WO2022134590A1 - 改性树脂组合物及其制备方法与应用 - Google Patents

改性树脂组合物及其制备方法与应用 Download PDF

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Publication number
WO2022134590A1
WO2022134590A1 PCT/CN2021/109676 CN2021109676W WO2022134590A1 WO 2022134590 A1 WO2022134590 A1 WO 2022134590A1 CN 2021109676 W CN2021109676 W CN 2021109676W WO 2022134590 A1 WO2022134590 A1 WO 2022134590A1
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Prior art keywords
resin
resin composition
parts
modified
modified resin
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PCT/CN2021/109676
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English (en)
French (fr)
Inventor
漆小龙
黄荣暖
张新权
布施健明
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Guangdong Hinno-Tech Co Ltd
Guangdong Hinno Tech Co Ltd
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Guangdong Hinno-Tech Co Ltd
Guangdong Hinno Tech Co Ltd
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Application filed by Guangdong Hinno-Tech Co Ltd, Guangdong Hinno Tech Co Ltd filed Critical Guangdong Hinno-Tech Co Ltd
Priority to EP21908595.8A priority Critical patent/EP4253477A4/en
Priority to US18/269,076 priority patent/US20240059888A1/en
Publication of WO2022134590A1 publication Critical patent/WO2022134590A1/zh
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4014—Nitrogen containing compounds
    • C08G59/4021—Ureas; Thioureas; Guanidines; Dicyandiamides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/5046—Amines heterocyclic
    • C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
    • C08G59/5073—Amines heterocyclic containing only nitrogen as a heteroatom having two nitrogen atoms in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C08G59/686—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
    • C08G2650/56—Polyhydroxyethers, e.g. phenoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2471/02—Polyalkylene oxides
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T50/00—Aeronautics or air transport
    • Y02T50/40—Weight reduction

Definitions

  • the invention relates to the technical field of composite resins, in particular to a modified resin composition and a preparation method and application thereof.
  • non-flow prepreg as a bonding material for bonding rigid PCB boards and flexible PCB boards.
  • the non-flow prepreg is in the B-stage resin section that has not been cured by hot pressing, there is no glue flow or very little glue flow under high temperature and high pressure, and the adhesion performance is good.
  • the shape and structure of circuit board products require mechanical punching of the prepreg, and then lamination with rigid printed boards and flexible printed boards.
  • Most of the traditional non-flow prepregs use rubber toughened modified epoxy resin as the main resin material. Although prepregs with no or very little glue flow can be obtained, the punching edges of the prepregs are cracked during the mechanical punching process. It is relatively large, which has an adverse effect on the subsequent processability and heat resistance of the resin material, thus limiting its application in the preparation of multifunctional high-end printed circuit boards.
  • the present invention provides a modified resin composition with excellent adhesion performance, heat resistance, and little edge cracking during punching treatment, and a preparation method and application thereof.
  • An aspect of the present invention provides a kind of modified resin composition, according to mass fraction, the preparation raw material of described modified resin composition comprises:
  • the mass fraction of the nano-silica is 0.5 to 15 parts.
  • the preparation raw materials of the modified resin composition include:
  • the matrix resin is selected from epoxy resins.
  • the phenoxy resin is shown in formula (1):
  • n is selected from any integer from 20 to 120, and R 1 , R 2 , R 3 and R 4 are independently selected from H atom, halogen atom or phosphorus-containing group.
  • the curing accelerator is selected from imidazole-based curing accelerators, peroxide-based curing accelerators, azo-based curing accelerators, tertiary amine-based curing accelerators, phenol-based curing accelerators, organometallic At least one of a salt curing accelerator and an inorganic metal salt curing accelerator.
  • Another aspect of the present invention also provides the preparation method of the above-mentioned modified resin composition, comprising the following steps:
  • nano-silica modified matrix resin, the phenoxy resin, the curing agent and the curing accelerator are mixed to obtain a modified resin composition.
  • the present invention also provides a composite resin prepared by using the raw materials comprising the modified resin composition as described above.
  • the present invention also provides a prepreg, the prepreg comprising a reinforcing material and a resin material supported on the surface of the reinforcing material, the resin material being the above-mentioned composite resin.
  • the present invention further provides a printed circuit board, the raw material for preparing the printed circuit board includes the above-mentioned prepreg.
  • a specific proportion of phenoxy resin and nano-silica are used to coordinately cooperate to modify the matrix resin.
  • the surface of nano-silica has active silanol groups, which can undergo chemical grafting reaction with epoxy groups on the phenoxy resin and active groups on the matrix resin, and introduce Si-O-C bonds into the resin system to form
  • the inorganic-organic skeleton forms dispersed elastomer particles after curing, which act as bridges or anchors in micro-cracks, preventing the formation of macroscopic fractures and achieving a good toughening effect; at the same time, phenoxy resin can block flow It can effectively reduce the fluidity of the resin composition, so as to achieve the purpose of controlling the low-flow glue or non-flow glue of the prepreg, and the phenoxy resin has excellent mechanical properties, electrical properties, creep resistance and strong adhesion.
  • the prepared modified resin composition has excellent toughness after curing. In the process, it shows excellent processability, has a low powder drop rate, and has excellent bonding performance and heat resistance. It can be used in the preparation of high temperature resistance and aging resistance, integrated circuit packaging, high frequency and high speed. Multi-functional printed circuit board (PCB), thus promoting the development of high-end integrated circuits.
  • PCB Multi-functional printed circuit board
  • the present invention also provides a composite resin prepared from raw materials comprising the thermosetting resin composition as described above, the composite resin having excellent adhesion properties, heat resistance, and less edge cracking during punching.
  • the present invention also includes a prepreg comprising a reinforcing material and a resin material supported on the surface of the reinforcing material, the resin material being the composite resin as described above.
  • the prepreg has excellent bonding performance, heat resistance, and small edge cracking during punching processing, and can be used to prepare high-density and multi-performance printed circuits such as high temperature resistance and aging resistance, integrated circuit packaging, high frequency and high speed, etc. board (PCB), thereby promoting the development of high-end integrated circuits.
  • PCB high frequency and high speed, etc. board
  • PCBs printed circuit boards
  • non-flow prepregs are considered as bonding materials between rigid PCB boards and flexible PCB boards.
  • Most of the traditional non-flow prepregs use rubber toughened modified epoxy resin as the main resin material.
  • prepregs with no or very little glue flow can be obtained, the punching edges of the prepregs are cracked during the mechanical punching process. It is relatively large, which has an adverse effect on the subsequent processability and heat resistance of the resin material, thus limiting its application in the preparation of multifunctional high-end printed circuit boards.
  • Embodiments of the present invention provide a modified resin composition, characterized in that, in parts by mass, the preparation raw materials of the modified resin composition include:
  • a specific proportion of phenoxy resin and nano-silica are used in synergy to modify the matrix resin.
  • the surface of nano-silica has active silanol groups, which can undergo chemical grafting reaction with epoxy groups on the phenoxy resin and active groups on the matrix resin, and introduce Si-O-C bonds into the resin system to form
  • the inorganic-organic skeleton forms dispersed elastomer particles after curing, which act as bridges or anchors in micro-cracks, preventing the formation of macroscopic fractures and achieving a good toughening effect; at the same time, phenoxy resin can block flow It can effectively reduce the fluidity of the resin composition, so as to achieve the purpose of controlling the low-flow glue or non-flow glue of the prepreg, and the phenoxy resin has excellent mechanical properties, electrical properties, creep resistance and strong adhesion.
  • the prepared modified resin has excellent toughness, which shows excellent toughness during the mechanical punching process. Excellent processability, low powder drop rate, excellent bonding performance and heat resistance, can be used in the preparation of high-temperature and anti-aging, integrated circuit packaging, high-frequency high-speed and other high-density and multi-performance products.
  • PCBs Printed circuit boards
  • the mass fraction of the aforementioned nano-silica is 0.5 to 15 parts by mass.
  • the mass fraction of the aforementioned nano-silica is 0.5 to 10 parts by mass.
  • the mass fraction of the phenoxy resin is 20 to 40 parts by mass.
  • the mass fraction of the aforementioned curing agent is 5 to 15 parts.
  • the mass fraction of the curing accelerator is 0.5 to 2 parts by mass.
  • the mass fraction of the coupling agent is 0.3 to 1 part.
  • the preparation raw materials of the above modified resin composition include:
  • the above-mentioned nano-silica is prepared by a gas phase method, that is, nano-fumed silica.
  • the above-mentioned matrix resin is selected from epoxy resins.
  • the above-mentioned matrix resin is selected from the group consisting of alicyclic epoxy resin, hydrogenated bisphenol A epoxy resin, glycidyl ester epoxy resin, cyanuric acid epoxy resin and hydantoin epoxy resin. at least one.
  • the base epoxy resin is modified.
  • the active silanol groups on the surface of nano-silica react with the epoxy groups on the phenoxy resin and epoxy resin to undergo chemical grafting reaction, and Si-O-C bonds are introduced into the resin system to form an inorganic-organic skeleton ( As shown below), after curing, dispersed elastomer particles are formed, which act as bridges or anchors in micro-cracks, preventing the formation of macro-fractures and achieving a good toughening effect.
  • the above-mentioned matrix resin is selected from bismaleimide resin; further, the above-mentioned matrix resin is selected from diphenylmethane bismaleimide resin, N-m-phenylene bismaleimide resin At least one of resin and polyaminobismaleimide resin.
  • the base epoxy resin is modified.
  • the active silanol groups on the surface of the nano-silica react with the epoxy groups on the phenoxy resin and the imide groups on the maleimide resin to undergo chemical grafting reaction, and Si-O-C is introduced into the resin system. key.
  • the above-mentioned phenoxy resin is shown in formula (1):
  • n is selected from any integer from 20 to 120, and R 1 , R 2 , R 3 and R 4 are independently selected from H atom, halogen atom or phosphorus-containing group.
  • the aforementioned halogen is selected from bromine; in this case, the phenoxy resin is not brominated.
  • the above-mentioned phosphorus-containing groups are selected from phosphoric acid groups, specifically, at least one selected from phosphorous acid groups and primary phosphorus groups.
  • R 1 , R 2 , R 3 and R 4 are all selected from H atoms.
  • the matrix resin is modified by synergistic coordination of a specific ratio of phenoxy resin and nano-silica.
  • the active silanol groups on the surface of the nano-silica react with the epoxy groups on the phenoxy resin and the active groups on the matrix resin to undergo chemical grafting reaction, and Si-O-C bonds are introduced into the resin system to form inorganic-organic
  • the skeleton after curing, forms dispersed elastomer particles, which act as bridges or anchors in micro-cracks, prevent the formation of macroscopic fractures, and achieve a good toughening effect; at the same time, phenoxy resin can play a blocking role and can It can effectively reduce the fluidity of the resin composition, so as to achieve the purpose of controlling the low-flow glue or non-flow glue of the prepreg, and the phenoxy resin has excellent mechanical properties, electrical properties, creep resistance and strong adhesion.
  • the above-mentioned curing accelerator is selected from imidazole-based curing accelerators, peroxide-based curing accelerators, azo-based curing accelerators, tertiary amine-based curing accelerators, phenol-based curing accelerators, and organic metal salts At least one of a curing accelerator and an inorganic metal salt curing accelerator.
  • the curing accelerator can be selected from imidazole curing accelerators, such as 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4 methylimidazole, or can be selected from organic metal salt curing accelerators, such as zinc octoate , at least one of zinc isooctanoate, stannous octoate, dibutyltin dilaurate, zinc naphthenate, cobalt naphthenate, aluminum acetylacetonate, cobalt acetylacetonate, and copper acetylacetonate.
  • imidazole curing accelerators such as 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4 methylimidazole
  • organic metal salt curing accelerators such as zinc octoate , at least one of zinc isooctanoate, stannous octoate, dibutyltin dilaurate, zinc naphthen
  • the above-mentioned curing agent is selected from cyanate ester curing agent, aliphatic polyvalent curing agent, alicyclic polyamine curing agent, aromatic amine curing agent, polyamide curing agent, latent curing agent , at least one of Lewis acid-amine complex curing agent and organic acid anhydride curing agent.
  • the above-mentioned curing agent is selected from aliphatic polyvalent curing agents, specifically, at least one selected from ethylenediamine, diethylenetriamine, triethylenetetramine, dimethylaminopropylamine and trimethylhexamethylene .
  • the above curing agent is selected from dicyandiamide.
  • the coupling agent can be selected from coupling agents commonly used in the field, including but not limited to: chromium complex coupling agent, silane type coupling agent, titanate type coupling agent and aluminate compound coupling agent.
  • the above-mentioned coupling agent is selected from silane coupling agents.
  • An embodiment of the present invention also provides a method for preparing the modified resin composition, including steps S10-S20.
  • Step S20 mixing the matrix resin, the nano-silica, the coupling agent and the organic solvent, and heating and reacting to obtain the nano-silica modified matrix resin.
  • the conditions for the above heating reaction are: react at 100° C. ⁇ 200° C. for 2 h ⁇ 3 h.
  • step S20 is to obtain nano-silica modified epoxy reaction, and the reaction mechanism is as follows:
  • Step S20 mixing the nano-silica modified matrix resin, the phenoxy resin, the curing agent and the curing accelerator to obtain a modified resin composition.
  • an organic solvent is also added in step S20, that is, a modified resin composition glue solution is obtained.
  • the selection range of the organic solvent used in the above steps S10 to S20 is the same, and can be selected from at least one of dimethylformamide and dimethylacetamide. Further, the organic solvent is selected from dimethylformamide.
  • the present invention also provides a composite resin, which is prepared from raw materials comprising any of the modified resin compositions described above.
  • the composite resin has excellent bonding performance and heat resistance, and has little edge cracking during punching processing, and especially has high bonding strength with polyimide, a material for preparing flexible PCBs.
  • An embodiment of the present invention further provides a prepreg, the prepreg comprising a reinforcing material and a resin material supported on the surface of the reinforcing material, and the resin material is the composite resin described above.
  • the reinforcing material is selected from inorganic fibrous materials or organic fibrous materials.
  • the prepreg has excellent bonding performance, heat resistance, and small edge cracking during punching processing, and can be used to prepare high-density and multi-performance printed circuits such as high temperature resistance and aging resistance, integrated circuit packaging, high frequency and high speed, etc. board (PCB), thereby promoting the development of high-end integrated circuits.
  • PCB printed circuit board
  • the above-mentioned inorganic fiber materials include, but are not limited to, glass fibers, carbon fibers, silicon carbide fibers, asbestos fibers, and the like.
  • Organic fiber materials include, but are not limited to, nylon, ultra-high molecular weight polyethylene fibers, aramid fibers, polyimide fibers, polyester fibers, and cotton fibers.
  • glass fibers include E, NE, D, S, T and other different types of glass fibers.
  • the preparation of the above-mentioned prepreg includes the following steps S30-S40.
  • Step S20 making the above thermosetting resin composition into a resin glue solution.
  • step S30 the reinforcing material is immersed in the resin glue obtained in step S20, and then heated and solidified after being taken out to obtain a prepreg.
  • the immersion condition is: immersion at room temperature for 10s.
  • the heating conditions are: heating and curing at 130° C. ⁇ 250° C. for 2 min ⁇ 10 min.
  • an embodiment of the present invention also provides a printed circuit board, and the raw materials for preparing the printed circuit board include the above-mentioned prepreg.
  • the raw materials for preparing the printed circuit board further include a rigid circuit board and a flexible circuit board; further, the prepreg is used to prepare an adhesive layer between the rigid circuit board and the flexible circuit board.
  • the above printed circuit board has the characteristics of high density and multi-performance, and can also meet the requirements of three-dimensional installation of electronic products, and can promote the development of high-end integrated circuits.
  • step 2 In terms of parts by mass, 5 parts of dicyandiamide and 100 parts of dimethylformamide are added to the batching bottle after fully stirring and dissolving, and under stirring conditions, 10 parts of phenoxy resin and the nanometer dicyandiamide obtained in step 1) are successively added. Silica-modified epoxy and 0.5 part of 2-methylimidazole were added to the batching bottle, and stirred evenly to prepare a glue solution.
  • step 3 Put 1078 glass fiber cloth (basic weight 47.5g/m 2 ) in the glue obtained in step 2), soak it at room temperature for 10s) take it out and place it in a hot air circulating oven at 180°C for 3 minutes, and obtain a resin content of (65 ⁇ 1) wt% non-flow prepreg.
  • step 2 In terms of parts by mass, 5 parts of dicyandiamide and 100 parts of dimethylformamide are added to the batching bottle after fully stirring and dissolving, and 40 parts of phenoxy resin and the nanometer dicyandiamide obtained in step 1) are successively mixed under stirring conditions. Silica-modified epoxy and 0.5 part of 2-methylimidazole were added to the batching bottle, and stirred evenly to prepare a glue solution.
  • step 3 Place 1078 glass fiber cloth (basic weight 47.5g/m 2 ) in the glue obtained in step 2), soak it at room temperature for 10s, take it out and place it in a hot air circulating oven at 180°C for 3min, to obtain a resin content of (65 ⁇ 1) wt% non-flow prepreg.
  • step 2 In terms of parts by mass, 5 parts of dicyandiamide and 100 parts of dimethylformamide are added to the batching bottle after fully stirring and dissolving, and under stirring conditions, 10 parts of phenoxy resin and the nanometer dicyandiamide obtained in step 1) are successively added. Silica-modified epoxy and 0.5 part of 2-methylimidazole were added to the batching bottle, and stirred evenly to prepare a glue solution.
  • step 3 Put 1078 glass fiber cloth (basic weight 47.5g/m 2 ) into the glue obtained in step 2), soak it at room temperature for 10s, take it out and place it in a hot air circulating oven at 180°C for 3min to obtain a resin content of (65 ⁇ 1) ) wt% of non-flow prepreg.
  • step 2 In terms of parts by mass, 5 parts of dicyandiamide and 100 parts of dimethylformamide are added to the batching bottle after fully stirring and dissolving, and 40 parts of phenoxy resin and the nanometer dicyandiamide obtained in step 1) are successively mixed under stirring conditions. Silica-modified epoxy and 0.5 part of 2-methylimidazole were added to the batching bottle, and stirred evenly to prepare a glue solution.
  • step 3 Place 1078 glass fiber cloth (basic weight 47.5g/m 2 ) in the glue obtained in step 2), soak it at room temperature for 10s, take it out and place it in a hot air circulating oven at 180°C for 3min, to obtain a resin content of (65 ⁇ 1) wt% non-flow prepreg.
  • step 2 In terms of parts by mass, 5 parts of dicyandiamide and 100 parts of dimethylformamide are added to the batching bottle after fully stirring and dissolving, and under stirring conditions, 10 parts of phenoxy resin and the nanometer dicyandiamide obtained in step 1) are successively added. Silica-modified epoxy and 0.5 part of 2-methylimidazole were added to the batching bottle, and stirred evenly to prepare a glue solution.
  • step 3 Put 1078 glass fiber cloth (basic weight 47.5g/m 2 ) into the glue obtained in step 2), soak it at room temperature for 10s, take it out and place it in a hot air circulating oven at 180°C for 3min to obtain a resin content of (65 ⁇ 1) ) wt% of non-flow prepreg.
  • step 2 In terms of parts by mass, 5 parts of dicyandiamide and 100 parts of dimethylformamide are added to the batching bottle after fully stirring and dissolving, and under stirring conditions, 10 parts of phenoxy resin and the nanometer dicyandiamide obtained in step 1) are successively added. Silica-modified epoxy and 0.5 part of 2-methylimidazole were added to the batching bottle, and stirred evenly to prepare a glue solution.
  • step 3 Place 1078 glass fiber cloth (basic weight 47.5g/m 2 ) in the glue obtained in step 2), soak it at room temperature for 10s, take it out and place it in a hot air circulating oven at 180°C and bake for 3min, to obtain a resin content of (65 ⁇ 1) wt% non-flow prepreg.
  • step 2 Place 1078 glass fiber cloth (basic weight 47.5g/m 2 ) in the glue obtained in step 1), immerse it at room temperature for 10s, take it out and place it in a hot air circulating oven at 180°C for 3min, to obtain a resin content of (65 ⁇ 1) wt% non-flow prepreg.
  • step 2 Place 1078 glass fiber cloth (basic weight 47.5g/m 2 ) in the glue obtained in step 1), immerse it at room temperature for 10s, take it out and place it in a hot air circulating oven at 180°C for 3min, to obtain a resin content of (65 ⁇ 1) wt% non-flow prepreg.
  • step 2 In terms of parts by mass, after adding 5 parts of dicyandiamide and 100 parts of dimethylformamide to the batching bottle and fully stirring and dissolving, under stirring conditions, 5 parts of phenoxy resin and the nanometer dicyandiamide obtained in step 1) were successively added. Silica-modified epoxy and 0.5 part of 2-methylimidazole were added to the batching bottle, and stirred evenly to prepare a glue solution.
  • step 3 Place 1078 glass fiber cloth (basic weight 47.5g/m 2 ) in the glue obtained in step 2), soak it at room temperature for 10s, take it out and place it in a hot air circulating oven at 180°C for 3min, to obtain a resin content of (65 ⁇ 1) wt% non-flow prepreg.
  • the matrix resin (epoxy resin) was purchased from (Kunshan Nanya), model number (NPEL-128).
  • Phenoxy resin was purchased from (Shandong Shengquan Chemical Industry), the model is (SQP-40AXM40).
  • CTBN-modified epoxy resin was purchased from (Chehe Chemical (Shanghai) Co., Ltd.), the model is (EPC-240);
  • Silane coupling agent was purchased from (SG-Si 121), the model is (Nanjing Shuguang Chemical Group Co., Ltd.);
  • the fumed nano-silica was purchased from (Dewar Chemical (Shanghai) Co., Ltd.), the model is (L20);
  • the test method is as follows:
  • Peel strength The test method is carried out according to (IPC-TM-650 2.4.8); the peel strength test is carried out with polyimide material as the substrate.
  • Powder drop rate The judgment is based on the degree of resin powder drop off of the prepreg after punching/shearing. The specific test is as follows, taking the prepreg prepared in Example 1 as an example:
  • Example 2 Take 4 pieces of the prepreg prepared in Example 1 with a size of 10 cm ⁇ 10 cm, weigh them and record them as m1. Use scissors to cut a notch of 9 cm in depth on one side of each, and cut a total of 29 knives. Each sample is made into 30 strips with a length of 9 cm, and each piece is treated in the same way.
  • Example 1 The treated sample was shaken up and down 30 times with the wrist as the center, and one back and forth was recorded as one vibration. After completion, weigh again and record as m2, and calculate by (m1-m2)/m1*100% to obtain the powder drop rate of the cured sheet. The same test was done for each tablet and its powder drop rate was calculated.
  • the formula for calculating the powder drop rate of the prepreg obtained in Example 1 is as follows:
  • the powder removal rate of the prepreg prepared in Example 1 the total value of the powder removal rate of 4 prepregs ⁇ 4.
  • the prepreg was punched out with a sampler for resin content testing, and the punched sample was placed under a magnifying glass of 50 times to measure the crack length.
  • the prepared non-flow prepreg has excellent bonding performance and heat resistance, and the edge cracking is small during punching treatment, and molecular chains are not easily generated at high temperature and high pressure. Movement to achieve no or very little glue flow under high temperature and high pressure.
  • traditional rubber-modified epoxy resin CBN-modified epoxy resin
  • phenoxy resin CPT-modified epoxy resin
  • ordinary silica was used as an inorganic filler to obtain
  • the adhesive property of the non-flow prepreg is poor, its peel strength (PI) is low, and the edge cracking is large when punching, and the powder drop rate is high.
  • Example 3 Compared with Example 3, in Comparative Example 3, the fumed nano-silicon dioxide exceeding the proportioning scope of the application was used to reduce the proportion of phenoxy resin, and the edge cracking of the non-flow prepreg prepared in Comparative Example 3 during punching treatment The length and powder drop rate are high, the peeling strength (PI) is poor, and the excess fumed nano-silica is prone to agglomeration, uneven dispersion, and precipitation.
  • PI peeling strength

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Abstract

本发明提供一种改性树脂组合物及其制备方法与应用；该改性树脂组合物的制备原料包括：65份～100份基体树脂、10份～40份苯氧树脂、0.5份～25份纳米二氧化硅、2份～15份固化剂、0～2份固化促进剂和0～1份偶联剂。该改性树脂组合物具有优异的韧性，在机械冲切处理过程中表现出优异的加工性，具有较低的掉粉率，同时具有优异的粘结性能、耐热性，能应用于制备耐高温抗老化、集成电路封装、高频高速等高密度化和多性能化的印制线路板(PCB)，从而促进发展高端的集成电路。

Description

改性树脂组合物及其制备方法与应用 技术领域
本发明涉及复合树脂技术领域，特别是涉及一种改性树脂组合物及其制备方法与应用。
背景技术
随着电子工业的飞速发展，电子产品向小型化、多功能化和高安全化方向发展，要求印刷线路板(PCB)高密度化和多性能化，同时还要满足电子产品的三维立体安装的需求。因此越来越多地考虑使用刚挠结合技术，即采用刚性电路板与挠性电路板通过粘结材料粘结制备印刷线路板的技术。
近年来，技术人员越来越多地考虑采用不流胶半固化片作为粘结刚性PCB板和挠性PCB板的粘结材料。不流胶半固化片(No flow prepreg)处于未经热压固化的B阶树脂段时，在高温高压下不流胶或极少流胶，同时粘接力性能良好，在压合前，根据印制电路板产品形状及结构，需要半固化片进行机械冲切处理，然后与刚性印制板和挠性印制板叠合后压合。传统的不流胶半固化片大多采用橡胶增韧改性环氧树脂作为主要树脂材料，虽然能获得不流胶或极少流胶的半固化片，但在机械冲切处理过程中，半固化片的冲切边缘开裂较大，对树脂材料后续的加工性和耐热性有不利影响，从而限制了它在制备多功能的高端印刷线路板时的应用。
因此，如何获得具有优异的粘结性能、耐热性，且冲切处理时边缘开裂小的树脂一直是本领域技术人员难以攻克的难题。
发明内容
基于此，本发明提供了一种具有优异的粘结性能、耐热性，且冲切处理时边缘开裂小的改性树脂组合物及其制备方法与应用。
本发明的技术方案如下。
本发明的一方面提供了一种改性树脂组合物，按照质量份数计，所述改性 树脂组合物的制备原料包括：
Figure PCTCN2021109676-appb-000001
在其中一些实施例中，所述改性树脂组合物的制备原料中，所述纳米二氧化硅的质量份数为0.5份～15份。
在其中一些实施例中，所述改性树脂组合物的制备原料包括：
Figure PCTCN2021109676-appb-000002
在其中一些实施例中，所述基体树脂选自环氧树脂。
在其中一些实施例中，所述苯氧树脂如式(1)所示：
Figure PCTCN2021109676-appb-000003
其中，n选自20～120任一整数，R 1、R 2、R 3和R 4分别独立地选自H原子、卤素原子或含磷基团。
在其中一些实施例中，所述固化促进剂选自咪唑类固化促进剂、过氧化物类固化促进剂、偶氮类固化促进剂、叔胺类固化促进剂、酚类固化促进剂、有机金属盐固化促进剂和无机金属盐固化促进剂中的至少一种。
本发明的另一方面还提供上述改性树脂组合物的制备方法，包括如下步骤：
将所述基体树脂、所述纳米二氧化硅、所述偶联剂和有机溶剂混合，加热反应，得到纳米二氧化硅改性基体树脂；
将所述纳米二氧化硅改性基体树脂、所述苯氧树脂、所述固化剂以及所述固化促进剂混合，得到改性树脂组合物。
本发明还提供一种复合树脂，所述复合树脂采用包括如上所述的改性树脂组合物的原料制得。
本发明还提供一种半固化片，该半固化片包括增强材料以及负载于所述增强材料表面的树脂材料，所述树脂材料为如上所述的复合树脂。
本发明进一步提供一种印制线路板，该印制线路板的制备原料包括如上所述的半固化片。
有益效果
本发明提供的改性树脂组合物中，采用特定配比的苯氧树脂与纳米二氧化硅协同配合，对基体树脂进行改性。其中，纳米二氧化硅表面具有活性硅醇基，其可与苯氧树脂上的环氧基团以及基体树脂上的活性基团发生化学接枝反应，在树脂体系中引入Si-O-C键，形成无机-有机的骨架，固化后形成分散的弹性体颗粒，在微裂纹中起到桥梁或钉锚作用，阻止形成宏观断裂，达到很好的增韧效果；与此同时苯氧树脂能起阻流作用，能有效的降低树脂组合物的流动度，从而达到控制半固化片低流胶或不流胶的目的，且苯氧树脂具有优良的机械性能、电性能、抗蠕变性和强粘结力，通过特定配比的气相法纳米二氧化硅与苯氧树脂协调作用，并进一步通过特定配比的原料的协同，使制得的改性树脂组合物固化后具有优异的韧性，在机械冲切处理过程中表现出优异的加工性，具有较低的掉粉率，同时具有优异的粘结性能、耐热性，能应用于制备耐高温抗老化、集成电路封装、高频高速等高密度化和多性能化的印制线路板(PCB)，从而促进发展高端的集成电路。
本发明还提供采用包括如上所述的热固性树脂组合物的原料制得复合树脂，该复合树脂具有优异的粘结性能、耐热性，且冲切处理时边缘开裂小。
本发明还包括一种半固化片，包括增强材料以及负载于增强材料表面的树脂材料，该树脂材料为如上所述的复合树脂。该半固化片具有优异的粘结性能、耐热性，且冲切处理时边缘开裂小，能应用于制备耐高温抗老化、集成电路封装、高频高速等高密度化和多性能化的印制线路板(PCB)，从而促进发展高端的集成电路。
具体实施方式
为了便于理解本发明，下面将对本发明进行更全面的描述，并给出了本发明的较佳实施例。但是，本发明可以以许多不同的形式来实现，并不限于本文所描述的实施例。相反地，提供这些实施例的目的是使对本发明的公开内容的理解更加透彻全面。
除非另有定义，本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。本文中在本发明的说明书中所使用的术语只是为了描述具体的实施例的目的，不是旨在于限制本发明。本文所使用的术语“和/或”包括一个或多个相关的所列项目的任意的和所有的组合。
随着印刷线路板(PCB)的发展，越来越多地考虑采用不流胶半固化片作为刚性PCB板和挠性PCB板之间的粘结材料。传统的不流胶半固化片大多采用橡胶增韧改性环氧树脂作为主要树脂材料，虽然能获得不流胶或极少流胶的半固化片，但在机械冲切处理过程中，半固化片的冲切边缘开裂较大，对树脂材料后续的加工性和耐热性有不利影响，从而限制了它在制备多功能的高端印刷线路板时的应用。
针对传统技术存在的问题，本领域的技术人员基于自身多年在印制线路板领域的研究经验，经过大量创造性的实验探究后发现：采用特定配比的苯氧树脂与纳米二氧化硅协同配合，对基体树脂进行改性；其中，纳米二氧化硅表面具有活性硅醇基，其可与苯氧树脂上的环氧基团以及基体树脂上的活性基团发生化学接枝反应，在树脂体系中引入Si-O-C键，形成无机-有机的骨架，固化后形成分散的弹性体颗粒，在微裂纹中起到桥梁或钉锚作用，阻止形成宏观断裂，达到很好的增韧效果，并进一步通过大量实验探究后，获得本发明的技术方案。
本发明实施方式提供了一种改性树脂组合物，其特征在于，按照质量份数计，该改性树脂组合物的制备原料包括：
Figure PCTCN2021109676-appb-000004
上述改性树脂组合物中，采用特定配比的苯氧树脂与纳米二氧化硅协同配合，对基体树脂进行改性。其中，纳米二氧化硅表面具有活性硅醇基，其可与苯氧树脂上的环氧基团以及基体树脂上的活性基团发生化学接枝反应，在树脂体系中引入Si-O-C键，形成无机-有机的骨架，固化后形成分散的弹性体颗粒，在微裂纹中起到桥梁或钉锚作用，阻止形成宏观断裂，达到很好的增韧效果；与此同时苯氧树脂能起阻流作用，能有效的降低树脂组合物的流动度，从而达到控制半固化片低流胶或不流胶的目的，且苯氧树脂具有优良的机械性能、电性能、抗蠕变性和强粘结力，通过特定配比的气相法纳米二氧化硅与苯氧树脂协调作用，并进一步通过特定配比的原料的协同，使制得的改性树脂具有优异的韧性，在机械冲切处理过程中表现出优异的加工性，具有较低的掉粉率，同时具有优异的粘结性能、耐热性，能应用于制备耐高温抗老化、集成电路封装、高频高速等高密度化和多性能化的印制线路板(PCB)，从而促进发展高端的集成电路。
在其中一些实施例中，上述改性树脂组合物的制备原料中，上述纳米二氧化硅的质量份数为0.5份～15份。
优选地，上述改性树脂组合物的制备原料中，上述纳米二氧化硅的质量份数为0.5份～10份。
在其中一些实施例中，上述改性树脂组合物的制备原料中，上述苯氧树脂的质量份数为20份～40份。
在其中一些实施例中，上述改性树脂组合物的制备原料中，上述固化剂的 质量份数为5份～15份。
在其中一些实施例中，上述改性树脂组合物的制备原料中，上述固化促进剂的质量份数为0.5份～2份。
在其中一些实施例中，上述改性树脂组合物的制备原料中，上述偶联剂的质量份数为0.3份～1份。
优选的，按照质量份数计，上述改性树脂组合物的制备原料包括：
Figure PCTCN2021109676-appb-000005
在其中一些实施例中，上述纳米二氧化硅采用气相法制备，即纳米气相二氧化硅。
在其中一些实施例中，上述基体树脂选自环氧树脂。
在其中一些实施例中，上述基体树脂选自脂环族环氧树脂、氢化双酚A环氧树脂、缩水甘油酯类环氧树脂、三聚氰酸环氧树脂和海因环氧树脂中的至少一种。
当采用特定配比的苯氧树脂与纳米二氧化硅协同配合，对基环氧树脂进行改性。其中，纳米二氧化硅表面的活性硅醇基与苯氧树脂上以及环氧树脂上的环氧基团发生化学接枝反应，在树脂体系中引入Si-O-C键，形成无机-有机的骨架(如下所示)，固化后形成分散的弹性体颗粒，在微裂纹中起到桥梁或钉锚作用，阻止形成宏观断裂，达到很好的增韧效果。
Figure PCTCN2021109676-appb-000006
在其中一些实施例中，上述基体树脂选自双马来酰亚胺树脂；进一步地，上述基体树脂选自二苯甲烷双马来酰亚胺树脂、N-间苯撑双马来酰亚胺树脂和聚氨基双马来酰亚胺树脂中的至少一种。
当采用特定配比的苯氧树脂与纳米二氧化硅协同配合，对基环氧树脂进行改性。其中，纳米二氧化硅表面的活性硅醇基与苯氧树脂上的环氧基团及以及马来酰亚胺树脂上的酰亚胺基发生化学接枝反应，在树脂体系中引入Si-O-C键。
在其中一些实施例中，上述苯氧树脂如式(1)所示：
Figure PCTCN2021109676-appb-000007
其中，n选自20～120任一整数，R 1、R 2、R 3和R 4分别独立地选自H原子、卤素原子或含磷基团。
在其中一些实施例中，上述卤素选自溴；此时，苯氧树脂未溴化苯氧树脂。
在其中一些实施例中，上述含磷基团选自磷酸基，具体地，选自亚磷酸基和伯磷基中的至少一种。
在其中一些实施例中，R 1、R 2、R 3和R 4均选自H原子。
采用特定配比的苯氧树脂与纳米二氧化硅协同配合，对基体树脂进行改性。其中，纳米二氧化硅表面的活性硅醇基与苯氧树脂上的环氧基团以及基体树脂 上的活性基团发生化学接枝反应，在树脂体系中引入Si-O-C键，形成无机-有机的骨架，固化后形成分散的弹性体颗粒，在微裂纹中起到桥梁或钉锚作用，阻止形成宏观断裂，达到很好的增韧效果；与此同时苯氧树脂能起阻流作用，能有效的降低树脂组合物的流动度，从而达到控制半固化片低流胶或不流胶的目的，且苯氧树脂具有优良的机械性能、电性能、抗蠕变性和强粘结力。
在其中一些实施例中，上述固化促进剂选自咪唑类固化促进剂、过氧化物类固化促进剂、偶氮类固化促进剂、叔胺类固化促进剂、酚类固化促进剂、有机金属盐固化促进剂和无机金属盐固化促进剂中的至少一种。例如固化促进剂可选自咪唑类固化促进剂，如2-甲基咪唑、2-苯基咪唑、2-乙基-4甲基咪唑，也可以选自有机金属盐固化促进剂，如辛酸锌、异辛酸锌、辛酸亚锡、二月桂酸二丁基锡、环烷酸锌、环烷酸钴、乙酰丙酮铝、乙酰丙酮钴、乙酰丙酮铜中的至少一种。
在其中一些实施例中，上述固化剂选自是氰酸酯类固化剂、脂肪多元类固化剂、脂环多元胺类固化剂、芳香胺类固化剂、聚酰胺类固化剂、潜伏型固化剂、路易斯酸-胺络合物类固化剂和有机酸酐类固化剂中的至少一种。
例如，上述固化剂选自脂肪多元类固化剂，具体地，选自乙二胺、二乙烯三胺、三乙烯四胺、二甲胺基丙胺和三甲基六亚甲基中的至少一种。具体的，上述固化剂选自双氰胺。
在本发明的改性树脂组合物中，对偶联剂的种类没有特定的要求，偶联剂可选自本领域中常用的偶联剂，包括但不限于：铬络合物偶联剂、硅烷类偶联剂、钛酸酯类偶联剂和铝酸化合物偶联剂。
在其中一些实施例中，上述偶联剂选自硅烷类偶联剂。
本发明一实施方法还提供上述改性树脂组合物的制备方法，包括步骤S10～S20。
步骤S20、将基体树脂、纳米二氧化硅、偶联剂和有机溶剂混合，加热反应，得到纳米二氧化硅改性基体树脂。
在其中一些实施例中，上述加热反应的条件为：于100℃～200℃下反应2h～3h。
当基体树脂为环氧树脂时，步骤S20即得到纳米二氧化硅改性环氧反应，反应机理如下所示：
Figure PCTCN2021109676-appb-000008
步骤S20、将纳米二氧化硅改性基体树脂、苯氧树脂、固化剂以及固化促进剂混合，得到改性树脂组合物。
在其中一些实施例中，步骤S20还加入了有机溶剂，即得到改性树脂组合物胶液。
上述步骤S10～步骤S20中所采用的有机溶剂的选择范围相同，可选自二甲基甲酰胺和二甲基乙酰胺中的至少一种。进一步地，有机溶剂选自二甲基甲酰胺。
进一步地，本发明还提供一种复合树脂，该复合树脂采用包括如上所述的任一种改性树脂组合物的原料制得。
该复合树脂具有优异的粘结性能、耐热性，且冲切处理时边缘开裂小，尤其是与柔性PCB的制备材料聚酰亚胺的粘结强度高。
本发明的一实施例方式还提供一种半固化片，该半固化片包括增强材料以及负载于增强材料表面的树脂材料，该树脂材料为如上所述的复合树脂。
在其中一些实施例中，增强材料选自无机纤维材料或有机纤维材料。
该半固化片具有优异的粘结性能、耐热性，且冲切处理时边缘开裂小，能应用于制备耐高温抗老化、集成电路封装、高频高速等高密度化和多性能化的印制线路板(PCB)，从而促进发展高端的集成电路。
上述无机纤维材料包括但不限于玻璃纤维，碳纤维、碳化硅纤维及石棉纤维等。机纤维材料包括但不限于尼龙、超高分子量聚乙烯纤维、芳纶纤维、聚酰亚胺纤维、聚酯纤维及棉纤维等。
其中，玻璃纤维包含E、NE、D、S、T等不同类型的玻璃纤维。
进一步地，上述半固化片的制备包括如下步骤S30～S40。
步骤S20、将上述热固性树脂组合物制成树脂胶液。
步骤S30、将增强材料置于步骤S20获得的树脂胶液中浸渍，取出后加热固化，得到半固化片。
在其中一些实施例中，步骤S30中，浸渍的条件为：于常温下浸渍10s。
在其中一些实施例中，步骤S30中，加热的条件为：于130℃～250℃下加热固化2min～10min。
进一步地，本发明一实施方式还提供了一种印制线路板，该印制线路板的制备原料包括如上所述的半固化片。
在其中一些实施例中，上述印制线路板的制备原料还包括刚性电路板与挠性电路板；进一步地，上述半固化片用于制备刚性电路板与挠性电路板之间的粘结层。
上述印制线路板具有高密度化和多性能化的特点，同时还能满足电子产品的三维立体安装的需求，能促进发展高端的集成电路。
下面将结合具体的实施例对本发明进行了说明，但本发明并不局限于下述实施例，应当理解，所附权利要求概括了本发明的范围，在本发明构思的引导下本领域的技术人员应意识到，对本发明的各实施例所进行的一定的改变，都将被本发明的权利要求书的精神和范围所覆盖。
具体实施例
实施例1
1)按照质量份数计，在装有搅拌器、温度计的干燥四口烧瓶中，加入0.3份硅烷偶联剂、100份基体树脂(环氧树脂)和3份二甲基甲酰胺，搅拌同时升温至150℃，然后搅拌条件下加入0.5份气相法纳米二氧化硅，保温反应2h，冷却得到纳米二氧化硅改性环氧树脂。
2)按照质量份数计，将5份双氰胺、100份二甲基甲酰胺加入到配料瓶充分搅拌溶解后，于搅拌条件下依次将10份苯氧树脂、步骤1)获得的纳米二氧化硅改性环氧和0.5份2-甲基咪唑加入到配料瓶中，搅拌均匀制备成胶液。
3)将1078玻璃纤维布(基重47.5g/m 2)置于步骤2)获得的胶液，常温浸渍10s)取出置于热风循环烤箱180℃烘烤3min后，得到树脂含量为(65±1)wt％ 的不流胶半固化片。
实施例2
1)按照质量份数计，在装有搅拌器、温度计的干燥四口烧瓶中，加入0.3份硅烷偶联剂、100份基体树脂(环氧树脂)和3份二甲基甲酰胺，搅拌同时升温至150℃，然后搅拌条件下加入0.5份气相法纳米二氧化硅，保温反应2h，冷却得到纳米二氧化硅改性环氧树脂。
2)按照质量份数计，将5份双氰胺、100份二甲基甲酰胺加入到配料瓶充分搅拌溶解后，于搅拌条件下依次将40份苯氧树脂、步骤1)获得的纳米二氧化硅改性环氧和0.5份2-甲基咪唑加入到配料瓶中，搅拌均匀制备成胶液。
3)将1078玻璃纤维布(基重47.5g/m 2)置于步骤2)获得的胶液，常温浸渍10s，取出置于热风循环烤箱180℃烘烤3min后，得到树脂含量为(65±1)wt％的不流胶半固化片。
实施例3
1)按照质量份数计，在装有搅拌器、温度计的干燥四口烧瓶中，加入0.3份硅烷偶联剂、100份基体树脂(环氧树脂)和3份二甲基甲酰胺，搅拌同时升温至150℃，然后搅拌条件下加入25份气相法纳米二氧化硅，保温反应2h，冷却得到纳米二氧化硅改性环氧树脂。
2)按照质量份数计，将5份双氰胺、100份二甲基甲酰胺加入到配料瓶充分搅拌溶解后，于搅拌条件下依次将10份苯氧树脂、步骤1)获得的纳米二氧化硅改性环氧和0.5份2-甲基咪唑加入到配料瓶中，搅拌均匀制备成胶液。
3)将1078玻璃纤维布(基重47.5g/m 2)置于步骤2)获得的胶液，常温浸渍10s，取出置于热风循环烤箱180℃烘烤3min后得到树脂含量为(65±1)wt％的不流胶半固化片。
实施例4
1)按照质量份数计，在装有搅拌器、温度计的干燥四口烧瓶中，加入0.3份 硅烷偶联剂、100份基体树脂(环氧树脂)和3份二甲基甲酰胺，搅拌同时升温至150℃，然后搅拌条件下加入25份气相法纳米二氧化硅，保温反应2h，冷却得到纳米二氧化硅改性环氧树脂。
2)按照质量份数计，将5份双氰胺、100份二甲基甲酰胺加入到配料瓶充分搅拌溶解后，于搅拌条件下依次将40份苯氧树脂、步骤1)获得的纳米二氧化硅改性环氧和0.5份2-甲基咪唑加入到配料瓶中，搅拌均匀制备成胶液。
3)将1078玻璃纤维布(基重47.5g/m 2)置于步骤2)获得的胶液，常温浸渍10s，取出置于热风循环烤箱180℃烘烤3min后，得到树脂含量为(65±1)wt％的不流胶半固化片。
实施例5
1)按照质量份数计，在装有搅拌器、温度计的干燥四口烧瓶中，加入0.3份硅烷偶联剂、100份基体树脂(环氧树脂)和3份二甲基甲酰胺，搅拌同时升温至150℃，然后搅拌条件下加入10份气相法纳米二氧化硅，保温反应2h，冷却得到纳米二氧化硅改性环氧树脂。
2)按照质量份数计，将5份双氰胺、100份二甲基甲酰胺加入到配料瓶充分搅拌溶解后，于搅拌条件下依次将10份苯氧树脂、步骤1)获得的纳米二氧化硅改性环氧和0.5份2-甲基咪唑加入到配料瓶中，搅拌均匀制备成胶液。
3)将1078玻璃纤维布(基重47.5g/m 2)置于步骤2)获得的胶液，常温浸渍10s，取出置于热风循环烤箱180℃烘烤3min后得到树脂含量为(65±1)wt％的不流胶半固化片。
实施例6
1)按照质量份数计，在装有搅拌器、温度计的干燥四口烧瓶中，加入0.3份硅烷偶联剂、100份基体树脂(环氧树脂)和3份二甲基甲酰胺，搅拌同时升温至150℃，然后搅拌条件下加入15份气相法纳米二氧化硅，保温反应2h，冷却得到纳米二氧化硅改性环氧树脂。
2)按照质量份数计，将5份双氰胺、100份二甲基甲酰胺加入到配料瓶充分 搅拌溶解后，于搅拌条件下依次将10份苯氧树脂、步骤1)获得的纳米二氧化硅改性环氧和0.5份2-甲基咪唑加入到配料瓶中，搅拌均匀制备成胶液。
3)将1078玻璃纤维布(基重47.5g/m 2)置于步骤2)获得的胶液，常温浸渍10s，取出置于热风循环烤箱180℃烘烤3min后,得到树脂含量为(65±1)wt％的不流胶半固化片。
对比例1
1)按照质量份数计，将5份双氰胺、100份二甲基甲酰胺加入到配料瓶充分搅拌溶解后，依次将100份基体树脂(环氧树脂)、50份苯氧树脂加入到配料瓶，于搅拌条件下加入0.3份硅烷偶联剂、25份的普通二氧化硅、0.5份的2-甲基咪唑后继续搅拌均匀制备成胶液。
2)将1078玻璃纤维布(基重47.5g/m 2)置于步骤1)获得的胶液，常温浸渍10s，取出置于热风循环烤箱180℃烘烤3min后，得到树脂含量为(65±1)wt％的不流胶半固化片。
对比例2
1)按照质量份数计，将6份双氰胺、100份二甲基甲酰胺加入到配料瓶充分搅拌溶解后，依次将100份的功能树脂(环氧树脂)、20份苯氧树脂、20份CTBN改性环氧树脂加入到配料瓶，于搅拌条件下加入0.3份硅烷偶联剂、25份的普通二氧化硅、0.5份2-甲基咪唑后继续搅拌均匀，制备成胶液。
2)将1078玻璃纤维布(基重47.5g/m 2)置于步骤1)获得的胶液，常温浸渍10s，取出置于热风循环烤箱180℃烘烤3min后，得到树脂含量为(65±1)wt％的不流胶半固化片。
对比例3
1)按照质量份数计，在装有搅拌器、温度计的干燥四口烧瓶中，加入0.3份硅烷偶联剂、100份基体树脂(环氧树脂)和3份二甲基甲酰胺，搅拌同时升温至150℃，然后搅拌条件下加入30份气相法纳米二氧化硅，保温反应2h，冷却得 到纳米二氧化硅改性环氧树脂。
2)按照质量份数计，将5份双氰胺、100份二甲基甲酰胺加入到配料瓶充分搅拌溶解后，于搅拌条件下依次将5份苯氧树脂、步骤1)获得的纳米二氧化硅改性环氧和0.5份2-甲基咪唑加入到配料瓶中，搅拌均匀制备成胶液。
3)将1078玻璃纤维布(基重47.5g/m 2)置于步骤2)获得的胶液，常温浸渍10s，取出置于热风循环烤箱180℃烘烤3min后，得到树脂含量为(65±1)wt％的不流胶半固化片。
上述原材料均可购自市售产品：
基体树脂(环氧树脂)购自(昆山南亚)，型号为(NPEL-128)。
苯氧树脂购自(山东圣泉化工)，型号为(SQP-40AXM40)。
CTBN改性环氧树脂购自(络合化学(上海)有限公司)，型号为(EPC-240)；
硅烷偶联剂购自(SG-Si 121)，型号为(南京曙光化工集团有限公司)；
气相法纳米二氧化硅购自(杜瓦化工(上海)有限公司)，型号为(L20)；
普通二氧化硅购自(重庆锦艺硅材料开发有限公司)，型号为(M10)。
实施例1～6及对比例1～3中的原料如表1所示
表1
Figure PCTCN2021109676-appb-000009
对比例3中，因原料配比超出特定范围，导致在改性过程中，气相法纳米二氧化硅发生团聚，分散不均匀，出现析出异常现象，影响材料各组分的相容性，导致材料改性不完全，组合物溢胶量变大，剥离强度变小，掉粉率变大， 冲切边缘开裂长度变大，浸锡耐热性变差。
对实施例1～6和对比例1～3制作得到的不流胶半固化片进行性能测试，结果如下表2所示：
表2
Figure PCTCN2021109676-appb-000010
测试方法如下：
1)剥离强度：测试方法按照(IPC-TM-650 2.4.8)进行；其中以聚酰亚胺材料作为基底进行剥离强度测试。
2)掉粉率：以半固化片经冲切/剪切处理后树脂粉脱落程度为判断依据。具体测试如下，以实施例1制得的半固化片为例：
取10cm×10cm大小的实施例1制得的半固化片4片，分别称重并记录为m1。用剪刀在分别其一边剪出9cm纵深的缺口，共剪29刀，每片样品制成含30条长9cm的小条，每片均做同样处理。
手持处理好的样品以腕部为中心位置上下振动30次，一个来回记为一次振动。完成后再次称重并记录为m2，按(m1-m2)/m1*100％计算即得该固化片的掉粉率。每片均做同样的测试并计算其掉粉率。则实施例1制得半固化片的掉粉率的计算公式如下：
实施例1制得半固化片的掉粉率＝4片半固化片的掉粉率的总值÷4。
3)溢胶量：依据(IPC-TM-650 2.3.17.2)测试；
4)耐热性：依据(IPC-TM-650 2.4.13.1)测试；
5)冲切边缘开裂长度的测试步骤如下：
将半固化片用树脂含量测试用的取样器冲切，将冲切下的样品置于50倍放大镜下测量开裂长度。
由表2的测试结果可知，按照本发明的技术方案，制得的不流胶半固化片具有优异的粘结性能、耐热性，且冲切处理时边缘开裂小，在高温高压时不易产生分子链运动，达到在高温高压下不流胶或极少流胶。对比例1和对比例2中采用传统的橡胶改性环氧树脂(CTBN改性环氧树脂)和苯氧树脂对基体树脂进行改性，并采用普通的二氧化硅作为无机填料，制得的不流胶半固化片的粘结性能较差，其剥离强度(PI)较低冲切处理时边缘开裂大，掉粉率较高。
与实施例3相比，对比例3中采用超出本申请配比范围的气相纳米二氧化硅，减少苯氧树脂配比，对比例3制得的不流胶半固化片在冲切处理时的边缘开裂长度和掉粉率较高，剥离强度(PI)变差，且过量的气相法纳米二氧化硅容易发生团聚，分散不均匀，出现析出现象。
以上实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。

Claims (10)

  1. 一种改性树脂组合物，其特征在于，按照质量份数计，所述改性树脂组合物的制备原料包括：
    Figure PCTCN2021109676-appb-100001
  2. 如权利要求1所述的改性树脂组合物，其特征在于，所述改性树脂组合物的制备原料中，所述纳米二氧化硅的质量份数为0.5份～15份。
  3. 如权利要求1所述的改性树脂组合物，其特征在于，所述改性树脂组合物的制备原料包括：
    Figure PCTCN2021109676-appb-100002
  4. 如权利要求1所述的改性树脂组合物，其特征在于，所述基体树脂选自环氧树脂。
  5. 如权利要求1～4任一项所述的改性树脂组合物，其特征在于，所述苯氧树脂如式(1)所示：
    Figure PCTCN2021109676-appb-100003
    其中，n选自20～120任一整数，R 1、R 2、R 3和R 4分别独立地选自H原子、卤素原子或含磷基团。
  6. 如权利要求1～4任一项所述的改性树脂组合物，其特征在于，所述固化促进剂选自咪唑类固化促进剂、过氧化物类固化促进剂、偶氮类固化促进剂、叔胺类固化促进剂、酚类固化促进剂、有机金属盐固化促进剂和无机金属盐固化促进剂中的至少一种。
  7. 如权利要求1～6任一项所述的改性树脂组合物的制备方法，其特征在于，包括如下步骤：
    将所述基体树脂、所述纳米二氧化硅、所述偶联剂和有机溶剂混合，加热反应，得到纳米二氧化硅改性基体树脂；
    将所述纳米二氧化硅改性基体树脂、所述苯氧树脂、所述固化剂以及所述固化促进剂混合，得到改性树脂组合物。
  8. 一种复合树脂，其特征在于，所述复合树脂采用包括如权利要求1～6任一项所述的改性树脂组合物的原料制得。
  9. 一种半固化片，其特征在于，所述半固化片包括增强材料以及负载于所述增强材料表面的树脂材料，所述树脂材料为如权利要求8所述的复合树脂。
  10. 一种印制线路板，其特征在于，所述印制线路板的制备原料包括如权利要求9所述的半固化片。
PCT/CN2021/109676 2020-12-22 2021-07-30 改性树脂组合物及其制备方法与应用 Ceased WO2022134590A1 (zh)

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