Resin composition and application thereof

Abstract

The invention provides a resin composition and application thereof. The resin composition comprises, by weight, 20 to 100 parts by weight of maleimide resin and / or maleimide prepolymer; 5 to 50 parts by weight of epoxy resin; 1 to 50 parts by weight of cyanate compound; and 1 to 70 parts by weight of elastomer. 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): (0 to 40). The elastomer A is an acrylate or methacrylate block copolymer; the elastomer B is a styrene block copolymer; and the elastomer C is an organosilicon copolymer. Different types of elastomers are added to the resin composition to reduce the disadvantages of each elastomer, improve the compatibility between resins, improve the cross-linking and curing reaction of the resins, and obtain a final cured product with high heat resistance, high toughness, low CTE, low water absorption and high adhesion.

Description

Technical Field

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

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

[0003] In the prior art, a high content of inorganic filler is generally added to the resin composition to meet the requirement of a lower thermal expansion coefficient. However, a high content of inorganic filler will increase the viscosity of the resin composition glue, 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 meets both low thermal expansion and excellent processability through this method.

[0004] BT resin, one of the thermosetting resin materials, is obtained by polymerization of cyanate resin and bismaleimide. It has excellent heat resistance, low dielectric constant and dielectric loss, moisture resistance, electrical insulation after moisture absorption, etc. In the field of electronic materials, BT resin is widely used as a substrate material for printed circuit boards. In particular, in recent years, it has been increasingly used in the field of semiconductor packaging substrates such as FCCSP (Flip Chip Chip Scale Package) that require low warpage and thinness. However, BT resin is relatively brittle, and warpage and CTE need to be further reduced in the field of packaging substrates. Summary of the invention

[0005] The purpose of the present invention is to provide a resin composition and application thereof.

[0006] To achieve the above-mentioned purpose, the present invention adopts the following technical scheme: a resin composition, which comprises, by weight:

[0007] Maleimide resin and / or maleimide prepolymer: 20 to 100 parts by weight;

[0008] Epoxy resin: 5 to 50 parts by weight;

[0009] Cyanate compound: 1 to 50 parts by weight;

[0010] Elastomer: 1 to 70 parts by weight;

[0011] Wherein, 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): (0-40);

[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 weight ratio of the elastomer A, elastomer B and elastomer C is (10-50):(5-20):(5-30).

[0016] As a further improvement of the present invention, the elastomer A contains structural unit (1) and / or structural unit (2):

[0017] Structural unit (1), R 1 C 1 ~C 5 An alkyl group, x is an integer from 1 to 100;

[0018] Structural unit (2), R 2 C 1 ~C 5 wherein y is an integer from 1 to 100.

[0019] As a further improvement of the present invention, the elastomer A contains a structural unit (3):

[0020] Structural unit (3), R 3 is hydrogen or methyl, and o is an integer of 1 to 100.

[0021] As a further improvement of the present invention, the epoxy value of the elastomer A is 0.01 to 0.65 eq / kg.

[0022] 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.

[0023] As a further improvement of the present invention, the elastomer C contains at least one structural unit among structural unit (4), structural unit (5) and structural unit (6):

[0024] Structural unit (4), wherein R is C 1 ~C 12 The hydrocarbon group or -OR;

[0025] Structural unit (5), wherein R is C 1 ~C 12 The hydrocarbon group or -OR;

[0026] Structural unit (6), wherein X in the structural unit (6) is a mercapto group, an epoxy group, a hydroxyl group or a methoxy group.

[0027] As a further improvement of the present invention, the cyanate compound is selected from the group consisting of structural formula (1) and / or structural formula (2),

[0028] Structural formula (1), wherein R is hydrogen or methyl, and n is an integer of 1 to 10.

[0029] In the structural formula (2), z is an integer of 1 to 10.

[0030] As a further improvement of the present invention, the resin composition also includes an inorganic filler, and / or a dispersant, and / or a coupling agent, and / or a flame retardant, and / or 0.01 to 5 parts by weight of a catalyst; wherein, based on 100 parts by weight of the maleimide resin and / or maleimide prepolymer, the epoxy resin and the cyanate ester compound in total, the inorganic filler is 30 to 250 parts by weight, and the flame retardant is 1 to 60 parts by weight; based on 100 parts by weight of the resin composition, the dispersant is 0.001 to 5 parts by weight, and the coupling agent is 0.001 to 10 parts by weight.

[0031] To achieve the above object of the invention, the present invention also provides a use of the above resin composition in prepregs, laminates and printed circuit boards.

[0032] Beneficial effects: Compared with the prior art, the present invention has the following advantages:

[0033] In the resin composition of the present invention, by adding different types of elastomers into the resin composition, the disadvantages of each elastomer are reduced, such as elastomer A has a high molecular weight, and when more elastomer A is added, the adhesion between the copper foil and the semi-cured sheet is affected, and the compatibility with the thermosetting resin is poor. The elastomer B content is too much and the compatibility is poor. The elastomer C has a low density and is easy to float to the surface in the resin composition glue, and it is difficult to mix a relatively homogeneous glue system. Therefore, the improvement of CTE is limited, and the peel strength is greatly affected. At the same time, it can improve the compatibility between resins, improve the cross-linking and curing reaction of the resin, 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, which meets the existing requirements for printed circuit boards. DETAILED DESCRIPTION

[0034] The following is a specific implementation of the embodiment of the present invention. It should be pointed out that for ordinary technicians in this field, several improvements and modifications can be made without departing from the principles of the embodiment of the present invention. These improvements and modifications are also considered to be within the scope of protection of the embodiment of the present invention.

[0035] The terms “comprising” and “containing” in the present specification mean that other components may be contained in addition to the components mentioned above, and these other components can impart different characteristics to the resin composition.

[0036] In this specification, "based on 100 parts by weight of the resin composition" means that the total amount of the components participating in the reaction in the resin composition is 100 parts by weight, excluding flame retardants, catalysts, inorganic fillers, dispersants, and coupling agents. Of course, this is not limited to this. It can be understood that when the flame retardant is a reactive flame retardant, the flame retardant is included in the "based on 100 parts by weight of the resin composition".

[0037] The present invention provides a resin composition, which comprises, by weight:

[0038] Maleimide resin and / or maleimide prepolymer: 20 to 100 parts by weight;

[0039] Epoxy resin: 5 to 50 parts by weight;

[0040] Cyanate compound: 1 to 50 parts by weight;

[0041] Elastomer: 1 to 70 parts by weight;

[0042] Wherein, 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): (0-40);

[0043] The elastomer A is an acrylate or methacrylate block copolymer;

[0044] The elastomer B is a styrene block copolymer;

[0045] The elastomer C is a silicone copolymer.

[0046] In the resin composition of the present invention, by adding different types of elastomers into the resin composition, the disadvantages of each elastomer are reduced, such as elastomer A has a high molecular weight, and when more elastomer A is added, the adhesion between the copper foil and the semi-cured sheet is affected, and the compatibility with the thermosetting resin is poor. The elastomer B content is too much and the compatibility is poor. The elastomer C has a low density and is easy to float to the surface in the resin composition glue, and it is difficult to mix a relatively homogeneous glue system. Therefore, the improvement of CTE is limited, and the peel strength is greatly affected. At the same time, it can improve the compatibility between resins, improve the cross-linking and curing reaction of the resin, 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, which meets the existing requirements for printed circuit boards.

[0047] It should be noted that the cured product in the present invention can be understood as a prepreg, a laminate, a printed circuit board, and the like.

[0048] In a specific embodiment, the weight ratio of the elastomer A, elastomer B and elastomer C is (10-50): (5-20): (5-30). Of course, this is not limited to the above, and the content of each elastomer can be adjusted according to the specific requirements of the final cured product.

[0049] Furthermore, the elastomer A contains structural unit (1) and / or structural unit (2):

[0050] Structural unit (1), R 1 C 1 ~C 5 An alkyl group, x is an integer from 1 to 100;

[0051] Structural unit (2), R 2 C 1 ~C 5 wherein y is an integer from 1 to 100.

[0052] In one embodiment, the R 1 is methyl, R 2 It is methyl, ethyl or butyl. Of course, it is not limited to this.

[0053] Preferably, the structural formula of the elastomer A is as follows:

[0054] Wherein, I, m and n are integers ranging from 1 to 100 respectively.

[0055] Furthermore, the weight average molecular weight of the elastomer A is 20,000 to 400,000.

[0056] Furthermore, the elastomer A further comprises a structural unit (3):

[0057] Structural unit (3), where R 3 is hydrogen or methyl, and o is an integer of 1 to 100.

[0058] Specifically, when the elastomer A contains an epoxy group, the epoxy value of the elastomer A is 0.01 to 0.65 eq / kg.

[0059] Specifically, the elastomer A can be selected from the brands M51, M52, M22 or D51N produced by Arkema; ​​the brands LA2250, LA2140, LA-2330, LA4285, etc. produced by Kuraray Co., Ltd.; SG-P3, SG-80H, PMS-22-1, PMS-22-4, PMS-19-5, PMS-22-5, etc. produced by Nagase, Japan.

[0060] Furthermore, 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.

[0061] 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 TM 7000 series (7125, 7311), SEPTONTM 8000 series (8004, 8006, 8007L, 8851), SEPTONTM V series (9461, 9475), SEPTONTM Q1250, etc.; Asahi Kasei H1041, H1043, H1051, H1052, H1053, H1221, etc.

[0062] Furthermore, the elastomer C contains at least one structural unit selected from structural unit (4), structural unit (5) and structural unit (6):

[0063] Structural unit (4), wherein R is C 1 ~C 12 The hydrocarbon group or -OR;

[0064] Structural unit (5), wherein R is C 1 ~C 12 The hydrocarbon group or -OR;

[0065] Structural unit (6), wherein X in the structural unit (6) is a mercapto group, an epoxy group, a hydroxyl group or a methoxy group.

[0066] Preferably, R in the structural unit (4), the structural unit (5) and the structural unit (6) is a methyl group or a phenyl group, and X in the structural unit (6) is an epoxy group or a mercapto group.

[0067] Specifically, the elastomer C can be SQ-20P or KHE-8000H manufactured by Nippon Kayaku, SQ502-8 manufactured by Arakawa Chemical, AY42-119 manufactured by DuPont Toray, X-40-2670, R-170S, X-40-2705, X-40-2701, KMP-600, KMP-605, X-52-7030 manufactured by Shin-Etsu Chemical Co., Ltd.; EP-2600, EP-2601, EP-2720, TMS-2670, EXL-2315, EXL-2655 of DOW, etc.

[0068] The cyanate compound is a compound containing at least one cyanate group in its molecular structure. The cyanate compound may be a monomer, a polymer, a prepolymer or a combination of any two.

[0069] Preferably, the cyanate compound is a prepolymer, a combination of a prepolymer and a monomer, or a combination of a prepolymer and a polymer.

[0070] Furthermore, the cyanate ester compound is selected from at least one of bisphenol A cyanate ester, bisphenol F cyanate ester, bisphenol E cyanate ester, bisphenol M cyanate ester, DCPD cyanate ester, naphthalene cyanate ester, phenolic cyanate ester and biphenyl cyanate ester.

[0071] Preferably, the cyanate ester compound is selected from structural formula (1) or / and structural formula (2),

[0072] Structural formula (1), wherein R is hydrogen or methyl, and n is an integer of 1 to 10.

[0073] In the structural formula (2), z is an integer of 1 to 10.

[0074] Furthermore, the epoxy resin is selected from one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, tetraphenylethane epoxy resin, triphenylmethane epoxy resin, biphenyl epoxy resin, naphthalene ring epoxy resin, dicyclopentadiene epoxy resin, isocyanate epoxy resin, aralkyl linear phenolic epoxy resin, bisphenol A novolac epoxy resin, polyphenylene ether modified epoxy resin, alicyclic epoxy resin, glycidyl amine epoxy resin, glycidyl ester epoxy resin, phosphorus-containing epoxy resin, nitrogen-containing epoxy resin, and multifunctional epoxy resin.

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

[0076]

[0077] Among them, in the structural formula (6), R 2 is hydrogen, methyl or ethyl, R 1 is methylene, ethylene or

[0078]

[0079] Wherein, in the structural formula (8), n is an integer from 1 to 10;

[0080] Wherein, in the structural formula (9), n is an integer from 1 to 10;

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

[0082] Wherein, in the structural formula (11), n ​​is an integer from 1 to 10;

[0083] In the structural formula (12), R is hydrogen, methyl or ethyl, and n is an integer of 1 to 10.

[0084] Furthermore, the maleimide prepolymer is selected from any one or a combination of at least two of a prepolymer of a diallyl compound and a maleimide compound, a prepolymer of a diamine and a maleimide compound, a prepolymer of a multifunctional amine and a maleimide compound, and a prepolymer of an acidic phenol compound and a maleimide compound.

[0085] Specifically, the maleimide compound can be selected from 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 Yamato Chemical Industry Co., Ltd.; BMI, BMI-70, BMI-80, etc. manufactured by KI Chemical Industry 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.

[0086] Preferably, the maleimide compound can be selected from BMI-2300 manufactured by Yamato Chemical Industry Co., Ltd., BMI-70 and BMI-80 manufactured by KI Chemical Industry Co., Ltd., and MIR-3000 manufactured by Nippon Kayaku Co., Ltd.

[0087] Furthermore, the resin composition further contains an inorganic filler, wherein the inorganic filler is in an amount of 30 to 250 parts by weight based on 100 parts by weight of the maleimide resin and / or maleimide prepolymer, the epoxy resin and the cyanate ester compound in total.

[0088] The inorganic filler is at least one of spherical silicon dioxide, aluminum hydroxide, aluminum oxide, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate, mica, and glass fiber powder.

[0089] Preferably, the inorganic filler is silicon dioxide.

[0090] Furthermore, the inorganic filler is an inorganic filler surface-treated with a silane coupling agent, wherein the silane coupling agent is at least one of an aminosilane coupling agent, a carbon-carbon double bond-containing silane coupling agent, and an epoxy silane coupling agent.

[0091] Preferably, the inorganic filler is spherical silica surface-treated with an aminophenylsilane coupling agent, wherein the aminophenylsilane coupling agent has the following structure:

[0092] Where R is C 1 -C 6 A straight chain alkylene group, X is a methoxy group or an ethoxy group.

[0093] In a specific embodiment, based on 100 parts by weight of the maleimide resin and / or maleimide prepolymer, the epoxy resin and the cyanate ester compound in total, 30 to 100 parts by weight of the inorganic filler is contained.

[0094] In the present invention, by appropriately adjusting the content ratio range of the three elastomers, a higher level of elastomer content is achieved. At the same time, the content of inorganic filler is reduced, so that a resin composition with a lower CTE can be obtained, and excellent drilling processability can be met, and the fluidity of the resin composition glue can be significantly reduced, thereby improving production processability.

[0095] Furthermore, the resin composition also includes a dispersant and a coupling agent. Based on 100 parts by weight of the resin composition, the content of the dispersant is 0.001 parts by weight to 5 parts by weight, and the content of the coupling agent is 0.001 parts by weight to 10 parts by weight.

[0096] Specifically, the dispersant may be BYK-161 or / and BYK-111 manufactured by BYK. The coupling agent may be KBM-402, KBM-403, KBM-502, KBE-503, KBM-603, KBM-903, KBM-573, KBM-602, KBM-1003, etc. manufactured by Shin-Etsu Chemical.

[0097] Furthermore, the resin composition further contains a flame retardant, which is 1 part by weight to 60 parts by weight based on 100 parts by weight of the maleimide resin and / or maleimide prepolymer, epoxy resin and cyanate compound in total, so as to improve the flame retardancy of the finally formed cured product, which can be understood as a prepreg, a laminate, a printed circuit board, etc.

[0098] Specifically, the flame retardant is at least one selected from bromine flame retardants, phosphorus flame retardants, nitrogen flame retardants, organic silicon flame retardants, organic metal flame retardants, and inorganic flame retardants.

[0099] Wherein, the bromine flame retardant may be decabromodiphenyl ether, decabromodiphenyl ethane, brominated styrene or tetrabromophthalamide. The phosphorus flame retardant may be inorganic phosphorus, condensed phosphate compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, 9,10-dihydro-9-oxa-10-phosphophananthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphophananthrene-10-oxide, 10-phenyl-9,10-dihydro-9-oxa-10-phosphophananthrene-10-oxide, tri(2,6-dimethylphenyl)phosphine,

[0100] (m is an integer from 1 to 5), Phosphazene and other organic phosphorus-containing compounds. Nitrogen flame retardants can be triazine compounds, cyanuric acid compounds, isocyanate compounds, phenothiazine, etc. Organosilicon flame retardants can be silicone oils, silicone rubbers, silicone resins, etc. Organometallic salt flame retardants can be ferrocene, acetylacetone metal complexes, organometallic carbonyl compounds, etc. Inorganic flame retardants can be aluminum hydroxide, magnesium hydroxide, aluminum oxide, barium oxide, etc.

[0101] Of course, the type of the flame retardant is not limited thereto. It is understood that the added flame retardant can be selected according to the specific application field of the laminate, for example, for application fields that require halogen, non-halogen flame retardants are preferred, such as phosphorus-containing or nitrogen-containing flame retardants, more preferably phosphazene or bis-DOPO.

[0102] Furthermore, the resin composition further contains 0.01 to 5 parts by weight of a catalyst, wherein the catalyst is at least one of an imidazole catalyst, a pyridine catalyst, and an organic metal salt catalyst.

[0103] Preferably, the catalyst is at least one of 4-dimethylaminopyridine, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, modified imidazole and zinc octoate.

[0104] Furthermore, the present invention also provides an application of the resin composition in prepregs, laminates and printed circuit boards.

[0105] Specifically, the prepreg comprises a reinforcing material and the above-mentioned resin composition attached to the surface of the reinforcing material.

[0106] The reinforcing material is selected from at least one of natural fibers, organic synthetic fibers, organic fabrics, and inorganic fabrics.

[0107] Preferably, the reinforcing material is glass fiber cloth, and the glass fiber cloth is preferably open fiber cloth or flat cloth. More preferably, the glass fiber cloth is E glass fiber cloth, S glass fiber cloth, T glass fiber cloth or Q glass fiber cloth.

[0108] In addition, when the reinforcing material is 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, and the coupling agent used is preferably epoxy silane coupling agent or amino silane coupling agent, etc., to provide good water resistance and heat resistance.

[0109] The preparation method of the prepreg is as follows:

[0110] Dissolving the resin composition with a solvent to prepare a resin composition glue solution;

[0111] The reinforcing material is immersed in the above-mentioned resin composition glue solution, and then the immersed reinforcing material is taken out and heated and dried to obtain the prepreg.

[0112] In a specific embodiment, the impregnated reinforcing material is baked at 100° C. to 180° C. for 1 min to 15 min, and the prepreg is obtained after drying.

[0113] Specifically, the solvent can be selected from one or a combination of any two of acetone, butanone, toluene, methyl isobutyl ketone, N,N-dimethylformamide, N,N-dimethylacetamide, ethylene glycol methyl ether, propylene glycol methyl ether, benzene, toluene, xylene, and cyclohexane.

[0114] The amount of the solvent used in the present invention is not specifically limited. The amount of the solvent is selected by a person skilled in the art based on his or her own experience, as long as the obtained resin composition glue liquid can reach a viscosity suitable for use.

[0115] The laminate includes at least one of the above-mentioned prepregs and a metal foil formed on at least one side of the prepreg.

[0116] In an embodiment where the laminate includes at least two of the above-mentioned semi-cured sheets, the at least two semi-cured sheets are stacked and bonded together by heating and pressurizing, and then metal foil is bonded on one side or both sides of the bonded semi-cured sheets by heating and pressurizing to form the laminate.

[0117] Specifically, the preparation steps of the laminate are as follows: a metal foil is coated on one or both sides of the above-mentioned semi-cured sheet, or at least two of the above-mentioned semi-cured sheets are stacked, and then coated on one or both sides with metal foil, and hot-pressed to obtain a laminate.

[0118] The pressing conditions of the above laminated board 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.

[0119] Specifically, the number of the prepreg sheets can be determined according to the required thickness of the laminate, and one or more prepreg sheets can be used.

[0120] The metal foil may be copper foil or aluminum foil, and its material is not limited; the thickness of the metal foil is not particularly limited, such as 5 μm, 8 μm, 12 μm, 18 μm, 35 μm or 70 μm.

[0121] The printed circuit board includes at least one of the above-mentioned prepregs, or the printed circuit board includes at least one of the above-mentioned laminates.

[0122] The method for preparing the printed circuit board can adopt existing processes, which will not be described in detail here.

[0123] The present invention will be described in detail below with reference to specific embodiments; of course, it is to be understood that the embodiments of the present invention are not limited to these embodiments.

[0124] Examples 1 to 6 and Comparative Examples 1 to 5:

[0125] The components and contents of the resin compositions of Examples 1 to 6 and Comparative Examples 1 to 5 are shown in Table 1 below:

[0126] Table 1

[0127]

[0128] Specifically, the information of each component involved in Table 1 above is shown in Table 2 below:

[0129] Table 2

[0130]

[0131]

[0132] The preparation method of the resin composition in Examples 1 to 6 and Comparative Examples 1 to 5 adopts a conventional preparation method, specifically: mixing with an appropriate amount of solvent according to the components and corresponding contents in Table 1, dispersing and mixing evenly to obtain a resin composition glue with a solid content of 60%, wherein the solid content of 60% is calculated by weight.

[0133] The obtained resin composition glue of Examples 1-6 and Comparative Examples 1-5 was coated on T-glass fiber cloth, taken out after soaking, placed in a 160° C. forced air drying oven, and baked for 3 to 6 minutes to prepare a prepreg.

[0134] Preparation of sample laminates for performance evaluation:

[0135] (1) Preparation of laminate

[0136] The prepregs prepared in the above Examples 1-6 and Comparative Examples 1-5 were cut into 300×300 mm, and a metal foil was placed on opposite sides of the prepreg to form a laminated structure, which was then pressed in a vacuum hot press to obtain laminated boards.

[0137] Specifically, the metal foil is 18 μm low-roughening electrolytic copper foil, but is not limited thereto.

[0138] Performance evaluation method:

[0139] (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;

[0140] (2) Glass transition temperature (Tg): tested using a dynamic mechanical analyzer (DMA) with a heating rate of 10°C / min.

[0141] (3) PCT 2HR water absorption rate determination: Take 3 samples of 10 cm × 10 cm, 0.40 mm thick, with metal foil removed from both sides, dry them at 100°C for 2 hours, weigh them, and record the weight as W1. Then, treat them in a pressure cooker tester at 121°C and 2 atmospheres for 2 hours, weigh them, and record the weight as W2. The water absorption rate is determined as (W2-W1) / W1×100%;

[0142] (4) X / Y thermal expansion coefficient (CTE) determination: TMA (thermomechanical analysis) was used, with a heating rate of 10°C / min and a test temperature range of 30 to 100°C;

[0143] (5) Heat resistance of tinning after wet heat treatment (PCT 1hr): Take 3 samples of 10 cm × 10 cm, 0.80 mm thick, with metal foil removed from both sides, dry them at 100°C for 2 hours, and then treat them at 121°C and 2 atmospheres for 1 hour using a pressure cooker tester. Then, tinnize them in a tin furnace at 288°C for 20 seconds and visually observe whether there is stratification. If there is no stratification among the 3 samples, it will be recorded as [Pass], and if there is stratification, it will be recorded as [Fail].

[0144] (6) Peel strength (PS, N / mm): The peel strength of the metal cover layer was tested according to the “after thermal stress” experimental conditions in the IPC-TM-650 2.4.8 method.

[0145] The properties of the laminates obtained using the prepregs in Examples 1-6 and Comparative Examples 1-5 are shown in Table 3 below.

[0146] Table 3

[0147]

[0148] It can be seen from Table 3 that the laminate obtained by using the resin composition of the present invention has a higher glass transition temperature, better heat resistance, lower dielectric constant, dielectric loss, water absorption, thermal expansion coefficient, and higher peel strength, and can 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 excellent comprehensive performance, which meets the existing requirements for printed circuit boards.

[0149] In particular, Example 1 and Comparative Example 1 are compared in parallel. It can be seen that compared with adding only a single type of elastomer A in Comparative Example 1, the resin composition in Example 1 adds different types of elastomers A, B, and C, which can reduce the shortcomings of elastomer A. The laminate prepared from the resin composition in Example 1 has a lower dielectric constant, dielectric loss, thermal expansion coefficient, water absorption, better heat resistance, and higher peel strength.

[0150] A parallel comparison is made between Example 2 and Comparative Example 2. It can be seen that, compared with adding only a single type of elastomer B in Comparative Example 2, adding different types of elastomers A, B, and C to the resin composition in Example 2 can reduce the shortcomings of elastomer B. The laminate prepared from the resin composition in Example 2 has a higher glass transition temperature, a lower thermal expansion coefficient, water absorption, better heat resistance, and higher peel strength.

[0151] A parallel comparison is made between Example 3 and Comparative Example 3. It can be seen that, compared with adding only a single type of elastomer C in Comparative Example 3, adding different types of elastomers A, B, and C to the resin composition in Example 3 can reduce the shortcomings of elastomer C. The laminate prepared from the resin composition in Example 3 has a higher glass transition temperature, lower dielectric constant, dielectric loss, thermal expansion coefficient, water absorption, better heat resistance, and higher peel strength.

[0152] A parallel comparison is made between Examples 2 and 5 and Comparative Example 5. It can be seen that, compared with only adding elastomer A and elastomer C in Comparative Example 5, the resin compositions in Examples 2 and 5 add different types of elastomers A, B, and C, which can reduce the shortcomings of elastomers A and C. The laminates prepared from the resin compositions in Examples 2 and 5 have higher glass transition temperatures, lower dielectric constants, dielectric losses, thermal expansion coefficients, water absorption rates, better heat resistance, and higher peel strength.

[0153] A parallel comparison is made between Example 6 and Comparative Example 4. It can be seen that, compared with only adding elastomer B and elastomer C in Comparative Example 4, the resin composition in Example 6 adds different types of elastomers A, B, and C, which can reduce the shortcomings of elastomers B and C. The laminate prepared from the resin composition in Example 6 has a higher glass transition temperature, a lower dielectric constant, thermal expansion coefficient, water absorption, better heat resistance, and higher peel strength.

[0154] It should be understood that although this specification is described according to implementation modes, not every implementation mode contains only one independent technical solution. This description of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each implementation mode may also be appropriately combined to form other implementation modes that can be understood by those skilled in the art.

[0155] The series of detailed descriptions listed above are only specific descriptions of feasible implementation methods of the present invention. They are not intended to limit the scope of protection of the present invention. Any equivalent implementation methods or changes that do not deviate from the technical spirit of the present invention should be included in the scope of protection of the present invention.

Claims

1. A resin composition, characterized in that: By weight, the resin composition comprises: Maleimide resin and / or maleimide prepolymer: 20 to 100 parts by weight; Epoxy resin: 5 to 50 parts by weight; Cyanate compound: 1 to 50 parts by weight; Elastomer: 1 to 70 parts by weight; Wherein, 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 (10-50): (5-20): (5-30); 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.

2. The resin composition according to claim 1, characterized in that: The elastomer A contains structural unit (1) and / or structural unit (2): Structural unit (1), R1 is a C1-C5 alkyl group, and x is an integer from 1 to 100; In the structural unit (2), R2 is a C1-C5 alkyl group, and y is an integer of 1-100.

3. The resin composition according to claim 1, characterized in that: The elastomer A contains a structural unit (3): In the structural unit (3), R3 is hydrogen or methyl, and o is an integer of 1 to 100.

4. The resin composition according to claim 3, characterized in that: The epoxy value of the elastomer A is 0.01 to 0.65 eq / kg.

5. The resin composition according to claim 1, characterized in that: 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.

6. The resin composition according to claim 1, characterized in that: The elastomer C contains at least one structural unit among structural unit (4), structural unit (5) and structural unit (6): Structural unit (4), wherein R in the structural unit (4) is C1 to C 12 The hydrocarbon group or -OR; Structural unit (5), wherein R in the structural unit (5) is C1 to C 12 The hydrocarbon group or -OR; Structural unit (6), wherein X in the structural unit (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 cyanate compound is selected from the group consisting of structural formula (1) and / or structural formula (2), Structural formula (1), wherein R is hydrogen or methyl, and n is an integer from 1 to 10; In the structural formula (2), z is an integer of 1 to 10.

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

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

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