A cyanogroup pre-polymerized thermosetting resin composition and a prepreg and a metal foil laminate thereof

Abstract

This invention discloses a cyano-based prepolymer thermosetting resin composition and its semi-cured sheet and metal foil laminate, comprising, by weight: 30-90 parts of modified maleimide prepolymer; and 5-60 parts of thermosetting resin. The modified maleimide prepolymer is prepared by reacting an amine modifier with a phthalonitrile compound to obtain a first prepolymer, then adding maleimide resin to the first prepolymer and continuing prepolymerization to obtain the modified maleimide prepolymer. The advantages of this invention are that it effectively reduces the XY axis CTE of the composition, increases the glass transition temperature, and further improves the peel strength.

Description

Technical Field

[0001] This invention relates to the field of copper clad laminate technology, and particularly to a cyano-based prepolymer thermosetting resin composition and its semi-cured sheet and metal foil laminate. Background Technology

[0002] A low coefficient of thermal expansion (CTE) along the XY axis of the packaging substrate is a core requirement for ensuring the reliability of the packaging structure. During high-temperature packaging processes and the long-term thermal cycling of electronic devices, if the difference between the CTE of the substrate and the chip is too large, significant thermal stress will be generated, leading to problems such as warping, delamination, and solder joint cracking in the packaging structure, ultimately causing circuit failure. Currently, a relatively effective solution for reducing the CTE of the XY axis of the packaging substrate is to introduce stress-absorbing molecular structures into the molecular structure through chemical prepolymerization. This also avoids the adverse effects of reduced adhesion, reduced toughness, and poor flowability caused by previous solutions that excessively increased the proportion of inorganic fillers or crosslinking density. However, as advanced packaging forms or processes such as SoC, ETS, and FCBGA develop towards higher density, thinner profiles, larger sizes, and more layers, higher requirements are placed on properties such as coefficient of thermal expansion, adhesion of ultra-thin carrier copper, glass transition temperature, and resin flowability. Current technical solutions often struggle to meet or simultaneously address these requirements. Summary of the Invention

[0003] The purpose of this invention is to provide a cyano-based prepolymer thermosetting resin composition and its semi-cured sheet and metal foil laminate, which can effectively reduce the XY axis CTE, increase the glass transition temperature, and further improve the peel strength.

[0004] The above-mentioned technical objective of the present invention is achieved through the following technical solution:

[0005] A cyano-based prepolymer thermosetting resin composition, by weight, comprising: Modified maleimide prepolymer: 30-90 parts; Thermosetting resin: 5-60 parts; The modified maleimide prepolymer is prepared by reacting an amine modifier with a phthalonitrile compound to obtain a first prepolymer, then adding maleimide resin to the first prepolymer and continuing prepolymerization to obtain the modified maleimide prepolymer.

[0006] Preferably, the modified maleimide prepolymer is prepared by reacting an amine modifier and a phthalonitrile compound at 80-160°C for 2-6 hours to obtain a first prepolymer, then adding maleimide resin to the first prepolymer, and continuing to react at 80-160°C for 2-6 hours to obtain the modified maleimide prepolymer.

[0007] Preferably, the reaction molar ratio of the amine modifier and the phthalonitrile compound is 1.05:1 to 3:1, and the reaction molar ratio of the maleimide resin and the amine modifier is 1:1 to 5:1. The amine modifier is selected from one or more of aromatic diamine compounds, aliphatic diamine compounds, and amino silicone oils.

[0008] Preferably, the aromatic diamine compound is selected from one or more of p-phenylenediamine, m-phenylenediamine, o-phenylenediamine and substituted phenylenediamines, biphenylenediamine, naphthylenediamine, fluoreneenediamine, diaminodiphenylmethane, diaminodiphenyl ether, diaminodiphenyl sulfone, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diaminodiphenylmethane, and 2-bis(4-(4-aminophenoxy)phenyl)propane.

[0009] Preferably, the aliphatic diamine compound is selected from one or more of ethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethyldiamine, 2,2,4-trimethylhexamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, 2,5-dimethylhexamethylenediamine, 3-methoxyhexamethylenediamine, 2,5-dimethylheptamethyldiamine, 3-methylheptamethyldiamine, 4,4'-dimethylheptamethyldiamine, 5-methylnonamethylenediamine, 1,4-diaminocyclohexane, and bis(4-aminocyclohexyl)methane.

[0010] Preferably, the amino-modified silicone oil is a linear silicone oil with dual amino-terminated ends.

[0011] Preferably, the phthalonitrile compound is a compound containing at least two groups as shown in Formula I in one molecular structure: Formula I.

[0012] Preferably, the phthalonitrile compound has the following structural formula II: Formula II; Where B is , , , , , , ,or One of them.

[0013] Preferably, the maleimide resin contains at least two maleimide groups in one molecular structure.

[0014] Preferably, the maleimide resin is one or more selected from the structures shown in Formula III, Formula IV, Formula V, Formula VI, or Formula VII: The structural formula of Formula III is as follows: Formula III; The structural formula of Formula IV is as follows: Formula IV; The structural formula of Equation V is as follows: Formula V; The structural formula of Formula VI is as follows: Formula VI; Where R2 is hydrogen or methyl, R1 is methylene or isopropyl, and n is an integer from 1 to 10; The structural formula of Equation VII is as follows: Formula VII; Where n is an integer from 1 to 10.

[0015] Preferably, the thermosetting resin is one or more selected from bis / domaleimide resin, bis / donadiximide, epoxy resin, cyanate ester resin, benzoxazine resin, polyphenylene ether resin, and hydrocarbon resin.

[0016] Preferably, the epoxy resin is selected from one or more of the following: bisphenol type epoxy resin, phosphorus-containing epoxy resin, nitrogen-containing epoxy resin, bisphenol A phenolic epoxy resin, phenolic epoxy resin, cresol phenolic epoxy resin, triphenylmethane epoxy resin, tetraphenylethane epoxy resin, biphenyl type epoxy resin, naphthyl ring type epoxy resin, dicyclopentadiene type epoxy resin, phenolphthalein type epoxy resin, fluorene type epoxy resin, anthracene type epoxy resin, isocyanate modified epoxy resin, aralkyl linear phenolic epoxy resin, alicyclic epoxy resin, glycidylamine type epoxy resin, and glycidyl ester type epoxy resin.

[0017] Preferably, the epoxy resin is selected from one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, biphenyl type epoxy resin, naphthalene ring type epoxy resin, dicyclopentadiene type epoxy resin, phenolphthalein type epoxy resin, fluorene type epoxy resin, anthracene type epoxy resin, or phosphorus-containing epoxy resin.

[0018] Preferably, the cyanate resin is a compound containing two or more cyanate groups in its molecular structure, specifically selected from one or more of bisphenol A type cyanate resin, bisphenol F cyanate resin, bisphenol M cyanate resin, dicyclopentadiene type cyanate resin, o-methylphenolic type cyanate resin, and phenolic type cyanate resin.

[0019] Preferably, the benzoxazine resin is a compound containing two or more oxazine rings in its molecular structure.

[0020] Preferably, the polyphenylene ether resin is a low molecular weight polyphenylene ether with a number average molecular weight of 1000~4000 g / mol.

[0021] Preferably, the hydrocarbon resin is at least one of butadiene oligomer, butadiene-styrene oligomer, butadiene-styrene-butadiene oligomer, and divinylbenzene-styrene-butadiene oligomer.

[0022] Preferably, the cyano-based prepolymer thermosetting resin composition further includes an elastomer, the amount of which is 5% to 40% by weight of the cyano-based prepolymer thermosetting resin composition. The elastomer is one or more of hydrogenated or non-hydrogenated styrene-olefin copolymers, polyesters, polyurethanes, polyamides, polyethers, polyacrylates, or silicones. From the perspective of better compatibility, adhesion, and reduction of the XY axis thermal expansion coefficient, the elastomer is preferably one whose molecular structure contains compatible groups, such as anhydride groups, epoxy groups, amide groups, maleimide groups, hydroxyl groups, phenolic groups, and mercapto groups. The weight-average molecular weight of the elastomer is preferably 500 to 1,000,000 g / mol, more preferably 10,000 to 600,000 g / mol.

[0023] Preferably, the cyano prepolymer thermosetting resin composition further includes a filler, wherein the amount of filler added is 50% to 90% by weight of the cyano prepolymer thermosetting resin composition; The filler is selected from inorganic fillers or organic fillers; The inorganic filler is selected from one or more of the following: obtuse-angled silica, acute-angled silica, spherical silica, hollow silica, aluminum hydroxide, boehmite, alumina, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate, mica, zinc molybdate, calcium molybdate, molybdenum disulfide, and glass fiber powder. The organic filler is selected from one or more of polytetrafluoroethylene powder, silicone resin powder, polymethyl methacrylate powder, silicone rubber powder, styrene-butadiene rubber powder, and polyacrylate rubber powder.

[0024] Preferably, the cyano prepolymer thermosetting resin composition further includes an accelerator, wherein the amount of the accelerator added is 0.01% to 2% of the weight percentage of the cyano prepolymer thermosetting resin composition, and the accelerator is one or more of imidazoles, tertiary amines, organic ureas, thermal free radicals, organophosphorus compounds, and metal carboxylates.

[0025] Preferably, antioxidants, polymerization inhibitors, ion traps, ultraviolet absorbers, colorants, adhesion enhancers, etc., may be added to the cyano-based prepolymer thermosetting resin composition as needed. These various additives can be used alone or in combination of two or more.

[0026] A semi-cured sheet is prepared by dissolving a cyano-based prepolymer thermosetting resin composition in a solvent, with a solid content of 50% to 75%, stirring evenly, and allowing it to mature to form a resin composition liquid. A reinforcing material is then impregnated in the resin composition liquid, and the impregnated reinforcing material is dried by baking at 50 to 200°C for 1 to 10 minutes to obtain the semi-cured sheet.

[0027] The reinforcing material can be organic or inorganic fabric. Inorganic fabric is particularly preferred, especially glass fiber cloth, which is preferably open-fiber cloth or flat cloth. Furthermore, to improve the interfacial bonding between the resin and the glass fiber cloth, the glass fiber cloth generally requires chemical treatment, primarily using silane coupling agents such as epoxy silane, amino silane, vinyl silane, and styrene silane.

[0028] The solvent is selected from one or more of acetone, butanone, methyl isobutyl ketone, cyclohexanone, N,N-dimethylformamide, N,N-dimethylacetamide, ethylene glycol methyl ether, propylene glycol methyl ether, toluene, and xylene.

[0029] A metal foil laminate is obtained by stacking prepreg sheets, covering one or both sides with metal foil, and then hot-pressing them. The number of prepreg sheets can be determined according to the required thickness of the laminate, and one or more sheets can be used. The metal foil can be copper foil or aluminum foil, and its thickness is generally 1~35μm. The pressing conditions for the laminate are: pressing at a pressure of 0.2~3MPa and a temperature of 180~250℃ for 2~4 hours.

[0030] In summary, the beneficial effects of this invention are as follows: by introducing a compound containing a phthalonitrile structure during the prepolymerization process of modified maleimide resin, the prepolymerization is first performed using a phthalonitrile compound and an excess of an amine modifier, followed by prepolymerization with the maleimide resin. On the one hand, the amine modifier can significantly reduce the XY axis CTE of the composition; on the other hand, after curing, the phthalonitrile compound forms a large number of aromatic heterocyclic structures, greatly enhancing the rigidity of the molecular chain. Furthermore, it may also form a certain amount of hydrogen bonds or chemical crosslinks between molecules, thereby further reducing the XY axis CTE and significantly increasing the glass transition temperature. Moreover, due to the high nitrogen content of phthalonitrile, the peel strength is further improved. Detailed Implementation

[0031] The specific embodiments of the present invention will be further described below. These embodiments do not constitute a limitation on the present invention.

[0032] The following are the manufacturers and models of the raw materials required: Multi / bismaleimide resins: 1: Japan KI BMI-80; 2: Nippon Chemical MIR3000; Amine-modified compounds: Diamino-terminated silicone oil compounds 1. Shin-Etsu Chemical KF8010; 2. Shin-Etsu Chemical X-22-9409; 3. Shin-Etsu Chemical X-22-161A; Domaleimide resin: Sichuan Dongcai DFE 950 Cyanate ester resin: Phenolic cyanate ester, Osada PT30s from Switzerland; Epoxy resin: Naphthalene ether type epoxy resin, DIC HP6000 from Japan; Benzoxazine: Diaminodiphenyl ether type benzoxazine, Guangdong Tongyu TBN8300K65; Elastomer: Polyacrylate rubber, Nagase SG-P3W1, Japan, Mw=300000; Filler: Inorganic filler, spherical silica slurry, Japanese Admatech SC2050MTX; Accelerator: Organophosphorus compound, Hokuko Chemical TPP-MK (Japan).

[0033] Synthesis example 1: The resin composition was prepared according to the following steps: (1) 15 parts of bisphenol A type phthalonitrile (Mn=480g / mol), 30 parts of amine modifier KF8010 (Mn=860g / mol) and 100 parts of propylene glycol monomethyl ether were added to the reactor and reacted at 110°C for 3 hours to obtain the first prepolymer.

[0034] (2) Add 50 parts of bismaleimide resin (BMI-80) to the first prepolymer and continue to react at 110°C for 3 hours to obtain modified maleimide prepolymer A.

[0035] Synthesis example 2: The resin composition was prepared according to the following steps: (1) 10 parts of bisphenol A type phthalonitrile (Mn=480g / mol), 40 parts of amine modifier X-22-9409 (Mn=1340g / mol) and 100 parts of propylene glycol monomethyl ether were added to the reactor and reacted at 110°C for 3 hours to obtain the first prepolymer.

[0036] (2) Add 55 parts of polymaleimide resin (MIR3000) to the first prepolymer and continue to react at 110°C for 3 hours to obtain modified maleimide prepolymer B.

[0037] Synthesis example 3: The resin composition was prepared according to the following steps: (1) Add 40 parts of amine modifier X-22-161A (Mn=1600g / mol), 60 parts of bismaleimide resin (BMI-80), and 100 parts of propylene glycol monomethyl ether to the reactor and react at 110°C for 4 hours to obtain modified maleimide prepolymer C.

[0038] Prepreg preparation: According to the component contents in Table 1, the above resin composition, accelerator, filler and appropriate amount of solvent were stirred and mixed evenly to obtain a glue solution with a solid content of 68%. The glue solution was impregnated and coated onto T fiberglass cloth (2118) and baked in an oven at 150°C for 3 minutes to obtain a semi-cured sheet.

[0039] Metal foil laminate preparation: Eight prepreg sheets prepared above were placed on top of each other with a 12-micron electrolytic copper foil, and then pressed in a vacuum hot press to obtain a metal foil laminate. The specific pressing process involved pressing at 2.5 MPa pressure and 230°C for 2 hours.

[0040] Table 1

[0041] Performance evaluation methods: 1. XY axis CTE: TMA, model TAQ450, heating rate 10℃ / min, take the second heating stage, value range 50~130℃, compression mode.

[0042] 2. Glass transition temperature: DMA, model TAQ850, heating rate is 10℃ / min, frequency is 10Hz.

[0043] The properties of the obtained metal foil laminate are shown in Table 2.

[0044] Table 2

[0045] Results analysis: Compared with the examples, the comparative examples did not have phthalonitrile compound modification, and there were differences in adhesion, Tg, and XY-CTE compared with the examples.

[0046] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Those skilled in the art can make various modifications or equivalent substitutions to the present invention within the scope of its essence and protection. Such modifications or equivalent substitutions should also be considered to fall within the protection scope of the present invention.

Claims

1. A cyanogroup pre-polymerized thermoset resin composition, characterized by, By weight, including: Modified maleimide prepolymer: 30-90 parts; Thermosetting resin: 5-60 parts; The modified maleimide prepolymer is prepared by reacting an amine modifier with a phthalonitrile compound to obtain a first prepolymer, then adding maleimide resin to the first prepolymer and continuing prepolymerization to obtain the modified maleimide prepolymer.

2. The cyanogroup pre-polymer thermoset resin composition according to claim 1, characterized in that: The reaction molar ratio of the amine modifier and the phthalonitrile compound is 1.05:1 to 3:1, and the reaction molar ratio of the maleimide resin and the amine modifier is 1:1 to 5:

1. The amine modifier is selected from one or more of aromatic diamine compounds, aliphatic diamine compounds, and amino silicone oils.

3. The cyanogroup pre-polymer thermoset resin composition according to claim 1, wherein: The phthalonitrile compound is a compound containing at least two groups as shown in Formula I in one molecular structure: Formula I.

4. The cyanogroup pre-polymer thermoset resin composition according to claim 1, wherein: The maleimide resin has a molecular structure containing at least two maleimide groups.

5. The cyano-based prepolymer thermosetting resin composition according to claim 1, characterized in that: The thermosetting resin is one or more of the following: bis / domaleimide resin, bis / donadiximide, epoxy resin, cyanate ester resin, benzoxazine resin, polyphenylene ether resin, and hydrocarbon resin.

6. The cyano-based prepolymer thermosetting resin composition according to claim 1, characterized in that: The cyano-based prepolymer thermosetting resin composition further includes an elastomer, wherein the amount of the elastomer added is 5% to 40% by weight of the cyano-based prepolymer thermosetting resin composition, and the elastomer is one or more of hydrogenated or non-hydrogenated styrene-olefin copolymers, polyesters, polyurethanes, polyamides, polyethers, polyacrylates, or silicones.

7. The cyano-based prepolymer thermosetting resin composition according to claim 1, characterized in that: The cyano-based prepolymer thermosetting resin composition further includes fillers, wherein the amount of fillers added is 50% to 90% by weight of the cyano-based prepolymer thermosetting resin composition; The filler is selected from inorganic fillers or organic fillers; The inorganic filler is selected from one or more of the following: obtuse-angled silica, acute-angled silica, spherical silica, hollow silica, aluminum hydroxide, boehmite, alumina, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate, mica, zinc molybdate, calcium molybdate, molybdenum disulfide, and glass fiber powder. The organic filler is selected from one or more of polytetrafluoroethylene powder, silicone resin powder, polymethyl methacrylate powder, silicone rubber powder, styrene-butadiene rubber powder, and polyacrylate rubber powder.

8. The cyano-based prepolymer thermosetting resin composition according to claim 1, characterized in that: The cyano prepolymer thermosetting resin composition further includes an accelerator, wherein the amount of the accelerator added is 0.01% to 2% of the weight percentage of the cyano prepolymer thermosetting resin composition, and the accelerator is one or more of imidazoles, tertiary amines, organic ureas, thermal free radicals, organophosphorus compounds, and metal carboxylates.

9. A semi-cured sheet, characterized in that: The cyano prepolymer thermosetting resin composition according to any one of claims 1 to 8 is dissolved in a solvent, stirred evenly, and cured to prepare a resin composition liquid. The reinforcing material is impregnated in the above resin composition liquid, and then the impregnated reinforcing material is baked and dried to obtain the semi-cured sheet.

10. A metal foil laminate, characterized in that: After stacking the prepregs as described in claim 9, metal foil is applied to one or both sides of the prepregs and then hot-pressed to form a metal foil laminate.

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