Resin composition, resin adhesive film and application thereof

Abstract

The invention provides a resin composition, a resin adhesive film and application thereof. The resin composition comprises the following components in parts by weight: (A) 30-55 parts of thermoplastic polyphenyl ether; (B) 10-35 parts of low molecular weight polyolefin resin; and (C) 20-50 parts of polyolefin resin with high tensile strength, wherein the tensile strength of the polyolefin resin with high tensile strength is greater than or equal to 20 MPa. By designing the specific composition of the resin composition, the resin composition with excellent performance is prepared, and then the resin adhesive film which is ultrathin, can be matched with a high-frequency base material, can tolerate the high-temperature pressing condition of the high-frequency base material and is suitable for processing of a thick copper product of a high-frequency hydrocarbon base material is prepared.

Description

Technical Field

[0001] The present invention belongs to the technical field of electronic materials, and specifically relates to a resin composition, a resin film and applications thereof, and more specifically relates to a resin composition, a resin film and a metal foil-clad laminate and a printed circuit board containing the same. Background Art

[0002] As printed circuit boards (PCBs) continue to develop towards high density and multi-layers, the current density required by various circuit board designs is getting higher and higher, and the heat generation is also increasing. On the other hand, with the rapid development of modern communication technology, circuit materials are gradually becoming high-frequency, and the operating frequency of electronic equipment is getting higher and higher, and the heat generation is getting higher and higher. These two factors drive the operating temperature of printed circuit boards to rise sharply. If the accumulated heat cannot be discharged in time, the operating temperature of the equipment will increase. In the long run, it will cause the electrical performance of components to decline or even be damaged, seriously damaging the life and reliability of the equipment.

[0003] In this context, PCB manufacturers began to pay attention to thick copper laminate products. Thick copper PCBs with copper thickness greater than or equal to 3OZ are increasingly used. However, with the advent of the 5G communication era, the requirements for high-speed transmission and processing of large-capacity information on circuit boards are gradually increasing. PCB manufacturers are no longer satisfied with FR-4-level thick copper products and have begun to actively seek high-frequency carbon-hydrogen thick copper laminates.

[0004] However, unlike traditional FR-4 thick copper products, high-frequency carbon-hydrogen thick copper laminates face different technical difficulties. Usually, the peel strength of the substrate is often related to the roughness of the copper foil. Generally speaking, using a copper foil with high roughness can achieve higher peel strength, but for thick copper, this rule has changed.

[0005] Thick copper usually refers to copper foil with a thickness of 3OZ or above. The characteristics of this type of copper foil are large copper foil roughness and long copper teeth. The characteristics of hydrocarbon system are high filler content and low resin fluidity. When thick copper and hydrocarbon prepreg are used, there are problems such as resin flow and copper teeth cannot be fully embedded in the substrate, resulting in poor peeling strength of copper clad laminates with hydrocarbon pressed thick copper, making them difficult to use.

[0006] CN116144209A provides a method for preparing a coated copper foil, which can greatly improve the bonding strength between the copper foil and the substrate by pre-coating a 5-10 μm thick high peeling resistance resin layer on the copper foil. However, thick copper cannot be coated with a resin layer using this process, because as the thickness of the copper foil increases, the rigidity of the copper foil also increases. Thick copper of 3OZ and above has poor flexibility and cannot be automatically coated using a coating machine.

[0007] Therefore, how to provide a resin film suitable for high-frequency hydrocarbon substrates and for bonding thick copper has become a technical problem that needs to be solved urgently. Summary of the invention

[0008] In view of the deficiencies of the prior art, the object of the present invention is to provide a resin composition, a resin film and applications thereof, and more specifically to provide a resin composition, a resin film and a metal foil-clad laminate and a printed circuit board containing the same. The present invention designs the specific composition of the resin composition, and prepares a resin composition with excellent performance by using thermoplastic polyphenylene ether, a low molecular weight polyolefin resin and a high tensile strength polyolefin resin in combination, and then can prepare a resin film with ultra-thin thickness, which can match high-frequency substrates, can withstand high-temperature pressing conditions of high-frequency substrates, and is suitable for processing thick copper products of high-frequency hydrocarbon substrates.

[0009] To achieve this object, the present invention adopts the following technical solutions:

[0010] In a first aspect, the present invention provides a resin composition, wherein the resin composition comprises the following components in parts by weight:

[0011] (A) thermoplastic polyphenylene ether, 30 to 55 parts;

[0012] (B) low molecular weight polyolefin resin, 10 to 35 parts;

[0013] (C) high tensile strength polyolefin resin, 20 to 50 parts, wherein the tensile strength of the high tensile strength polyolefin resin is ≥ 20 MPa.

[0014] Based on the problems existing in the prior art, the purpose of the present invention is to provide a resin film which has high tensile strength for stacking materials, has ultra-thin thickness to reduce the influence on the dielectric constant of the substrate, has dielectric loss matching the high-frequency substrate, can withstand the high-temperature pressing conditions of the high-frequency substrate, and the final pressed thick copper substrate has high peel strength and good heat resistance, and has no color difference with the original substrate, and is suitable for the processing of thick copper products of high-frequency hydrocarbon substrates.

[0015] Based on this, the present invention designs the specific composition of the resin composition to prepare a resin composition with excellent performance, and then prepares a resin film with excellent performance.

[0016] In the present invention, the inventors found that the thermoplastic polyphenylene ether of component (A) can improve the high temperature pressing performance of the resin film. The curing temperature of the high frequency substrate exceeds that of the common FR-4 resin system, which is usually above 240°C. If the heat resistance of the resin itself is insufficient, the functional groups will break during curing, releasing small molecules, thereby reducing the peeling resistance. The resin film needs to have heat resistance to withstand the curing temperature of the high frequency substrate.

[0017] The inventors found that when the proportion of the thermoplastic polyphenylene ether in component (A) exceeds 55 parts by weight, the strength of the resin film is poor and it is easy to break. When the proportion of the thermoplastic polyphenylene ether is less than 30 parts by weight, the peeling resistance of the resin film is low and the viscosity is large. When the proportion of the thermoplastic polyphenylene ether is 30 to 50 parts by weight, the strength and peeling strength of the prepreg film are good, the viscosity is low, and it is easy to use.

[0018] The inventors have found that the low molecular weight polyolefin resin of the component (B) can improve the fluidity of the resin film and the heat resistance after curing. When the low molecular weight olefin resin is added to the resin composition, the softening point of the resin composition can be reduced, the resin can have better fluidity during lamination, can more fully wrap the copper teeth, and improve the peel strength; the crosslinking density of the resin composition after curing can be increased, the degree of curing can be increased, and the heat resistance can be improved.

[0019] The inventors found that when the proportion of the low molecular weight polyolefin resin in component (B) exceeds 35 parts by weight, the viscosity of the resin film is high and it is difficult to separate from the carrier film. When the proportion of the low molecular weight polyolefin resin is less than 10 parts by weight, the fluidity of the resin film is poor, the anti-peeling of the thick copper pressed hydrocarbon substrate is low, and the cross-linking density after curing is low. When the proportion of the low molecular weight polyolefin resin is 10 to 35 parts by weight, the thick copper substrate after pressing has good anti-peeling and heat resistance, low viscosity, and is easy to use.

[0020] The inventors have found that when there is only a small molecular weight olefin resin in the resin composition, the film-forming property of the coated resin composition is poor, and the resin composition tends to directly break after the coating carrier is removed, and the thinner the thickness of the coated resin film, the worse the strength. The inventors have found through research and experiments that adding the component (C) high tensile strength polyolefin resin with a tensile strength ≥ 20MPa to the formula has a good effect of improving the film-forming property and strength of the resin composition, and the higher the tensile strength, the greater the improvement. The inventors have found that adding a high tensile strength polyolefin resin with a tensile strength ≥ 20MPa to the formula can improve the moldability and strength of the coated resin film, and can meet the requirements of the resin film having good film-forming property and strength when the thickness is 10 to 25μm, and meet the thinning requirements of the resin film.

[0021] The inventors found that when the proportion of the high tensile strength polyolefin resin of component (C) is less than 20 parts by weight, the strength of the resin film is poor. When the proportion of the high tensile strength polyolefin resin exceeds 50 parts by weight, the softening point of the resin film is high, the resin is not easy to soften and the copper teeth and the resin are fully engaged, and the peeling resistance becomes poor. When the proportion of the high tensile strength polyolefin resin is 20 to 50 parts by weight, the strength of the resin film is good, the appearance of the coating is good, and the peeling resistance of the pressed plate is good.

[0022] In the present invention, in the resin composition, the weight proportion of component (A) thermoplastic polyphenylene ether can be 30 parts, 33 parts, 36 parts, 39 parts, 42 parts, 45 parts, 47 parts, 50 parts, 52 parts or 55 parts.

[0023] In the resin composition, the weight proportion of component (B) low molecular weight polyolefin resin can be 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, 22 parts, 24 parts, 27 parts, 30 parts, 33 parts or 35 parts, etc.

[0024] In the resin composition, the weight proportion of component (C) high tensile strength polyolefin resin can be 20 parts, 22 parts, 25 parts, 27 parts, 30 parts, 33 parts, 36 parts, 40 parts, 42 parts, 44 parts, 46 parts or 50 parts, etc., and the tensile strength of the high tensile strength polyolefin resin is ≥20MPa, for example, it can be 20MPa, 21MPa, 22MPa, 23MPa, 24MPa, 25MPa, 26MPa, 27MPa, 28MPa, 29MPa or 30MPa, etc.

[0025] The tensile strength test method in this invention is based on the ASTM D412 tensile test.

[0026] The following are preferred technical solutions of the present invention, but are not intended to limit the technical solutions provided by the present invention. Through the following preferred technical solutions, the objectives and beneficial effects of the present invention can be better achieved and realized.

[0027] It should be noted that the thermoplastic polyphenylene ether refers to polyphenylene ether that does not contain unsaturated functional groups. Unsaturated functional groups refer to groups with unsaturated chemical bonds in the molecule, usually referring to groups containing double bonds or triple bonds. For example, unsaturated functional groups exemplarily include but are not limited to any one or a combination of at least two of vinyl, styrene or methacrylate groups. The inventors have found that when using thermoplastic polyphenylene ether that does not contain unsaturated functional groups as the main resin, the coated resin composition is matched with a high-frequency substrate and has good peel resistance after high-temperature pressing, and there will be no problem of peel resistance reduction, and the heat resistance is good, and no stratification and bubbling will occur after tinning.

[0028] Preferably, the thermoplastic polyphenylene ether resin comprises the following structural units:

[0029]

[0030] Wherein, R1, R2, R3 and R4 are each independently selected from any one of hydrogen, a halogen atom (for example, F, Cl, Br or I), a C1-C7 (C1, C2, C3, C4, C5, C6 or C7) alkyl, a C1-C7 (C1, C2, C3, C4, C5, C6 or C7) haloalkyl, a C1-C7 (C1, C2, C3, C4, C5, C6 or C7) aminoalkyl, a C1-C7 (C1, C2, C3, C4, C5, C6 or C7) alkoxy, a C6-C10 (C6 or C10, etc.) aryl or a C6-C10 (C6, C7, C8, C9 or C10) aryloxy.

[0031] Preferably, the thermoplastic polyphenylene ether is selected from poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,3,6-trimethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, poly (2,6-dipropyl-1,4-phenylene) ether, poly (2-methyl-6-allyl-1,4-phenylene) ether, poly (di-tert-butyl-dimethoxy-1,4-phenylene) ether, poly (2,6-dichloromethyl Any one or a combination of at least two of poly(2,6-dibromomethyl-1,4-phenylene) ether, poly(2,6-bis(2-chloroethyl)-1,4-phenylene) ether, poly(2,6-xylyl-1,4-phenylene) ether, poly(2,6-dichloro-1,4-phenylene) ether, poly(2,6-diphenyl-1,4-phenylene) ether and poly(2,5-dimethyl-1,4-phenylene) ether.

[0032] Specific examples of commercial thermoplastic polyphenylene ether include, but are not limited to, Blendex HPP820 manufactured by Chemtura Corporation of the United States, Noryl 640-111 and SA90 manufactured by SABIC, and SQP40 manufactured by Shandong Shengquan Company.

[0033] As a preferred technical solution of the present invention, the number average molecular weight (Mn) of the low molecular weight polyolefin resin is ≤10000 g / mol, for example, it can be 1000 g / mol, 2000 g / mol, 3000 g / mol, 4000 g / mol, 5000 g / mol, 6000 g / mol, 7000 g / mol, 8000 g / mol, 9000 g / mol or 10000 g / mol, etc.

[0034] In the present invention, the molecular weight of each polymer is tested according to GB / T 21863-2008, and the weight average molecular weight is determined by gel permeation chromatography based on polystyrene calibration.

[0035] Preferably, the weight ratio of butadiene units added at the 1,2 positions in the low molecular weight polyolefin resin is ≥ 65%, for example, it can be 65%, 66%, 68%, 70%, 72%, 75%, 77%, 78%, 80%, 81%, 84%, 86%, 88% or 90%, etc.

[0036] In the present invention, if the number average molecular weight of the low molecular weight polyolefin resin is too large, the fluidity of the resin film will deteriorate, and it will not be able to fully flow to wrap the copper teeth during the lamination process, and the peel strength cannot be improved; if the weight ratio of the butadiene units added at the 1,2 positions in the low molecular weight polyolefin resin is too low, the cross-linking density after curing will be small, resulting in insufficient heat resistance and failure to meet the use requirements.

[0037] Preferably, the low molecular weight olefin resin is selected from any one of a polybutadiene resin with unsaturated double bonds, a modified polybutadiene resin with unsaturated double bonds, and a polybutadiene copolymer resin with unsaturated double bonds, or a combination of at least two thereof.

[0038] Preferably, the polybutadiene resin having unsaturated double bonds includes 1,2-polybutadiene resin.

[0039] Preferably, the modified polybutadiene resin with unsaturated double bonds is selected from any one of maleic anhydride modified polybutadiene resin, acrylate modified polybutadiene resin, epoxy modified polybutadiene resin, amine modified polybutadiene resin, terminal carboxyl modified polybutadiene resin, and terminal hydroxyl modified polybutadiene resin, or a combination of at least two thereof.

[0040] Preferably, the polybutadiene copolymer resin with unsaturated double bonds is selected from any one of polybutadiene-styrene copolymer resin, polybutadiene-styrene-divinylbenzene graft copolymer resin, maleic anhydride modified styrene-butadiene copolymer resin and acrylate modified styrene-butadiene copolymer resin or a combination of at least two thereof.

[0041] Specific examples of commercial low molecular weight polyolefin resins include, but are not limited to: B1000, B2000, B3000, JP200, TE2000 manufactured by Japan Soda Co., Ltd., Ricon 100, Ricon 181, Ricon 154, Ricon 130MA8 manufactured by American Crayon & Williams Co., Ltd.

[0042] As a preferred technical solution of the present invention, the high tensile strength polyolefin resin is selected from any one of elastomeric block copolymers, ethylene-propylene rubber, polybutadiene rubber, and styrene-butadiene rubber, or a combination of at least two thereof.

[0043] Preferably, the elastomeric block copolymer is selected from any one or a combination of at least two of a styrene-butadiene diblock copolymer, a styrene-butadiene-styrene triblock copolymer, a styrene-(ethylene-butylene)-styrene triblock copolymer, a styrene-isoprene diblock copolymer, a styrene-isoprene-styrene triblock copolymer, a styrene-(ethylene-propylene)-styrene triblock copolymer, and a styrene-(ethylene-butylene) diblock copolymer.

[0044] Specific examples of high tensile strength polyolefin resins include, but are not limited to, Kraton D1101, Kraton D1152, Kraton D1184, and Kraton D1192 manufactured by Kraton Corporation of the United States, and JSR RB810, JSR RB820, and JSR RB830 manufactured by Japan Synthetic Rubber Co., Ltd.

[0045] As a preferred technical solution of the present invention, the resin composition also includes a flame retardant.

[0046] Preferably, the flame retardant is selected from bromine-containing flame retardants and / or phosphorus-containing flame retardants.

[0047] Preferably, the bromine-containing flame retardant is any one of decabromodiphenyl ether, brominated polystyrene, brominated polycarbonate, decabromodiphenyl ethane or ethylenebistetrabromophthalimide, or a combination of at least two thereof.

[0048] Preferably, the phosphorus-based flame retardant is selected from any one or a combination of at least two of tris(2,6-dimethylphenyl)phosphine, triphenyl phosphate, bisphenol A bis(diphenyl phosphate), poly(di(phenoxy)aphosphazene, resorcinol bis[di(2,6-dimethylphenyl) phosphate], 2,6-bis(2,6-dimethylphenyl)phosphinobenzene, 9,10-dihydro-9-oxa-10-phosphophanol-10-oxide, 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphophanol-10-oxide, and 10-phenyl-9,10-dihydro-9-oxa-10-phosphophanol-10-oxide.

[0049] Specific examples of commercial halogen-free flame retardants include, but are not limited to: PX200 and PX202 manufactured by Daihachi Co., Ltd. of Japan, OP935 manufactured by Klein AG of Germany, SPB-100 and SPV-100 manufactured by Otsuka Chemical Co., Ltd. of Japan, XP-7866 manufactured by Albemarle Corporation of the United States, etc.

[0050] The flame retardant is included in the resin film of the present invention due to the need for flame retardancy, so that the resin film or the high-frequency hydrocarbon substrate laminated with the resin film has flame retardant properties and meets the UL 94V-0 requirement.

[0051] In the present invention, there is no particular limitation on the amount of flame retardant added as needed. The dielectric properties, heat resistance and peel strength of the cured product are not sacrificed. Based on 100 parts by weight of the component (A), component (B) and component (C), the weight of the flame retardant is 0 to 25 parts (for example, 0, 0.5, 1, 2, 5, 7, 10, 13, 15, 18, 20, 22, 24 or 25 parts, etc.), and more preferably 10 to 20 parts.

[0052] Preferably, the resin composition further comprises a free radical initiator.

[0053] Preferably, the free radical initiator is selected from organic peroxide free radical initiators and / or carbon-based free radical initiators.

[0054] Preferably, the organic peroxide free radical initiator is selected from di-tert-butyl peroxide, dilauroyl peroxide, dibenzoyl peroxide, cumyl peroxide, t-butyl peroxide, t-butyl peroxide, t-butyl isobutyrate, t-butyl peroxide-3,5,5-trimethylhexanoate, t-butyl peroxide benzoate, 1,1-di-tert-butyl peroxide-3,5,5-trimethylcyclohexane, 1,1-di-tert-butyl peroxide cyclohexane, 2,2-di(tert-butyl peroxide)butane, di(4-tert-butyl peroxide)butane, di( ... one or a mixture of at least two of the following: 2,4-di-(tert-butylperoxy)butyl peroxide, 2,5-di-(2,5-hexyl)peroxydicarbonate, 2,6-di-hexadecyl peroxydicarbonate, 2,4-di-tetradecyl peroxydicarbonate, di-tert-amyl peroxide, diisopropyl benzene peroxide, bis(tert-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-di-tert-butylperoxyhexane, 2,5-dimethyl-2,5-di-tert-butylperoxyisopropyl benzene, diisopropyl benzene hydroperoxide, tert-butyl peroxycarbonate-2-ethylhexyl ester, n-butyl 4,4-di(tert-butylperoxy)valerate, methyl ethyl ketone peroxide or cyclohexane peroxide;

[0055] Preferably, the carbon-based free radical initiator is selected from any one of 2,3-dimethyl-2,3-diphenylbutane, 2,3-dimethyl-2,3-di(4-methylphenyl)butane, 2,3-dimethyl-2,3-di(4-isopropylphenyl)butane, and 3,4-dimethyl-3,4-diphenylhexane, or a combination of at least two thereof.

[0056] In the present invention, there is no specific limitation on the amount of the additive. Based on 100 parts by weight of the component (A), component (B) and component (C), the weight of the free radical initiator is 0.1 to 5 parts (for example, 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5 or 5 parts, etc.).

[0057] The resin composition of the present invention may also contain additives introduced to solve certain problems, and the additives include any one or a combination of at least two of a crosslinking agent, a coupling agent, a leveling agent, a defoaming agent, an antioxidant, a heat stabilizer, an antistatic agent, an ultraviolet absorber, a pigment, a colorant or a lubricant.

[0058] It should be noted that the present invention has no special restrictions on the specific selection of crosslinking agents, coupling agents, leveling agents, defoaming agents, antioxidants, heat stabilizers, antistatic agents, ultraviolet absorbers, pigments, colorants, and lubricants, and all of the above additives commonly used in the field are applicable.

[0059] In the present invention, the amount of the additive is not specifically limited. Based on 100 parts by weight of the component (A), component (B) and component (C), the weight of the additive is 0.1 to 8 parts (for example, 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5 or 8 parts, etc.), more preferably 0.1 to 5 parts, and even more preferably 0.1 to 3 parts.

[0060] In the present invention, there is no special limitation on the preparation method of the resin composition, and any commonly used preparation method in the art is applicable, including but not limited to:

[0061] The components of the resin composition and the solvent are mixed uniformly to obtain the resin composition.

[0062] In the present invention, there is no special restriction on the specific selection of solvents, and commonly used solvents in the art are applicable, including but not limited to aromatic hydrocarbon solvents such as toluene, xylene, and mesitylene, or ketone solvents such as acetone, butanone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.

[0063] Similarly, in the present invention, there is no special restriction on the specific amount of solvent used, and the commonly used solvent amounts in the art are applicable, including but not limited to: 10%, 15%, 20%, 25%, 30%, 40%, etc.

[0064] In a second aspect, the present invention provides a resin adhesive film, wherein the resin adhesive film is obtained by coating the resin composition described in the first aspect on a release material.

[0065] In the present invention, there is no special limitation on the preparation method of the resin film, and any commonly used preparation method in the art is applicable, including but not limited to:

[0066] The resin composition is coated on the surface of the release film, dried, and after removing the solvent, the release film is removed to obtain the resin adhesive film.

[0067] Preferably, the drying temperature is 90-180°C, for example, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C or 180°C.

[0068] Preferably, the resin film has a thickness of 10 to 25 μm (eg, 10 μm, 13 μm, 15 μm, 17 μm, 18 μm, 20 μm, 23 μm or 25 μm, etc.), preferably 15 to 20 μm.

[0069] The inventors found that when the thickness of the resin film is less than 10 μm, its strength is relatively poor and it is easy to tear when separated from the release film; when the thickness of the resin film is greater than 25 μm, since its own performance is far from that of the high-frequency substrate, there are large differences in Dk, CTE, thermal conductivity and other various indicators, which will greatly affect the performance of the substrate. The thinner the metal foil laminate, the greater the impact of the thickness of the resin film on the performance of the metal foil laminate.

[0070] In a third aspect, the present invention provides a metal foil-clad laminate, the metal foil-clad laminate comprising a copper foil and at least one resin film as described in the second aspect;

[0071] In the present invention, the resin film is used as an adhesive layer, and the adhesive layer is located between two metal foils, and the structure is metal foil + one or more resin films + metal foil.

[0072] Preferably, the metal foil clad laminate further comprises one or more prepregs, the resin film is located between the metal foil and the prepreg, and the structure is metal foil + resin film + one or more prepregs + resin film + metal foil, which is used to improve the adhesion between the metal foil and the prepreg.

[0073] As a preferred technical solution of the present invention, the copper foil is a thick copper foil with a thickness ≥ 3OZ (105 μm), and the thickness of the thick copper foil can be 3OZ, 4OZ, 5OZ or 6OZ, etc.

[0074] In the present invention, the method for preparing the metal foil-clad laminate comprises the following steps:

[0075] The copper foil, the resin film and the optional prepreg are stacked in the required order, placed in a press layer, and pressed to prepare a metal foil-clad laminate.

[0076] Preferably, the lamination is preferably vacuum lamination, which can be achieved by a vacuum laminator. The lamination time is 60 to 150 min, such as 60 min, 70 min, 80 min, 90 min, 100 min, 110 min, 120 min, 130 min, 140 min, 150 min, etc.; the lamination temperature is 200 to 265 ° C, such as 200 ° C, 210 ° C, 220 ° C, 230 ° C, 240 ° C, 245 ° C, 250 ° C, 255 ° C, 260 ° C, 265 ° C, etc.; the lamination pressure is 20 to 60 kg / cm 2 , for example 20kg / cm 2 , 25kg / cm 2 、30kg / cm 2 、35kg / cm 2 , 40kg / cm 2 , 45kg / cm 2 , 50kg / cm 2 、55kg / cm 2 or 60kg / cm 2 wait.

[0077] In the present invention, the specific parameters of the lamination molding time, temperature and pressure are determined based on the prepreg used in combination. According to the differences in different formulations, the lamination parameters can be flexibly adjusted within a limited range.

[0078] In a fourth aspect, the present invention provides a printed circuit board, the printed circuit board comprising the resin film according to the second aspect;

[0079] Preferably, the printed circuit board is a high-frequency substrate.

[0080] Compared with the prior art, the present invention has the following beneficial effects:

[0081] (1) The present invention designs the specific composition of the resin composition and controls the amount of thermoplastic polyphenylene ether, low molecular weight polyolefin resin, and high tensile strength polyolefin resin within a specific range, thereby preparing a resin composition with excellent performance, and further preparing a resin film with ultra-thin thickness, which can match high-frequency substrates, can withstand high-temperature pressing conditions of high-frequency substrates, and is suitable for processing thick copper products of high-frequency hydrocarbon substrates.

[0082] (2) The resin adhesive film provided by the present invention can be coated on a carrier such as a release film or release paper. When used, it can be peeled off from the carrier and stacked between copper foils or between copper foils and prepregs to improve the peeling strength. In the prior art, the process of coating copper foil by coating can only be used for copper foils of 2OZ and below, and cannot be applied to thick copper of 3OZ and above. This is because the thicker the copper foil, the greater its rigidity and the worse its flexibility, and continuous batch production cannot be achieved through the coating process. The resin adhesive film provided by the present invention can be applied to thick copper of 3OZ and above, and its peeling strength is relatively high.

[0083] (3) The resin film provided by the present invention has a great advantage in storage cost. Compared with the adhesive-coated copper foil, its material cost only includes the resin film and the release film as a carrier. The adhesive-coated copper foil is a cheap resin coated on an expensive copper foil. When the adhesive-coated copper foil needs to be scrapped due to expiration or oxidation, the loss caused is relatively large.

[0084] (4) The resin film provided by the present invention has an ultra-thin thickness (10 to 25 μm), which minimizes the impact of the resin film on the performance of the substrate, especially for plates with a thickness of more than 0.5 mm, and basically does not affect the performance of the substrate. Under the premise of meeting this thickness, the resin film has a very uniform appearance and good strength and operability.

[0085] (5) The resin film provided by the present invention has a dielectric loss matching that of a high-frequency substrate, has a high peel strength for bonding thick copper, and has good heat resistance. There is no delamination or bubbling after tinning at 288°C for 5 minutes. The color before and after curing is similar to that of the hydrocarbon substrate without color difference, which facilitates product upgrades and is very suitable for making high-frequency hydrocarbon thick copper products. DETAILED DESCRIPTION

[0086] For the convenience of understanding the present invention, the present invention lists the following embodiments. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0087] The sources of some materials in the embodiments and comparative examples are shown in Table 1 below:

[0088] Table 1

[0089]

[0090]

[0091] Examples 1-17 and Comparative Examples 1-8, Comparative Examples 10-12, Comparative Example 14

[0092] Examples 1-17 and Comparative Examples 1-8, Comparative Examples 10-12, and Comparative Example 14 respectively provide a resin composition, a resin film, and a copper-clad laminate. The specific composition of the resin composition is shown in Table 2-5 below:

[0093] The preparation method of the resin composition is as follows:

[0094] The components of the resin component are added into a stirring kettle, diluted with toluene to a solid content of 30%, and stirred and mixed to obtain a resin composition.

[0095] The preparation method of the resin film is as follows:

[0096] The above resin composition was coated on a release film, dried at 120° C. to a semi-cured state, and the release film was removed to obtain a resin film. The thickness of the resin film is shown in Table 2-5 below.

[0097] The preparation method of the copper clad laminate is as follows:

[0098] Six 1080-gauge, 3.33-mil-thick S7135 hydrocarbon prepregs were stacked, and a resin film was stacked on each of the top and bottom sheets. A copper foil was stacked on the outside of the film, and the sheets were put into a press for curing to obtain a copper-clad laminate. The curing time was 180 minutes, the curing temperature was 240°C, and the curing pressure was 50 kg / cm 2 , and obtain the copper-clad laminate.

[0099] Comparative Example 9

[0100] This comparative example provides a copper-clad laminate, which differs from Example 1 only in that:

[0101] The preparation method of the copper clad laminate is as follows:

[0102] Six 1080-gauge, 3.33-mil-thick S7135 hydrocarbon prepregs were stacked, and a copper foil (3OZ NPM copper foil, H-1) was stacked on each of the upper and lower sides of the prepregs formed after stacking. No resin film was stacked, and the prepregs were put into a press for curing to obtain a copper-clad laminate. The curing time was 180 min, the curing temperature was 240°C, and the curing pressure was 50 kg / cm 2 , and obtain the copper-clad laminate.

[0103] Other conditions are the same as in Example 1.

[0104] Comparative Example 13

[0105] This comparative example provides a copper-clad laminate, which differs from Example 1 only in that:

[0106] The preparation method of the copper clad laminate is as follows:

[0107] Six 1080-gauge, 3.33-mil-thick S7135 hydrocarbon prepregs were stacked, and a copper foil (HOZ RTF-3, H-2, Changchun, Taiwan, China) was stacked on each of the upper and lower sides of the prepregs. The laminates were put into a press for curing to obtain copper-clad laminates. The curing time was 180 min, the curing temperature was 240 ° C, and the curing pressure was 50 kg / cm 2 , and obtain the copper-clad laminate.

[0108] Other conditions are the same as in Example 1.

[0109] Performance Testing:

[0110] The film strength of the resin films provided in the above embodiments and comparative examples, the dielectric constant (Dk), dielectric loss tangent (Df), sheet peel strength (PS), thermal stress and flame retardancy of the copper clad laminate were tested. The specific test methods are as follows:

[0111] Release effect: The easier it is to peel the film off the release film, the better the release effect. On the contrary, if the film is torn during the peeling process and the film cannot be obtained intact, or it is difficult to peel off, the release effect is poor.

[0112] Note: ◎ indicates high strength and easy to peel off from the release film; ○ indicates average strength and can be peeled off from the release film to obtain a complete film; △ indicates poor strength and is relatively brittle, so a complete film cannot be obtained or is difficult to peel off.

[0113] Dielectric constant (Dk) and dielectric loss tangent (Df): measured at 10 GHz using the Split Dielectric Pillar Resonator (SPDR) method as specified in IPC-TM-650 2.5.5.15.

[0114] Sheet peel strength (PS): Test the peel strength of copper foil according to the "after thermal stress" experimental conditions in IPC-TM-650 2.4.8 method, unit N / mm.

[0115] Thermal stress: Tested in accordance with IPC-TM-650 2.4.13.1 method.

[0116] Flame retardancy: Test and classify according to the material flammability method specified in UL-94.

[0117] The above performance test results are detailed in Table 2 below.

[0118] Table 2

[0119]

[0120] Table 3

[0121]

[0122] Table 4

[0123]

[0124]

[0125] Note: When the release effect is "△", it is impossible to obtain a complete resin film for pressing, and there is no plate index.

[0126] Table 5

[0127]

[0128] From the above content, it can be seen that the present invention designs the composition of the resin composition, uses a thermoplastic polyphenylene ether, a low molecular weight polyolefin resin, and a high tensile strength polyolefin resin in combination, and controls the dosage of the three within a specific range, thereby preparing a resin composition with excellent performance, and then preparing a resin film with ultra-thin thickness, which can match the high-frequency substrate, can withstand the high-temperature pressing conditions of the high-frequency substrate, and is suitable for the processing of thick copper products of high-frequency hydrocarbon substrates. The prepared resin film is easy to peel off from the release film, and the metal foil-clad laminate prepared from the resin film has a dielectric constant of 3.34-3.69, a dielectric loss tangent of 0.0033-0.0039, and a sheet peel strength of 1.14-1.59, and can pass the thermal stress test, the thermal stress (288°C copper tin immersion)>180s, and has good flame retardancy, and its flame retardancy grade is V-0.

[0129] It can be seen from Example 1, Examples 10-15 and Comparative Examples 1-6 that the present invention prepares resin films and metal foil-clad laminates with excellent performance by controlling the amounts of thermoplastic polyphenylene ether, low molecular weight polyolefin resin, and high tensile strength polyolefin resin within specific ranges.

[0130] It can be seen from Example 1, Examples 16-17 and Comparative Examples 7-8 that the present invention prepares a resin film and a metal foil-clad laminate with excellent performance by controlling the thickness of the resin film within a specific range.

[0131] It can be seen from Examples 1-17 and Comparative Example 9 that the present invention prepares a metal foil-clad laminate with excellent performance by using a resin film.

[0132] It can be seen from Examples 1-17 and Comparative Examples 10-12 that the present invention prepares a resin composition and a resin film with excellent performance by designing the specific composition of the resin composition, thereby improving the comprehensive performance of the metal foil-clad laminate.

[0133] It can be seen from Examples 1-17 and Comparative Examples 13-14 that the resin film provided by the present invention is suitable for processing thick copper products of high-frequency hydrocarbon substrates, and the metal foil-clad laminate prepared thereby has a high peel strength of the sheet material. In summary, the present invention designs the composition of the resin composition, uses thermoplastic polyphenylene ether, low molecular weight polyolefin resin, and high tensile strength polyolefin resin in combination, and controls the dosage of the three within a specific range, thereby preparing a resin composition with excellent performance, and then preparing a resin film with ultra-thin thickness, which can match the high-frequency substrate, can withstand the high-temperature pressing conditions of the high-frequency substrate, and is suitable for processing thick copper products of high-frequency hydrocarbon substrates.

[0134] The applicant declares that the present invention illustrates the detailed process flow of the present invention through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned detailed process flow, that is, it does not mean that the present invention must rely on the above-mentioned detailed process flow to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of various raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A resin composition, characterized in that The resin composition comprises the following components in parts by weight: (A) thermoplastic polyphenylene ether, 30 to 55 parts; (B) low molecular weight polyolefin resin, 10 to 35 parts; (C) high tensile strength polyolefin resin, 20 to 50 parts, wherein the tensile strength of the high tensile strength polyolefin resin is ≥ 20 MPa.

2. The resin composition according to claim 1, characterized in that The thermoplastic polyphenylene ether resin comprises the following structural units: Wherein, R1, R2, R3 and R4 are each independently selected from any one of hydrogen, a halogen atom, a C1-C7 alkyl group, a C1-C7 haloalkyl group, a C1-C7 aminoalkyl group, a C1-C7 alkoxy group, a C6-C10 aryl group or a C6-C10 aryloxy group; Preferably, the thermoplastic polyphenylene ether is selected from poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,3,6-trimethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, poly (2,6-dipropyl-1,4-phenylene) ether, poly (2-methyl-6-allyl-1,4-phenylene) ether, poly (di-tert-butyl-dimethoxy-1,4-phenylene) ether, poly (2,6-dichloromethyl Any one or a combination of at least two of poly(2,6-dibromomethyl-1,4-phenylene) ether, poly(2,6-bis(2-chloroethyl)-1,4-phenylene) ether, poly(2,6-xylyl-1,4-phenylene) ether, poly(2,6-dichloro-1,4-phenylene) ether, poly(2,6-diphenyl-1,4-phenylene) ether and poly(2,5-dimethyl-1,4-phenylene) ether.

3. The resin composition according to claim 1 or 2, characterized in that The number average molecular weight of the low molecular weight polyolefin resin is ≤10000 g / mol; Preferably, the weight ratio of the butadiene units added at the 1,2 positions in the low molecular weight polyolefin resin is ≥ 65%; Preferably, the low molecular weight olefin resin is selected from any one or a combination of at least two of a polybutadiene resin with an unsaturated double bond, a modified polybutadiene resin with an unsaturated double bond, or a polybutadiene copolymer resin with an unsaturated double bond; Preferably, the polybutadiene resin with unsaturated double bonds comprises 1,2-polybutadiene resin; Preferably, the modified polybutadiene resin with unsaturated double bonds is selected from any one of maleic anhydride modified polybutadiene resin, acrylate modified polybutadiene resin, epoxy modified polybutadiene resin, amine modified polybutadiene resin, carboxyl modified polybutadiene resin, and hydroxyl modified polybutadiene resin, or a combination of at least two thereof; Preferably, the polybutadiene copolymer resin with unsaturated double bonds is selected from any one of polybutadiene-styrene copolymer resin, polybutadiene-styrene-divinylbenzene graft copolymer resin, maleic anhydride modified styrene-butadiene copolymer resin and acrylate modified styrene-butadiene copolymer resin or a combination of at least two thereof.

4. The resin composition according to any one of claims 1 to 3, characterized in that The high tensile strength polyolefin resin is selected from any one or a combination of at least two of elastomeric block copolymers, ethylene-propylene rubber, polybutadiene rubber, and styrene-butadiene rubber; Preferably, the elastomeric block copolymer is selected from any one or a combination of at least two of a styrene-butadiene diblock copolymer, a styrene-butadiene-styrene triblock copolymer, a styrene-(ethylene-butylene)-styrene triblock copolymer, a styrene-isoprene diblock copolymer, a styrene-isoprene-styrene triblock copolymer, a styrene-(ethylene-propylene)-styrene triblock copolymer, and a styrene-(ethylene-butylene) diblock copolymer.

5. The resin composition according to any one of claims 1 to 4, characterized in that The resin composition also includes a flame retardant; Preferably, the flame retardant is selected from bromine-containing flame retardants and / or phosphorus-containing flame retardants; Preferably, the resin composition further comprises a free radical initiator; Preferably, the free radical initiator is selected from organic peroxide free radical initiators and / or carbon-based free radical initiators; Preferably, the resin composition further comprises an additive; Preferably, the additive includes any one or a combination of at least two of a crosslinking agent, a coupling agent, a leveling agent, a defoaming agent, an antioxidant, a heat stabilizer, an antistatic agent, an ultraviolet absorber, a pigment, a colorant or a lubricant.

6. A resin film, characterized in that: The resin film is obtained by coating the resin composition according to any one of claims 1 to 5 on a release material.

7. The resin film according to claim 6, characterized in that: The thickness of the resin film is 10-25 μm, preferably 15-20 μm.

8. A metal foil-clad laminate, characterized in that: The metal foil-clad laminate comprises copper foil and at least one resin film as claimed in claim 6 or 7. Preferably, the metal foil clad laminate further comprises a prepreg.

9. The metal foil-clad laminate according to claim 8, characterized in that: The copper foil is a thick copper foil with a thickness of ≥3OZ (105μm).

10. A printed circuit board, characterized in that: The printed circuit board comprises the resin film according to claim 6 or 7; Preferably, the printed circuit board is a high-frequency substrate.

Images