped when the total weight of the addition reactants with a weight-average molecular weight of 1100 - 20000 in BMI A4 accounted for 60% of the component (A).

[0135] Comparative Preparation Example 1

[0136] Preparation of an addition reactant (hereinafter simply referred to as BMI C1), the preparation method is as follows:

[0137] In a three-necked flask equipped with a thermometer, a stirring paddle, and a reflux condenser, 10 parts by weight of an amine compound having two primary amino groups (Kayahard A-A of Nippon Kayaku Co., Ltd., 3,3'-diethyl-4,4'-diaminodiphenylmethane), 90 parts by weight of a maleimide compound (BMI-4000 of Daiwa Chemical Industry Co., Ltd., 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane), and 100 parts by weight of propylene glycol monomethyl ether were added. After stirring and heating to 115 °C, the mixture was kept warm and continuously reacted. During the reaction, the weight-average molecular weight of the addition reactant (BMI C1) was monitored by gel permeation chromatography (GPC, with tetrahydrofuran as the mobile phase). The reaction was stopped when the total weight of the addition reactants with a weight-average molecular weight of 1100 - 20000 in BMI C1 accounted for 20% of component (A).

[0138] Comparative Preparation Example 2

[0139] Preparation of an addition reactant (abbreviated as BMI C2), the preparation method is as follows:

[0140] BMI C2 was obtained in the same manner as in Preparation Example 1, except that the reaction was stopped when the total weight of the addition reactants with a weight-average molecular weight of 1100 - 20000 in BMI C2 accounted for 5% of component (A).

[0141] Comparative Preparation Example 3

[0142] Preparation of an addition reactant (abbreviated as BMI C3), the preparation method is as follows:

[0143] BMI C3 was obtained in the same manner as in Preparation Example 4, except that the reaction was stopped when the total weight of the addition reactants with a weight-average molecular weight of 1100 - 20000 in BMI C3 accounted for 75% of component (A).

[0144] The experimental materials involved in the following examples and comparative examples of the present invention include:

[0145] 1) Component (A):

[0146] BMI A1, Preparation Example 1;

[0147] BMI A2, Preparation Example 2;

[0148] BMI A3, Preparation Example 3;

[0149] BMI A4, Preparation Example 4;

[0150] BMI C1, Comparative Preparation Example 1;

[0151] BMI C2, Comparative Preparation Example 2;

[0152] BMI C3, Comparative Preparation Example 3;

[0153] 2) Component (B): Thermosetting resin

[0154] OPE-2st 2200, a polyphenylene ether having vinylbenzyl groups at its terminals, Mitsubishi Chemical Corporation;

[0155] PT-30, a phenolic cyanate ester resin, Lonza;

[0156] NC-3000H, a biphenyl epoxy resin, Nippon Kayaku Co., Ltd.;

[0157] 3) Component (C): Polyolefin resin

[0158] Tuftec H1051, a hydrogenated styrene-butadiene copolymer, Asahi Kasei Chemicals Corporation;

[0159] 4) Component (D): Curing accelerator

[0160] Triginox 311, 3,3,5,7,7-pentamethyl-1,2,4-trioxapane, Akzo Nobel N.V.;

[0161] 2PZ, 2-phenylimidazole, Shikoku Kasei Co., Ltd.;

[0162] 5) Component (E): Inorganic filler

[0163] SC2300-SVJ, spherical silica surface-treated with a vinylsilane coupling agent, median particle size D 50 is 0.5 μm, Admatechs Co., Ltd.;

[0164] SC2300-SEJ, spherical silica surface-treated with an epoxy group-containing silane coupling agent, median particle size D 50 is 0.5 μm, Admatechs Co., Ltd.;

[0165] 6) Component (F): Coupling agent

[0166] KBM-573, N-phenyl-3-aminopropyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd.;

[0167] 7) Component (A’):

[0168] A biphenyl polymaleimide compound, MIR-3000-70MT, Nippon Kayaku Co., Ltd.

[0169] Example 1

[0170] This embodiment provides a resin composition, which comprises the following components by weight: (A) 70 parts of BMI A1, (B) 30 parts of unsaturated bond-containing polyphenylene ether OPE-2st 2200, 1 part of curing accelerator Triginox 311, 2 parts of coupling agent KBM-573, and 150 parts of inorganic filler SC2300-SVJ.

[0171] This embodiment also provides a metal-clad laminate, and the specific preparation method is as follows:

[0172] (1) Mix the resin composition provided in this embodiment, toluene, and methyl ethyl ketone, fully dissolve and disperse them evenly to obtain a resin solution with a solid content of 60%;

[0173] (2) Impregnate a glass fiber cloth (Low Dk 3313 manufactured by Hubbell) with the resin solution obtained in step (1), and heat and dry it in a forced-air oven at 130 °C for 4 min to convert the resin composition in the varnish state into a resin composition in a semi-cured state, obtaining a prepreg with a thickness controlled to be 0.10 mm;

[0174] (3) Stack 2 pieces of the prepreg obtained in step (2), press and laminate an electrolytic copper foil with a thickness of 12 μm on its upper and lower sides, and cure at 220 °C and 45 kg / cm 2 for 2 h to obtain a metal-clad laminate with a core board thickness of 0.20 mm.

[0175] After etching the copper foil of the above metal-clad laminate, a laminate with a thickness of 0.20 mm is obtained.

[0176] Examples 2 to 6, Comparative Examples 1 to 4

[0177] A resin composition, the components and their contents are shown in Tables 1 - 2; the dosage unit of each component in Tables 1 - 2 is "part".

[0178] Table 1

[0179]

[0180] Table 2

[0181]

[0182] Manufacture the above resin composition into a metal-clad laminate according to the method in Example 1, and the test method for the performance of the laminate is as follows:

[0183] (1) Coefficient of thermal expansion in the plane (XY-CTE): A laminate with a length of 60 mm, a width of 4 mm, and a thickness of 0.20 mm was used as a sample. The direction of the glass fiber warp was the Y direction, and the direction of the glass fiber weft was the X direction. After drying the sample in an oven at 105°C for 1 h, it was cooled to room temperature in a desiccator. The measurement was carried out using the thermomechanical analysis method (TMA) with a heating rate of 10°C / min, heating from room temperature to 260°C, and two heating runs were performed. The coefficient of thermal expansion in the plane direction from 60°C to 120°C during the second heating run was taken as the result, with the unit of ppm / °C.

[0184] (2) Dielectric loss tangent (D f ): A laminate with a length of 100 mm, a width of 100 mm, and a thickness of 0.20 mm was used as a sample. After ultrasonic cleaning the surface impurities of the sample in deionized water, it was dried in an oven at 105°C for 1 h and then cooled to room temperature in a desiccator. The dielectric loss tangent (D f ) at a frequency of 10 GHz was measured using a cavity resonator device;

[0185] Dielectric loss tangent (Df) after thermo-oxidative treatment: For the sample used to measure the dielectric loss tangent (D f ), after baking at 125°C for 500 hours (thermo-oxidative treatment condition 1), the dielectric loss tangent (D f ) at a frequency of 10 GHz was measured using a cavity resonator device;

[0186] Dielectric loss tangent (D f ) after thermo-oxidative treatment: For the sample used to measure the dielectric loss tangent (Df), after baking at 150°C for 720 hours (thermo-oxidative treatment condition 2), the dielectric loss tangent (D f ) at a frequency of 10 GHz was measured using a cavity resonator device;

[0187] △D f : Dielectric loss tangent (D f ) after thermo-oxidative treatment - dielectric loss tangent (D f ) before thermo-oxidative treatment.

[0188] Regarding the change amount of △D f , those less than or equal to 0.001 are denoted as "A", those greater than 0.001 and less than or equal to 0.002 are denoted as "B", those greater than 0.002 and less than or equal to 0.003 are denoted as "C", and those greater than 0.003 are denoted as "D". The smaller the change amount of △D f , the better the heat-aging resistance characteristics of the material.

[0189] The performance test results are shown in Table 3:

[0190] Table 3

[0191]

[0192] According to the performance test data in Table 3, in Examples 1-6 of the present invention, the XY-CTE of the laminate prepared from the resin composition is 12.8 ppm / °C or less, and D f (10 GHz) is 0.0061 or less. Even after baking at 150 °C for 720 hours under severe conditions (thermal oxidation treatment condition 2), the change amount ΔD of the dielectric loss tangent f is also 0.002 or less, and some are even 0.001 or less. The prepared laminate has excellent low planar thermal expansion coefficient, low dielectric loss tangent, and good heat and oxygen aging resistance. In the addition reactant (A) of Comparative Example 1, the siloxane compound a2 containing at least 2 primary amino groups in one molecule was not used, resulting in a significant increase in the XY-CTE of the laminate. At the same time, after severe thermal oxidation treatment condition 2, the change amount ΔD of the dielectric loss tangent f can only be 0.003 or less; in Comparative Examples 2 and 3, since the total weight of the addition reactants with a weight average molecular weight of 1100-20000 in component (A) does not fall within the scope of the present invention, the processability is poor and laminates cannot be prepared; in Comparative Example 4, the use of a biphenyl polyimide compound results in a significant increase in the XY-CTE of the laminate, and the change range of the dielectric loss tangent after thermal oxidation treatment conditions is large. Especially after more severe thermal oxidation treatment condition 2, the change amount ΔD of the dielectric loss tangent f is greater than 0.003.

[0193] The applicant declares that the present invention uses the above examples to illustrate the resin composition of the present invention and the prepreg and metal-clad laminate containing the same. However, the present invention is not limited to the above process steps, that is, it does not mean that the present invention must rely on the above process steps to be implemented. Those skilled in the art should understand that any improvement to the present invention, the equivalent replacement of the raw materials selected for the present invention, the addition of auxiliary components, and the selection of specific methods, etc., all fall within the protection scope and the disclosure scope of the present invention.

Claims

1. A resin composition, characterized in that, The resin composition comprises the following components: an addition reaction product (A) of a maleimide compound a1 containing at least 2 N-substituted maleimide groups in one molecule and a siloxane compound a2 containing at least 2 primary amino groups in one molecule, and a thermosetting resin (B); The total weight of the addition reaction products having a weight average molecular weight of 1100 to 20000 in component (A) accounts for 10 to 70% of component (A).

2. The resin composition according to claim 1, characterized in that, The weight of the siloxane compound a2 containing at least 2 primary amino groups in one molecule accounts for 2 to 30% of the addition reaction product (A).

3. The resin composition according to claim 1 or 2, characterized in that The addition reaction product (A) is an addition reaction product of a maleimide compound a1 containing at least 2 N-substituted maleimide groups in one molecule, a siloxane compound a2 containing at least 2 primary amino groups in one molecule, and an amine compound a3 containing at least 2 primary amino groups in one molecule; Preferably, the maleimide compound a1 containing at least 2 N-substituted maleimide groups in one molecule is selected from any one or a combination of at least two of N,N'-ethylenebismaleimide, N,N'-hexamethylenebismaleimide, N,N'-(1,3-phenylene)bismaleimide, N,N'-(1,3-(2-methylphenylene))bismaleimide, N,N'-(1,3-(4-methylphenylene))bismaleimide, N,N'-(1,4-phenylene)bismaleimide, bis(4-maleimidophenyl)methane, bis(3-methyl-4-maleimidophenyl)methane, bis(3,5-dimethyl-4-maleimidophenyl)methane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, bis(3-ethyl-4-maleimidophenyl)methane, bis(3,5-diethyl-4-maleimidophenyl)methane, bis(4-maleimidophenyl)ether, bis(4-maleimidophenyl)ketone, bis(4-maleimidophenyl)sulfone, bis(4-maleimidocyclohexyl)methane, 1,4-bis(4-maleimidophenyl)cyclohexane, 1,4-bis(maleimidomethyl)cyclohexane, 1,4-bis(maleimidomethyl)benzene, 1,3-bis(4-maleimidophenoxy)benzene, 1,3-bis(3-maleimidophenoxy)benzene, bis(4-(3-maleimidophenoxy)phenyl)methane, bis(4-(4-maleimidophenoxy)phenyl)methane, 1,1-bis(4-(3-maleimidophenoxy)phenyl)ethane, 1,1-bis(4-(4-maleimidophenoxy)phenyl)ethane, 1,2-bis(4-(3-maleimidophenoxy)phenyl)ethane, 1,2-bis(4-(4-maleimidophenoxy)phenyl)ethane, 2,2-bis(4-(3-maleimidophenoxy)phenyl)propane, 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane, 2,2-bis(4-(3-maleimidophenoxy)phenyl)butane, 2,2-bis(4-(4-maleimidophenoxy)phenyl)butane, 4,4'-bis(3-maleimidophenoxy)biphenyl, 4,4'-bis(4-maleimidophenoxy)biphenyl, bis(4-(3-maleimidophenoxy)phenyl)ketone, bis(4-(4-maleimidophenoxy)phenyl)ketone, bis(4-(3-maleimidophenoxy)phenyl)ether, bis(4-(4-maleimidophenoxy)phenyl)ether, polyphenylmethane maleimide, 1,6-bis(maleimide)-(2,2,4-trimethyl)hexane, and long-chain alkyl-based bismaleimide.

4. The resin composition according to any one of claims 1 to 3, characterized in that The thermosetting resin (B) is selected from any one or a combination of at least two of epoxy resin, cyanate resin, hydrocarbon resin, polyphenylene ether resin, a crosslinking agent having a carbon-carbon unsaturated double bond in the molecule, and other maleimide compounds; Preferably, the polyphenylene ether resin is a polyphenylene ether having unsaturated groups at its ends; Preferably, the unsaturated group includes any one or a combination of at least two of vinylbenzyl, vinylphenyl or acrylate groups.

5. The resin composition according to any one of claims 1 to 4, characterized in that, In the resin composition by weight, the content of the addition reactant (A) is 10 to 90 parts, and the content of the thermosetting resin (B) is 10 to 80 parts.

6. The resin composition according to any one of claims 1-5, characterized in that, The resin composition further includes one or a combination of at least two of a polyolefin resin (C), a curing accelerator (D) and an inorganic filler (E); Preferably, in the resin composition by weight, the content of the polyolefin resin (C) is 5 to 30 parts; Preferably, in the resin composition by weight, the content of the curing accelerator (D) is 0.01 to 5 parts; Preferably, in the resin composition by weight, the content of the inorganic filler (E) is 5 to 250 parts.

7. A resin glue solution, characterized in that, The resin glue solution is obtained by dissolving or dispersing the resin composition according to any one of claims 1-6 in a solvent.

8. A prepreg, characterized in that, The prepreg includes a substrate, and the resin composition according to claims 1-6 attached to the substrate by impregnation and drying.

9. A metal foil clad laminate, the metal foil clad laminate includes at least 1 sheet of the prepreg according to claim 8, and metal foils provided on one or both sides of the prepreg.

10. A printed circuit board, the printed circuit board includes at least 1 sheet of the prepreg according to claim 8 or the metal foil clad laminate as described above.

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