Search

CN-121975301-A - Resin composition, application thereof in preparation of copper-clad plate and copper-clad plate

CN121975301ACN 121975301 ACN121975301 ACN 121975301ACN-121975301-A

Abstract

The invention provides a resin composition, application thereof in preparation of a copper-clad plate and the copper-clad plate, and relates to the technical field of copper-clad plate preparation. According to the invention, the fluorine-containing polyurethane crosslinked network is constructed by introducing the trifiunctional isocyanate crosslinking agent containing trifluoromethyl, so that the water absorption and dielectric loss of the material are reduced, the dielectric stability after wet and hot is improved, and the heat resistance, the dimensional stability and the comprehensive reliability of a cured product are improved, thereby meeting the application requirements of high-frequency high-speed copper-clad plates, antennas/radars and millimeter wave device materials.

Inventors

  • WANG JIALE
  • LI BINGBING
  • ZHANG JIAFU

Assignees

  • 南亚新材料科技(江苏)有限公司

Dates

Publication Date
20260505
Application Date
20260319

Claims (10)

  1. 1. A resin composition is characterized by comprising the following raw materials of hydroxyl modified low molecular weight polyphenyl ether, bismaleimide resin, trifiuoromethyl-containing difunctional isocyanate cross-linking agent, filling material and initiator.
  2. 2. The resin composition according to claim 1, wherein the raw materials of the resin composition comprise, in parts by mass, 40-150 parts of hydroxyl-modified low molecular weight polyphenylene ether, 5-35 parts of bismaleimide resin, 30-60 parts of trifiuoromethyl-containing difunctional isocyanate cross-linking agent, 50-150 parts of filler and 0.1-10 parts of initiator; Preferably, the bismaleimide resin comprises one or more of 4, 4-bismaleimide diphenylmethane, bismaleimide diphenyl ether, bismaleimide diphenyl sulfone, bismaleimide xylene, and a multi-functional bismaleimide prepolymer; Preferably, the filler material comprises spherical silica, the spherical silica having been surface-modified with at least one surface treatment agent selected from the group consisting of vinylsilane, allylsilane and (meth) acryloyloxy silane, the spherical silica having a dielectric dissipation factor of less than 0.0015 at a frequency of 10GHz, the spherical silica having a volume average particle diameter of 0.5 μm to 5.0 μm, more preferably 0.8 μm to 3.0 μm, still more preferably 1.0 μm to 2.0 μm; Preferably, the initiator comprises a peroxide initiator or an azo initiator, wherein the peroxide initiator comprises at least one of dicumyl peroxide, benzoyl peroxide, di-tert-butyl peroxide and methyl ethyl ketone peroxide, and the azo initiator comprises one or more of azobisisobutyronitrile and azobisisoheptonitrile.
  3. 3. The resin composition of claim 1 wherein the trifiuoromethyl-containing difunctional isocyanate crosslinker has the following structural formula: ; Wherein R is a diisocyanate residue, ar (CF 3 ) m is an aromatic diol residue containing trifluoromethyl, m is the substitution number of trifluoromethyl on each aromatic ring, and m is more than or equal to 1; Preferably, the R includes one or more of p-phenylene (pp-phenylene), diphenylmethane diisocyanate (MDI) type, and Hexamethylene Diisocyanate (HDI) type.
  4. 4. The resin composition according to claim 1, wherein the trifluoromethyl group-containing difunctional isocyanate crosslinking agent is a trifluoromethyl group-containing NCO-terminated urethane diisocyanate having the following structural formula: 。
  5. 5. the resin composition of claim 1, wherein the hydroxy-modified low molecular weight polyphenylene ether has the structural formula: ; Wherein a, b and c are integers, a is an integer from 2 to 50, b is an integer from 1 to 10, c is an integer from 2 to 50; Wherein R 1 、R 2 、R 4 and R 5 are each independently selected from hydrogen, C1-C12 alkyl, C2-C12 alkenyl, C6-C18 aryl, or the above groups substituted with at least one of halogen, alkoxy, aryloxy, at least one of R 1 、R 2 、R 4 and R 5 is hydrogen; R 3 is selected from one or more of the following (a) - (g): (a) A chemical bond; (b) C6-C18 arylene optionally substituted by C1-C6 alkyl, halogen or phenyl, of the formula C 6 R 6 4 ; (C) General formula (VI) CR 7 2 A C1-C12 alkylene group represented, wherein R 7 is independently selected from hydrogen or C1-C6 alkyl; (d) General formula (VI) [(OCH 2 ) 2 O]x Or (b) [(OCH 2 CH(CH 3 ) 2 O)] y Wherein x and y are each independently integers of 1 to 50; (e) The general formula is [(CH 2 ) p O] q Wherein p is an integer from 2 to 6 and q is an integer from 1 to 100; (f) The general formula is C(O) Or (b) C(O)O A divalent carbonyl or ester group linker; (g) A divalent linking group consisting of two or more of the above (b), (c), (d), (e) and (f); Preferably, the hydroxyl-modified low molecular weight polyphenylene ether has a number average molecular weight of 1500 to 10000 g/mol, more preferably 2000 to 6000 g/mol; preferably, the hydroxyl equivalent weight of the hydroxyl modified low molecular weight polyphenyl ether is 100-1500 g/mol, and more preferably 500-1000 g/mol; preferably, the hydroxyl-modified low molecular weight polyphenylene ether has a molecular weight distribution index of 1.0 to 3.0, more preferably 1.5 to 2.5.
  6. 6. Use of the resin composition according to any one of claims 1 to 5 for the preparation of copper-clad laminate.
  7. 7. The copper-clad plate is characterized by being prepared by the following steps: (A) Mixing the raw materials of the resin composition according to any one of claims 1 to 5 to obtain a resin dope; (B) Impregnating the resin glue solution with a reinforcing material, and then pre-curing to obtain a prepreg; (C) And (3) overlapping the prepreg and the copper foil, and performing hot press curing to obtain the copper-clad plate.
  8. 8. The copper-clad plate according to claim 7, wherein the pre-curing temperature is 40-120 ℃, further preferably 60-100 ℃; Preferably, the pre-curing time is 0.5-6 hours; preferably, the reinforcing material comprises one or more of an electronic grade glass fiber cloth and a quartz fiber cloth; Preferably, the electronic grade glass fiber cloth comprises one or more of E-glass cloth, NE-glass cloth and D-glass cloth.
  9. 9. The copper-clad laminate according to claim 7, wherein the equivalent ratio of NCO groups in the trifiuoromethyl group-containing difunctional isocyanate crosslinking agent to OH groups in the hydroxyl-modified low molecular weight polyphenylene ether in the raw material of the resin composition is 0.9 to 2.5:1, more preferably 1.0 to 2.0:1, still more preferably 1.05 to 1.60:1.
  10. 10. The copper-clad plate according to claim 7, wherein the trifiuoromethyl-containing difunctional isocyanate crosslinking agent in the raw material of the resin composition is prepared by the steps of: step 1, under the inert atmosphere and anhydrous conditions, dissolving dry bisphenol AF in an anhydrous aromatic hydrocarbon or ester inert solvent, wherein the solid content is 30% -50%; Step 2, adding diisocyanate at the temperature of 40-90 ℃ and the equivalent ratio of NCO to OH functional groups is 2.0-2.5:1; Step 3, stirring at a constant temperature of 3-8 h to obtain a trifiunctional isocyanate crosslinking agent containing trifluoromethyl; Preferably, the temperature of step 2 is 60-80 ℃.

Description

Resin composition, application thereof in preparation of copper-clad plate and copper-clad plate Technical Field The invention relates to the technical field of copper-clad plate preparation, in particular to a resin composition, application thereof in preparation of a copper-clad plate and the copper-clad plate. Background The rapid development of high frequency and high speed electronic information technology has driven the evolution of Printed Circuit Board (PCB) substrates to higher signal rates, higher carrier frequencies and higher integration levels. Copper-clad plates (coppers CLAD LAMINATE, CCL) and bonding sheets/resin systems thereof, which are key dielectric materials, are required to meet both low dielectric constant (Dk) and low dielectric loss (Df) at high frequency (e.g., GHz to millimeter wave frequency bands) to reduce transmission delay and insertion loss and improve impedance consistency, and to maintain stable dielectric parameters in reflow soldering, long-term thermal aging and humid and hot environments (e.g., 85 ℃/85%rh) to avoid degradation of signal integrity due to dielectric drift caused by moisture absorption or aging. In addition to electrical properties, high frequency, high speed CCLs require dielectric materials with higher glass transition temperatures (Tg), lower coefficients of thermal expansion (CTE, especially Z-CTE), good dimensional stability and thermo-mechanical reliability (e.g., thermal shock resistance, delamination resistance, warp resistance), and viscosity-gel time windows and cure kinetics required to adapt the coating, dipping, lamination, and thermal press curing processes. Polyphenylene oxide (Polyphenylene Ether, PPO) and its modified system are considered as one of important candidate systems for high-frequency high-speed low-dielectric resin because of the characteristics of less polar groups, lower dielectric loss, better heat resistance and the like in the molecular structure. The PPO is functionally modified and a crosslinking component is introduced, so that the processability, solvent resistance and thermo-mechanical properties of the PPO after curing can be improved to a certain extent, and the application of the PPO in high-frequency high-speed copper-clad plates, antenna/radar and millimeter wave device dielectric materials and resin matrix composite materials is expanded. In order to improve the dielectric stability of a resin system under the damp-heat condition, the prior art generally adopts a strategy for reducing the water absorption rate of the system so as to inhibit polarization loss and dielectric drift caused by water molecules. The introduction of fluorine-containing structures, in particular trifluoromethyl (-CF 3) structural units, is one of the practical and verified technical paths, namely that the CF 3 has lower polarizability, can reduce the surface energy of materials, weaken the dissolution and diffusion capacity of water molecules in a resin network, and the hydrophobicity and the steric hindrance effect are also beneficial to reducing the exposure of effective water absorption sites, so that the dielectric holding capacity under the damp-heat condition is improved. The prior patents such as CN119661846A, CN120484258A and CN120665282A respectively propose a technical scheme for reducing water absorption and improving wet heat stability by introducing trifluoromethyl into a resin network system from the angles of fluorine-containing structure construction, introduction of a CF 3 component or fluorine-containing cross-linking network design. Despite the advantages of PPO-based systems in low dielectric applications, the prior art still suffers from the following disadvantages: First, low molecular weight or flowable PPO systems often require reduced molecular weight or introduction of reactive diluent components to meet processing flowability and fiber wetting requirements, and if the crosslink density is insufficient after cure, it is prone to reduced chemical resistance, solvent resistance and creep resistance and exhibits insufficient thermo-mechanical reliability under thermal cycling or reflow of the electrode. Secondly, the modification route for improving heat resistance and strength is realized by improving crosslinking density or introducing polar functional groups, more polar structures or water absorption sites capable of acting with water molecules can be introduced synchronously, so that Dk and Df are obviously increased after the material absorbs moisture in a damp-heat environment, and dielectric parameter drift is aggravated. Although both CN119661846A, CN120484258a and CN120665282a involve the introduction of-CF 3 structure, in the PPO-based multi-component crosslinking system, there is still a great difficulty in formulation and network structure design, how to further compromise high Tg, low CTE, low dielectric loss, and long-term reliability while ensuring low water absorption advantage. Thirdly, when high