Resin composition and application thereof

Abstract

The invention provides a resin composition and application thereof. The resin composition comprises the following components: component (A): an addition reactant comprising a maleimide compound and an amine compound a2 containing at least two primary amino groups in one molecule; component (B): another resin; wherein the maleimide compound at least comprises a maleimide compound a1 with a structure as shown in a formula (I). The addition reactant in the resin composition has the characteristics of high heat resistance and low thermal expansion coefficient of the maleimide compound, and also has the characteristic of low dielectric loss of the cyclobutene compound, so that the problems that the resin composition taking the maleimide resin as a main body is insufficient in electrical property and large in water absorption rate can be solved; the composite material is especially suitable for the fields with high requirements on heat resistance and dielectric loss in different environments, such as high-speed packaging substrate materials and the like.

Description

Technical Field

[0001] The present invention belongs to the technical field of printed circuit boards, and relates to a resin composition and its application. Background Art

[0002] In recent years, communication technology has developed rapidly, putting forward higher requirements for the speed and stability of signal transmission. On the one hand, it requires lower signal loss, putting forward requirements for the low dielectric properties of materials. On the other hand, it requires the stability of signal transmission, especially in environments with large fluctuations in temperature and humidity, high temperature or low temperature, and high humidity. 5G communication technologies represented by applications such as high-frequency RF (such as PA, WiGig, WiHD / 60GHz, etc.), large-size chips, and DDR5 (3.2 - 6.4Gbps) have put forward demands for high-speed packaging substrate materials, which can meet requirements such as low planar thermal expansion coefficient, high heat resistance, and low dielectric loss tangent.

[0003] For high-speed packaging substrate materials, maleimide resins are generally used in combination with resins having good dielectric properties. Maleimide resins have relatively high monomer activity, and their cured products have high glass transition temperatures and good heat resistance. The finished products have stable properties and can maintain high physical and mechanical properties within a relatively wide temperature range. For example, CN109825081A discloses a thermosetting resin composition including a combination of resins such as bismaleimide resin and benzoxazine resin. The prepared laminate has high heat resistance and low planar thermal expansion coefficient, but a relatively high dielectric loss tangent. Resins with good dielectric properties include thermosetting polyphenylene ether resins, bismaleimide resins, hydrocarbon resins, etc. For example, a composite resin material containing an alkenyl-terminated thermosetting polyphenylene ether resin and triallyl isocyanurate (TAIC) has been used in the mass production of printed circuit boards (PCBs), but its dielectric properties, especially the dielectric property stability in different environments, are poor. When hydrocarbon resins are used in combination with other thermosetting resins, the problem of insufficient dielectric properties can be solved, but there are problems of insufficient heat resistance and relatively large planar thermal expansion coefficients. None of the above can simultaneously meet the requirements of high-speed packaging substrate materials for heat resistance, planar thermal expansion coefficient, dielectric properties, etc.

[0004] Therefore, developing prepregs, laminates, and metal-clad laminates with low thermal expansion coefficient, high heat resistance, especially good dielectric properties and high stability in environments with large fluctuations in temperature and humidity, high temperature or low temperature, and high humidity to meet the requirements of high-speed packaging substrate materials is the research focus in this field. Summary of the Invention

[0005] Aiming at the deficiencies of the prior art, the purpose of the present invention is to provide a resin composition and its application.

[0006] To achieve this purpose, the present invention adopts the following technical solutions:

[0007] On the one hand, the present invention provides a resin composition, which comprises the following components: Component (A): an addition reaction product of a maleimide compound and an amine compound a2 containing at least 2 primary amino groups in one molecule; Component (B): other resins.

[0008] Among them, the maleimide compound contains at least the maleimide compound a1 having the structure shown in formula (I).

[0009]

[0010] Among them, R1 is independently selected from a hydrocarbon group, a hydrocarbon thio group, a hydrocarbon oxy group, an electron-withdrawing group or an electron-donating group; R2 is independently selected from a cyano group, a halogen or an electron-donating group; X is a direct bond or a divalent organic group; a is an integer from 0 to 3, such as 0, 1, 2 or 3; b is an integer from 0 to 2, such as 0, 1 or 2.

[0011] The addition reaction product provided by the present invention has the high heat resistance and low coefficient of thermal expansion characteristics of the maleimide compound, and also has the low dielectric loss characteristics of the cyclobutene compound, which can solve the problems of insufficient electrical properties and large water absorption rate of the resin composition mainly composed of maleimide resin, and is particularly suitable for fields with high requirements for heat resistance and dielectric loss in different environments, such as high-speed packaging substrate materials, etc.

[0012] In the present invention, each R1 is independently selected from an alkyl group having 1 to 20 carbon atoms (such as 1, 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18 or 20), an alkylthio group having 1 to 20 carbon atoms (such as 1, 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18 or 20), an alkoxy group having 1 to 20 carbon atoms (such as 1, 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18 or 20), an aryl group having 6 to 20 carbon atoms (such as 6, 8, 10, 12, 14, 16, 18 or 20), an arylthio group having 6 to 20 carbon atoms (such as 6, 8, 10, 12, 14, 16, 18 or 20), an aryloxy group having 6 to 20 carbon atoms (such as 6, 8, 10, 12, 14, 16, 18 or 20), an aralkyl group having 7 to 20 carbon atoms (such as 7, 8, 10, 12, 14, 16, 18 or 20), an aralkylthio group having 7 to 20 carbon atoms (such as 7, 8, 10, 12, 14, 16, 18 or 20), an aralkyloxy group having 7 to 20 carbon atoms (such as 7, 8, 10, 12, 14, 16, 18 or 20), an alkaryl group having 7 to 20 carbon atoms (such as 7, 8, 10, 12, 14, 16, 18 or 20), an alkarylthio group having 7 to 20 carbon atoms (such as 7, 8, 10, 12, 14, 16, 18 or 20), an alkaryloxy group having 7 to 20 carbon atoms (such as 7, 8, 10, 12, 14, 16, 18 or 20), a cyano group, a carboxylic acid ester group, a hydrocarbonylcarbonyloxy group, a nitro group, a halogen, a hydrocarbonylsulfinyl group, a hydrocarbonylsulfonyl group or an amino group.

[0013] Preferably, each R1 is independently selected from an alkyl group having 1 to 20 carbon atoms (such as 1, 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18 or 20), a halogen, a nitro group or a cyano group.

[0014] Preferably, each R1 is independently selected from an alkyl group having 1 to 3 carbon atoms (such as 1, 2, 3), a halogen, a nitro group or a cyano group.

[0015] In the present invention, each R2 is independently selected from a cyano group, a halogen, a carboxylic acid ester group, a hydrocarbonylcarbonyloxy group, a nitro group, a hydrocarbonylsulfonyl group, a hydrocarbonylsulfinyl group, an alkyl group, an acylamino group or an alkoxy group.

[0016] Preferably, each R2 is independently selected from a cyano group, a nitro group or a halogen.

[0017] Preferably, R2 is selected from a cyano group.

[0018] Preferably, when b is 0, there are no substituents on the cyclobutene ring and all are hydrogen atoms.

[0019] In the present invention, the maleimide compound in the component (A) further includes other maleimide compounds a3 in addition to the structure shown in (I).

[0020] Preferably, the other maleimide compounds a3 include maleimide compounds containing at least 1 (e.g., 1, 2, 3, 4, 5 or more) N-substituted maleimide groups in 1 molecule. When 1 molecule contains 1 N-substituted maleimide group, it is a monomaleimide compound; when 1 molecule contains 2 N-substituted maleimide groups, it is a bismaleimide compound; when 1 molecule contains 3 or more N-substituted maleimide groups, it is a polymaleimide compound.

[0021] To ensure that the resin composition has a certain melt fluidity, if the melt fluidity is too high, the resin composition on the prepreg flows out before curing under the action of force and heat, resulting in extremely poor thickness uniformity of the laminate and the metal-clad laminate, and "gully" defects appear at the edge positions of the laminate and the metal-clad laminate; if the melt fluidity is too low, the resin composition on the prepreg is not easy to flow under the action of force and heat, the bonding force between the resin composition and the metal foil is poor, and the wettability of the resin composition with the reinforcing material (such as fiberglass cloth) is poor, resulting in a decrease in the reliability of the laminate and the metal-clad laminate.

[0022] Preferably, from the perspective of melt fluidity, the other maleimide compounds a3 are maleimide compounds containing 2 N-substituted maleimide groups in 1 molecule, that is, bismaleimide compounds, to ensure that the addition reaction product of the maleimide compound a3 and the amine compound a2 has a sufficient chain extension length without causing a crosslinking reaction due to the overall functionality > 2.

[0023] In the present invention, the maleimide compound containing two N-substituted maleimide groups in one molecule includes 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-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 or bis(4-(4-maleimidophenoxy)phenyl)ether, and any one or a combination of at least two of them, more preferably any one or a combination of at least two of bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, bis(4-maleimidophenyl)methane or 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane.

[0024] In the present invention, the amine compound a2 is preferably an amine compound containing two primary amino groups in one molecule.

[0025] In the present invention, the amine compound containing two primary amino groups in one molecule includes a siloxane compound containing two primary amino groups in one molecule, diaminobenzidine, 3,3'-dimethoxy-4,4'-diaminobenzene, 3,3'-dimethyl-4,4'-diaminobenzene, 3,3'-diethyl-4,4'-diaminobenzene, 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'-diaminobenzene or 4,4'-diamino-3,3'-dihydroxybenzene, any one of them or a combination of at least two of them; more preferably, it is any one 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 them.

[0026] In the present invention, the siloxane compound containing two primary amino groups per molecule can be a commercially available product, which can endow the resin composition with the property of low planar thermal expansion coefficient. The siloxane compound containing two primary amino groups per molecule can be a commercially available product, and examples include but are not limited to any one or a combination of at least two of: PAM-E (side chain methyl type, functional group equivalent weight 130 g / mol), KF-8010 (side chain methyl type, functional group equivalent weight 430 g / mol), X-22-161A (side chain methyl type, functional group equivalent weight 800 g / mol), X-22-161B (side chain methyl type, functional group equivalent weight 1500 g / mol), KF-8012 (side chain methyl type, functional group equivalent weight 2200 g / mol), KF-8008 (side chain methyl type, functional group equivalent weight 5700 g / mol), X-22-1660B-3 (side chain phenyl type, functional group equivalent weight 2200 g / mol), or X-22-9409 (side chain phenyl type, functional group equivalent weight 670 g / mol) of Shin-Etsu Chemical Co., Ltd.

[0027] In the present invention, the type of the other resin B is not limited, as long as it can react with the addition reactant A.

[0028] Preferably, the other resin B is selected from any one or a combination of at least two of epoxy resins, acid anhydride compounds, or compounds having a carbon-carbon unsaturated double bond in the molecule.

[0029] Preferably, the other resin B is selected from epoxy resins and / or compounds having a carbon-carbon unsaturated double bond in the molecule.

[0030] More preferably, the other resin B is selected from compounds having a carbon-carbon unsaturated double bond in the molecule, including any one or a combination of at least two of unsaturated polyphenylene ether compounds, polyfunctional vinyl compounds, allyl compounds, acrylate compounds, acenaphthylene compounds, or polybutadiene compounds, and more preferably any one or a combination of at least two of unsaturated polyphenylene ether compounds, polyfunctional vinyl compounds, allyl compounds, acenaphthylene compounds, or polybutadiene compounds.

[0031] In the present invention, the dosages of component (A) and component (B) are not limited, as long as the resin composition can be completely cured.

[0032] Preferably, from the perspective of heat resistance, based on 100 parts by weight of the resin composition, the dosage of component (A) is 50 to 90 parts (such as 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 85 parts, or 90 parts), and the dosage of component (B) is 10 to 40 parts (such as 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, or 40 parts).

[0033] In the present invention, from the perspective of reducing dielectric loss, the resin composition further comprises 5 to 30 parts by weight (such as 5 parts, 8 parts, 10 parts, 13 parts, 15 parts, 18 parts, 20 parts, 23 parts, 25 parts, 28 parts or 30 parts) of a hydrogenated styrene-based elastomer and / or a polyolefin resin.

[0034] In the present invention, the resin composition further comprises 30 to 250 parts by weight (such as 30 parts, 50 parts, 80 parts, 100 parts, 120 parts, 150 parts, 180 parts, 200 parts, 220 parts or 250 parts) of an inorganic filler.

[0035] In the present invention, the inorganic filler is an inorganic filler pretreated with a silane coupling agent.

[0036] In the present invention, the resin composition further comprises 0.01 to 5 parts by weight (such as 0.01 part, 0.05 part, 0.1 part, 0.5 part, 1 part, 2 parts, 3 parts, 4 parts or 5 parts) of a curing accelerator.

[0037] In the present invention, the curing accelerator includes any one or a combination of at least two of an acidic curing accelerator, an organic phosphorus-based curing accelerator, an imidazole-based curing accelerator, a pyridine-based curing accelerator, an amine-based curing accelerator, a peroxide or an organic metal salt.

[0038] In the present invention, the resin composition further comprises 0.01 to 10 parts by weight (such as 0.01 part, 0.05 part, 0.1 part, 0.5 part, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts or 10 parts) of a coupling agent.

[0039] In the present invention, the coupling agent includes a silane coupling agent.

[0040] 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.

[0041] In the present invention, the substrate includes any one of a glass fiber cloth, an organic fiber cloth or a glass fiber paper.

[0042] On the other hand, the present invention provides a laminate, which includes at least 1 sheet of the prepreg as described above.

[0043] 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 foils provided on one or both sides of the prepreg.

[0044] Preferably, the metal foil is a copper foil.

[0045] On the other hand, the present invention provides a printed circuit board, which comprises at least one piece of the prepreg or the metal foil-clad laminate as described above.

[0046] Compared with the prior art, the present invention has the following beneficial effects:

[0047] The addition reactant in the resin composition of the present invention has the high heat resistance and low coefficient of thermal expansion characteristics of the maleimide compound, and also has the low dielectric loss characteristics of the cyclobutene compound. It can solve the problems of insufficient electrical properties and large water absorption rate of the resin composition mainly composed of maleimide resin, and is particularly suitable for fields with high requirements for heat resistance and dielectric loss in different environments, such as high-speed packaging substrate materials, etc. Description of the Drawings

[0048] Figure 1 It is the DSC spectrum of N-(benzocyclobuten-4-yl) maleimide;

[0049] Figure 2 It is the GPC spectrum of N-(benzocyclobuten-4-yl) maleimide. Detailed Embodiments

[0050] 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.

[0051] The materials involved in the embodiments and comparative examples of the present invention are as follows:

[0052] 1. Component A: An addition reactant of a maleimide compound a1 having the structure shown in formula (I) and an amine compound a2 containing at least 2 primary amino groups in one molecule:

[0053] Prepared according to the following method:

[0054] Prepolymer A1:

[0055] 2 parts by weight of the amine compound Kayahard A-A (3,3'-diethyl-4,4'-diaminodiphenylmethane, Nippon Kayaku Co., Ltd.), 18 parts by weight of X-22-161A (a siloxane compound containing 2 primary amino groups at the molecular end, Shin-Etsu Chemical Co., Ltd.), 20 parts by weight of N-(benzocyclobuten-4-yl) maleimide and 30 parts by weight of the solvent propylene glycol monomethyl ether were added to a three-necked flask equipped with a thermometer, a stirring paddle and a reflux condenser, and reacted at 115°C for 360 min to obtain prepolymer A1;

[0056] Synthesis of N-(benzocyclobuten-4-yl) maleimide:

[0057] In a three-necked flask equipped with a thermometer, a stirring paddle, and a reflux condenser, 24 parts by weight of 5-aminobenzocyclobutene, 22 parts by weight of maleic anhydride, and 34 parts by weight of the solvent toluene were added. The reaction was carried out with heat preservation at 40 °C under a nitrogen atmosphere to obtain N-arylcyclobutenyl amidoalkenoic acid; in a three-necked flask equipped with a thermometer, a stirring paddle, and a reflux condenser, 4 parts by weight of N-arylcyclobutenyl amidoalkenoic acid, 20 parts by weight of acetic anhydride, 4 parts by weight of triethylamine, and 52 parts by weight of the solvent acetone were added. The reaction was carried out with heat preservation at 15 °C under a nitrogen atmosphere to obtain N-(benzocyclobuten-4-yl) maleimide.

[0058] Figure 1 It is the DSC spectrum of N-(benzocyclobuten-4-yl) maleimide. It can be seen that the melting temperature of N-(benzocyclobuten-4-yl) maleimide is 85.59 °C, and the initial reaction temperature is 218.22 °C.

[0059] Figure 2 It is the GPC spectrum of N-(benzocyclobuten-4-yl) maleimide. It can be seen that the Mn of N-(benzocyclobuten-4-yl) maleimide is 274 and the Mw is 333.

[0060] For DSC (differential scanning calorimeter), the test instrument is TA DSC Q20. Weigh 10 mg of N-(benzocyclobuten-4-yl) maleimide, set the N2 atmosphere, the heating rate is 5 °C / min, scan from 30 °C to 250 °C, and mark the melting endothermic peak temperature and the initial reaction temperature.

[0061] For GPC (gel permeation chromatography), the test instrument is Tosoh HLC-8420GPC gel permeation chromatograph, the mobile phase is tetrahydrofuran, the test method is GB / T 21863-2008, and the measurement is carried out by gel permeation chromatography based on polystyrene calibration. The results are taken as Mn (number average molecular weight) and Mw (weight average molecular weight).

[0062] Prepolymer A2:

[0063] In a three-necked flask equipped with a thermometer, a stirring paddle, and a reflux condenser, 3 parts by weight of amine compound Kayahard A-A (3,3'-diethyl-4,4'-diaminodiphenylmethane, Nippon Kayaku Co., Ltd.), 1 part by weight of X-22-161A (a siloxane compound with 2 primary amino groups at the molecular end, Shin-Etsu Chemical Co., Ltd.), 30 parts by weight of maleimide compound BMI-4000 (2,2-bis(4-(4-maleimidophenoxy)phenyl)propane, Daiwa Kasei Kogyo Co., Ltd.), 6 parts by weight of N-(benzocyclobuten-4-yl) maleimide, and 30 parts by weight of the solvent propylene glycol monomethyl ether were added. The reaction was carried out with heat preservation at 115 °C for 360 min to obtain prepolymer A2;

[0064] 2. Component A': The addition reaction product of other maleimide compounds a3 outside the structure shown in (I) and an amine compound a2 containing at least 2 primary amino groups in 1 molecule:

[0065] Prepared according to the following method:

[0066] Prepolymer A3:

[0067] Add 3 parts by weight of amine compound Kayahard A-A (3,3'-diethyl-4,4'-diaminodiphenylmethane, Nippon Kayaku Co., Ltd.), 1 part by weight of X-22-161A (a siloxane compound with 2 primary amino groups at the molecular end, Shin-Etsu Chemical Co., Ltd.), 36 parts by weight of maleimide compound BMI-4000 (2,2-bis(4-(4-maleimidophenoxy)phenyl)propane, Daiwa Kasei Kogyo Co., Ltd.) and 30 parts by weight of solvent propylene glycol monomethyl ether into a three-necked flask equipped with a thermometer, a stirring paddle and a reflux condenser, and keep the reaction at 115 °C for 360 min to obtain prepolymer A3;

[0068] 3. Component B:

[0069] OPE-2st 1200, a polyphenylene ether with vinylbenzyl groups at the ends, Mitsubishi Chemical Corporation, Japan;

[0070] NC-7000L, a naphthol phenyl aralkyl type epoxy resin, Nippon Kayaku Co., Ltd.;

[0071] SMA EF-30, a styrene-maleic anhydride copolymer, styrene / maleic anhydride = 3 / 1 (molar ratio), Cray Valley USA.

[0072] 4. Hydrogenated styrenic elastomer

[0073] Tuftec M1913, a hydrogenated styrene-butadiene copolymer with maleic anhydride structural units, Asahi Kasei Chemicals Corporation.

[0074] 5. Inorganic filler

[0075] SC2500-SXJ, spherical silica modified with anilinyl siloxane, average particle size D 50 is 0.5 μm, Admatechs Co., Ltd., Japan.

[0076] 6. Coupling agent

[0077] KBM-573, a phenylamino silane coupling agent, Shin-Etsu Chemical Co., Ltd.

[0078] Examples 1-7, Comparative Examples 1-3

[0079] A resin composition, the types and dosages of each component are shown in Table 1 and Table 2, and the dosage unit of each component is "parts". The "parts" and "weight parts" involved in the present invention are calculated based on the solid content and do not include solvents, dispersants, etc. therein.

[0080] A prepreg and a metal-clad laminate comprising the resin composition are prepared as follows:

[0081] (1) Mix and disperse each component of the resin composition with toluene solvent according to the formulation amount to make a resin solution with a solid content of 65%.

[0082] (2) Impregnate a glass fiber cloth (3313L glass fiber cloth manufactured by Hubel, Taiwan, China) with the resin solution, and then heat and dry it in a blast drying oven at 140 °C for 5 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 of 100 μm.

[0083] (3) Stack 2 (or 8) prepregs obtained in step (2), press and laminate electrolytic copper foils with a thickness of 12 μm on both the upper and lower sides thereof, and cure at 220 - 225 °C and 45 kg / cm 2 for 90 min to obtain a metal-clad laminate with a core board thickness of 0.20 mm (or 0.80 mm). After etching the copper foil of the above metal-clad laminate, a laminate with a certain thickness is obtained.

[0084] Perform performance tests on the metal-clad laminate / laminate, and the specific method is as follows:

[0085] (1) Glass transition temperature Tg: Take a laminate with a length of 60 mm, a width of 10 mm, and a thickness of 0.80 mm as a sample, and measure it using a dynamic mechanical thermal analyzer (DMA) with a heating rate of 10 °C / min. The result is taken as the transition peak temperature of tanδ, and the unit is °C.

[0086] (2) Coefficient of thermal expansion in the plane XY-CTE: Take a laminate with a length of 60 mm, a width of 4 mm, and a thickness of 0.20 mm as a sample. The warp direction of the glass fiber is the Y direction, and the weft direction of the glass fiber is the X direction. The sample is dried in an oven at 105 °C for 1 h and then cooled to room temperature in a desiccator. Measure it using a thermomechanical analysis method (TMA) with a heating rate of 10 °C / min, heat from room temperature to 200 °C, and perform two heating processes. After the first heating process is completed and cooled to room temperature, re-sample for the second heating process. The result is taken as the coefficient of thermal expansion in the plane direction from 60 °C to 120 °C during the second heating process, and the unit is ppm / °C.

[0087] (3) Dielectric loss tangent Df: A laminate with a length of 100 mm, a width of 100 mm, and a thickness of 0.20 mm is taken as a sample. After the surface impurities of the sample are removed by ultrasonic cleaning in deionized water, it is dried in an oven at 105 °C for 1 h and then cooled to room temperature in a desiccator; the dielectric loss tangent (Df) at a frequency of 10 GHz is measured using a cavity resonator device;

[0088] Dielectric loss tangent (D f ) after moisture absorption: Take the sample for testing the dielectric loss tangent (D f ). After being placed in an environment with a temperature of 25 °C and a humidity of 55% for one week, the dielectric loss tangent (D f ) at a frequency of 10 GHz is measured using a cavity resonator device.

[0089] △D f : Dielectric loss tangent (D f ) after moisture absorption - dielectric loss tangent (D f ) before moisture absorption;

[0090] (4) Water absorption rate: A laminate with a length of 50 mm, a width of 50 mm, and a thickness of 0.80 mm is taken as a sample. After the surface impurities of the sample are removed by ultrasonic cleaning in deionized water, it is dried in an oven at 105 °C for 1 h, and then weighed as W0. It is soaked in water at a temperature of 30 °C for 24 hours, the sample is taken out and air-dried naturally, and then weighed as W1. The water absorption rate = 100% × (W1 - W0) / W0.

[0091] The test results are shown in Table 1 and Table 2.

[0092] Table 1

[0093]

[0094]

[0095] Table 2

[0096]

[0097] According to the performance test data in Table 1 and Table 2, it can be seen that the resin compositions provided in Examples 1-7 of the present invention can solve the problems of large change in dielectric loss tangent and high water absorption rate after moisture absorption of the cured resin composition, so that the △Df of the cured resin composition after moisture absorption is below 0.0007, the water absorption rate is below 0.15%, the XY-CTE is below 10 ppm / °C, and the Tg is above 287 °C. It is especially suitable for fields with high requirements for heat resistance and dielectric loss in different environments, such as high-speed packaging substrate materials, etc.

[0098] According to the performance test data in Table 2, when the component does not contain the maleimide compound having the structure shown in formula (I) (Comparative Example 1), that is, when the addition reaction product of the maleimide compound having the structure shown in formula (I) and the amine compound a2 having at least 2 primary amino groups in 1 molecule is not used, △Df increases to 0.0010 and the water absorption rate increases to 0.20%; when the amount of component A is greater than 90 parts (Comparative Example 2), although higher Tg and lower XY-CTE can be obtained, the dielectric properties deteriorate severely, Df increases to 0.0038, and the water absorption rate increases significantly. After moisture absorption, △D f increases to 0.0012, and the maleimide compound having the structure shown in formula (I) cannot effectively reduce the hygroscopicity; when the amount of component B is too high (Comparative Example 3), XY-CTE increases significantly and Tg decreases significantly, which does not meet the requirements of the packaging substrate for low XY-CTE and high heat resistance.

[0099] The applicant declares that the present invention uses the above embodiments to illustrate the resin composition and its application of the present invention, but the present invention is not limited to the above embodiments, that is, it does not mean that the present invention must rely on the above embodiments to be implemented. Those skilled in the art should understand that any improvement to the present invention, the equivalent replacement of each raw material of the product of the present invention, the addition of auxiliary components, 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: Component (A): an addition reaction product of a maleimide compound and an amine compound a2 containing at least two primary amino groups in one molecule; Component (B): other resins. Among them, the maleimide compound at least contains a maleimide compound a1 having the structure shown in formula (I). Among them, R1 are each independently selected from a hydrocarbon group, a hydrocarbonthio group, a hydrocarbonoxy group, an electron-withdrawing group or an electron-donating group; R2 are each independently selected from a cyano group, a halogen or an electron-donating group; X is a direct bond or a divalent organic group; a is an integer from 0 to 3, and b is an integer from 0 to 2.

2. The resin composition according to claim 1, wherein, R1 are each independently selected from an alkyl group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylthio group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkylthio group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, an alkaryl group having 7 to 20 carbon atoms, an alkarylthio group having 7 to 20 carbon atoms, an alkaryloxy group having 7 to 20 carbon atoms, a cyano group, a carboxylic acid ester group, a hydrocarbonyl oxy group, a nitro group, a halogen, a hydrocarbon sulfinyl group, a hydrocarbon sulfonyl group or an amino group. Preferably, R1 are each independently selected from an alkyl group having 1 to 20 carbon atoms, a halogen, a nitro group or a cyano group. Preferably, R1 are each independently selected from an alkyl group having 1 to 3 carbon atoms, a halogen, a nitro group or a cyano group.

3. The resin composition according to claim 1, wherein R2 are each independently selected from a cyano group, a halogen, a carboxylic acid ester group, a hydrocarbonyl oxy group, a nitro group, a hydrocarbon sulfonyl group, a hydrocarbon sulfinyl group, an alkyl group, an acylamino group or an alkoxy group. Preferably, R2 are each independently selected from a cyano group, a nitro group or a halogen. Preferably, R2 is selected from a cyano group.

4. The resin composition according to any one of claims 1 to 3, characterized in that, The maleimide compound in the component (A) further includes other maleimide compounds a3 other than the structure shown in (I). Preferably, the other maleimide compounds a3 include maleimide compounds containing at least one N-substituted maleimide group in one molecule. Preferably, the other maleimide compounds a3 include maleimide compounds containing two N-substituted maleimide groups in one molecule. Preferably, the maleimide compound containing two N-substituted maleimide groups in one molecule includes 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-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 or bis(4-(4-maleimidophenoxy)phenyl)ether, and any one or a combination of at least two of them, and further preferably any one or a combination of at least two of bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, bis(4-maleimidophenyl)methane or 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane.

5. The resin composition according to any one of claims 1 to 4, characterized in that, The amine compound a2 is an amine compound containing two primary amino groups in one molecule; Preferably, the amine compound containing two primary amino groups in one molecule includes any one or a combination of at least two of a siloxane compound containing two primary amino groups in one molecule, 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.

6. The resin composition according to any one of claims 1-5, characterized in that, The other resin B is selected from any one or a combination of at least two of an epoxy resin, an acid anhydride compound or a compound having a carbon-carbon unsaturated double bond in the molecule; Preferably, the other resin B is selected from an epoxy resin and / or a compound having a carbon-carbon unsaturated double bond in the molecule; More preferably, the other resin B is selected from compounds having a carbon-carbon unsaturated double bond in the molecule, including any one or a combination of at least two of an unsaturated polyphenylene ether compound, a polyfunctional vinyl compound, an allyl compound, an acrylate compound, an acenaphthylene compound or a polybutadiene compound; Preferably, based on 100 parts by weight of the resin composition, the amount of component (A) is 50 to 90 parts, and the amount of component (B) is 10 to 40 parts; Preferably, the resin composition further comprises 5 to 30 parts by weight of a hydrogenated styrene-based elastomer and / or a polyolefin resin; Preferably, the resin composition further comprises 30 to 250 parts by weight of an inorganic filler; Preferably, the inorganic filler is an inorganic filler pretreated with a silane coupling agent; Preferably, the resin composition further comprises 0.01 to 5 parts by weight of a curing accelerator; Preferably, the curing accelerator comprises any one or a combination of at least two of an acidic curing accelerator, an organic phosphorus-based curing accelerator, an imidazole-based curing accelerator, a pyridine-based curing accelerator, an amine-based curing accelerator, a peroxide or an organic metal salt; Preferably, the resin composition further comprises 0.01 to 10 parts by weight of a coupling agent; Preferably, the coupling agent comprises a silane coupling agent.

7. A prepreg, characterized in that, The prepreg comprises a substrate, and the resin composition according to any one of claims 1-6 attached to the substrate by impregnation and drying; Preferably, the substrate comprises any one of a glass fiber cloth, an organic fiber cloth or a glass fiber paper.

8. A laminate, characterized in that, The laminate comprises at least 1 sheet of the prepreg according to claim 7.

9. A metal-clad laminate, characterized in that, The metal foil-clad laminate comprises at least 1 sheet of the prepreg according to claim 7, and metal foils provided on one or both sides of the prepreg.

10. A printed circuit board, characterized in that, The printed circuit board comprises at least 1 sheet of the prepreg according to claim 7 or the metal foil-clad laminate according to claim 9.

Images