CN116987385A - Resin composition and use thereof - Google Patents

Abstract

The application provides a resin composition and application thereof. The resin composition comprises 20-100 parts by weight of maleimide resin and/or maleimide prepolymer, 5-50 parts by weight of epoxy resin, 1-50 parts by weight of cyanate ester compound and 1-70 parts by weight of elastomer, wherein the elastomer is a mixture of reactive elastomer and non-reactive elastomer. Thus, the application maintains excellent heat resistance, high modulus and low CTE, simultaneously improves the original problem of large brittleness of the maleimide resin, namely improves toughness, reduces thermal expansion coefficient to reduce warping defect, and can lead the resin composition to have high compatibility, high cohesiveness and low water absorption rate, obtain unexpected comprehensive performance improvement and production process performance, be applied to IC packaging and high-speed high-frequency fields and have wide application prospect.

Description

Resin compositions and their applications

Technical field

The present invention belongs to the technical field of electronic materials, and in particular relates to a resin composition and the application of the resin composition. Specifically, it relates to a prepreg, laminate, insulating plate, insulating film, circuit substrate and the like using the resin composition. Electrical devices.

Background technique

During the semiconductor packaging process, if the thermal expansion coefficient difference between the semiconductor component and the substrate is too large, stress can easily occur and cause the substrate to warp, resulting in serious problems such as poor connection between the semiconductor component and the substrate. Therefore, a lower coefficient of thermal expansion is required for the substrate material.

Maleimide resin has excellent heat resistance, high modulus, and low CTE, so it is widely used in high-performance circuit substrates; however, maleimide resin has problems such as high curing temperature, high water absorption, and The disadvantage of high brittleness.

Regarding the material system of maleimide resin, currently, one solution is to use diamine or allyl compounds to modify the maleimide resin, and another solution is to add liquid crystal polymer. Although these solutions can improve toughness, but it will lead to a decrease in heat resistance; another option is to add a block copolymer, which can also improve the toughness, but on the one hand has poor compatibility with thermosetting resins, on the other hand it will cause the resin composition to The adhesion between copper foils is reduced, which in turn affects production and processability.

In summary, it is difficult for existing technical solutions to ensure excellent heat resistance, high modulus, and low CTE while also taking into account excellent toughness, compatibility, adhesion, and water absorption, thereby achieving better processability and performance. .

Contents of the invention

In view of the problems existing in the prior art, the object of the present invention is to provide a resin composition and the application of the resin composition, specifically to provide a prepreg, laminate, insulating plate, and insulating film using the resin composition. , circuit substrates and electrical devices.

In order to achieve the above object, one embodiment of the present invention provides a resin composition. Specifically, the following technical solutions are adopted:

The resin composition includes, based on solid weight, 20 to 100 parts by weight of maleimide resin and/or maleimide prepolymer, 5 to 50 parts by weight of epoxy resin, and 1 to 50 parts by weight of cyanide. An acid ester compound and 1 to 70 parts by weight of an elastomer, the elastomer being a mixture of a reactive elastomer and a non-reactive elastomer.

As an alternative, the reactive elastomer and the non-reactive elastomer are different types of compounds.

As an alternative, the reactive elastomer contains at least one of a hydroxyl group, an epoxy group, an amino group, a cyano group, an unsaturated double bond, a mercapto group, and an acid anhydride group.

Preferably, the reactive elastomer containing acrylate groups is a reactive elastomer containing methacrylate groups.

As an alternative, the reactive elastomer can be partially hydrogenated polybutadiene, partially hydrogenated styrene-butadiene copolymer, partially hydrogenated styrene-butadiene-styrene copolymer, partially hydrogenated styrene -Pentadiene copolymer, anhydride-modified styrene-butadiene copolymer, epoxy-modified polybutadiene resin, epoxy-modified acrylate copolymer, epoxy-modified methacrylate copolymer, containing At least one of cyanoacrylate copolymer, cyanomethacrylate copolymer, epoxy group-containing silicone rubber, and epoxy group-containing silicone resin.

For example, the reactive elastomer is selected from any one or more of the following brands of materials: Asahi Kasei P1083,/> P1500,/> P5051,/> P2000, M1943,/> M1913,/> M1911; HYBRAR ^TM 5125, HYBRAR ^TM 5127, SEPTON ^TM HG252 made by KURARE; SG-P3, SG-80H, PMS-22-1, PMS-22-4, PMS-19-5, PMS-22- made by Nagase, Japan 5; SQ-20P, KHE-8000H manufactured by Nippon Kayaku; SQ502-8 manufactured by Arakawa Chemical; AY42-119 manufactured by DuPont Toray; etc.

As an alternative, the non-reactive elastomer is at least one of styrene, silicone, and acrylate.

For example, the styrenic non-reactive elastomer is selected from any one or more of the following materials: SEPTON ^TM 2000 series (2002, 2004, 2005, 2006, 2063, 2104), SEPTON manufactured by KURARE, Japan ^TM 4000 series (4033, 4044, 4055, 4077), HYBRAR ^TM 7000 series (7125, 7311), SEPTON ^TM 8000 series (8004, 8006, 8007L, 8851), SEPTON ^TM V series (9461, 9475), SEPTON ^TM Q1250 ; H1041, H1043, H1051, H1052, H1053, H1221 made by Asahi Kasei; etc.

For example, the non-reactive silicone elastomer is selected from any one or more of the following materials: X-40-2670, R-170S, X-40-2705, X-40 manufactured by Shin-Etsu Chemical Co., Ltd. -2701, KMP-600, KMP-605, X-52-7030; DOW's EP-2600, EP-2601, EP-2720, TMS-2670, EXL-2315, EXL-2655, etc.

Preferably, the acrylate-based non-reactive elastomer is a methacrylate-based non-reactive elastomer.

For example, the acrylic non-reactive elastomer is selected from any one or more of the following materials: M51, M52, M22 or D51N made by Arkema; LA2250, LA2140, LA-2330 made by Kuraray Co., Ltd. , LA4285; etc.

As an alternative, the content ratio of the reactive elastomer and the non-reactive elastomer is 1: (0.1-20) based on solid weight.

As an alternative, the content of the reactive elastomer is less than the content of the non-reactive elastomer based on solid weight.

Preferably, based on solid weight, the content ratio of the reactive elastomer and the non-reactive elastomer is 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14, 1:15, 1:16, 1:17, 1:18, 1:19 or 1: 20.

Preferably, the elastomer is a mixture of a partially hydrogenated styrene elastomer (which is a reactive elastomer) and a methacrylate non-reactive elastomer, or is an epoxy modified polybutadiene copolymer. A mixture of a reactive elastomer (which is a reactive elastomer) and a methacrylate-based non-reactive elastomer, or a partially hydrogenated styrenic copolymer (which is a reactive elastomer) and a silicone-based non-reactive elastomer. body mixture.

As an alternative, the epoxy resin contains at least 1 naphthyl group and/or the cyanate ester compound contains at least 1 naphthyl group.

As an alternative, the epoxy resin includes a compound of structural formula (1) or/and a compound of structural formula (2):

Structural formula (1); where n is an integer from 1 to 10;

Structural formula (2). Of course, in addition to this, the epoxy resin can also be selected from bisphenol A epoxy resin, bisphenol F epoxy resin, tetraphenylethane epoxy resin, triphenylmethane epoxy resin, biphenyl-type epoxy resin, etc. Epoxy resin, naphthalene ring-type epoxy resin other than structural formula (1) and structural formula (2), dicyclopentadiene-type epoxy resin, isocyanate-type epoxy resin, aralkyl-based linear phenolic epoxy resin, bisphenol A Phenolic 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 , one or more of the multifunctional epoxy resins.

Further, the cyanate ester compound is a compound containing at least one cyanate ester group, which can be a monomer, a polymer, a prepolymer or a combination thereof.

Preferably, the cyanate ester compound is a prepolymer, or a combination of a prepolymer and a monomer, or a combination of a prepolymer and a polymer.

As an alternative, the cyanate ester compound is selected from bisphenol A type cyanate ester, bisphenol F type cyanate ester, bisphenol E type cyanate ester, bisphenol M type cyanate ester, DCPD type cyanate ester. At least one of acid ester, naphthalene cyanate ester, and biphenyl cyanate ester.

As an alternative, the cyanate ester compound includes a compound of structural formula (3):

Structural formula (3); wherein, R is hydrogen or methyl, and n is an integer from 1 to 10.

Further, based on a total of 100 parts by weight of epoxy resin, maleimide resin and/or maleimide prepolymer, and cyanate ester compound, the resin composition also includes 30 to 250 parts by weight of Inorganic fillers.

As an alternative, the inorganic filler is selected from spherical silica, aluminum hydroxide, alumina, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, At least one of calcium carbonate, calcium silicate, mica, and glass fiber powder.

Preferably, the inorganic filler contains silica.

As an alternative, the inorganic filler is surface treated with a silane coupling agent, which is an amino silane coupling agent, a carbon-carbon double bond silane coupling agent or an epoxy silane coupling agent. At least one.

Further, based on 100 parts by weight, the resin composition includes 0.001-5 parts by weight of dispersant and 0.001-10 parts by weight of coupling agent.

As an optional solution, the dispersant is selected from BYK-161 or/and BYK-111 manufactured by BYK Company, and the coupling agent is selected from KBM-402, KBM-403, KBM-502, KBE manufactured by Shinyue Chemical Co., Ltd. -503, KBM-603, KBM-903, KBM-573, KBM-602, KBM-1003, etc.

As an alternative, the maleimide resin contains structural formula (4):

Structural formula (4), wherein R is hydrogen or C1-C5 alkyl.

Preferably, the maleimide resin and/or maleimide prepolymer is selected from the group consisting of 4,4'-diphenylmethane bismaleimide, polyphenylmethane maleimide, m- Phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenyl Methane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6-bismaleimide-(2,2,4-trimethyl)hexane alkane, 2,3-dimethylbenzene maleimide, 2,6-dimethylbenzene maleimide, N-phenylmaleimide, maleimide with aliphatic long chain structure Amine, allyl compound modified maleimide prepolymer, amine modified maleimide prepolymer, acidic phenolic compound modified maleimide prepolymer, cyanate ester modified maleimide prepolymer Any one or a combination of at least two leimide prepolymers.

As a preferred option, the maleimide resin and/or maleimide prepolymer is selected from the group consisting of allyl compound modified maleimide prepolymer, amine modified maleimide Any one or a combination of at least two of amine prepolymers, acidic phenolic compound-modified maleimide prepolymers, and cyanate ester-modified maleimide prepolymers.

For example, the maleimide resin is selected from any one or more of the following brands of materials: BMI-1000, BMI-1000H, BMI-1100, BMI-1100H, BMI-2000, BMI manufactured by Yamato Kasei Co., Ltd. -2300, BMI-3000, BMI-3000H, BMI-4000H, BMI-5000, BMI-5100, BMI-7000, BMI-7000H; BMI, BMI-70, BMI-80 manufactured by Japan KI Chemical Co., Ltd.; Nippon Chemical Co., Ltd. Manufactured by MIR-3000, MIR-5000; X9-450, X9-470 manufactured by Japan DIC Company; D936, D937, D939, D950 manufactured by Sichuan Dongcai Company; etc.

Further, based on a total of 100 parts by weight of epoxy resin, maleimide resin and/or maleimide prepolymer, and cyanate ester compound, the resin composition also includes 1 to 60 parts by weight of Flame retardants.

As an optional solution, the flame retardant is selected from the group consisting of bromine flame retardants, phosphorus flame retardants, nitrogen flame retardants, silicone flame retardants, organic metal flame retardants, and inorganic flame retardants. At least one.

As an alternative, the brominated flame retardant is selected from decabromodiphenyl ether, decabromodiphenyl ethane, brominated styrene or tetrabromophthalamide.

As an alternative, the phosphorus-based flame retardant is set to be inorganic phosphorus, an inorganic phosphorus compound or an organic phosphorus-containing compound. Wherein, the inorganic phosphorus compound is any one of a phosphoric acid compound, a hypophosphorous compound, and an oxidized phosphorus compound, and the organic phosphorus-containing compound is a condensed phosphate ester compound, 9,10-dihydro-9oxa-10-phospha Phenanthrene-10-oxide, 10-(2,5dihydroxyphenyl)-9,10-dihydro-9oxa-10-phosphaphenanthrene-10-oxide, 10-phenyl-9,10- Dihydro-9-oxa-10-phosphenanthrene-10-oxide, tris(2,6 dimethylphenyl)phosphorus, Or phosphazene, wherein m is an integer from 1 to 5.

As an alternative, the nitrogen-based flame retardant is selected from triazine compounds, cyanuric acid compounds, isocyanate compounds, phenothiazine, etc.

As an alternative, the silicone flame retardant can be silicone oil, silicone rubber, silicone resin, etc.

As an alternative, the organometallic flame retardant may be ferrocene, acetylacetonate metal complex, organometallic carbonyl compound, etc.

As an alternative, the inorganic flame retardant may be aluminum hydroxide, magnesium hydroxide, aluminum oxide, barium oxide, etc.

Further, the resin composition further includes 0.01 to 5 parts by weight of a catalyst, and the catalyst is at least one of an imidazole catalyst, a pyridine catalyst, and an organic metal salt catalyst.

As an alternative, the catalyst is at least one of 4-dimethylaminopyridine, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, modified imidazole, and zinc octoate. kind.

In order to achieve the above-mentioned object of the invention, one embodiment of the present invention provides an application of a resin composition. Specifically, the following technical solutions are adopted:

The resin composition adopts the resin composition described above. The resin composition includes 20 to 100 parts by weight of maleimide resin and/or maleimide prepolymer, 5 to 100 parts by weight based on solid weight. 50 parts by weight of epoxy resin, 1-50 parts by weight of cyanate ester compound and 1-70 parts by weight of elastomer, the elastomer being a mixture of reactive elastomer and non-reactive elastomer;

The application is the application of the resin composition in prepregs, laminates, insulation boards, insulation films, circuit substrates and electrical devices.

As an alternative, the resin composition is applied to a prepreg, the prepreg includes the resin composition and a reinforcing material, and the resin composition is attached to the surface of the reinforcing material.

As an alternative, the preparation method of the prepreg is: dissolving the resin composition in a solvent to form a glue solution, immersing the reinforcing material in the glue solution, and then dipping the reinforced material into the glue solution. The material is baked in an environment of 100 to 180°C for 1 to 15 minutes, and the prepreg can be obtained after drying.

As an alternative, the selected from the group consisting of acetone, methyl ethyl ketone, toluene, methyl isobutyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide, ethylene glycol methyl ether, At least one of propylene glycol methyl ether, benzene, toluene, xylene, and cyclohexane.

As an optional solution, the reinforcing material is selected from at least one of natural fibers, organic synthetic fibers, organic fabrics, and inorganic fabrics. More preferably, the reinforcing material is glass fiber cloth, and the glass fiber cloth is preferably open fiber cloth or flat cloth; and the glass fiber cloth is preferably E glass fiber cloth, S glass fiber cloth, T glass fiber cloth or Q fiberglass cloth.

Preferably, the glass fiber cloth is chemically treated with a coupling agent such as epoxy silane or aminosilane to provide good water resistance and heat resistance and improve the interface between the resin composition and the glass fiber cloth. combine.

Further, the resin composition is applied to a laminate, and the laminate is a metal foil-clad laminate.

As an optional solution, the laminate includes a piece of the prepreg sheet and a metal foil attached to at least one side surface of the prepreg sheet.

Specifically, the preparation method of the laminate is: covering one or both sides of the prepreg with metal foil, pressing it under the conditions of 0.2 to 2MPa and 150 to 250°C for 2 to 4 hours, and then hot pressing. A metal foil laminate is formed.

As an optional solution, the laminate includes a composite sheet formed by laminating two or more prepreg sheets, and a metal foil attached to at least one side surface of the composite sheet.

Specifically, the preparation method of the laminate is: superimpose two or more pieces of the prepreg sheets to form a combined sheet, cover one or both sides of the combined sheet with metal foil, Press at 250°C for 2 to 4 hours to obtain a metal foil laminate by hot pressing.

As an alternative, the metal foil can be copper foil, aluminum foil or other metal materials, and its thickness can be preferably 5 μm, 8 μm, 12 μm, 18 μm, 35 μm or 70 μm.

Further, the resin composition is applied to an insulating board.

Further, the resin composition is applied to an insulating film, and the insulating film includes an insulating resin layer composed of the resin composition.

Further, the resin composition is applied to a circuit substrate, and the circuit substrate includes any one of the prepreg, the laminate, the insulating plate, and the insulating film.

Further, the resin composition is applied to electrical devices, and the electrical devices include any one of the prepreg, the laminate, the insulating plate, the insulating film, and the circuit substrate.

In summary, compared with the prior art, the beneficial effect of one embodiment of the present invention is that in the system of maleimide resin, epoxy resin, and cyanate ester compound, reactive elastomer and non-reactive elastomer are added The mixed use of these two elastomers maintains excellent heat resistance, high modulus, and low CTE, while also improving the original brittleness problem of maleimide resin, that is, It improves the toughness and reduces the thermal expansion coefficient to reduce warpage defects. In addition, it can also make the resin composition have high compatibility, high adhesion, and low water absorption, achieving unexpected comprehensive performance improvements and production process performance, and can be used in IC packaging and high-speed and high-frequency fields have broad application prospects.

Detailed ways

The following is the specific implementation of the embodiments of the present invention. It should be noted that those of ordinary skill in the art can also make several improvements and modifications without departing from the principles of the embodiments of the present invention. These improvements and Retouching is also considered to be within the scope of protection of the embodiments of the present invention.

In order to solve the problem that it is difficult for existing solutions to ensure excellent heat resistance, high modulus, and low CTE while taking into account toughness, compatibility, adhesion, and water absorption, the present invention provides a method with improved performance in these aspects. The resin composition, and based on the resin composition, further provides prepregs, laminates, insulating plates, insulating films, circuit substrates and electrical devices using the resin composition.

Specifically, one embodiment of the present invention provides a resin composition. The resin composition includes, based on solid 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 cyanate ester compound and 1 to 70 parts by weight of an elastomer, the elastomer being a mixture of a reactive elastomer and a non-reactive elastomer.

In this way, reactive elastomers and non-reactive elastomers are added to the maleimide resin and/or maleimide prepolymer system, and the two elastomers are mixed and used to maintain excellent heat resistance. While having good properties, high modulus and low CTE, it also improves the problem of high brittleness, that is, improves the toughness, and reduces the thermal expansion coefficient to reduce warpage defects. In addition, the resin composition has high compatibility, high adhesion, Low water absorption does not produce new defects such as poor compatibility and poor adhesion as mentioned in the background technology. It achieves unexpected comprehensive performance improvements and production process performance. It can be used in IC packaging and high-speed and high-frequency fields, and has broad application prospects. Application prospects.

As an alternative, the reactive elastomer and the non-reactive elastomer are different types of compounds. Specifically, the reactive elastomer and the non-reactive elastomer do not contain the same repeating structural units. For example, when the reactive elastomer contains butadiene repeating structural units, the non-reactive elastomer does not contain butadiene repeating structural units. Diene repeating structural units.

As an alternative, the reactive elastomer contains at least one of a hydroxyl group, an epoxy group, an amino group, a cyano group, an unsaturated double bond, a mercapto group, and an acid anhydride group.

As an alternative, the reactive elastomer can be partially hydrogenated polybutadiene, partially hydrogenated styrene-butadiene copolymer, partially hydrogenated styrene-butadiene-styrene copolymer, partially hydrogenated styrene -Pentadiene copolymer, anhydride-modified styrene-butadiene copolymer, epoxy-modified polybutadiene resin, epoxy-modified acrylate copolymer, epoxy-modified methacrylate copolymer, containing At least one of cyanoacrylate copolymer, cyanomethacrylate copolymer, epoxy group-containing silicone rubber, and epoxy group-containing silicone resin.

For example, the reactive elastomer is selected from any one or more of the following brands of materials: Asahi Kasei P1083,/> P1500,/> P5051,/> P2000, M1943,/> M1913,/> M1911; HYBRAR ^TM 5125, HYBRAR ^TM 5127, SEPTON ^TM HG252 made by KURARE; SG-P3, SG-80H, PMS-22-1, PMS-22-4, PMS-19-5, PMS-22- made by Nagase, Japan 5; SQ-20P, KHE-8000H manufactured by Nippon Kayaku; SQ502-8 manufactured by Arakawa Chemical; AY42-119 manufactured by DuPont Toray; etc.

As an alternative, the non-reactive elastomer is at least one of styrene, silicone, and acrylate.

For example, the styrenic non-reactive elastomer is selected from any one or more of the following materials: SEPTON ^TM 2000 series (2002, 2004, 2005, 2006, 2063, 2104), SEPTON manufactured by KURARE, Japan ^TM 4000 series (4033, 4044, 4055, 4077), HYBRAR ^TM 7000 series (7125, 7311), SEPTON ^TM 8000 series (8004, 8006, 8007L, 8851), SEPTON ^TM V series (9461, 9475), SEPTON ^TM Q1250 ; H1041, H1043, H1051, H1052, H1053, H1221 made by Asahi Kasei; etc.

For example, the non-reactive silicone elastomer is selected from any one or more of the following materials: X-40-2670, R-170S, X-40-2705, X-40 manufactured by Shin-Etsu Chemical Co., Ltd. -2701, KMP-600, KMP-605, X-52-7030; DOW's EP-2600, EP-2601, EP-2720, TMS-2670, EXL-2315, EXL-2655, etc.

Preferably, the acrylate-based non-reactive elastomer is a methacrylate-based non-reactive elastomer.

For example, the acrylic non-reactive elastomer is selected from any one or more of the following materials: M51, M52, M22 or D51N made by Arkema; LA2250, LA2140, LA-2330 made by Kuraray Co., Ltd. , LA4285; etc.

As an alternative, the content ratio of the reactive elastomer and the non-reactive elastomer is 1: (0.1-20) based on solid weight.

As an alternative, the content of the reactive elastomer is less than the content of the non-reactive elastomer based on solid weight.

Preferably, based on solid weight, the content ratio of the reactive elastomer and the non-reactive elastomer is 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14, 1:15, 1:16, 1:17, 1:18, 1:19 or 1: 20.

In this way, when too much reactive elastomer is added to the resin composition, the compatibility between different resins is better at room temperature, but the tougher groups with larger molecular weights are difficult to be evenly distributed in the overall cured product under high temperature conditions. Affects CTE, water absorption and heat resistance; when too little reactive elastomer is added to the resin composition, the compatibility between different resins is poor, which affects the mass production process and makes it difficult to obtain stable comprehensive performance. Resin composition. Based on the content ratio of the reactive elastomer and the non-reactive elastomer of the present invention, compatibility, CTE, water absorption and heat resistance can be taken into consideration.

Preferably, the elastomer is a mixture of a partially hydrogenated styrene elastomer (which is a reactive elastomer) and a methacrylate non-reactive elastomer, or is an epoxy modified polybutadiene copolymer. A mixture of a reactive elastomer (which is a reactive elastomer) and a methacrylate-based non-reactive elastomer, or a partially hydrogenated styrenic copolymer (which is a reactive elastomer) and a silicone-based non-reactive elastomer. body mixture.

As an alternative, the epoxy resin contains at least 1 naphthyl group and/or the cyanate ester compound contains at least 1 naphthyl group.

As an alternative, the epoxy resin includes a compound of structural formula (1) or/and a compound of structural formula (2):

Structural formula (1); where n is an integer from 1 to 10;

Structural formula (2). Of course, in addition to this, the epoxy resin can also be selected from bisphenol A epoxy resin, bisphenol F epoxy resin, tetraphenylethane epoxy resin, triphenylmethane epoxy resin, biphenyl-type epoxy resin, etc. Epoxy resin, naphthalene ring-type epoxy resin other than structural formula (1) and structural formula (2), dicyclopentadiene-type epoxy resin, isocyanate-type epoxy resin, aralkyl-based linear phenolic epoxy resin, bisphenol A Phenolic 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 , one or more of the multifunctional epoxy resins.

Further, the cyanate ester compound is a compound containing at least one cyanate ester group, which can be a monomer, a polymer, a prepolymer or a combination thereof.

Preferably, the cyanate ester compound is a prepolymer, or a combination of a prepolymer and a monomer, or a combination of a prepolymer and a polymer.

As an alternative, the cyanate ester compound is selected from bisphenol A type cyanate ester, bisphenol F type cyanate ester, bisphenol E type cyanate ester, bisphenol M type cyanate ester, DCPD type cyanate ester. At least one of acid ester, naphthalene cyanate ester, and biphenyl cyanate ester.

As an alternative, the cyanate ester compound includes a compound of structural formula (3):

Structural formula (3); wherein, R is hydrogen or methyl, and n is an integer from 1 to 10.

Further, based on a total of 100 parts by weight of epoxy resin, maleimide resin and/or maleimide prepolymer, and cyanate ester compound, the resin composition also includes 30 to 250 parts by weight of Inorganic fillers.

As an alternative, the inorganic filler is selected from spherical silica, aluminum hydroxide, alumina, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, At least one of calcium carbonate, calcium silicate, mica, and glass fiber powder.

Preferably, the inorganic filler contains silica.

As an alternative, the inorganic filler is surface treated with a silane coupling agent, which is an amino silane coupling agent, a carbon-carbon double bond silane coupling agent or an epoxy silane coupling agent. At least one.

Further, based on 100 parts by weight, the resin composition includes 0.001-5 parts by weight of dispersant and 0.001-10 parts by weight of coupling agent.

As an optional solution, the dispersant is selected from BYK-161 or/and BYK-111 manufactured by BYK Company, and the coupling agent is selected from KBM-402, KBM-403, KBM-502, KBE manufactured by Shinyue Chemical Co., Ltd. -503, KBM-603, KBM-903, KBM-573, KBM-602, KBM-1003, etc.

As an alternative, the maleimide resin contains structural formula (4):

Structural formula (4), wherein R is hydrogen or C1-C5 alkyl.

Preferably, the maleimide resin and/or maleimide prepolymer is selected from the group consisting of 4,4'-diphenylmethane bismaleimide, polyphenylmethane maleimide, m- Phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenyl Methane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6-bismaleimide-(2,2,4-trimethyl)hexane alkane, 2,3-dimethylbenzene maleimide, 2,6-dimethylbenzene maleimide, N-phenylmaleimide, maleimide with aliphatic long chain structure Amine, allyl compound modified maleimide prepolymer, amine modified maleimide prepolymer, acidic phenolic compound modified maleimide prepolymer, cyanate ester modified maleimide prepolymer Any one or a combination of at least two leimide prepolymers.

As an alternative, the maleimide resin and/or maleimide prepolymer is selected from the group consisting of allyl compound-modified maleimide prepolymer, amine-modified maleimide prepolymer, Any one or a combination of at least two of imine prepolymers, acidic phenolic compound-modified maleimide prepolymers, and cyanate ester-modified maleimide prepolymers.

For example, the maleimide resin is selected from any one or more of the following brands of materials: BMI-1000, BMI-1000H, BMI-1100, BMI-1100H, BMI-2000, BMI manufactured by Yamato Kasei Co., Ltd. -2300, BMI-3000, BMI-3000H, BMI-4000H, BMI-5000, BMI-5100, BMI-7000, BMI-7000H; BMI, BMI-70, BMI-80 manufactured by Japan KI Chemical Co., Ltd.; Nippon Chemical Co., Ltd. Manufactured by MIR-3000, MIR-5000; X9-450, X9-470 manufactured by Japan DIC Company; D936, D937, D939, D950 manufactured by Sichuan Dongcai Company; etc.

Further, based on a total of 100 parts by weight of epoxy resin, maleimide resin and/or maleimide prepolymer, and cyanate ester compound, the resin composition also includes 1 to 60 parts by weight of Flame retardants.

As an optional solution, the flame retardant is selected from the group consisting of bromine flame retardants, phosphorus flame retardants, nitrogen flame retardants, silicone flame retardants, organic metal flame retardants, and inorganic flame retardants. At least one. Of course, the type of the flame retardant is not limited to this. It can be understood that the added flame retardant can be selected according to the specific application field of the laminate, for example, application fields that require halogen, preferably non- Halogen flame retardants, such as phosphorus-based flame retardants (for example, preferably phosphazene or a flame retardant containing bis-DOPO) or nitrogen-based flame retardants.

As an alternative, the brominated flame retardant is selected from decabromodiphenyl ether, decabromodiphenyl ethane, brominated styrene or tetrabromophthalamide.

As an alternative, the phosphorus-based flame retardant is set to be inorganic phosphorus, an inorganic phosphorus compound or an organic phosphorus-containing compound. Wherein, the inorganic phosphorus compound is any one of a phosphoric acid compound, a hypophosphorous compound, and an oxidized phosphorus compound, and the organic phosphorus-containing compound is a condensed phosphate ester compound, 9,10-dihydro-9oxa-10-phospha Phenanthrene-10-oxide, 10-(2,5dihydroxyphenyl)-9,10-dihydro-9oxa-10-phosphaphenanthrene-10-oxide, 10-phenyl-9,10- Dihydro-9-oxa-10-phosphenanthrene-10-oxide, tris(2,6 dimethylphenyl)phosphorus, Or phosphazene, wherein m is an integer from 1 to 5.

As an alternative, the nitrogen-based flame retardant is selected from triazine compounds, cyanuric acid compounds, isocyanate compounds, phenothiazine, etc.

As an alternative, the silicone flame retardant can be silicone oil, silicone rubber, silicone resin, etc.

As an alternative, the organometallic flame retardant may be ferrocene, acetylacetonate metal complex, organometallic carbonyl compound, etc.

As an alternative, the inorganic flame retardant may be aluminum hydroxide, magnesium hydroxide, aluminum oxide, barium oxide, etc.

Furthermore, the flame retardant is preferably a phosphorus-based flame retardant.

Further, the resin composition further includes 0.01 to 5 parts by weight of a catalyst, and the catalyst is at least one of an imidazole catalyst, a pyridine catalyst, and an organic metal salt catalyst.

As an alternative, the catalyst is at least one of 4-dimethylaminopyridine, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, modified imidazole, and zinc octoate. kind.

Further, one embodiment of the present invention provides an application of the resin composition. Specifically, the following technical solutions are adopted:

The resin composition adopts the resin composition described above. The resin composition includes 20 to 100 parts by weight of maleimide resin and/or maleimide prepolymer, 5 to 100 parts by weight based on solid weight. 50 parts by weight of epoxy resin, 1-50 parts by weight of cyanate ester compound and 1-70 parts by weight of elastomer, the elastomer being a mixture of reactive elastomer and non-reactive elastomer;

The application is the application of the resin composition in prepregs, laminates, insulation boards, insulation films, circuit substrates and electrical devices.

As an alternative, the resin composition is applied to a prepreg, the prepreg includes the resin composition and a reinforcing material, and the resin composition is attached to the surface of the reinforcing material.

As an alternative, the preparation method of the prepreg is: dissolving the resin composition in a solvent to form a glue solution, immersing the reinforcing material in the glue solution, and then dipping the reinforced material into the glue solution. The material is baked in an environment of 100 to 180°C for 1 to 15 minutes, and the prepreg can be obtained after drying.

As an alternative, the selected from the group consisting of acetone, methyl ethyl ketone, toluene, methyl isobutyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide, ethylene glycol methyl ether, At least one of propylene glycol methyl ether, benzene, toluene, xylene, and cyclohexane.

As an optional solution, the reinforcing material is selected from at least one of natural fibers, organic synthetic fibers, organic fabrics, and inorganic fabrics. More preferably, the reinforcing material is glass fiber cloth, and the glass fiber cloth is preferably open fiber cloth or flat cloth; and the glass fiber cloth is preferably E glass fiber cloth, S glass fiber cloth, T glass fiber cloth or Q fiberglass cloth.

Preferably, the glass fiber cloth is chemically treated with a coupling agent such as epoxy silane or aminosilane to provide good water resistance and heat resistance and improve the interface between the resin composition and the glass fiber cloth. combine.

Further, the resin composition is applied to a laminate, and the laminate is a metal foil-clad laminate.

As an optional solution, the laminate includes a piece of the prepreg sheet and a metal foil attached to at least one side surface of the prepreg sheet.

Specifically, the preparation method of the laminate is: covering one or both sides of the prepreg with metal foil, pressing it under the conditions of 0.2 to 2MPa and 150 to 250°C for 2 to 4 hours, and then hot pressing. A metal foil laminate is formed.

As an optional solution, the laminate includes a composite sheet formed by laminating two or more prepreg sheets, and a metal foil attached to at least one side surface of the composite sheet.

Specifically, the preparation method of the laminate is: superimpose two or more pieces of the prepreg sheets to form a combined sheet, cover one or both sides of the combined sheet with metal foil, Press at 250°C for 2 to 4 hours to obtain a metal foil laminate by hot pressing.

As an alternative, the metal foil can be copper foil, aluminum foil or other metal materials, and its thickness can be preferably 5 μm, 8 μm, 12 μm, 18 μm, 35 μm or 70 μm.

Further, the resin composition is applied to an insulating board.

Further, the resin composition is applied to an insulating film, and the insulating film includes an insulating resin layer composed of the resin composition.

Preferably, the insulating film further includes a carrier film, and the insulating resin layer is attached to the surface of the carrier film through a coating process.

Preferably, the carrier film is selected from polyethylene terephthalate film, release film, copper foil or aluminum foil, preferably polyethylene terephthalate film.

Preferably, the insulating film further includes a protective film layer, which is attached to a side of the insulating resin layer facing away from the carrier film and covers the insulating resin layer. Preferably, the material of the protective film layer and the carrier film is the same, but of course, it is not limited thereto.

The preparation method of the insulating film includes: adding the resin composition into a solvent to dissolve the glue liquid of the resin composition; applying the glue liquid of the resin composition on the carrier film; and then applying the glue liquid of the resin composition to the carrier film. After the carrier film is heated and dried, the glue of the resin composition forms the insulating resin layer, and the insulating film can be obtained.

Preferably, the solvent is selected from acetone, methyl ethyl ketone, toluene, methyl isobutyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide, ethylene glycol methyl ether, and propylene glycol methyl ether. one or more of them.

Preferably, in the step of "heating and drying the carrier film", the heating and drying condition is baking at 100-200°C for 1-10 minutes, but of course, it is not limited to this.

Further, the resin composition is applied to a circuit substrate, and the circuit substrate includes any one of the prepreg, the laminate, the insulating plate, and the insulating film.

Further, the resin composition is applied to electrical devices, and the electrical devices include any one of the prepreg, the laminate, the insulating plate, the insulating film, and the circuit substrate.

Compared with the existing technology, the present invention has the following beneficial effects: in the maleimide resin system, reactive elastomers and non-reactive elastomers are added, and the two elastomers are mixed and used to maintain excellent heat resistance. While having good properties, high modulus and low CTE, it also improves the original brittleness problem of maleimide resin, that is, it improves the toughness and reduces the thermal expansion coefficient to reduce warpage defects. In addition, it can also make The resin composition has high compatibility, high adhesion, and low water absorption, and has achieved unexpected comprehensive performance improvements and production process performance. It can be used in IC packaging and high-speed and high-frequency fields, and has broad application prospects.

The content of the present invention will be described in detail below with specific examples and comparative examples.

Specifically, each embodiment and comparative example provides a resin composition. The components of the resin composition and the weight parts of each component (based on solid weight) are as shown in Table 1, and each component in Table 1 The specific grade materials are shown in Table 2.

[Table 1]

[Table 2]

Material Trademark Maleimide resin 1 Yamato Kasei Co., Ltd., BMI-2300 Maleimide resin 2 Nippon Kayaku, MIR-3000 Epoxy resin 1 Made by DIC, HP-6000 Epoxy Resin 2 Nippon Kayaku, NC-3000 Cyanate ester resin 1 Bisphenol A type, manufactured by Yangzhou Tianqi Cyanate ester resin 2 Naphthalene type, made by Yangzhou Tianqi Reactive elastomer 1 Made in Japan, Nagase, SG-P3 Reactive elastomer 2 Made by Asahi Kasei, M1913 Non-reactive elastomer1 Made by Asahi Kasei, H1052 Non-reactive elastomer 2 Made by Kuraray, LA2140 flame retardant Decabromobisphenol A, made by Albemarle catalyst 2-ethyl-4-methylimidazole filler Spherical silica

The resin compositions of each example and comparative example were weighed according to the components and weight parts shown in Table 1, and then dissolved in a solvent to prepare a glue solution with a solid content of 60%. Coat it on T glass fiber cloth and soak it, take it out, and then bake it in a blast drying oven at 160°C for 3 to 6 minutes to make a prepreg.

Cut the prepared prepreg to 300mm×300mm, then stack a piece of electrolytic copper foil on the upper and lower sides of the prepreg to form a certain stack, and send it to a vacuum press for lamination to obtain a copper-clad laminate.

The properties of the copper-clad laminates obtained in each of the above examples and comparative examples are shown in Table 3.

[table 3]

Notes to Table 3:

1) Tg: glass transition temperature, using DMA (thermal mechanical analysis), and the heating rate is 10°C/min;

2) Dk and Df: measured at 10GHz using the flat plate method in accordance with IPC-TM-650 2.5.5.9;

3) CTE (X-Y, α1): X/Y thermal expansion coefficient, using TMA (thermal mechanical analysis), heating rate 10℃/min, test temperature range 30~100℃;

4) Water absorption: Take three samples of 10cm×10cm, thickness 0.40mm, with metal foil removed from both sides, dry at 100°C for 2 hours, weigh, and record the weight as W1; then put it in a pressure cooker test machine , treat it at 121°C and 2 atmospheric pressure for 2 hours, weigh it, record the weight as W2, and measure the water absorption rate (W2-W1)/W1×100%;

5) PCT 1hr: For the heat resistance of immersed tin after moist heat treatment, take three samples of 10cm×10cm, thickness 0.80mm, with metal foil removed from both sides, dry at 100°C for 2 hours, and then use a pressure cooker test (Pressure Cooker test) Machine, after processing for 1 hour at 121°C and 2 atmospheric pressure, immerse tin in a tin furnace at 288°C for 20 seconds, and visually observe whether there is delamination. If there is no delamination in the 3 pieces, it will be recorded as [Pass], if there is any The delamination phenomenon is recorded as [fail];

6) Peel strength: Test the peel strength of the metal cover layer according to the "after thermal stress" experimental conditions in the IPC-TM-650 2.4.8 method.

It should be understood that although this specification is described in terms of implementations, not each implementation only contains an independent technical solution. This description of the specification is only for the sake of clarity. Persons skilled in the art should take the specification as a whole and understand each individual solution. The technical solutions in the embodiments can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

The series of detailed descriptions listed above are only specific descriptions of feasible implementations of the present application. They are not intended to limit the protection scope of the present application. Any equivalent implementations or implementations that do not deviate from the technical spirit of the present application or All changes should be included in the protection scope of this application.

Claims (10)

1. A resin composition comprising, by weight of solids, 20 to 100 parts by weight of a maleimide resin and/or a maleimide prepolymer, 5 to 50 parts by weight of an epoxy resin, 1 to 50 parts by weight of a cyanate ester compound, and 1 to 70 parts by weight of an elastomer which is a mixture of a reactive elastomer and a non-reactive elastomer.

2. The resin composition of claim 1, wherein the reactive elastomer and the non-reactive elastomer are different types of compounds.

3. The resin composition according to claim 2, wherein the reactive elastomer contains at least one of a hydroxyl group, an epoxy group, an amino group, a cyano group, an unsaturated double bond, a mercapto group, and an acid anhydride group.

4. The resin composition according to claim 3, wherein the reactive elastomer is at least one selected from the group consisting of partially hydrogenated polybutadiene, partially hydrogenated styrene-butadiene copolymer, partially hydrogenated styrene-butadiene-styrene copolymer, partially hydrogenated styrene-pentadiene copolymer, anhydride-modified styrene-butadiene copolymer, epoxy-modified polybutadiene resin, epoxy-modified acrylate copolymer, epoxy-modified methacrylate copolymer, cyanoacrylate-containing copolymer, cyanomethacrylate copolymer, epoxy-containing silicone rubber, and epoxy-containing silicone resin.

5. The resin composition of claim 2, wherein the non-reactive elastomer is at least one of styrenes, silicones, or acrylates.

6. The resin composition according to claim 1, wherein the content ratio of the reactive elastomer and the non-reactive elastomer is 1 (0.1 to 20) by solid weight.

7. The resin composition of claim 6, wherein the reactive elastomer is present in an amount less than the non-reactive elastomer on a solids basis.

8. The resin composition according to claim 1, wherein the epoxy resin contains at least 1 naphthyl group and/or the cyanate ester compound contains at least 1 naphthyl group.

9. The resin composition according to claim 8, wherein the epoxy resin comprises a compound of structural formula (1) or/and a compound of structural formula (2):

wherein n is an integer of 1 to 10;

10. use of the resin composition according to any one of claims 1 to 9 in prepregs, laminates, insulating boards, insulating films, circuit substrates and electrical devices.