Resin Composition and Its Applications

Abstract

The present invention provides a resin composition and its application. By weight, the resin composition includes: maleimide resin and / or maleimide prepolymer: 20 parts by weight to 100 parts by weight; allyl-modified imide resin: 1 part by weight to 80 parts by weight; elastomer: 5 parts by weight to 70 parts by weight; the elastomer is a combination of elastomer A, elastomer B, and elastomer C, and the weight ratio of elastomer A, elastomer B, and elastomer C is (5 to 50):(1 to 30):(5 to 40); the elastomer A is an acrylate or methacrylate block copolymer; the elastomer B is a styrene block copolymer; the elastomer C is a silicone copolymer; the disadvantages of each elastomer are reduced, the compatibility between the resins is improved, the resin crosslinking and curing reaction is improved, and a cured product with high heat resistance, high toughness, low CTE, low water absorption, and high adhesiveness is obtained.

Description

Technical Field

[0001] The present invention relates to the technical field of electronic materials, and particularly relates to a resin composition and its application. Background Art

[0002] In recent years, electronic devices have been developing towards miniaturization and high performance, which has led to the continuous development of the wiring density in printed circuit boards towards high density and high concentration. This has put forward higher requirements for the heat resistance and reliability of copper clad laminates. Especially in semiconductor packaging substrates, the difference in thermal expansion coefficients between the chip and the organic substrate during packaging assembly easily causes warping problems.

[0003] In the prior art, generally, a high content of inorganic fillers is added to the resin composition to meet the requirement of a low coefficient of thermal expansion. However, the high content of inorganic fillers will increase the viscosity of the resin composition solution, seriously affecting the product preparation process and the drilling processability of the final printed circuit board. Therefore, it is difficult to obtain a final cured product that simultaneously meets low thermal expansion and excellent processability through this method.

[0004] Nadic acid type allylated imide resin (Bisallylnadic Imide, abbreviated as BANI) has an allyl norbornene structure in its molecular structure. Therefore, BANI resin has excellent solvent solubility and a low melting point, very excellent compatibility with other resins, and the cured product finally formed has good heat resistance. In BANI resin, the allyl group in the structure and the carbon-carbon double bond in norbornene undergo an addition reaction, and at the same time, an addition reaction also occurs with other resins (such as maleimide) to form a crosslinked network structure. However, the crosslinked network structure has a large rigidity and a large coefficient of thermal expansion under high temperature conditions, and it is difficult to meet the warping requirements of thin packaging substrates.

[0005] Elastomers belong to thermoplastic materials and have excellent flexibility and good elasticity. They can improve brittleness in thermosetting resin compositions and reduce CTE and warping. However, thermoplastic elastomers have poor compatibility in thermosetting resin compositions, it is difficult to control the production processability, and they are likely to precipitate when a relatively large content is added, and the required performance cannot be achieved when a relatively small content is added. Summary of the Invention

[0006] The purpose of the present invention is to provide a resin composition and its application.

[0007] To achieve the above-mentioned invention purpose, the present invention adopts the following technical scheme: A resin composition, by weight, the resin composition includes:

[0008] Maleimide resin and / or maleimide prepolymer: 20 parts by weight to 100 parts by weight;

[0009] Allyl-modified imide resin: 1 to 80 parts by weight;

[0010] Elastomer: 5 to 70 parts by weight;

[0011] The elastomer is a combination of elastomer A, elastomer B, and elastomer C, and the weight ratio of elastomer A, elastomer B, and elastomer C is (5 to 50):(1 to 30):(5 to 40);

[0012] The elastomer A is an acrylate or methacrylate block copolymer;

[0013] The elastomer B is a styrene block copolymer;

[0014] The elastomer C is a silicone copolymer.

[0015] As a further improvement of the present invention, the allyl-modified imide resin contains the following structural formula (1),

[0016] Structural formula (1);

[0017] Among them, the R group in the structural formula (1) is , , , , or .

[0018] As a further improvement of the present invention, the resin composition further contains an allyl compound other than the allyl-modified imide resin, and the content of the allyl compound is 1 to 50 parts by weight.

[0019] As a further improvement of the present invention, the allyl compound is at least one of diallyl bisphenol A, diallyl bisphenol S, allyl phenoxy resin, allyl phenolic resin, and diallyl diphenyl ether.

[0020] As a further improvement of the present invention, the elastomer A contains the structural formula (2) and / or the structural formula (3):

[0021] Structural formula (2), in the structural formula (2), R1 is an alkyl group of C1 to C5, and x is an integer of 1 to 100;

[0022] Structural formula (3), in the structural formula (3), R2 is an alkyl group of C1 to C5, and y is an integer of 1 to 100.

[0023] As a further improvement of the present invention, the elastomer B is at least one of a hydrogenated styrene and butadiene diblock copolymer, a hydrogenated styrene and butadiene triblock copolymer, a hydrogenated styrene and pentadiene diblock copolymer, and a hydrogenated styrene and pentadiene triblock copolymer.

[0024] As a further improvement of the present invention, the elastomer C contains at least one unit of the structures in formula (4), formula (5), and formula (6):

[0025] Formula (4), in formula (4), R is a C1-C 12 hydrocarbyl group;

[0026] Formula (5), in formula (5), R is a C1-C 12 hydrocarbyl group;

[0027] Formula (6), in formula (6), X is a mercapto group, an epoxy group, a hydroxyl group, or a methoxy group.

[0028] As a further improvement of the present invention, the resin composition further contains an epoxy resin or / and a cyanate resin.

[0029] As a further improvement of the present invention, the resin composition further includes an inorganic filler, and / or a dispersant, and / or a coupling agent, and / or a flame retardant, and / or a catalyst in an amount of 0.01 to 5 parts by weight; wherein, based on a total of 100 parts by weight of the maleimide resin and / or the maleimide prepolymer and the allyl-modified imide resin, the inorganic filler is 30 to 250 parts by weight, the dispersant is 0.001 to 5 parts by weight, the coupling agent is 0.001 to 10 parts by weight, and the flame retardant is 1 to 60 parts by weight.

[0030] To achieve the above-mentioned invention object, the present invention also provides an application of the above resin composition in prepregs, laminates, and printed circuit boards.

[0031] Beneficial effects: Compared with the prior art, the present invention has the following advantages:

[0032] In the resin composition of the present invention, by adding different types of elastomers to the resin composition, the disadvantages of each elastomer are reduced. For example, elastomer A has a relatively high molecular weight. When a large amount of elastomer A is added, it affects the adhesion between the copper foil and the prepreg and has poor compatibility with the thermosetting resin. Elastomer B has poor compatibility when its content is excessive. Elastomer C has a relatively small density and is likely to float to the surface in the resin composition glue solution, making it difficult to mix a relatively homogeneous glue solution system. Therefore, its improvement in CTE is limited, and it has a greater impact on the peel strength. At the same time, it can improve the compatibility between resins, improve the resin cross-linking and curing reaction, inhibit the decrease in heat resistance, improve toughness, reduce CTE, and obtain a final cured product with high heat resistance, high toughness, low CTE, low water absorption, and high adhesion, thereby obtaining a cured product with relatively excellent comprehensive performance, meeting the existing requirements for printed circuit boards. Detailed Embodiments

[0033] The following are the detailed embodiments of the embodiments of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the principles of the embodiments of the present invention, several improvements and refinements can be made, and these improvements and refinements are also regarded as the protection scope of the embodiments of the present invention.

[0034] The "including" and "containing" in this specification mean that in addition to the components described, other components can also be included, and these other components can endow the resin composition with different characteristics.

[0035] The present invention provides a resin composition, which, by weight, includes:

[0036] Maleimide resin and / or maleimide prepolymer: 20 parts by weight to 100 parts by weight;

[0037] Allyl-modified imide resin: 1 part by weight to 80 parts by weight;

[0038] Elastomer: 5 parts by weight to 70 parts by weight;

[0039] The elastomer is a combination of elastomer A, elastomer B, and elastomer C, and the weight ratio of elastomer A, elastomer B, and elastomer C is (5 - 50):(1 - 30):(5 - 40);

[0040] The elastomer A is an acrylate or methacrylate block copolymer;

[0041] The elastomer B is a styrene block copolymer;

[0042] The elastomer C is a silicone copolymer.

[0043] In the resin composition of the present invention, by adding different types of elastomers to the resin composition, the disadvantages of each elastomer are reduced. For example, elastomer A has a relatively high molecular weight. When a large amount of elastomer A is added, it affects the adhesion between the copper foil and the prepreg, and has poor compatibility with the thermosetting resin. Elastomer B has poor compatibility when its content is excessive. Elastomer C has a relatively small density and is likely to float to the surface in the resin composition glue solution, making it difficult to mix a relatively homogeneous glue solution system. Therefore, its improvement in CTE is limited, and it has a greater impact on the peel strength. At the same time, it can improve the compatibility between resins, improve the resin cross-linking and curing reaction, inhibit the decrease in heat resistance, improve toughness, reduce CTE, and obtain a final cured product with high heat resistance, high toughness, low CTE, low water absorption, and high adhesion, thereby obtaining a cured product with relatively excellent comprehensive performance, meeting the existing requirements for printed circuit boards.

[0044] It should be noted that the cured product described in the present invention can be understood as a prepreg, a laminate, a printed circuit board, etc.

[0045] Furthermore, the allyl-modified imide resin contains the following structural formula (1):

[0046] Structural formula (1);

[0047] Among them, the R group in structural formula (1) is , , , , or .

[0048] Specifically, the allyl-modified imide resin can be selected from BANI-M, BANI-H, or BANI-X manufactured by Maruzen Chemical Co., Ltd. of Japan.

[0049] Furthermore, the resin composition further contains an allyl compound other than the allyl-modified imide resin, and the content of the allyl compound is 1 part by weight to 50 parts by weight. Adding an appropriate amount of allyl monomer compound to the maleimide resin and allyl-modified imide resin system can make the cross-linking and curing reaction proceed more fully, better introduce high-molecular-weight elastomers into the curing system, improve toughness while further increasing the peel strength, and make the overall cross-linking structure more dense.

[0050] Preferably, the allyl compound is at least one of diallyl bisphenol A, diallyl bisphenol S, allyl phenolic resin, allyl novolak resin, and diallyl diphenyl ether.

[0051] Furthermore, the elastomer A contains structural formula (2) and / or structural formula (3):

[0052] Structural formula (2), in which R1 is an alkyl group with 1 to 5 carbon atoms, and x is an integer from 1 to 100;

[0053] Structural formula (3), in which R2 is an alkyl group with 1 to 5 carbon atoms, and y is an integer from 1 to 100.

[0054] In a specific embodiment, R1 is methyl, and R2 is methyl, ethyl or butyl. Of course, it is not limited thereto.

[0055] Preferably, the structural formula of the elastomer A is as follows:

[0056] , where I, m and n are integers from 1 to 100 respectively.

[0057] Further, the weight-average molecular weight of the elastomer A is 20,000 to 400,000.

[0058] Further, the elastomer A may further contain the following structural units:

[0059] , where R3 is hydrogen or methyl, and o is an integer from 1 to 100.

[0060] Specifically, when the elastomer A contains epoxy groups, the epoxy value of the elastomer A is 0.01 - 0.65 eq / kg.

[0061] Specifically, the elastomer A can be selected from those with the trade names M51, M52, M22 or D51N prepared by Arkema; those with the trade names LA2250, LA2140, LA-2330, LA4285, etc. prepared by Kuraray Co., Ltd.; SG-P3, SG-80H, PMS-22-1, PMS-22-4, PMS-19-5, PMS-22-5, etc. prepared by Nagase ChemteX Corporation of Japan.

[0062] Further, the elastomer B is at least one of a hydrogenated styrene and butadiene diblock copolymer, a hydrogenated styrene and butadiene triblock copolymer, a hydrogenated styrene and pentadiene diblock copolymer, and a hydrogenated styrene and pentadiene triblock copolymer.

[0063] Specifically, the elastomer B can be selected from SEPTONTM 2000 series (2002, 2004, 2005, 2006, 2063, 2104), SEPTONTM 4000 series (4033, 4044, 4055, 4077), HYBRAR™ 7000 series (7125, 7311), SEPTONTM 8000 series (8004, 8006, 8007L, 8851), SEPTONTM V series (9461, 9475), SEPTONTM Q1250, etc. manufactured by KURARE of Japan; H1041, H1043, H1051, H1052, H1053, H1221, etc. manufactured by Asahi Kasei.

[0064] Further, the elastomer C contains at least one unit of the structures in structural formula (4), structural formula (5) and structural formula (6):

[0065] Structural formula (4), in which R in structural formula (4) is a C1-C 12 hydrocarbyl group or ;

[0066] Structural formula (5), in which R in structural formula (5) is a C1-C 12 hydrocarbyl group or ;

[0067] Structural formula (6), in which X in structural formula (6) is a mercapto group, an epoxy group, a hydroxyl group or a methoxy group.

[0068] Preferably, R in structural formula (4), structural formula (5) and structural formula (6) is a methyl group or a phenyl group. X in structural formula (6) is an epoxy group or a mercapto group.

[0069] Specifically, the elastomer C can be selected from SQ-20P or KHE-8000H manufactured by Nippon Kayaku Co., Ltd., SQ502-8 manufactured by Arakawa Chemical Industries, Ltd., AY42-119 manufactured by DuPont Toray Co., Ltd., and the grades X-40-2670, R-170S, X-40-2705, X-40-2701, KMP-600, KMP-605, X-52-7030 prepared by Shin-Etsu Chemical Co., Ltd.; EP-2600, EP-2601, EP-2720, TMS-2670, EXL-2315, EXL-2655, etc. of DOW.

[0070] In a preferred embodiment, the weight ratio of elastomer A, elastomer B, and elastomer C is (20 to 50):(1 to 10):(5 to 20). At this time, in the elastomer composition, acrylate or methacrylate block copolymer elastomer A is used as the main component, and an appropriate amount of styrenic elastomer B and silicone elastomer C are combined, which can ensure relatively high toughness while reducing the dielectric properties and water absorption rate, and the elastomer does not precipitate during the processing, and the resin composition has good fluidity of the glue solution.

[0071] In another preferred embodiment, the weight ratio of elastomer A, elastomer B, and elastomer C is (5 to 20):(15 to 30):(5 to 10). At this time, in the elastomer composition, styrenic elastomer B is used as the main component, and an appropriate amount of acrylate or methacrylate elastomer A and silicone elastomer C are combined, which can ensure very excellent dielectric properties while reducing the CTE and water absorption rate, and the elastomer does not precipitate during the processing, and the resin composition has good fluidity of the glue solution.

[0072] In yet another preferred embodiment, the weight ratio of elastomer A, elastomer B, and elastomer C is (5 to 20):(1 to 15):(20 to 40). At this time, in the elastomer composition, silicone elastomer C is used as the main component, and an appropriate amount of acrylate or methacrylate elastomer A and styrenic elastomer B are combined, which can ensure a very low CTE while reducing the dielectric properties and water absorption rate, and the elastomer does not precipitate during the processing, and the resin composition has good fluidity of the glue solution.

[0073] It is known that the content of various elastomers can be adjusted according to the specific performance requirements of the final cured product.

[0074] Furthermore, the total content of elastomer A, elastomer B, and elastomer C is 20 parts by weight to 55 parts by weight.

[0075] Furthermore, the maleimide resin is at least one of the following structural formulas:

[0076] Structural formula (7);

[0077] Structural formula (8);

[0078] Structural formula (9);

[0079] Structural formula (10); wherein, in structural formula (10), R2 is hydrogen, methyl or ethyl, and R1 is methylene, ethylene or ;

[0080] Structural formula (11);

[0081] Structural formula (12), wherein n in the structural formula (12) is an integer from 1 to 10;

[0082] Structural formula (13), wherein n in the structural formula (13) is an integer from 1 to 10;

[0083] Structural formula (14), wherein n in the structural formula (14) is an integer from 1 to 10;

[0084] Structural formula (15), wherein n in the structural formula (15) is an integer from 1 to 10;

[0085] Structural formula (16), wherein R in the structural formula (16) is hydrogen, methyl or ethyl, and n is an integer from 1 to 10.

[0086] Further, the maleimide prepolymer is selected from any one or a combination of at least two of prepolymers of diallyl compounds and maleimide compounds, prepolymers of diamines and maleimide compounds, prepolymers of polyfunctional amines and maleimide compounds, and prepolymers of acidic phenolic compounds and maleimide compounds.

[0087] Specifically, the maleimide compounds may include BMI-1000, BMI-1000H, BMI-1100, BMI-1100H, BMI-2000, BMI-2300, BMI-3000, BMI-3000H, BMI-4000H, BMI-5000, BMI-5100, BMI-7000 and BMI-7000H manufactured by Daiwa Kasei Co., Ltd.; BMI, BMI-70, BMI-80, etc. manufactured by KI Kasei Co., Ltd. of Japan; MIR-3000, MIR-5000, etc. manufactured by Nippon Kayaku Co., Ltd.; X9-450, X9-470, etc. manufactured by DIC Corporation of Japan; D936, D937, D939, D950, etc. manufactured by Sichuan Dongcai Co., Ltd.

[0088] Preferably, the maleimide compounds may include BMI-2300 manufactured by Daiwa Kasei Co., Ltd., BMI-70 and BMI-80 manufactured by KI Kasei Co., Ltd., and MIR-3000 manufactured by Nippon Kayaku Co., Ltd.

[0089] Further, the resin composition further contains epoxy resin or / and cyanate resin.

[0090] Preferably, the epoxy resin is selected from one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol E epoxy resin, phosphorus-containing epoxy resin, o-cresol novolac epoxy resin, bisphenol A phenolic epoxy resin, phenol phenolic epoxy resin, cresol phenolic epoxy resin, triphenylmethane epoxy resin, tetraphenylethane epoxy resin, biphenyl type epoxy resin, naphthalene ring type epoxy resin, dicyclopentadiene type epoxy resin, isocyanate type epoxy resin, aralkyl linear phenolic epoxy resin, alicyclic epoxy resin, glycidylamine type epoxy resin, glycidyl ether type epoxy resin, glycidyl ester type epoxy resin.

[0091] Based on a total of 100 parts by weight of maleimide resin and / or maleimide prepolymer and allyl-modified imide resin, the epoxy resin contains 1 to 30 parts by weight.

[0092] Furthermore, the cyanate resin is a compound containing at least one cyanate group in its molecular structure, and the cyanate resin can be a monomer, polymer, prepolymer or a combination thereof.

[0093] Preferably, the cyanate resin is a prepolymer, a combination of prepolymer and monomer or a combination of prepolymer and polymer.

[0094] Specifically, the cyanate resin can be selected from at least one of bisphenol A cyanate, bisphenol F cyanate, bisphenol E cyanate, bisphenol M cyanate, DCPD cyanate, naphthalene cyanate, phenolic cyanate, biphenyl cyanate.

[0095] Based on a total of 100 parts by weight of maleimide resin and / or maleimide prepolymer and allyl-modified imide resin, the cyanate resin contains 1 to 35 parts by weight.

[0096] Furthermore, the resin composition further contains an inorganic filler. Based on a total of 100 parts by weight of maleimide resin and / or maleimide prepolymer and allyl-modified imide resin, the inorganic filler is 30 to 250 parts by weight.

[0097] The inorganic filler is at least one of spherical silica, aluminum hydroxide, alumina, talc powder, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate, mica, glass fiber powder.

[0098] Preferably, the inorganic filler is silica.

[0099] Furthermore, the inorganic filler is an inorganic filler surface-treated with a silane coupling agent. Among them, the silane coupling agent is at least one of an amino silane coupling agent, a carbon-carbon double bond-containing silane coupling agent, and an epoxy silane coupling agent.

[0100] Preferably, the inorganic filler is spherical silica surface-treated with a phenylamino silane coupling agent. Among them, the phenylamino silane coupling agent has the following structure:

[0101] , where R is a straight-chain alkylene group with 1 to 6 carbon atoms, and X is a methoxy group or an ethoxy group.

[0102] In a specific embodiment, based on a total of 100 parts by weight of the maleimide resin and / or maleimide prepolymer and the allyl-modified imide resin, 30 to 100 parts by weight of the inorganic filler is contained.

[0103] In the present invention, by appropriately adjusting the content ratio range of the three elastomers to achieve a relatively high level of elastomer content, and at the same time reducing the content of the inorganic filler, a resin composition with a lower CTE can be obtained, which can meet excellent drilling processability, and significantly reduce the fluidity of the resin composition glue solution, improving the production processability.

[0104] Furthermore, the resin composition further includes a dispersant and a coupling agent. Based on a total of 100 parts by weight of the maleimide resin and / or maleimide prepolymer and the allyl-modified imide resin, the content of the dispersant is 0.001 to 5 parts by weight, and the content of the coupling agent is 0.001 to 10 parts by weight.

[0105] Specifically, the dispersant can be selected from BYK-161 or / and BYK-111 manufactured by BYK Company. The coupling agent can be selected from KBM-402, KBM-403, KBM-502, KBE-503, KBM-603, KBM-903, KBM-573, KBM-602, KBM-1003, etc. manufactured by Shin-Etsu Chemical.

[0106] Furthermore, the resin composition further contains a flame retardant. Based on a total of 100 parts by weight of the maleimide resin and / or maleimide prepolymer and the allyl-modified imide resin, the flame retardant is 1 to 60 parts by weight. It can improve the flame retardancy of the finally formed cured product, and the cured product can be understood as a prepreg, a laminate, a printed circuit board, etc.

[0107] Specifically, the flame retardant is selected from at least one of bromine-based flame retardants, phosphorus-based flame retardants, nitrogen-based flame retardants, silicone-based flame retardants, organometallic flame retardants, and inorganic flame retardants.

[0108] Among them, the bromine-based flame retardant can be decabromodiphenyl ether, decabromodiphenylethane, brominated styrene or tetrabromo phthalic amide. The phosphorus-based flame retardant can be inorganic phosphorus, condensed phosphate ester compound, phosphonic acid compound, hypophosphorous acid compound, phosphine oxide compound, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-phenyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, tris(2,6-dimethylphenyl)phosphine, (where m is an integer from 1 to 5), , and organic phosphorus-containing compounds such as phosphonitrile. The nitrogen-based flame retardant can be triazine compound, cyanuric acid compound, isocyanate compound, phenothiazine, etc. The organosilicon flame retardant can be organosilicone oil, organosilicone rubber, organosilicone resin, etc. The organometallic salt flame retardant can be ferrocene, acetylacetone metal complex, organometallic carbonyl compound, etc. The inorganic flame retardant can be aluminum hydroxide, magnesium hydroxide, aluminum oxide, barium oxide, etc.

[0109] Specifically, the flame retardant can be SPB-100 manufactured by Otsuka Chemical, FP-100, FP-300B or FP-390 manufactured by Fushimi Pharmaceutical Co., Ltd., PX-200, PX-201 or PX-202 manufactured by Daihachi Chemical Industry Co., Ltd., OP-935 or OP-930 manufactured by Clariant, SAYTEX8010, HP-7010 or BT-93W manufactured by Albemarle, OL3001 or OL5000 manufactured by FRX of the United States, etc.

[0110] Furthermore, the resin composition further contains 0.01 to 5 parts by weight of a catalyst. The catalyst is at least one of imidazole catalysts, pyridine catalysts, and organometallic salt catalysts.

[0111] Preferably, the catalyst is at least one of 4-dimethylaminopyridine, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, modified imidazole, and zinc octoate.

[0112] Furthermore, the present invention also provides an application of the above resin composition in prepregs, laminates, and printed circuit boards.

[0113] Specifically, the prepreg includes a reinforcing material and the above resin composition attached to the surface of the reinforcing material.

[0114] The reinforcing material is selected from at least one of natural fibers, organic synthetic fibers, organic fabrics, and inorganic fabrics.

[0115] Preferably, the reinforcing material is a glass fiber cloth, and among the glass fiber cloths, an open-fiber cloth or a flat cloth is preferably used. More preferably, the glass fiber cloth is an E glass fiber cloth, an S glass fiber cloth, a T glass fiber cloth, or a Q glass fiber cloth.

[0116] In addition, when the reinforcing material is a glass fiber cloth, the glass fiber cloth generally needs to be chemically treated to improve the bonding between the resin composition and the interface of the glass fiber cloth. The main method of the chemical treatment is coupling agent treatment. The coupling agent used is preferably an epoxy silane coupling agent or an amino silane coupling agent, etc., to provide good water resistance and heat resistance.

[0117] The method for preparing the prepreg is as follows:

[0118] Dissolve the resin composition in a solvent to make a resin composition solution;

[0119] Immerse the reinforcing material in the above resin composition solution, and then take out the impregnated reinforcing material and heat it for drying to obtain the prepreg.

[0120] In a specific embodiment, the impregnated reinforcing material is baked in an environment of 100°C to 180°C for 1 minute to 15 minutes, and after drying, the prepreg can be obtained.

[0121] Specifically, the solvent can be selected from one or any combination of acetone, butanone, toluene, methyl isobutyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide, ethylene glycol methyl ether, propylene glycol methyl ether, benzene, toluene, xylene, cyclohexane.

[0122] In the present invention, the addition amount of the solvent used is not specifically limited. The addition amount of the solvent is selected by those skilled in the art according to their own experience, as long as the obtained resin composition solution can reach a suitable viscosity for use.

[0123] The laminate includes at least one of the above prepregs and a metal foil formed on at least one surface of the prepreg.

[0124] In the embodiment where the laminate includes at least two of the above prepregs, the at least two prepregs are laminated and bonded together by heating and pressing, and then a metal foil is bonded to one side or both sides of the bonded prepregs by heating and pressing to form the laminate.

[0125] Specifically, the preparation steps of the laminate are as follows: Cover a metal foil on one side or both sides of one of the above prepregs, or stack at least 2 of the above prepregs and then cover a metal foil on one side or both sides of them, and hot press to form a laminate.

[0126] The pressing conditions of the above laminate are: pressing at a pressure of 0.2 to 2 MPa and a temperature of 150°C to 250°C for 2 to 4 hours.

[0127] Specifically, the number of the prepregs can be determined according to the thickness of the required laminate, and one or more prepregs can be used.

[0128] The metal foil can be copper foil or aluminum foil, and its material is not limited; the thickness of the metal foil is not particularly limited either, and for example, 5 μm, 8 μm, 12 μm, 18 μm, 35 μm or 70 μm are all acceptable.

[0129] The printed circuit board includes at least one of the above prepregs, or the printed circuit board includes at least one of the above laminates.

[0130] The preparation method of the printed circuit board can adopt the existing process, which will not be elaborated here.

[0131] The following will specifically illustrate the content of the present invention with specific examples; of course, it can be understood that the embodiments of the present invention are not limited to these examples.

[0132] Examples 1 to 7 and Comparative Examples 1 to 6:

[0133] The components and contents of the resin compositions in Examples 1 to 7 and Comparative Examples 1 to 6 are shown in Table 1 below:

[0134] Table 1

[0135]

[0136] Specifically, the information of each component involved in Table 1 above is shown in Table 2 below:

[0137] Table 2

[0138]

[0139] The preparation method of the resin compositions in Examples 1 to 7 and Comparative Examples 1 to 6 adopts a conventional preparation method, specifically: mixing with an appropriate amount of solvent according to the components and corresponding contents in Table 1, and dispersing and mixing evenly to obtain a resin composition glue solution with a solid content of 60%, wherein the solid content of 60% is based on weight.

[0140] Coat the obtained resin composition glue solutions in Examples 1 - 7 and Comparative Examples 1 - 6 on T glass fiber cloth, take it out after infiltration, and place it in a forced-air drying oven at 160°C for baking for 3 - 6 min to make prepregs.

[0141] Prepare sample laminates for performance evaluation:

[0142] (1) Prepare laminates

[0143] Cut the prepregs obtained in the above Examples 1-7 and Comparative Examples 1-6 into 300×300 mm respectively. Place a metal foil on each of the opposite sides of the prepreg to form a laminate structure, and place it in a vacuum hot press to press and obtain laminates respectively.

[0144] Specifically, the metal foil is an 18μm low-profile electrolytic copper foil. Of course, it is not limited thereto.

[0145] Performance evaluation method:

[0146] (1) Dielectric constant (Dk) / Dielectric loss (Df): Measured at 10 GHz using the flat plate method in accordance with IPC-TM-650 2.5.5.9;

[0147] (2) Glass transition temperature (Tg): Tested using a dynamic mechanical analysis (DMA) instrument, where the heating rate is 10°C / min, and "none" indicates that the Tg is higher than 350°C.

[0148] (3) PCT 2HR water absorption measurement: Take 3 samples of 10 cm×10 cm, 0.40 mm thick, with the metal foil removed from both sides, dry them at 100°C for 2 hours, weigh them, record the weight as W1, then place them in a pressure cooker test machine, process them at 121°C and 2 atmospheres for 2 hours, weigh them, record the weight as W2, and measure the water absorption as (W2 - W1) / W1×100%;

[0149] (4) X / Y coefficient of thermal expansion (CTE) measurement: Use TMA (Thermomechanical Analysis), with a heating rate of 10°C / min and a test temperature range of 30~100°C;

[0150] (5) Heat resistance to tin immersion after damp heat treatment (PCT 1 hr): Take 3 samples of 10 cm×10 cm, 0.80 mm thick, with the metal foil removed from both sides, dry them at 100°C for 2 hours, then use a pressure cooker test machine, process them at 121°C and 2 atmospheres for 1 hour, and then immerse them in a tin bath at 288°C for 20 s. Visually observe whether there is delamination. If there is no delamination among the 3 samples, it is recorded as [Pass], and if there is delamination, it is recorded as [Fail].

[0151] (6) Peel strength (PS, N / mm): Test the peel strength of the metal cover layer according to the experimental conditions of "after thermal stress" in the method of IPC-TM-650 2.4.8.

[0152] (7) Plate thickness accuracy: After etching the copper clad laminate, measure the thickness difference between the center and the edge of the test board, and calculate the average value after testing 3 times. When the thickness difference is greater than 0.05 mm, it is marked as Ⅹ; when the thickness difference is 0.01 - 0.05 mm, it is marked as Δ; when the thickness difference is less than 0.01 mm, it is marked as О.

[0153] The laminate properties obtained from the prepregs in Examples 1 - 7 and Comparative Examples 1 - 6 above are shown in Table 3 below.

[0154] Table 3

[0155]

[0156] As can be seen from Table 3, the laminate obtained by using the resin composition of the present invention has a higher glass transition temperature, lower dielectric constant, dielectric loss, coefficient of thermal expansion, water absorption rate, better heat resistance, higher peel strength, and higher plate thickness accuracy, and can obtain a final cured product with high heat resistance, high toughness, low CTE, low water absorption, high adhesion, and high plate thickness accuracy, thereby obtaining a cured product with relatively excellent comprehensive performance, meeting the existing requirements for printed circuit boards.

[0157] In particular, by making a parallel comparison between Example 1 and Comparative Example 1, it can be seen that compared with Comparative Example 1 where only a single type of elastomer A is added, the resin composition in Example 1 contains different types of elastomers A, B, and C, which can reduce the disadvantages of elastomer A. The laminate prepared from the resin composition in Example 1 has lower dielectric constant, dielectric loss, coefficient of thermal expansion, water absorption rate, higher peel strength, and plate thickness accuracy.

[0158] By making a parallel comparison between Example 2 and Comparative Example 2, it can be seen that compared with Comparative Example 2 where only a single type of elastomer B is added, the resin composition in Example 2 contains different types of elastomers A, B, and C, which can reduce the disadvantages of elastomer B. The laminate prepared from the resin composition in Example 2 has lower coefficient of thermal expansion, water absorption rate, better heat resistance, higher peel strength, and plate thickness accuracy.

[0159] By making a parallel comparison between Example 3 and Comparative Example 3, it can be seen that compared with Comparative Example 3 where only a single type of elastomer C is added, the resin composition in Example 3 contains different types of elastomers A, B, and C, which can reduce the disadvantages of elastomer C. The laminate prepared from the resin composition in Example 3 has lower dielectric constant, dielectric loss, coefficient of thermal expansion, water absorption rate, better heat resistance, higher peel strength, and plate thickness accuracy.

[0160] Example 4 and Comparative Example 6 were compared in parallel. It can be seen from the comparison that, compared with Comparative Example 6 which does not contain allyl-modified imide resin, allyl-modified imide resin is added to the resin composition in Example 4. The laminate prepared from the resin composition in Example 4 has a higher glass transition temperature, higher heat resistance, lower dielectric constant, dielectric loss, coefficient of thermal expansion, and water absorption rate.

[0161] Example 5 and Example 2 were compared in parallel. It can be seen from the comparison that the contents of elastomer B and elastomer C in Example 5 are less than those in Example 2. The laminate prepared from the resin composition in Example 2 has lower dielectric constant, dielectric loss, coefficient of thermal expansion, and water absorption rate; while, the laminate prepared from the resin composition in Example 2 has higher peel strength.

[0162] Example 3 and Comparative Example 5 were compared in parallel. It can be seen from the comparison that the contents of elastomer A, B, and C in Comparative Example 5 are less than those in Example 3. The laminate prepared from the resin composition in Example 3 has lower dielectric constant, dielectric loss, coefficient of thermal expansion, and water absorption rate, and higher peel strength.

[0163] Example 3 and Example 7 were compared in parallel. It can be seen from the comparison that diallyl bisphenol A is added in Example 7, that is, the resin composition in Example 7 includes allyl compounds in addition to allyl-modified imide resin. The laminate prepared from the resin composition in Example 7 has lower dielectric constant, dielectric loss, coefficient of thermal expansion, and water absorption rate, and higher peel strength.

[0164] It can be seen from Comparative Example 4 that the contents of elastomer A, B, and C in Comparative Example 4 are too high, exceeding 70 parts by weight, and most of elastomer A, B, and C are granular or thermoplastic resins, and the adhesion to the metal foil is poor. Therefore, the laminate cannot be prepared.

[0165] It should be understood that although this specification is described according to the embodiments, not each embodiment only contains an independent technical solution. This narrative way of the specification is only for clarity. Those skilled in the art should regard the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

[0166] The series of detailed descriptions listed above are only specific descriptions of the feasible embodiments of the present invention, and they are not used to limit the protection scope of the present invention. Any equivalent embodiments or changes made without departing from the technical spirit of the present invention should be included in the protection scope of the present invention.

Claims

1. A resin composition, characterized in that: The resin composition by weight comprises: Maleimide resin and / or maleimide prepolymer: 20 to 100 parts by weight; Allyl-modified imide resin: 1 to 80 parts by weight; Elastomer: 5 to 70 parts by weight; The elastomer is a combination of elastomer A, elastomer B and elastomer C, and the weight ratio of elastomer A, elastomer B and elastomer C is (5 to 50):(1 to 30):(5 to 40); The elastomer A is an acrylate or methacrylate block copolymer; The elastomer B is a styrene block copolymer; The elastomer C is a silicone copolymer; The allyl-modified imide resin contains the following structural formula (1), Structural formula (1); Among them, the R group in the structural formula (1) is , , , , or .

2. The resin composition according to claim 1, characterized in that: The resin composition further contains an allyl compound other than the allyl-modified imide resin, and the content of the allyl compound is 1 to 50 parts by weight.

3. The resin composition according to claim 2, characterized in that: The allyl compound is at least one of diallyl bisphenol A, diallyl bisphenol S, allyl phenolic resin, allyl novolac resin, diallyl diphenyl ether.

4. The resin composition according to claim 1, characterized in that: The elastomer A contains structural formula (2) and / or structural formula (3): Structural formula (2), in which R1 is an alkyl group having 1 to 5 carbon atoms, and x is an integer from 1 to 100; Structural formula (3), wherein R2 in the structural formula (3) is an alkyl group with 1 to 5 carbon atoms, and y is an integer from 1 to 100.

5. The resin composition according to claim 1, characterized in that: The elastomer B is at least one of hydrogenated styrene and butadiene diblock copolymer, hydrogenated styrene and butadiene triblock copolymer, hydrogenated styrene and pentadiene diblock copolymer, hydrogenated styrene and pentadiene triblock copolymer.

6. The resin composition according to claim 1, characterized in that: The elastomer C contains at least one unit of the structures in structural formula (4), structural formula (5) and structural formula (6): Structural formula (4), where R in structural formula (4) is a C1-C 12 hydrocarbyl group; Structural formula (5), in which R in the structural formula (5) is a C1-C 12 hydrocarbyl group; Structural formula (6), wherein X in the structural formula (6) is a mercapto group, an epoxy group, a hydroxyl group or a methoxy group.

7. The resin composition according to claim 1, characterized in that: The resin composition further contains epoxy resin and / or cyanate resin.

8. The resin composition according to claim 1, characterized in that: The resin composition further includes inorganic filler, and / or dispersant, and / or coupling agent, and / or flame retardant, and / or 0.01 to 5 parts by weight of catalyst; wherein, based on a total of 100 parts by weight of maleimide resin and / or maleimide prepolymer and allyl-modified imide resin, the inorganic filler is 30 to 250 parts by weight, the dispersant is 0.001 to 5 parts by weight, the coupling agent is 0.001 to 10 parts by weight, and the flame retardant is 1 to 60 parts by weight.

9. Application of the resin composition according to any one of claims 1 to 8 in prepregs, laminates and printed circuit boards.

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