Resin composition and use thereof

Abstract

The present application provides a resin composition and its application, the resin composition comprises, by weight: maleimide resin and / or maleimide prepolymer: 20-100 parts by weight; epoxy resin: 10-70 parts by weight; phenolic resin: 5-50 parts by weight; elastomer: 10-70 parts by weight; the elastomer is a combination of elastomer A, elastomer B and elastomer C, the weight ratio of elastomer A, elastomer B and elastomer C is (5-50):(1-30):(5-40); the elastomer A is acrylate or methacrylate block copolymer; the elastomer B is styrene block copolymer; the elastomer C is silicone copolymer; the epoxy resin or / and phenolic resin contains at least one naphthyl; the disadvantages of each elastomer are reduced, the compatibility between resins is improved, the resin crosslinking curing reaction is improved, and the cured product with high heat resistance, high toughness, low CTE, low water absorption and high adhesion is obtained.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of electronic material, in particular to a resin composition and application thereof. BACKGROUND

[0002] In recent years, electronic devices are developing towards miniaturization and high performance, which makes the wiring density in printed circuit board developing towards high degree and high aggregation, which puts forward higher requirements on the heat resistance and reliability of copper clad plate. Especially in the field of semiconductor packaging substrate, the difference in thermal expansion rate between the chip and the organic substrate during packaging and assembly easily leads to warping problem.

[0003] In the prior art, a high content of inorganic filler is generally added to the resin composition to meet the requirement of low thermal expansion coefficient, but the high content of inorganic filler will increase the viscosity of the resin composition glue solution, which seriously affects the product preparation process and affects the drilling process of the final printed circuit board, so it is difficult to obtain a final cured product which meets the requirements of low thermal expansion and excellent processability by this method.

[0004] BT resin, one of thermosetting resin materials, is obtained by the polymerization reaction of cyanate ester resin and bismaleimide, and has excellent heat resistance, low dielectric constant and dielectric loss, moisture resistance, and electrical insulation after moisture absorption. In the field of electronic materials, BT resin is widely used as a substrate material for printed circuit boards, and 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) which require low warpage and thinness. However, BT resin is relatively brittle, and the warpage and CTE need to be further reduced in the field of packaging substrates.

[0005] Epoxy resin refers to a class of high molecular compounds containing two or more epoxy groups in the molecular structure, and has excellent process performance, mechanical properties, electrical properties, physical properties and relatively low cost, and has long dominated the application of substrate materials for printed circuit boards. However, the heat resistance, thermal expansion, dielectricity and other aspects of epoxy resin are difficult to meet the requirements of high-performance substrates such as packaging substrates.

[0006] Elastomers belong to thermoplastic materials, have excellent softness and good elasticity, can improve brittleness in thermosetting resin composition, and reduce CTE and warpage. However, the compatibility of thermoplastic elastomers in thermosetting resin composition is poor, it is difficult to control the production process, and when a large amount of content is added, it is easy to precipitate, and when a small amount of content is added, the required performance cannot be achieved. SUMMARY

[0007] The present application relates to the technical field of electronic material, in particular to a resin composition and application thereof.

[0008] To achieve the above object, the present application adopts the following technical solution: A resin composition, comprising, by weight,

[0009] The maleimide resin and / or maleimide prepolymer is 20-100 parts by weight;

[0010] The epoxy resin is 10-70 parts by weight;

[0011] The phenolic resin is 5-50 parts by weight;

[0012] The elastomer is 10-70 parts by weight;

[0013] 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);

[0014] The elastomer A is an acrylate or methacrylate block copolymer;

[0015] The elastomer B is a styrene block copolymer;

[0016] The elastomer C is an organic silicon copolymer;

[0017] The epoxy resin and / or phenolic resin contains at least one naphthyl group.

[0018] As a further improvement of the present application, the epoxy resin is at least one of the following structural formulas (1)-(10):

[0019] Structural formula (1);

[0020] Structural formula (2);

[0021] Structural formula (3);

[0022] Structural formula (4);

[0023] Structural formula (5);

[0024] Structural formula (6);

[0025] Structural formula (7);

[0026] Structural formula (8);

[0027] Structural formula (9);

[0028] Structural Formula (10); wherein n in Structural Formula (1)~Structural Formula (10) is an integer from 1 to 10.

[0029] As a further improvement of the present application, the phenolic resin is at least one of Structural Formula (11)~Structural Formula (13):

[0030] Structural Formula (11);

[0031] Structural Formula (12);

[0032] Structural Formula (13); wherein n in Structural Formula (11)~Structural Formula (13) is an integer greater than 1.

[0033] As a further improvement of the present application, the weight ratio of the elastomer A, the elastomer B and the elastomer C is (20~50):(1~10):(5~20); or the weight ratio of the elastomer A, the elastomer B and the elastomer C is (5~20):(15~30):(5~10); or the weight ratio of the elastomer A, the elastomer B and the elastomer C is (5~20):(1~15):(20~40).

[0034] As a further improvement of the present application, the elastomer A contains Structural Formula (14) and / or Structural Formula (15):

[0035] Structural Formula (14), wherein R1 in Structural Formula (14) is C1~C5 alkyl, and x is an integer from 1 to 100;

[0036] Structural Formula (15), wherein R2 in Structural Formula (15) is C1~C5 alkyl, and y is an integer from 1 to 100.

[0037] As a further improvement of the present application, 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, and hydrogenated styrene and pentadiene triblock copolymer.

[0038] As a further improvement of the present application, the elastomer C contains at least one unit of Structural Formula (16), Structural Formula (17) and Structural Formula (18):

[0039] Structural Formula (16), wherein R in Structural Formula (16) is C1-C 12 hydrocarbon group or ;

[0040] Formula (17), wherein R is a C1-C 12 hydrocarbon group or ;

[0041] Formula (18), wherein X is a mercapto group, an epoxy group, a hydroxyl group or a methoxyl group.

[0042] As a further improvement of the present application, the resin composition further comprises an inorganic filler, and / or a dispersing agent, and / or a coupling agent, and / or a flame retardant, and / or 0.01-5 parts by weight of a catalyst; wherein the inorganic filler is 30-250 parts by weight, and the flame retardant is 1-60 parts by weight, based on 100 parts by weight of the total of the maleimide resin and / or maleimide prepolymer, the epoxy resin and the phenolic resin; and the dispersing agent is 0.001-5 parts by weight, and the coupling agent is 0.001-10 parts by weight, based on 100 parts by weight of the resin composition.

[0043] As a further improvement of the present application, the flame retardant has a 5% weight loss temperature higher than 320℃.

[0044] To achieve the above-mentioned objects, the present application further provides an application of the above-mentioned resin composition in a prepreg, a laminated board and a printed circuit board.

[0045] Advantages: Compared with the prior art, the present application has the following advantages:

[0046] In the resin composition of the present application, by adding different types of elastomers in the resin composition, the shortcomings of each elastomer are reduced, such as the high molecular weight of elastomer A, which affects the adhesion between the copper foil and the prepreg when a large amount of elastomer A is added, and the poor compatibility with the thermosetting resin, the poor compatibility of elastomer B when the content of elastomer B is too high, the small density of elastomer C, which is easy to float to the surface in the resin composition glue solution, and difficult to mix a homogeneous glue solution system, thus improving the CTE to a limited extent, and greatly affecting the peel strength; at the same time, the compatibility between the resins is improved, the crosslinking and curing reaction of the resins is improved, the heat resistance is inhibited from decreasing, the toughness is improved, the CTE is reduced, and the final cured product with high heat resistance, high toughness, low CTE, low water absorption and high adhesion is obtained, so that the cured product with excellent comprehensive performance is obtained, which meets the requirements of the existing printed circuit board. DETAILED DESCRIPTION

[0047] The following is a specific embodiment of the present application, it should be pointed out that for those skilled in the art, without departing from the principles of the present application, a number of improvements and refinements can be made, which are also considered to be within the scope of protection of the present application.

[0048] In the present specification, "include", "contain" means that other components can be included in addition to the components described, and these other components can impart different properties to the resin composition.

[0049] In the present specification, "100 parts by weight of the resin composition" means that the total amount of components involved in the reaction in the resin composition is 100 parts by weight, excluding the flame retardant, catalyst, inorganic filler, dispersant, coupling agent. Of course, it is not limited thereto, and it is understood that when the flame retardant is a reactive flame retardant, the "100 parts by weight of the resin composition" includes the flame retardant.

[0050] The present application provides a resin composition, which includes, by weight:

[0051] Maleimide resin and / or maleimide prepolymer: 20 parts by weight ~ 100 parts by weight;

[0052] Epoxy resin: 10 parts by weight ~ 70 parts by weight;

[0053] Phenolic resin: 5 parts by weight ~ 50 parts by weight;

[0054] Elastomer: 10 parts by weight ~ 70 parts by weight;

[0055] 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);

[0056] The elastomer A is an acrylate or methacrylate block copolymer;

[0057] The elastomer B is a styrene block copolymer;

[0058] The elastomer C is a silicone copolymer;

[0059] The epoxy resin or / and phenolic resin contains at least one naphthyl group.

[0060] In the resin composition in the present application, by adding different kinds of elastomers in the resin composition, the shortcomings of each elastomer are reduced, such as the molecular weight of elastomer A is relatively high, when more elastomer A is added, the adhesion between the copper foil and the prepreg is affected, and the compatibility with the thermosetting resin is poor, the elastomer B is too much, the compatibility is poor, the density of the elastomer C is relatively small, and it is easy to float to the surface in the resin composition glue solution, it is difficult to mix a relatively homogeneous glue solution system, therefore the improvement of CTE is limited, and the peeling strength is affected; at the same time, the compatibility between the resins can be improved, the crosslinking curing reaction of the resin is improved, the decrease of heat resistance is inhibited, the toughness is improved, the CTE is reduced, the final cured product with high heat resistance, high toughness, low CTE, low water absorption and high adhesion is obtained, so that the cured product with excellent comprehensive performance is obtained, which meets the requirements of the existing printed circuit board.

[0061] Moreover, the resin composition of the present application uses the epoxy resin or / and phenolic resin containing at least one naphthyl group, that is, the naphthalene type epoxy resin or / and phenolic resin, which exhibits high heat resistance and low CTE in the resin composition, and when combined with the elastomer, it can still maintain very excellent heat resistance, and at the same time, high peeling strength is obtained.

[0062] It should be noted that the cured product in the present application can be understood as a prepreg, a laminated board, a printed circuit board, etc.

[0063] Further, the epoxy resin is at least one of structural formula (1)~structural formula (10):

[0064] Structural formula (1);

[0065] Structural formula (2);

[0066] Structural formula (3);

[0067] Structural formula (4);

[0068] Structural formula (5);

[0069] Structural formula (6);

[0070] Structural formula (7);

[0071] Structural formula (8);

[0072] Structural formula (9);

[0073] Structure formula (10); wherein, n in structure formula (1)~structure formula (10) is an integer from 1 to 10.

[0074] Specifically, the naphthalene type epoxy resin containing naphthyl can be selected from HP-4032SS, HP-4770, EXA-4750, HP-4700, HP-4710, HP-6000, HP-9500, HP-9540, HP-9900 or EXA-7311 manufactured by DIC.

[0075] Further, in addition to the naphthalene type epoxy resin containing naphthyl described above, the epoxy resin can further include one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, phosphorus-containing epoxy resin, o-cresol novolac epoxy resin, bisphenol A novolac epoxy resin, phenol novolac epoxy resin, trifunctional phenol type epoxy resin, tetraphenyl ethane epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, isocyanate type epoxy resin, aralkyl novolac epoxy resin, alicyclic type epoxy resin, glycidyl amine type epoxy resin, and glycidyl ester type epoxy resin.

[0076] Further, the phenolic resin is at least one of structure formula (11)~structure formula (13):

[0077] Structure formula (11);

[0078] Structure formula (12);

[0079] Structure formula (13); wherein, n in structure formula (11)~structure formula (13) is an integer greater than 1.

[0080] Specifically, the naphthalene type epoxy resin containing naphthyl can be selected from HP-4032SS, HP-4770, EXA-4750, HP-4700, HP-4710, HP-6000, HP-9500, HP-9540, HP-9900 or EXA-7311 manufactured by DIC.

[0081] Further, in addition to the naphthalene type epoxy resin containing naphthyl described above, the epoxy resin can further include one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, phosphorus-containing epoxy resin, o-cresol novolac epoxy resin, bisphenol A novolac epoxy resin, phenol novolac epoxy resin, trifunctional phenol type epoxy resin, tetraphenyl ethane epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, isocyanate type epoxy resin, aralkyl novolac epoxy resin, alicyclic type epoxy resin, glycidyl amine type epoxy resin, and glycidyl ester type epoxy resin.

[0082] In a preferred embodiment, the weight ratio of the elastomer A, the elastomer B and the elastomer C is (20~50):(1~10):(5~20). At this time, the acrylate or methacrylate block copolymer elastomer A is used as the main component in the elastomer composition, and the appropriate amount of the styrene elastomer B and the organic silicon elastomer C are used in combination, so that the high toughness can be ensured, the dielectric property and the water absorption rate are reduced, the elastomer is not precipitated during the processing, and the resin composition glue solution has good fluidity.

[0083] In another preferred embodiment, the weight ratio of the elastomer A, the elastomer B and the elastomer C is (5-20):(15-30):(5-10). In this case, the elastomer composition uses the styrene-based elastomer B as the main component, and is combined with an appropriate amount of the acrylate-based or methacrylate-based elastomer A and the silicone-based elastomer C, so that the very excellent dielectric properties can be ensured, the CTE and the water absorption are reduced, the elastomer does not precipitate during the processing, and the resin composition has good sizing fluidity.

[0084] In another preferred embodiment, the weight ratio of the elastomer A, the elastomer B and the elastomer C is (5-20):(15-30):(5-10). In this case, the elastomer composition uses the styrene-based elastomer B as the main component, and is combined with an appropriate amount of the acrylate-based or methacrylate-based elastomer A and the silicone-based elastomer C, so that the very excellent dielectric properties can be ensured, the CTE and the water absorption are reduced, the elastomer does not precipitate during the processing, and the resin composition has good sizing fluidity.

[0085] It can be understood that the content of various elastomers can be adjusted according to the specific performance requirements of the final cured product.

[0086] Further, the total content of the elastomer A, the elastomer B and the elastomer C is 20-55 parts by weight.

[0087] Further, the elastomer A contains the structural formula (14) and / or the structural formula (15):

[0088] The structural formula (14), wherein R1 is C1-C5 alkyl, and x is an integer of 1-100;

[0089] The structural formula (15), wherein R2 is C1-C5 alkyl, and y is an integer of 1-100.

[0090] In a specific embodiment, R1 is methyl, and R2 is methyl, ethyl or butyl. Of course, it is not limited thereto.

[0091] Preferably, the structural formula of the elastomer A is as follows:

[0092] wherein I, m and n are respectively integers of 1-100.

[0093] Further, the weight average molecular weight of the elastomer A is 20,000-400,000.

[0094] Further, the elastomer A can further contain the following structural formula unit:

[0095] wherein R3 is hydrogen or methyl, and o is an integer from 1 to 100.

[0096] Specifically, when the elastomer A contains an epoxy group, the epoxy value of the elastomer A is 0.01-0.65 eq / kg.

[0097] Specifically, the elastomer A can be selected from the group consisting of M51, M52, M22, and D51N manufactured by Arkema, LA2250, LA2140, LA-2330, LA4285, and the like manufactured by Kao Corporation, SG-P3, SG-80H, PMS-22-1, PMS-22-4, PMS-19-5, PMS-22-5, and the like manufactured by Nippon Gosei.

[0098] Further, 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, and hydrogenated styrene and pentadiene triblock copolymer.

[0099] Specifically, the elastomer B can be selected from the group consisting of SEPTON™ 2000 series (2002, 2004, 2005, 2006, 2063, 2104), SEPTON™ 4000 series (4033, 4044, 4055, 4077), HYBRAR™ 7000 series (7125, 7311), SEPTON™ 8000 series (8004, 8006, 8007L, 8851), SEPTON™ V series (9461, 9475), SEPTON™ Q1250, and the like manufactured by KURARE, H1041, H1043, H1051, H1052, H1053, H1221, and the like manufactured by Asahi Kasei.

[0100] Further, the elastomer C contains at least one unit of the structure of formula (16), formula (17), and formula (18):

[0101] Formula (16), wherein R in formula (16) is a carbon hydrogen group of C1-C 12 or ;

[0102] Formula (17), wherein R in formula (17) is a carbon hydrogen group of C1-C 12 or ;

[0103] Formula (18), wherein X in formula (18) is a mercapto group, an epoxy group, a hydroxyl group, or a methoxyl group.

[0104] Preferably, R in structural formula (16), structural formula (17), and structural formula (18) is methyl or phenyl. X in structural formula (18) is an epoxy group or a mercapto group.

[0105] Specifically, the elastomer C can be selected from SQ-20P or KHE-8000H manufactured by Japan Chemical, SQ502-8 manufactured by Akaragawa Chemical, AY42-119 manufactured by DuPont Toray, and 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, and the like manufactured by DOW.

[0106] Further, the maleimide resin is at least one of the following structural formulas:

[0107] Structural formula (19);

[0108] Structural formula (20);

[0109] Structural formula (21);

[0110] Structural formula (22); wherein, in structural formula (22), R2 is hydrogen, methyl, or ethyl, and R1 is methylene, ethylene, or ;

[0111] Structural formula (23);

[0112] Structural formula (24); wherein, in structural formula (24), n is an integer from 1 to 10;

[0113] Structural formula (25); wherein, in structural formula (25), n is an integer from 1 to 10;

[0114] Structural formula (26); wherein, in structural formula (26), n is an integer from 1 to 10;

[0115] Structural formula (27); wherein, in structural formula (27), n is an integer from 1 to 10;

[0116] Structural formula (28); wherein, in structural formula (28), R is hydrogen, methyl, or ethyl, and n is an integer from 1 to 10.

[0117] Further, the maleimide prepolymer is selected from any one of a prepolymer of a diallyl compound and a maleimide compound, a prepolymer of a diamine and a maleimide compound, a prepolymer of a polyfunctional amine and a maleimide compound, a prepolymer of an acidic phenol compound and a maleimide compound, or a combination of at least two of them.

[0118] 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, etc. manufactured by DAIKIN INDUSTRIES, LTD., BMI, BMI-70, BMI-80, etc. manufactured by KI CHEMICAL CO., LTD., MIR-3000, MIR-5000, etc. manufactured by NIPPON KAYAKU CO., LTD., X9-450, X9-470, etc. manufactured by DIC, and D936, D937, D939, D950, etc. manufactured by Sichuan Dongcai Co., Ltd.

[0119] Preferably, the maleimide compound can be selected from BMI-2300 manufactured by DAIKIN INDUSTRIES, LTD., BMI-70 and BMI-80 manufactured by KI CHEMICAL CO., LTD., and MIR-3000 manufactured by NIPPON KAYAKU CO., LTD.

[0120] Further, the resin composition further contains an inorganic filler. The inorganic filler is 30 parts by weight to 250 parts by weight, based on 100 parts by weight of the maleimide resin and / or the maleimide prepolymer, the epoxy resin, and the phenolic resin in total.

[0121] The inorganic filler is at least one of spherical silica, 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.

[0122] Preferably, the inorganic filler is silica.

[0123] Further, the inorganic filler is an inorganic filler that has been surface-treated with a silane coupling agent. 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.

[0124] Preferably, the inorganic filler is spherical silica that has been surface-treated with a phenylamino silane coupling agent. The phenylamino silane coupling agent is as shown in the following structure:

[0125] wherein R is a linear alkylene group having 1 to 6 carbon atoms, and X is a methoxy group or an ethoxy group.

[0126] In one embodiment, the resin composition contains 30 to 100 parts by weight of the inorganic filler, based on 100 parts by weight of the total amount of the maleimide resin and / or maleimide prepolymer, the epoxy resin, and the phenol resin.

[0127] In the present application, by properly adjusting the content ratio range of the three elastomers, a higher level of elastomer content is achieved, while reducing the content of inorganic fillers, a resin composition with a lower CTE can be obtained, excellent drilling processability is satisfied, and the flowability of the resin composition glue solution is significantly reduced, improving the production processability.

[0128] Further, the resin composition further comprises a dispersing agent and a coupling agent, the content of the dispersing agent 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, based on 100 parts by weight of the resin composition.

[0129] Specifically, the dispersing agent can be BYK-161 or / and BYK-111 made by BYK. The coupling agent can be KBM-402, KBM-403, KBM-502, KBE-503, KBM-603, KBM-903, KBM-573, KBM-602, KBM-1003, etc. made by Shin-Etsu Chemical.

[0130] Further, the resin composition further contains a flame retardant, the content of the flame retardant is 1 part by weight to 60 parts by weight, based on 100 parts by weight of the total amount of the maleimide resin and / or maleimide prepolymer, the epoxy resin, and the phenol resin. The flame retardancy of the final formed cured product can be improved, and the cured product can be understood as prepreg, laminated board, and printed circuit board, etc.

[0131] Specifically, the flame retardant is selected from at least one of a bromine-based flame retardant, a phosphorus-based flame retardant, a nitrogen-based flame retardant, an organic silicon flame retardant, an organic metal flame retardant, and an inorganic flame retardant.

[0132] The bromine-based flame retardant can be decabromodiphenyl ether, decabromodiphenyl ethane, brominated styrene, or tetrabromophthalic diamide. The phosphorus-based flame retardant can be inorganic phosphorus, condensed phosphoric acid 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, (m is an integer from 1 to 5), The nitrogen-based flame retardant can be triazine compounds, cyanuric acid compounds, isocyanic acid compounds, phenothiazine, and the like. The silicone-based flame retardant can be silicone oil, silicone rubber, silicone resin, and the like. The organic metal salt-based flame retardant can be ferrocene, acetylacetone metal complex, organic metal carbonyl compounds, and the like. The inorganic flame retardant can be aluminum hydroxide, magnesium hydroxide, aluminum oxide, barium oxide, and the like.

[0133] Further, the 5% weight loss temperature of the flame retardant is higher than 320°C.

[0134] Specifically, the flame retardant can be selected from SPB-100 manufactured by Otsuka Chemical Co., Ltd., FP-100, FP-300B or FP-390 manufactured by Fumie Pharmaceutical Co., Ltd., PX-200, PX-201 or PX-202 manufactured by Ohta Chemical Co., Ltd., OP-935 or OP-930 manufactured by Clariant, SAYTEX 8010, HP-7010 or BT-93W manufactured by Albemarle, OL3001 or OL5000 manufactured by FRX, and the like.

[0135] Further, the resin composition further contains 0.01 to 5 parts by weight of a catalyst. The catalyst is at least one of imidazole-based catalysts, pyridine-based catalysts, and organic metal salt-based catalysts.

[0136] Preferably, the catalyst is at least one of 4-dimethylaminopyridine, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, modified imidazole, and zinc octoate.

[0137] Further, the present application also provides an application of the above resin composition in prepreg, laminated board and printed circuit board.

[0138] Specifically, the prepreg comprises a reinforcing material and the above resin composition attached to the surface of the reinforcing material.

[0139] The reinforcing material is selected from at least one of natural fibers, organic synthetic fibers, organic fabrics, and inorganic fabrics. Preferably, the reinforcing material is glass fiber cloth, and preferably, the glass fiber cloth is 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.

[0140] 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 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.

[0141] The preparation method of the prepreg is as follows:

[0142] The resin composition is dissolved with a solvent to form a resin composition glue;

[0143] The reinforcing material is impregnated in the resin composition glue as described above, and then the impregnated reinforcing material is taken out and dried by heating to obtain the prepreg.

[0144] In a specific embodiment, the impregnated reinforcing material is baked at 100°C to 180°C for 1 minute to 15 minutes, and then dried to obtain the prepreg.

[0145] Specifically, the solvent can be selected from one or a combination of any 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.

[0146] The amount of solvent added is not specifically limited in the present application. The amount of solvent added can be selected by a person skilled in the art according to his / her experience, as long as the obtained resin composition glue reaches a suitable viscosity for use.

[0147] The laminate includes at least one prepreg as described above, and a metal foil formed on at least one side of the prepreg.

[0148] In an embodiment in which the laminate includes at least two prepregs as described above, 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 prepregs bonded together by heating and pressing to form the laminate.

[0149] Specifically, the laminate is prepared by covering a metal foil on one side or both sides of one prepreg as described above, or covering a metal foil on one side or both sides of at least two prepregs laminated together, and then hot-pressing to form the laminate.

[0150] The pressing conditions of the laminate are as follows: pressing at a pressure of 0.2 to 2 MPa and a temperature of 150°C to 250°C for 2 to 4 hours.

[0151] Specifically, the number of prepregs can be determined according to the thickness of the laminate required, and one or more prepregs can be used.

[0152] The metal foil can be a copper foil or an aluminum foil, and the material of the metal foil is not limited. The thickness of the metal foil is also not particularly limited, and can be, for example, 5 μm, 8 μm, 12 μm, 18 μm, 35 μm, or 70 μm.

[0153] The printed circuit board comprises at least one of the prepreg or at least one of the laminated board.

[0154] The printed circuit board can be prepared by using the existing process, which is not described herein.

[0155] The content of the present application will be described in detail below with specific examples. It should be understood that the examples of the present application are not limited to these examples.

[0156] Examples 1-6 and Comparative Examples 1-6:

[0157] The components and contents of the resin composition of Examples 1-6 and Comparative Examples 1-6 are shown in Table 1 below:

[0158] Table 1

[0159]

[0160] Specifically, the component information involved in Table 1 above is shown in Table 2 below:

[0161] Table 2

[0162]

[0163] The preparation method of the resin composition in Examples 1-6 and Comparative Examples 1-6 uses a conventional preparation method, specifically: mixing the components in Table 1 and the corresponding contents with an appropriate amount of solvent, and uniformly dispersing and mixing to obtain a resin composition glue with a solid content of 60%, wherein the solid content of 60% is by weight.

[0164] The resin composition glue obtained in Examples 1-6 and Comparative Examples 1-6 is coated on a T glass fiber cloth, soaked and taken out, and placed in a 160°C air drying oven for baking for 3-6 min to prepare a prepreg.

[0165] The sample laminated boards for performance evaluation are prepared:

[0166] (1) Preparation of laminated board

[0167] The prepregs prepared in Examples 1-6 and Comparative Examples 1-6 above are respectively cut to 300×300mm, and one metal foil is placed on each of the opposite sides of the prepreg to form a laminated structure, which is placed in a vacuum hot press to press to obtain a laminated board.

[0168] Specifically, the metal foil is an 18μm low roughening electrolytic copper foil. Of course, it is not limited thereto.

[0169] Performance evaluation method:

[0170] (1) Dielectric Constant (Dk) / Dielectric Loss (Df): measured at 10 GHz using the plate method according to IPC-TM-650 2.5.5.9;

[0171] (2) Glass Transition Temperature (Tg): measured using a dynamic mechanical analysis (DMA) instrument with a temperature ramp of 10 °C / min.

[0172] (3) PCT 2HR Water Uptake: 3 samples of 10 cm x 10 cm, 0.40 mm thick, with metal foil removed from both sides, were dried at 100 °C for 2 hours, weighed, and the weight recorded as W1. The samples were then treated in a Pressure Cooker test machine at 121 °C, 2 atmospheres, for 2 hours, weighed, and the weight recorded as W2. The water uptake was determined as (W2-W1) / W1 x 100%.

[0173] (4) X / Y Coefficient of Thermal Expansion (CTE) Measurement: measured using TMA (Thermal Mechanical Analysis) with a temperature ramp of 10 °C / min and a temperature range of 30-100 °C.

[0174] (5) PCT 1 hr Tin Immersion Resistance after Moisture Heat Treatment: 3 samples of 10 cm x 10 cm, 0.80 mm thick, with metal foil removed from both sides, were dried at 100 °C for 2 hours, then treated in a Pressure Cooker test machine at 121 °C, 2 atmospheres, for 1 hour. The samples were then immersed in a tin bath at 288 °C for 20 seconds. The samples were visually inspected for delamination. If no delamination was observed, the samples were recorded as “Pass”. If delamination was observed, the samples were recorded as “Fail”.

[0175] (6) Peel Strength (PS, N / mm): measured according to the “After Thermal Stress” test conditions in IPC-TM-650 2.4.8 to determine the peel strength of the metal cover layer.

[0176] (7) Board Thickness Accuracy: the thickness difference between the center and the edge of the etched copper clad plate was measured, and the average value was calculated. When the thickness difference was greater than 0.05 mm, it was marked as X; when the thickness difference was 0.01-0.05 mm, it was marked as Δ; and when the thickness difference was less than 0.01 mm, it was marked as O.

[0177] The properties of the laminates obtained using the prepregs in Examples 1-6 and Comparative Examples 1-6 above are shown in Table 3 below.

[0178] Table 3

[0179]

[0180] As shown in Table 3, the laminate obtained using the resin composition of this invention has a higher glass transition temperature, lower dielectric constant, dielectric loss, coefficient of thermal expansion, water absorption, better heat resistance, higher peel strength, and higher thickness accuracy. It can obtain a final cured product with high heat resistance, high toughness, low CTE, low water absorption, high adhesion, and high thickness accuracy, thus obtaining a cured product with excellent comprehensive performance, which meets the current requirements for printed circuit boards.

[0181] In particular, a parallel comparison between Example 1 and Comparative Example 1 shows that, compared to Comparative Example 1 which only added a single type of elastomer A, the resin composition in Example 1, which added different types of elastomers A, B, and C, can reduce the disadvantages of elastomer A. The laminate prepared from the resin composition in Example 1 has a higher glass transition temperature, lower dielectric constant, lower dielectric loss, lower water absorption, better heat resistance, and higher peel strength and thickness accuracy.

[0182] A parallel comparison between Example 2 and Comparative Example 2 shows that, compared to Comparative Example 2 which only added a single type of elastomer B, the resin composition in Example 2, which added different types of elastomers A, B, and C, can reduce the disadvantages of elastomer B. The laminate prepared from the resin composition in Example 2 has a higher glass transition temperature, lower water absorption, better heat resistance, higher peel strength, and higher thickness accuracy.

[0183] A parallel comparison between Example 3 and Comparative Example 3 shows that, compared to Comparative Example 3 which only added a single type of elastomer C, the resin composition in Example 3, which added different types of elastomers A, B, and C, can reduce the disadvantages of elastomer C. The laminate prepared from the resin composition in Example 3 has a lower dielectric constant, dielectric loss, better heat resistance, higher peel strength, and higher thickness accuracy.

[0184] A parallel comparison was made between Example 4 and Comparative Example 6. It can be seen that, compared with Comparative Example 6 which does not contain naphthalene-type epoxy resin and naphthalene-type phenolic resin, the resin composition of Example 4 contains naphthalene-type epoxy resin and naphthalene-type phenolic resin. The laminate prepared from the resin composition of Example 4 has a higher glass transition temperature, higher heat resistance, lower dielectric constant, dielectric loss, coefficient of thermal expansion, water absorption rate, and higher peel strength.

[0185] A parallel comparison was made between Example 6 and Comparative Example 4. It can be seen that, compared with Comparative Example 4 which does not contain elastomers A, B, and C, the resin composition of Example 6 contains different types of elastomers A, B, and C. The laminate prepared from the resin composition of Example 6 has a higher glass transition temperature, higher heat resistance, lower dielectric constant, dielectric loss, coefficient of thermal expansion, water absorption rate, and higher peel strength.

[0186] From Comparative Example 5, it can be seen that the content of the elastomers A, B, and C in Comparative Example 5 is too high, exceeding 70 parts by weight, and most of the elastomers A, B, and C are in the form of particles or thermoplastic resins, and the adhesion between the elastomers and the metal foil is poor, so that the laminate cannot be prepared.

[0187] It should be understood that although the present specification is described in terms of embodiments, not every embodiment contains only one independent technical solution, and the present specification is described in this way only for the sake of clarity, and those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that those skilled in the art can understand.

[0188] The above series of detailed descriptions are only specific descriptions of the feasible embodiments of the present application, and are not intended to limit the protection scope of the present application, and any equivalent embodiments or changes made without departing from the spirit of the present application should be included in the protection scope of the present application.

Claims

1. A resin composition characterized by: The resin composition comprises, by weight: The maleimide resin and / or maleimide prepolymer: 20-100 parts by weight; The epoxy resin: 10-70 parts by weight; The phenolic resin: 5-50 parts by weight; The elastomer: 10-70 parts by weight; The elastomer is a combination of elastomer A, elastomer B and elastomer C, and the weight ratio of the elastomer A, elastomer B and elastomer C is (20-50):(1-10):(5-20), or the weight ratio of the elastomer A, elastomer B and elastomer C is (5-20):(1-15):(20-40); 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 epoxy resin and the phenolic resin each contain at least one naphthyl group.

2. The resin composition according to claim 1, characterized by: The epoxy resin is at least one of structural formula (1)-(6) and structural formula (8) and (9): Formula (1); Formula (2); Formula (3); Formula (4); Structural formula (5); Structural formula (6); Structural formula (8); Structural Formula (9); wherein n in Structural Formula (1) to Structural Formula (6) and Structural Formula (8), Structural Formula (9) is an integer from 1 to 10.

3. The resin composition according to claim 1, characterized by: The phenolic resin is structural formula (12): Formula (12); wherein n in Formula (12) is an integer greater than 1.

4. The resin composition according to claim 1, characterized by: The elastomer A contains structural formula (14) and / or structural formula (15): Formula (14) wherein R1is a C1-C5alkyl group and x is an integer from 1 to 100; Formula (15), wherein R2is a C1-C5 alkyl group and y is an integer from 1 to 100.

5. The resin composition according to claim 1, characterized by: 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 by: The elastomer C contains at least one unit of structural formula (16), structural formula (17) and structural formula (18): Formula (16) wherein R is a C1-C 12 hydrocarbon group; Formula (17), wherein R is a C1-C 12 hydrocarbon group; Formula (18), wherein X is a thiol group, an epoxy group, a hydroxyl group, or a methoxy group.

7. The resin composition according to claim 1, characterized by: The resin composition further comprises an inorganic filler, and / or a dispersing agent, and / or a coupling agent, and / or a flame retardant, and / or 0.01-5 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 phenolic resin, the inorganic filler is 30-250 parts by weight, the flame retardant is 1-60 parts by weight; based on 100 parts by weight of the resin composition, the dispersing agent is 0.001-5 parts by weight, and the coupling agent is 0.001-10 parts by weight.

8. The resin composition according to claim 7, characterized by: The 5% weight loss temperature of the flame retardant is higher than 320°C.

9. Use of the resin composition according to any one of claims 1-8 in a prepreg, a laminate and a printed circuit board.

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