Resin composition, prepreg containing same, and metal-clad laminate

Abstract

Provided in the present invention are a resin composition, a prepreg containing same, and a metal-clad laminate. The resin composition comprises the following components: an addition reaction product (A) of a maleimide compound a1 that contains at least two N-substituted maleimide groups per molecule and a siloxane compound a2 that contains at least two primary amino groups per molecule; and a thermosetting resin (B), wherein in the component (A), the weight of the addition reaction product with the weight average molecular weight of 1100-20000 accounts for 10-70% of the weight of the component (A). The resin composition of the present invention has a low in-plane coefficient of thermal expansion and low dielectric loss, and involves low changes on △Df after thermal oxidization treatment, and thus is particularly suitable for high-frequency and high-speed packaging.

Description

Resin composition, prepreg and metal foil-clad laminate containing the same Technical Field

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

[0002] In recent years, information technology has entered a phase of high-speed signaling and high-frequency transmission. To keep pace with the ever-increasing amount of data being processed, the frequency of electronic devices has continued to increase, placing higher demands on the electrical performance of substrates to minimize high-frequency signal loss and latency. With the advent of the 5G era, applications such as high-frequency RF (such as PA, WiGig, WiHD / 60GHz), large-size chips, and DDR5 (3.2-6.4Gbps) are placing even higher demands on the performance of packaging substrate materials: low in-plane thermal expansion coefficient and even lower dielectric loss tangent.

[0003] Bismaleimide (BMI) resin is a traditional encapsulation substrate resin system with high monomer activity, no molecular release during polymerization, stable finished product performance, and the ability to maintain high physical and mechanical properties over a wide temperature range. CN109825081A discloses a thermosetting resin composition comprising the following components: a combination of a bismaleimide resin and a benzoxazine resin or a prepolymer of a bismaleimide resin and a benzoxazine resin, an epoxy resin, and an active ester. The metal-clad laminate prepared from this resin composition has a high glass transition temperature, a low thermal expansion coefficient, a high high-temperature modulus, and good heat resistance. However, the cured product of the maleimide resin system is brittle, has a short shelf life, and exhibits poor dielectric loss tangent performance, thus limiting its application in high-frequency and high-speed electronic products.

[0004] The current mainstream high-speed, low dielectric loss tangent resin system usually includes polyphenylene ether resin. The molecular structure of polyphenylene ether resin contains benzene rings, which gives it good physical and mechanical properties, as well as a low dielectric constant and dielectric loss tangent. However, polyphenylene ether resin is a thermoplastic resin and has problems such as high melting point, poor processing performance, and poor solvent resistance. Therefore, polyphenylene ether needs to be modified in actual use. CN109988298A discloses a modified polyphenylene ether resin, a thermosetting resin composition, and their uses. The modified polyphenylene ether resin is a resin structure obtained by reacting a low-molecular-weight, double-terminated hydroxyl polyphenylene ether with a diacyl halide or dicarboxylic acid containing specific structural units, a monofunctional aromatic phenol, a monofunctional aromatic acyl halide, or a monofunctional aromatic carboxylic acid. Prepregs, circuit boards, and laminated films made from this thermosetting resin composition have low dielectric constants, low dielectric loss tangents, and good heat resistance. However, the presence of incompletely reacted hydroxyl groups in the polyphenylene ether resin system containing terminal hydroxyl groups increases the water absorption of the prepreg or circuit board during use, reducing its moisture and heat resistance, and affecting the reliability of the board.

[0005] Polyolefin resins have excellent toughness and dielectric properties, and combining them with polyphenylene ether resins can improve overall performance. CN111154197A discloses a polyolefin resin composition comprising 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 polyolefin resin composition, used as a resin matrix to impregnate fiberglass cloth, produces a copper-clad laminate with a low dielectric constant and dielectric loss tangent, as well as good peel strength. However, the polyolefin resin composition has a high coefficient of thermal expansion and poor dimensional stability, making it difficult to meet the performance requirements of high-frequency devices for packaging substrates.

[0006] At the same time, as the chip size increases and the operating frequency increases, the low △D f These changes have put forward the requirement that the substrate can still maintain low dielectric properties after experiencing high-temperature environments, but existing packaging substrates are difficult to meet this requirement.

[0007] Therefore, a novel dielectric material with excellent dielectric properties and low △D after thermal oxidation treatment was developed. f Resin materials with variable and low thermal expansion coefficients are the research focus in this field.

[0008] Summary of the Invention

[0009] In view of the shortcomings of the prior art, the present invention aims to provide a resin composition and a prepreg and a metal foil-clad laminate comprising the same, wherein the resin composition has a low planar thermal expansion coefficient and low dielectric loss, and a low ΔD after thermal oxidation treatment. fChanges, especially suitable for high frequency and high speed packaging.

[0010] In order to achieve the purpose of the invention, the present invention adopts the following technical solutions:

[0011] 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);

[0012] The total weight of the addition reactants having a weight average molecular weight of 1,100 to 20,000 in the (A) component accounts for 10 to 70% of the (A) component.

[0013] 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) is ensured to account 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.

[0014] In the present invention, the total weight of the addition reactants with a weight average molecular weight of 1100 to 20000 in component (A) of the resin composition accounts for 10 to 70% (the weight average molecular weight can be measured according to GB / T21863-2008 and determined 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 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 percentage of component (A), the processability will deteriorate, and there will even be a tendency for resin precipitation in the resin glue; 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 percentage of component (A), 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 and processed.

[0015] In the present invention, the addition reaction product (A) 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 in-plane thermal expansion coefficient.

[0016] Preferably, the weight of the siloxane compound a2 containing at least two primary amino groups per molecule accounts for 2 to 30% of the addition reactant (A), for example, 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 per molecule in the addition reactant (A) is less than 2%, it will result in a decrease in CTE and ΔD after thermal oxidation treatment. f If the percentage of the siloxane compound a2 containing at least two primary amino groups in one molecule of the addition reactant (A) is greater than 30%, the processability will deteriorate and the Tg will be reduced.

[0017] Preferably, the addition reactant (A) is an addition reactant 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.

[0018] In the present invention, when the raw materials for preparing the addition reactant (A) are added with an amine compound a3 containing at least two primary amino groups in one molecule, it is beneficial to adjust the processability.

[0019] Preferably, the primary amine value of component (A) is 0.10 to 1.00 mmol / g, for example, 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., and the primary amine value can be determined by potassium hydrogen phthalate titration. Due to the specific content of primary amine value in 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 component (A) will be rapidly shortened during storage, thereby affecting the timeliness of use of component (A) in the resin composition; if the primary amine value is too low, resin will precipitate from component (A) during storage, also affecting the timeliness of use of component (A) in the resin composition.

[0020] In the present invention, the primary amine value can be measured by the following method: preparing a 0.1 mol / L perchloric acid-acetic acid solution, standardizing the concentration with potassium hydrogen phthalate, and calculating C; taking an addition reaction product of a maleimide compound a1 containing at least two N-substituted maleimide groups per molecule and an amine compound a2 containing at least two primary amino groups per molecule with a solid content of A, adding 50 mL of acetic acid and 5 mL of acetone, and stirring until completely mixed; using an automatic potentiometric titrator, titrating with the standard concentration of the perchloric acid-acetic acid solution, and recording the volume of solvent consumed at the endpoint, and calculating V; primary amine value = 10 × C × V / M / A, unit: mmol / g.

[0021] In the present invention, there is no particular limitation on the specific examples of the maleimide compound a1, as long as it is a maleimide compound containing at least two N-substituted maleimide groups in one molecule, and illustratively 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, imide, 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)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)ethane 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) any one or a combination of at least two of the following: aminophenoxy)phenyl)ketone, bis(4-(4-maleimidophenoxy)phenyl)ketone, bis(4-(3-maleimidophenoxy)phenyl)ether, bis(4-(4-maleimidophenoxy)phenyl)ether, polyphenylmethanemaleimide, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, and long-chain alkyl bismaleimides.

[0022] 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):

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

[0024] Preferably, A1 is selected from the group represented by formula (1), formula (2), formula (3) or formula (4).

[0025] In formula (1), 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 selected from an integer of 0 to 4 (e.g., 0, 1, 2, 3, or 4);

[0026] The aliphatic hydrocarbon group having 1 to 5 carbon atoms can be selected, for example, 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 or ethyl;

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

[0028] In formula (2), R 2a 、R 2b 、R 3a 、R 3b Each is 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, and qb are each independently selected from an integer of 0 to 4 (e.g., 0, 1, 2, 3, or 4), and pa+pb≤4, qa+qb≤4;

[0029] The aliphatic hydrocarbon group having 1 to 5 carbon atoms can be selected, for example, 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 or ethyl;

[0030] As the linear or branched alkylene group having 1 to 5 carbon atoms, for example, it can 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 a methylene group;

[0031] As the straight-chain or branched alkylidene group having 2 to 5 carbon atoms, for example, it can be selected from ethylidene, propylidene, isopropylidene, butylidene, isobutylidene, pentylidene, isopentylidene, preferably isopropylidene;

[0032] 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 having both 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 greater than 2, multiple R 2a Each other, R 2b Each other, R 3a Each other or R 3b They can be the same or different from each other;

[0033] In formula (2-1), R 4a 、R 4b 、R 5a 、R 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 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, or a single bond; ka, kb, la, and lb are each independently selected from an integer of 0 to 4 (e.g., 0, 1, 2, 3, or 4), and ka+kb≤4, la+lb≤4;

[0034] The aliphatic hydrocarbon group having 1 to 5 carbon atoms can be selected, for example, 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 or ethyl;

[0035] As the linear or branched alkylene group having 1 to 5 carbon atoms, for example, it can 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 a methylene group;

[0036] As the straight-chain or branched alkylidene group having 2 to 5 carbon atoms, for example, it can be selected from ethylidene, propylidene, isopropylidene, butylidene, isobutylidene, pentylidene, isopentylidene, preferably isopropylidene;

[0037] 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 having both 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 greater than 2, multiple R 4a Each other, R 4b Each other, R 5a Each other or R 5b They can be the same or different from each other;

[0038] In formula (2-2), 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 selected from an integer of 0 to 4;

[0039] The aliphatic hydrocarbon group having 1 to 5 carbon atoms can be selected, for example, 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 or ethyl;

[0040] 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 greater, a plurality of R8s may be the same as or different from each other.

[0041] In formula (3), m is an integer selected from 1 to 10. From the viewpoint of availability, m is preferably an integer of 1 to 5, and more preferably an integer of 1 to 3.

[0042] 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 selected from an integer of 1 to 10;

[0043] The aliphatic hydrocarbon group having 1 to 5 carbon atoms can be selected, for example, 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 or ethyl;

[0044] From the perspective of lower CTE, n is preferably an integer of 1 to 8, more preferably an integer of 1 to 3, and even more preferably 1. When n is an integer of 2 or greater, multiple R6s or multiple R7s may be the same or different.

[0045] 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 access bonds of the group, not the methyl group.

[0046] Preferably, the maleimide compound a1 contains two N-substituted maleimide groups in one molecule, which can impart better solubility to the addition reactant (A).

[0047] From the perspective of better processability, CTE, and dielectric properties, the maleimide compound a1 is further preferably 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, or a combination of at least two thereof.

[0048] The maleimide compound a1 may be used alone or in combination of at least two.

[0049] In the present invention, the siloxane compound a2 containing at least two primary amino groups in one molecule is not particularly limited, as long as it contains at least two primary amino groups in one molecule and contains a siloxane segment in its molecular structure. Preferably, the siloxane compound a2 containing at least two primary amino groups in one molecule contains a divalent organic group represented by formula (I-2) in its molecular structure:

[0050] In formula (I-2), R9, R 10 、R 11 、R 12 、R 13 、R 14 Each is 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 a divalent organic group, and r is selected from an integer of 1 to 100;

[0051] The aliphatic hydrocarbon group having 1 to 5 carbon atoms can be selected, for example, 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 a methyl group;

[0052] As the aryl group, illustratively, it can be selected from phenyl, biphenyl, naphthyl, etc., preferably phenyl;

[0053] The substituted aryl group may be exemplarily selected from substituted phenyl, substituted biphenyl, substituted naphthyl, etc., preferably substituted phenyl; the substituent of the aryl group in the substituted aryl group may be exemplarily selected 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.; the aliphatic hydrocarbon groups having 1 to 5 carbon atoms may be exemplarily selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, etc.; the alkenyl groups having 2 to 5 carbon atoms may be exemplarily selected from vinyl, allyl, etc.; the alkynyl groups having 2 to 5 carbon atoms may be exemplarily selected from ethynyl, propargyl, etc.

[0054] The divalent organic group independently selected from A4 and A5 may be exemplarily selected from an alkylene group, an alkenylene group, an alkynylene group, an arylene group, -O-, or a divalent linking group formed by a combination thereof; the alkylene group may be exemplarily selected from an alkylene group having 1 to 10 carbon atoms, such as a methylene group, an ethylene group, and a propylene group; the alkenylene group may be exemplarily selected from an alkenylene group having 2 to 10 carbon atoms; the alkynylene group may be exemplarily selected from an alkynylene group having 2 to 10 carbon atoms; the arylene group may be exemplarily selected from an arylene group having 6 to 20 carbon atoms, such as a phenylene group and a naphthylene group; the divalent organic group independently selected from A4 and A5 is preferably an alkylene group or an arylene group, and more preferably an alkylene group;

[0055] r is preferably an integer of 1 to 50, more preferably an integer of 3 to 40, and even more preferably an integer of 5 to 40. When r is an integer of 2 or more, a plurality of R9s or a plurality of R 10 They may be the same as or different from each other.

[0056] In the present invention, the functional group equivalent weight of the siloxane compound a2 containing at least two primary amino groups in one molecule is not particularly limited, but is preferably 100 to 6000 g / mol, more preferably 300 to 3000 g / mol, more preferably 400 to 2000 g / mol, and most preferably 600 to 2000 g / mol.

[0057] Preferably, the siloxane compound a2 containing at least two primary amino groups in one molecule includes a siloxane compound containing two primary amino groups at the molecular terminals.

[0058] In the present invention, the siloxane compound a2 containing at least two primary amino groups in one molecule can be a commercially available product, including but 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 800 g / mol), and X-22-161B (side chain methyl type) of Shin-Etsu Chemical Co., Ltd. base type, functional group equivalent 1500g / mol), KF-8012 (side chain methyl type, functional group equivalent 2200g / mol), KF-8008 (side chain methyl type, functional group equivalent 5700g / mol), X-22-1660B-3 (side chain phenyl type, functional group equivalent 2200g / mol) or X-22-9409 (side chain phenyl type, functional group equivalent 670g / mol) or a combination of at least two thereof.

[0059] The addition reaction of 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 more preferably used.

[0060] In the present invention, the temperature of the addition reaction of 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 react. As a preferred technical solution of the present invention, from the perspective of reaction rate and solvent boiling point, preferably, the temperature of the addition reaction is 100-130°C, for example, 102°C, 105°C, 108°C, 110°C, 112°C, 115°C, 118°C, 120°C, 122°C, 125°C or 128°C.

[0061] In the present invention, the addition reaction time of 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 addition reaction time is 2 to 10 hours, for example, it can be 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours, 7.5 hours, 8 hours, 8.5 hours, 9 hours, 9.5 hours, etc., and more preferably 3 to 8 hours.

[0062] In the present invention, the amine compound a3 containing at least two primary amino groups in one molecule is not particularly limited. Preferably, the amine compound a3 containing at least two primary amino groups in one molecule is selected from 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'-diaminodiphenylmethane, -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 -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'-dihydroxy further preferably 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) or a combination of at least two of 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diaminodiphenylmethane or 2,2-bis(4-(4-aminophenoxy)phenyl)propane.

[0063] 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 resins, hydrocarbon resins, polyphenylene ether resins, cross-linking agents having carbon-carbon unsaturated double bonds in the molecule, and other maleimide compounds.

[0064] Preferably, the polyphenylene ether resin is a polyphenylene ether containing an unsaturated group at the end;

[0065] Preferably, the unsaturated group includes any one of vinylbenzyl, vinylphenyl or acrylate groups, or a combination of at least two of them.

[0066] In the present invention, the structural formula of the vinylbenzyl group is Dashed lines represent the attachment sites of the groups.

[0067] The structural formula of the acrylate group is The dotted line represents the attachment site of the group; R3 is selected from hydrogen, C1-C20 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, C10, C12, C14, C16, C18 or C19, etc.) straight chain or branched chain alkyl, more preferably hydrogen, C1-C10 straight chain or branched chain alkyl.

[0068] The acrylic acid ester group is further preferably an acrylate group or a methacrylate group.

[0069] As a preferred technical solution of the present invention, the unsaturated bond-containing polyphenylene ether of component (B) is a polyphenylene ether containing a vinyl benzyl group at the end, which is more conducive to improving the dielectric properties and heat resistance of the resin composition. The polyphenylene ether containing a vinyl benzyl group at the end can be a commercially available product, illustratively including but not limited to: OPE-2st 1200 (number average molecular weight M n 1200) and / or OPE-2st 2200 (number average molecular weight M n The number average molecular weight can be measured according to GB / T 21863-2008 and determined by gel permeation chromatography (GPC) based on polystyrene calibration.

[0070] In the resin composition of the present invention, the content of the addition reactant (A) is 10 to 90 parts by weight, for example, 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, the content of the thermosetting resin (B) is 10 to 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.

[0071] The “parts” and “parts by weight” involved in the present invention are all calculated based on solid content and do not include solvents, dispersants, etc.

[0072] Preferably, the resin composition further comprises one or a combination of at least two of a polyolefin resin (C), a curing accelerator (D) and an inorganic filler (E).

[0073] As a preferred technical solution of the present invention, the polyolefin resin helps improve the dielectric properties of the resin composition. However, if the polyolefin resin content is too high, the adhesion between the resin composition and the metal foil is reduced, and the melt flowability of the resin composition is reduced, which is not conducive to preparing a resin composition with uniform thickness.

[0074] 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 comprising an olefin structural unit and a styrene structural unit. The olefin structural unit is derived from an olefin monomer, such as a structural unit derived from butadiene, a structural unit derived from isoprene, etc.; the styrene structural unit is derived from a styrene monomer, such as a structural unit derived from styrene, a structural unit derived from styrene with a substituent, etc. In addition to containing structural units derived from olefin structural units and styrene structural units, the styrene copolymer may also contain structural units other than olefin structural units and styrene structural units, such as structural units derived from epoxy groups, structural units derived from amino groups, structural units derived from maleic anhydride, etc.

[0075] 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 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 blocks are arranged. The olefin block is composed of a plurality of olefin structural units, and the styrene block is composed of a plurality of styrene structural units.

[0076] The structural units derived from olefins in the polyolefin resin may be hydrogenated or partially hydrogenated. Based on considerations of dielectric properties, the structural units derived from olefins in the polyolefin resin may preferably be hydrogenated.

[0077] The polyolefin resin may be a commercially available product, illustratively including but 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 styrene content of 42% by mass, Asahi Kasei Chemicals Corporation), or Tuftec M1913 (hydrogenated styrene-butadiene copolymer with maleic anhydride structural units, with a styrene content of 30% by mass, Asahi Kasei Chemicals Corporation).

[0078] Preferably, the resin composition contains 5 to 30 parts of polyolefin resin (C) by weight, for example, 6 parts, 8 parts, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts or 28 parts.

[0079] In the present invention, the curing accelerator (D) is not particularly limited. Preferably, the curing accelerator (D) includes any one of an acidic curing accelerator, an organophosphorus curing accelerator, an imidazole curing accelerator, a pyridine curing accelerator, an amine curing accelerator, a peroxide or an organic metal salt, or a combination of at least two thereof.

[0080] For example, the acidic curing accelerator includes p-toluenesulfonic acid, the organophosphorus curing accelerator includes triphenylphosphine, the imidazole curing accelerator includes imidazole or an imidazole derivative (e.g., 2-ethyl-4-methylimidazole), the pyridine curing accelerator includes pyridine or a pyridine derivative (e.g., 4-dimethylaminopyridine), the amine curing accelerator includes a secondary amine compound, a tertiary amine compound, or a quaternary ammonium salt, the peroxide includes dicumyl peroxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexyne-3, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, or α,α'-bis(tert-butylperoxy)diisopropylbenzene, and the organometallic salt includes zinc naphthenate, cobalt naphthenate, tin octoate, or cobalt octoate. The curing accelerators may be used alone or in combination of at least two.

[0081] Preferably, the resin composition contains 0.01 to 5 parts of curing accelerator (D) by weight, 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.

[0082] Preferably, the present invention is not particularly limited to the type of inorganic filler (E), and illustratively includes: silicon dioxide, 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 silicon powder, glass powder, short glass fiber or hollow glass any one or at least two combinations. In order to make the resin composition have higher heat resistance, resistance to moisture and heat and dimensional stability, it is preferably silicon dioxide, aluminum hydroxide, magnesium hydroxide, boehmite, boron nitride, aluminum nitride, silicon carbide, aluminum oxide, composite silicon powder, glass powder, short glass fiber or hollow glass any one or at least two combinations. Wherein, the silicon dioxide can be crystalline silica, fused silica, amorphous silica, spherical silica or hollow silica, etc., more preferably spherical silica.

[0083] The average particle size of the inorganic filler (D 50 ) is not particularly limited, but from the perspective of dispersibility, the average particle size (D 50 ) is preferably 0.01-20 μm, for example, 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, more preferably 0.1-10 μm. Inorganic fillers of different types, different particle size distributions or different average particle sizes can be used alone or in combination as needed.

[0084] Preferably, the resin composition is measured in parts by weight, and the content of the inorganic filler (E) is 5 to 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. The inorganic filler helps to improve the heat resistance, moisture resistance and mechanical properties of the resin composition and reduce the thermal expansion coefficient. If the amount of inorganic filler is too much, the dielectric loss tangent of the resin composition will increase, which is not conducive to signal transmission.

[0085] Preferably, the resin composition further comprises 0.01 to 10 parts of a coupling agent (F) by weight, for example, the coupling agent may be 0.03, 0.05, 0.1, 0.3, 0.5, 1, 2, 3, 4, 5, 6, 7, 8 or 9 parts, etc., more preferably 0.1 to 6 parts of a coupling agent; the coupling agent helps to improve the compatibility of the inorganic filler and the resin composition.

[0086] Preferably, the coupling agent comprises a silane coupling agent.

[0087] The present invention does not particularly limit the type of silane coupling agent, and illustratively, it can be any one or a combination of at least two of epoxy silane coupling agents, amino silane coupling agents, vinyl silane coupling agents, styrene silane coupling agents, isobutylene silane coupling agents, acrylic silane coupling agents, urea silane coupling agents, mercapto silane coupling agents, chloropropyl silane coupling agents, sulfide silane coupling agents, or isocyanate silane coupling agents.

[0088] Preferably, the resin composition further comprises a flame retardant (G). The flame retardant is not particularly limited and can be selected from halogen or non-halogen flame retardants that are soluble or insoluble in an organic solvent. Exemplarily, the non-halogen flame retardant includes an inorganic phosphorus flame retardant, an organic phosphorus flame retardant, a metal hydrate, and the like.

[0089] From the perspectives of environmental issues and excellent dielectric properties, flame retardants are preferably organophosphorus flame retardants. Exemplary organophosphorus flame retardants include aromatic phosphates, monosubstituted phosphonic acid diesters, disubstituted phosphinates, metal salts of disubstituted phosphinic acids, organic nitrogen-containing phosphorus compounds, and cyclic organophosphorus compounds.

[0090] For example, the aromatic phosphates include triphenyl phosphate, tricresyl phosphate, tri(xylene) phosphate, cresyl diphenyl phosphate, cresyl di-2,6-xylene phosphate, resorcinol bis(diphenyl phosphate), 1,3-phenylene bis(di(2,6-dimethylphenyl) phosphate), 4,4'-biphenyl 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 acid diesters include divinyl phenylphosphonate, diallyl phenylphosphonate, bis(1-butenyl)phenylphosphonate, etc.; the disubstituted phosphinates include Phenyl diphenylphosphinate, methyl diphenylphosphinate, etc.; the metal salts of the disubstituted phosphinic acid include metal salts of dialkylphosphinic acid, metal salts of diallylphosphinic acid, metal salts of divinylphosphinic acid, metal salts of diarylphosphinic acid, etc.; the organic nitrogen-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.

[0091] The flame retardants may be used alone or in combination of at least two.

[0092] On the other hand, the present invention provides a resin adhesive, which is obtained by dissolving or dispersing the resin composition described above in a solvent.

[0093] In the present invention, the amount of the solvent is not limited, as long as the components in the resin composition can be dissolved and dispersed and do not separate during mixing.

[0094] 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.

[0095] In another aspect, the present invention provides a prepreg comprising a substrate, and the resin composition as described above attached to the substrate by impregnation and drying.

[0096] 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.

[0097] The glass fiber cloth includes Q-glass fiber cloth, E-glass fiber cloth, D-glass fiber cloth, L-glass fiber cloth, M-glass fiber cloth, S-glass fiber cloth, T-glass fiber cloth or NE-glass fiber cloth, etc.

[0098] The organic fiber cloth includes polyimide fiber cloth, polyamide fiber cloth, polyester fiber cloth, polyphenylene ether fiber cloth or liquid crystal polymer fiber cloth.

[0099] Illustratively, the prepreg is prepared by impregnating a substrate with a resin glue of the resin composition, and then drying the substrate to obtain the prepreg.

[0100] Preferably, the solvent in the resin glue is not particularly limited, and is further preferably any one of acetone, butanone, methyl ethyl ketone, cyclohexanone, toluene or xylene, or a combination of at least two thereof.

[0101] Preferably, the drying temperature is 100-180°C, for example, 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.

[0102] Preferably, the drying time is 1 to 10 minutes, for example, 2 minutes, 3 minutes, 4 minutes, 5 minutes, 6 minutes, 7 minutes, 8 minutes or 9 minutes.

[0103] In another aspect, the present invention provides a metal foil-clad laminate comprising at least one prepreg as described above, and a metal foil disposed on one side or both sides of the prepreg.

[0104] The metal foil may be copper foil, aluminum foil, nickel foil or alloy foil; preferably, the metal foil is copper foil.

[0105] Preferably, the number of prepregs in the metal foil-clad laminate is 1 to 20, for example, 1, 3, 5, 7, 9, 10, 11, 13, 15, 17 or 19 sheets.

[0106] Illustratively, the preparation method of the metal-clad laminate is: pressing metal foil on one side or both sides of a prepreg, curing, and obtaining the metal-clad laminate; or, stacking at least two prepregs, and then pressing metal foil on one side or both sides of the stacked prepregs, curing, and obtaining the metal-clad laminate.

[0107] Preferably, the curing is performed in a press.

[0108] Preferably, the curing temperature is 200-250°C, for example, 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.

[0109] Preferably, the curing pressure is 10-60 kg / cm 2 , for example 15kg / cm 2 , 20kg / cm 2 , 25kg / cm 2 、30kg / cm 2 、35kg / cm 2 , 40kg / cm 2 , 45kg / cm 2 , 50kg / cm 2 or 55kg / cm 2 wait.

[0110] Preferably, the curing time is 30 to 180 min, for example, 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.

[0111] In another aspect, the present invention provides a printed circuit board comprising at least one prepreg as described above or one metal foil-clad laminate as described above.

[0112] Compared with the prior art, the present invention has the following beneficial effects:

[0113] 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) is ensured to account 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. DETAILED DESCRIPTION

[0114] The technical solution of the present invention is further described below by way of specific embodiments. It should be understood by those skilled in the art that the embodiments are merely to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0115] Preparation Example 1

[0116] An addition reactant (referred to as BMI A1) is prepared by the following method:

[0117] Into a three-necked flask equipped with a thermometer, a stirring paddle and a reflux condenser were added 15 parts by weight of a siloxane compound containing two primary amino groups (X-22-161A of Shin-Etsu Chemical Co., Ltd.), 5 parts by weight of an amine compound containing two primary amino groups (Kayahard AA of Nippon Kayaku Kogyo Co., Ltd., 3,3'-diethyl-4,4'-diaminodiphenylmethane), 80 parts by weight of a maleimide compound (BMI-4000 of Yamato Chemical Industry Co., Ltd., 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane) and 100 parts by weight of propylene glycol monomethyl ether. The mixture was stirred and heated to 115° C., then kept warm for continuous reaction. During the reaction, the weight average molecular weight of the addition reactant (BMI A1) was monitored by gel permeation chromatography (GPC, with tetrahydrofuran as the mobile phase). When BMI The reaction is stopped when the total weight of the addition reactants with a weight average molecular weight of 1100 to 20000 in A1 accounts for 40% of the (A) component.

[0118] Preparation Example 2

[0119] An addition reactant (hereinafter referred to as BMI A2) is prepared by the following method:

[0120] Into a three-necked flask equipped with a thermometer, a stirring paddle and a reflux condenser were added 7 parts by weight of a siloxane compound containing two primary amino groups (X-22-161B of Shin-Etsu Chemical Co., Ltd.), 7 parts by weight of an amine compound containing two primary amino groups (2,2-bis(4-(4-aminophenoxy)phenyl)propane of Tokyo Chemical Industry Co., Ltd., Japan), 86 parts by weight of a maleimide compound (BMI-4000 of Yamato Chemical Industry Co., Ltd., 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane) and 100 parts by weight of propylene glycol monomethyl ether. The mixture was stirred and heated to 115° C., then kept warm for continuous reaction. During the reaction, the weight average molecular weight of the addition reactant (BMI A2) was monitored by gel permeation chromatography (GPC, with tetrahydrofuran as the mobile phase). When BMI The reaction is stopped when the total weight of the addition reactants with a weight average molecular weight of 1100 to 20000 in A2 accounts for 20% of the (A) component.

[0121] Preparation Example 3

[0122] An addition reactant (hereinafter referred to as BMI A3) is prepared by the following method:

[0123] In a three-necked flask equipped with a thermometer, a stirring blade and a reflux condenser, 25 parts by weight of a siloxane compound containing two primary amino groups (X-22-161A from Shin-Etsu Chemical Co., Ltd.), 5 parts by weight of an amine compound containing two primary amino groups (Kayahard from Nippon Kayaku Kogyo Co., Ltd.) were added. AA, 3,3'-diethyl-4,4'-diaminodiphenylmethane), 10 parts by weight of a maleimide compound (BMI-1000, bis(4-maleimidophenyl)methane, produced by Yamato Chemical Industry Co., Ltd.), 60 parts by weight of a maleimide compound (BMI-4000, 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane, produced by Yamato Chemical Industry Co., Ltd.), and 100 parts by weight of propylene glycol monomethyl ether were stirred, heated to 115°C, and then maintained at this temperature for continuous reaction. During the reaction, the weight average molecular weight of the addition reactant (BMI A3) was monitored by gel permeation chromatography (GPC, with tetrahydrofuran as the mobile phase). The reaction was terminated when the total weight of the addition reactants with a weight average molecular weight of 1,100 to 20,000 in BMI A3 accounted for 40% of component (A).

[0124] Preparation Example 4

[0125] An addition reactant (hereinafter referred to as BMI A4) is prepared by the following method:

[0126] In a three-necked flask equipped with a thermometer, a stirring paddle, and a reflux condenser, 20 parts by weight of a siloxane compound containing two primary amino groups (KF-8010, Shin-Etsu Chemical Co., Ltd.), 80 parts by weight of a maleimide compound (BMI-1000, bis(4-maleimidophenyl)methane, Yamato Chemical Industry Co., Ltd.), and 100 parts by weight of propylene glycol monomethyl ether were added. The mixture was stirred, heated to 115° C., and then maintained at this temperature for continuous reaction. During the reaction, the weight-average molecular weight of the addition reactant (BMI A4) was monitored by gel permeation chromatography (GPC, with tetrahydrofuran as the mobile phase). The reaction was terminated when the total weight of the addition reactants with a weight-average molecular weight of 1,100 to 20,000 in BMI A4 accounted for 60% of component (A).

[0127] Comparative Preparation Example 1

[0128] An addition reactant (hereinafter referred to as BMI C1) is prepared by the following method:

[0129] In a three-necked flask equipped with a thermometer, a stirring paddle, and a reflux condenser, 10 parts by weight of an amine compound containing two primary amino groups (Kayahard AA, 3,3'-diethyl-4,4'-diaminodiphenylmethane, manufactured by Nippon Kayaku Kogyo Co., Ltd.), 90 parts by weight of a maleimide compound (BMI-4000, 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane, manufactured by Yamato Chemical Industry Co., Ltd.), and 100 parts by weight of propylene glycol monomethyl ether were added. The mixture was stirred, heated to 115° C., and then maintained at this temperature for continuous reaction. 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 terminated when the total weight of the addition reactants having a weight-average molecular weight of 1,100 to 20,000 in BMI C1 accounted for 20% of component (A).

[0130] Comparative Preparation Example 2

[0131] An addition reactant (referred to as BMI C2) is prepared by the following method:

[0132] BMI C2 was obtained in the same manner as in Preparation Example 1 except that the reaction was stopped when the weight of the addition reactants having a weight average molecular weight of 1,100 to 20,000 in BMI C2 accounted for 5% of the total weight of component (A).

[0133] Comparative Preparation Example 3

[0134] An addition reactant (referred to as BMI C3) is prepared by the following method:

[0135] BMI C3 was obtained by the same method as in Preparation Example 4 except that the reaction was stopped when the weight of the addition reactants having a weight average molecular weight of 1,100 to 20,000 in BMI C3 accounted for 75% of the total weight of component (A).

[0136] The experimental materials involved in the following embodiments and comparative examples of the present invention include:

[0137] 1) Component (A):

[0138] BMI A1, Preparation Example 1;

[0139] BMI A2, Preparation Example 2;

[0140] BMI A3, Preparation Example 3;

[0141] BMI A4, Preparation Example 4;

[0142] BMI C1, comparative preparation example 1;

[0143] BMI C2, comparative preparation example 2;

[0144] BMI C3, comparative preparation example 3;

[0145] 2) Component (B): Thermosetting resin

[0146] OPE-2st 2200, polyphenylene ether containing vinyl benzyl groups at the end, Mitsubishi Chemical Corporation;

[0147] PT-30, phenolic cyanate resin, Lonza;

[0148] NC-3000H, biphenyl epoxy resin, Nippon Kayaku Co., Ltd.;

[0149] 3) Component (C): polyolefin resin

[0150] Tuftec H1051, hydrogenated styrene-butadiene copolymer, Asahi Kasei Chemicals Corporation;

[0151] 4) Component (D): Curing accelerator

[0152] Triginox 311, 3,3,5,7,7-pentamethyl-1,2,4-trioxypropane, Akzo Nobel, USA;

[0153] 2PZ, 2-phenylimidazole, Shikoku Chemical Co., Ltd., Japan;

[0154] 5) Component (E): Inorganic filler

[0155] SC2300-SVJ, spherical silica surface treated with vinyl silane coupling agent, median particle size D 50 0.5 μm, Japan Admatechs Co., Ltd.

[0156] SC2300-SEJ, spherical silica surface treated with epoxy silane coupling agent, median particle size D 50 0.5 μm, Japan Admatechs Co., Ltd.

[0157] 6) Component (F): coupling agent

[0158] KBM-573, N-phenyl-3-aminopropyltrimethoxysilane, Shin-Etsu Corporation, Japan;

[0159] 7) Component (A'):

[0160] Biphenyl polymaleimide compound, MIR-3000-70MT, Nippon Kayaku Industry Co., Ltd.

[0161] Example 1

[0162] This embodiment provides a resin composition comprising the following components, in parts 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.

[0163] This embodiment also provides a metal foil-clad laminate, the specific preparation method of which is as follows:

[0164] (1) The resin composition provided in this embodiment, toluene and butanone were mixed, fully dissolved and evenly dispersed to obtain a resin glue solution with a solid content of 60%;

[0165] (2) impregnating glass fiber cloth (Low Dk 3313 manufactured by Huber, Taiwan, China) with the resin glue obtained in step (1), heating and drying in a blast oven at 130° C. for 4 min to convert the varnish state resin composition into a semi-cured state resin composition to obtain a prepreg with a thickness controlled to be 0.10 mm;

[0166] (3) Two sheets of prepreg obtained in step (2) were stacked and electrolytic copper foil with a thickness of 12 μm was pressed on the upper and lower sides of the prepreg. The prepreg was heated at 220°C and 45 kg / cm 2 After curing for 2 hours, a metal foil-clad laminate with a core thickness of 0.20 mm was obtained.

[0167] The copper foil of the metal-clad laminate was etched to obtain a laminate having a thickness of 0.20 mm.

[0168] Examples 2 to 6, Comparative Examples 1 to 4

[0169] A resin composition, the components and contents of which are shown in Tables 1 and 2; the dosage units of the components in Tables 1 and 2 are all "parts".

[0170] Table 1

[0171] Table 2

[0172] The resin composition was prepared into a metal foil-clad laminate according to the method in Example 1. The performance of the laminate was tested as follows:

[0173] (1) In-plane thermal expansion coefficient (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 glass fiber warp direction was the Y direction, and the glass fiber weft direction was the X direction. The sample was dried in a 105°C oven for 1 hour and then cooled to room temperature in a desiccator. The measurement was performed using the thermal mechanical analysis (TMA) method, with a heating rate of 10°C / min, from room temperature to 260°C, in two steps. The result was the in-plane thermal expansion coefficient at the second heating step from 60°C to 120°C, and the unit was ppm / °C.

[0174] (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 taken as a sample. After the sample was ultrasonically cleaned in deionized water to remove impurities on the surface, it was dried in an oven at 105°C for 1 hour and then cooled to room temperature in a desiccator. The dielectric loss tangent (D) at a frequency of 10 GHz was measured using a cavity resonator device. f );

[0175] Dielectric loss tangent after thermal oxidation treatment (Df): Take the above test dielectric loss tangent (D f ) sample was baked at 125°C for 500 hours (thermal oxidation treatment condition 1), and the dielectric loss tangent (D f );

[0176] Dielectric loss tangent after thermal oxidation treatment (D f ): Take the above-mentioned test dielectric loss tangent (Df) sample, bake it at 150℃ for 720 hours (thermal oxidation treatment condition 2), and then use a cavity resonator device to measure the dielectric loss tangent (Df) at a frequency of 10GHz. f );

[0177] △D f : Dielectric loss tangent after thermal oxidation treatment (D f )-Dielectric loss tangent before thermal oxidation treatment (D f ).

[0178] About △D f The change in value is recorded as "A" if it is less than 0.001, "B" if it is greater than 0.001 and less than 0.002, "C" if it is greater than 0.002 and less than 0.003, and "D" if it is greater than 0.003. f The smaller the change, the better the material's resistance to thermal oxidative aging.

[0179] The performance test results are shown in Table 3:

[0180] Table 3

[0181] According to the performance test data in Table 3, in Examples 1-6 of the present invention, the XY-CTE of the laminated boards prepared by the resin compositions is below 12.8 ppm / °C, and D f (10GHz) is less than 0.0061, and even after a harsh 150°C baking for 720 hours (thermal oxidation treatment condition 2), the change in dielectric loss tangent △D f The XY-CTE of the laminated board is also below 0.002, and some are even below 0.001. The prepared laminated board has excellent low-plane thermal expansion coefficient, low dielectric loss tangent and good thermal oxidation aging resistance. In Comparative Example 1, the addition reactant (A) does not use the siloxane compound a2 containing at least two primary amino groups in one molecule, resulting in a significant increase in the XY-CTE of the laminated board. At the same time, after undergoing the harsh thermal oxidation treatment condition 2, the change in dielectric loss tangent ΔD f It can only be achieved below 0.003; in Comparative Examples 2 and 3, the total weight of the addition reactants with a weight average molecular weight of 1100 to 20,000 in component (A) is not within the scope of the present invention, resulting in poor processability and failure to produce laminates; in Comparative Example 4, the use of biphenyl polymaleimide compounds results in a significant increase in the XY-CTE of the laminate, and a large change in the dielectric loss tangent after the thermal oxidation treatment conditions, especially after the more severe thermal oxidation treatment condition 2, the change in the dielectric loss tangent ΔD f Greater than 0.003.

[0182] The applicant states that while the above-described embodiments illustrate the resin composition, prepreg, and metal-clad laminate comprising the same, the present invention is not limited to the aforementioned process steps, nor does it necessarily rely on the aforementioned process steps for implementation. Persons skilled in the art will appreciate that any improvements to the present invention, equivalent substitutions for the raw materials used, addition of auxiliary components, and selection of specific methods, etc., fall within the scope of protection and disclosure 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 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); In component (A), the total weight of the addition reaction products having a weight average molecular weight of 1100 to 20000 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 two 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 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; Preferably, the maleimide compound a1 containing at least two N-substituted maleimide groups in one molecule is selected from 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-maleimidoben 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, or any one or a combination of at least two of long-chain alkyl bis maleimides.

4. The resin composition according to any one of claims 1 to 3, characterized in that, 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; Preferably, the polyphenylene ether resin is a polyphenylene ether having an unsaturated group at the end; 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, based on parts 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 polyolefin resin (C), curing accelerator (D), and inorganic filler (E); Preferably, based on parts by weight, the content of the polyolefin resin (C) in the resin composition is 5 to 30 parts; Preferably, based on parts by weight, the content of the curing accelerator (D) in the resin composition is 0.01 to 5 parts; Preferably, based on parts by weight, the content of the inorganic filler (E) in the resin composition is 5 to 250 parts.

7. A resin glue solution, characterized in that, The resin 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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