CN115011293B

CN115011293B - Build-up adhesive film for low-dielectric FC-BGA packaging loading board and preparation method and application thereof

Info

Publication number: CN115011293B
Application number: CN202210623201.1A
Authority: CN
Inventors: 刘飞; 许伟鸿; 杨柳; 何岳山; 练超; 李东伟; 王粮萍; 刘汉成
Original assignee: Shenzhen Newfield New Material Technology Co ltd
Current assignee: Shenzhen Newfield New Material Technology Co ltd
Priority date: 2022-06-01
Filing date: 2022-06-01
Publication date: 2023-08-08
Anticipated expiration: 2042-06-01
Also published as: CN115011293A

Abstract

The invention provides a low-dielectric layer-added adhesive film for an FC-BGA packaging loading board, and a preparation method and application thereof. The laminated adhesive film comprises the following components in parts by weight: 45-100 parts of epoxy resin, 40-100 parts of inorganic filler, 25-45 parts of cyanate ester, 35-55 parts of bismaleimide, 1-3 parts of MOFs material, 5-10 parts of acrylic resin and 5-10 parts of phenoxy resin; the cyanate is unmodified cyanate and/or DOPO modified cyanate; the bismaleimide is unmodified bismaleimide and/or silicon-containing bismaleimide. The laminated adhesive film provided by the invention has excellent dielectric property and better flame retardance, and can meet the application requirements of the laminated adhesive film in an FC-BGA packaging loading plate.

Description

Build-up adhesive film for low-dielectric FC-BGA packaging loading board and preparation method and application thereof

Technical Field

The invention belongs to the technical field of resin composite materials, and particularly relates to a low-dielectric build-up adhesive film for an FC-BGA packaging loading plate, and a preparation method and application thereof.

Background

FC-BGA (Flip Chip Ball Grid Array), a packaging format known as flip chip ball grid array, is also currently the most dominant packaging format for graphics accelerator chips. This packaging technology began in 1960 s, when IBM developed the so-called C4 (Controlled Collapse Chip Connection) technology for the assembly of large computers, and then further developed to support the weight of the chip and control the height of the bumps by using the surface tension of the molten bumps, and became the development direction of the flip-chip technology.

FC-BGA solves the electromagnetic compatibility (EMC) and electromagnetic interference (EMI) problems. In general, a chip employing BGA packaging technology, in which signal transmission is performed through a metal wire having a certain length, generates a so-called impedance effect at a high frequency, and forms an obstacle on a signal path; however, the FC-BGA uses balls instead of pins originally used to connect the processor, and the package uses 479 balls in total, but the balls are 0.78 mm in diameter, which provides the shortest external connection distance. The package not only provides excellent electrical performance, but also can reduce the loss and inductance between components, reduce the problem of electromagnetic interference, bear higher frequency and become possible to break through the over-frequency limit.

Second, as display chip designers embed denser and denser circuits in the same silicon die area, the number of input/output terminals and pins increases rapidly, and another advantage of FC-BGA is that I/O density can be increased. Generally, the I/O leads are arranged around the chip by WireBond technology, but after FC-BGA packaging, the I/O leads can be arranged on the surface of the chip in an array manner, providing a higher density I/O layout, resulting in optimal use efficiency, and because of this advantage, the flip-chip technology is reduced in area by 30% to 60% compared to the conventional packaging.

Finally, in a new generation of high speed, high integration display chips, the heat dissipation problem would be a great challenge. Based on the unique flip-chip packaging form of FC-BGA, the back surface of the chip can be contacted with air, and heat can be directly dissipated. Meanwhile, the substrate can also be used for improving the heat dissipation efficiency through the metal layer, or a metal heat dissipation sheet is additionally arranged on the back of the chip, so that the heat dissipation capacity of the chip is further enhanced, and the stability of the chip in high-speed operation is greatly improved.

Although the FC-BGA package board is a development direction of a future semiconductor package board, a high-density package board capable of realizing high-speed and multi-functionalization of a chip is realized, an increase in circuit wiring density in the FC-BGA makes resistance of metal interconnection wires and capacitance of interlayer dielectrics in an electronic component easily form an RC (resistance-capacitance delay) delay effect, thereby causing adverse effects such as signal transmission delay power loss. The dielectric property of the laminated adhesive film material disclosed in the prior art is insufficient, and the application of the laminated adhesive film material in FC-BGA is seriously affected; in addition, the main component in the laminated adhesive film is a polymer material, the polymer material belongs to a flammable material, and a great amount of dense smoke and toxic gas are released in the combustion process, so that the flame retardant property of the polymer material is improved, and the main component is also the important direction of the laminated adhesive film.

Therefore, how to reduce the dielectric constant and dielectric loss of the laminated adhesive film, thereby reducing RC delay effect and improving signal transmission speed and efficiency; meanwhile, the laminated adhesive film is guaranteed to have good flame retardant property, the reliability of the product in practical application is improved, and the technical problem to be solved is urgent at present.

Disclosure of Invention

Aiming at the defects of the prior art, the invention aims to provide a low-dielectric-property build-up adhesive film for an FC-BGA packaging loading board, and a preparation method and application thereof. According to the invention, through the design of the raw materials of the laminated adhesive film, and further through the use of MOFs materials and DOPO modified cyanate ester and/or silicon-containing bismaleimide, the prepared laminated adhesive film has excellent dielectric property and better flame retardance, and can meet the application of the laminated adhesive film in an FC-BGA packaging loading plate.

To achieve the purpose, the invention adopts the following technical scheme:

in a first aspect, the invention provides a build-up adhesive film for a low dielectric FC-BGA packaging carrier board, which comprises the following components in parts by weight:

45-100 parts of epoxy resin, 40-100 parts of inorganic filler, 25-45 parts of cyanate ester, 35-55 parts of bismaleimide, 1-3 parts of MOFs material, 5-10 parts of acrylic resin and 5-10 parts of phenoxy resin;

the cyanate is unmodified cyanate and/or DOPO modified cyanate;

the bismaleimide is unmodified bismaleimide and/or silicon-containing bismaleimide.

The build-up adhesive film at least comprises one of DOPO modified cyanate ester or silicon-containing bismaleimide.

According to the invention, through the design of the components of the laminated adhesive film, on the basis of the components such as epoxy resin, inorganic filler, acrylic resin, phenoxy resin and the like, the prepared laminated adhesive film has excellent dielectric property and better flame retardance by further using MOFs (metal oxide semiconductor field effect transistors) materials, DOPO modified cyanate ester and silicon-containing bismaleimide, and the application requirements of the laminated adhesive film in the FC-BGA packaging carrier plate are met.

The DOPO group in the DOPO modified cyanate ester has low chemical bond polarizability, belongs to a large-volume functional group, and can increase the free volume of the polymer, so that the dielectric property of the laminated adhesive film can be effectively improved by introducing the DOPO group with low polarity and large volume; when the prepared laminated adhesive film burns, phosphorus groups in DOPO groups are decomposed to generate phosphoric acid, the resin is catalyzed to form carbon in advance, a nitrogen-containing structure of cyanate forms a cross-linked structure with higher thermal stability at high temperature, the carbon forming rate of the resin is improved, and the carbon forming rate and the nitrogen-containing structure play a role in coacervation phase synergistic flame retardance.

The silicon-containing bismaleimide contains benzene rings with larger molar volume and the like, and the large-volume functional groups can limit the movement of a high polymer chain segment and reduce the polarization degree, so that the dielectric constant and dielectric loss are effectively reduced; the silicon element in the silicon-containing bismaleimide is decomposed to generate an oxide carbon layer, and the nitrogen element generates a flame-retardant nitrogen-containing gas, so that the phosphorus and the silicon cooperate to realize flame retardance in a condensed phase and a gas phase to play a flame retardance effect.

The MOFs material has large pore volume and specific surface area, and can introduce an air medium into a resin system, so that the dielectric constant of the laminated adhesive film can be obviously reduced under the condition of low addition amount, and excellent dielectric performance can be obtained.

In the present invention, the weight part of the epoxy resin may be 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 85 parts, 90 parts, 95 parts, 100 parts, or the like.

The inorganic filler may be 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 85 parts, 90 parts, 95 parts, 100 parts, or the like by weight.

The cyanate ester may be 25 parts, 27 parts, 30 parts, 33 parts, 35 parts, 38 parts, 40 parts, 42 parts, 45 parts, or the like by weight.

The weight portion of the bismaleimide can be 35 portions, 37 portions, 40 portions, 43 portions, 45 portions, 48 portions, 50 portions, 52 portions or 55 portions, etc.

The MOFs material may be 1 part, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts, 2 parts, 2.2 parts, 2.4 parts, 2.6 parts, 2.8 parts, or 3 parts by weight, etc.

The weight part of the acrylic resin may be 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts, 8.5 parts, 9 parts, 9.5 parts, 10 parts, or the like.

The weight part of the phenoxy resin may be 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts, 8.5 parts, 9 parts, 9.5 parts, 10 parts, or the like.

The low dielectric in the invention means that the dielectric constant of the build-up adhesive film is less than 3.0, and the dielectric loss tangent is less than 0.0042.

The following is a preferred technical scheme of the present invention, but not a limitation of the technical scheme provided by the present invention, and the following preferred technical scheme can better achieve and achieve the objects and advantages of the present invention.

As a preferable technical scheme of the invention, the laminated adhesive film at least comprises one of DOPO modified cyanate ester or silicon-containing bismaleimide.

According to the invention, through the synergistic effect of MOFs material and DOPO modified cyanate ester and/or silicon-containing bismaleimide, the dielectric loss of the laminated adhesive film is further reduced, and the flame retardant property of the laminated adhesive film is further improved.

Preferably, the epoxy resin is selected from any one or a combination of at least two of bisphenol a type liquid epoxy resin, bisphenol F type liquid epoxy resin, bisphenol AF type liquid epoxy resin, biphenyl type epoxy resin, phenol type epoxy resin, naphthalene type epoxy resin, novolac type liquid epoxy resin, dicyclopentadiene type novolac epoxy resin, aralkyl biphenyl type novolac epoxy resin, or naphthol type novolac epoxy resin.

Preferably, the inorganic filler is selected from any one or a combination of at least two of silica, alumina, glass, cordierite, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate, calcium zirconate, or zirconium phosphate.

As a preferable technical scheme of the invention, the DOPO modified cyanate is selected from any one of the following compounds I to III:

the sources of DOPO modified cyanate esters (compounds I to III) are not particularly limited, and they can be obtained by commercial purchase or prepared by themselves, and the present invention is not particularly limited to the preparation method thereof, and reference is made to the preparation methods described in "Lin C H.Synthesis of novel phosphorus-containing cyanate esters and their curing reaction with epoxy resin [ J ]. Polymer,2004,45 (23): 7911-7926", "Lin C H, yang K Z, leu T S, et al Synthesis, development, and properties of novel epoxy resins and cyanate esters [ J ]. Journal of Polymer Science Part A Polymer Chemistry,2010,44 (11): 3487-3502 ], and" Chen X, liang G, gu A, et al flame Retarding Cyanate Ester Resin with Low Curing Temperature, high Thermal Resistance, outstanding Dielectric Property, and Low Water Absorption for High Frequency and High Speed Printed Circuit Broads [ J ]. Industrial & Engineering Chemistry Research,2015,54 (6): 150206100850009.

As a preferable technical scheme of the invention, the silicon-containing bismaleimide is selected from any one of the following compounds 1 to 4:

the source of the Silicon-containing bismaleimides (compounds 1 to 4) is not particularly limited, and the Silicon-containing bismaleimides can be obtained by commercial purchase or prepared by itself, and the preparation method of the Silicon-containing bismaleimides is not particularly limited, and can be exemplified by the preparation methods described in Tang H, song N, chen X, et al Synthesis and properties of Silicon-containing bismaleimide resins [ J ]. Journal of Applied Polymer Science,2010,109 (1): 190-199 ], and Wei-Jye, shu, ruey-Shi, et al Studies of Silicon-Containing Bismaleimide resins, part I: synthesis and Characteristics of Model Compounds and Polyaspartimides [ J ]. Designed Monomers & Polymers,2010 ].

As a preferred technical scheme of the invention, the MOFs material is selected from any one or a combination of at least two of SIFSIX-1-Cu, SIFSIX-2-Cu-i or SIFSIX-3-Ni;

the structural formulas of the SIFSIX-1-Cu, the SIFSIX-2-Cu-i and the SIFSIX-3-Ni are respectively

In the invention, the dielectric constant of the build-up resin can be further reduced by selecting specific MOFs materials, and the flame retardance of the build-up resin is improved. The MOFs material has large pore volume and specific surface area, and can introduce an air medium into a resin system, so that the dielectric constant of the laminated adhesive film can be obviously reduced under the condition of low addition amount, and excellent dielectric performance can be obtained; in addition, metal sites on MOFs materials can be used as active catalytic centers to have good catalytic performance, good catalytic activity is achieved in CO catalytic oxidation reaction, the release amount of CO during combustion of polymer materials can be reduced, and flame-retardant elements such as silicon, nitrogen and the like contained in organic groups can improve the flame-retardant effect through synergistic effect.

As a preferable technical scheme of the invention, the laminated adhesive film comprises the following components in parts by weight:

45-100 parts of epoxy resin, 40-100 parts of inorganic filler, 25-45 parts of DOPO modified cyanate ester, 35-55 parts of silicon-containing bismaleimide, 1-3 parts of MOFs material, 5-10 parts of acrylic resin and 5-10 parts of phenoxy resin.

In the invention, the dielectric property of the build-up resin is further reduced by the synergistic effect of DOPO modified cyanate ester, silicon-containing bismaleimide and MOFs material.

As a preferable technical scheme of the invention, the build-up adhesive film further comprises 0.1 to 1 part of a curing accelerator, for example, 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part or 1 part, etc.

Preferably, the curing accelerator is selected from any one or a combination of at least two of 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl-4, 5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-ethyl-4-methylimidazole or 4-dimethylaminopyridine.

Preferably, the laminated adhesive film further comprises 3-9 parts of other auxiliary agents, for example, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts or 9 parts, etc.

Preferably, the other auxiliary agent is selected from any one or a combination of at least two of a thickener, an antifoaming agent or a leveling agent.

Preferably, the build-up adhesive film further comprises 200-300 parts of an organic solvent, for example, 200 parts, 210 parts, 220 parts, 230 parts, 240 parts, 250 parts, 260 parts, 270 parts, 280 parts, 290 parts or 300 parts, etc.

Preferably, the organic solvent is selected from any one or a combination of at least two of toluene, xylene, butanone, methyl ethyl ketone, cyclohexanone, ethyl acetate or N, N-dimethylformamide.

In a preferred embodiment of the present invention, the thickness of the build-up adhesive film is 10 to 100. Mu.m, for example, 10. Mu.m, 20. Mu.m, 30. Mu.m, 40. Mu.m, 50. Mu.m, 60. Mu.m, 70. Mu.m, 80. Mu.m, 90. Mu.m, 100. Mu.m, etc.

In a second aspect, the present invention provides a method for preparing the laminated adhesive film according to the first aspect, the method comprising the following steps:

and uniformly mixing the components of the laminated adhesive film, coating the adhesive film on a substrate, and drying to obtain the laminated adhesive film.

The thickness of the base material is preferably 10 to 150 μm (for example, 10 μm, 20 μm, 25 μm, 40 μm, 50 μm, 70 μm, 85 μm, 100 μm, 120 μm, 150 μm, or the like may be used), and more preferably 25 to 50 μm.

In the present invention, the material of the substrate is not particularly limited, and any substrate commonly used in the art is suitable.

Preferably, the drying temperature is 80 to 130 ℃, and may be 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃ or the like, for example.

Preferably, the drying time is 3 to 10min, for example, 3min, 4min, 5min, 6min, 7min, 8min, 9min or 10min, etc.

Preferably, the drying further comprises a post-treatment step.

Preferably, the post-treatment is performed by removing the substrate.

In a third aspect, the present invention provides an application of the build-up adhesive film according to the first aspect in packaging a carrier.

Preferably, the package carrier is an FC-BGA package carrier.

Compared with the prior art, the invention has the following beneficial effects:

according to the invention, through the design of raw materials of the laminated adhesive film, further through the use of MOFs materials and DOPO modified cyanate ester and/or silicon-containing bismaleimide, the prepared laminated adhesive film has excellent dielectric property and better flame retardance, can meet the requirement of the laminated adhesive film on the application of the FC-BGA packaging carrier plate, has a dielectric constant of 2.5-2.8, has a dielectric loss tangent of 0.003-0.0038, and has a flame retardance grade of V-0 after the flame retardance test of the adhesive film is carried out by UL-94V standard.

Detailed Description

To facilitate understanding of the present invention, examples are set forth below. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.

Some of the component sources in the examples and comparative examples are as follows:

epoxy resin: NC-3000-L (Japanese chemical Co., ltd.), WHR-991S (Japanese chemical Co., ltd.), jER828EL (Mitsubishi chemical Co., ltd.), HP-6000 (DIC Co., japan);

spherical silica: SOC2 (japan Dou Ma corporation);

cyanate ester: BA230S75 (Lonza Japan Co., ltd.), BA230S (Lonza Japan Co., ltd.);

bismaleimide: BMI5100 (japan large and chemical industry company);

acrylic resin: ext> XXext> -ext> 5598ext> Zext> (ext> Japaneseext> productext> Waterext> industryext> Coext>.ext>,ext> Ltdext>.ext>)ext>,ext> DOGext> -ext> Aext> (ext> Japaneseext> Xinzhongcunext> chemicalext> Coext>.ext>,ext> Ltdext>.ext>)ext>;ext>

Phenoxy resin: YX7553BH30 (mitsubishi chemical company of japan), TER240C30 (guangdong homogyu).

Example 1

The embodiment provides a layer-added adhesive film and a preparation method thereof, wherein the layer-added adhesive film comprises the following components in parts by weight:

30 parts of biphenyl type epoxy resin (NC-3000-L), 5 parts of phenol type epoxy resin (WHR-991S), 10 parts of bisphenol A type liquid epoxy resin (jER 828 EL), 100 parts of spherical silicon dioxide (SOC 2), 25 parts of DOPO modified cyanate ester (compound I), 55 parts of silicon-containing bismaleimide (compound 4), 1 part of MOFs material (SIFSIX-1-Cu), 10 parts of acrylic resin (XX-5598Z), 5 parts of phenoxy resin (YX 7553BH 30), 0.1 part of 4-Dimethylaminopyridine (DMAP) and 200 parts of butanone.

The preparation method of the laminated adhesive film comprises the following steps:

and (3) uniformly mixing the components of the laminated adhesive film, coating the laminated adhesive film on a PET release film, drying the PET release film at 80 ℃ for 10min, and removing the PET release film to obtain the laminated adhesive film with the thickness of 100 mu m.

Example 2

The implementation provides a layer-added adhesive film and a preparation method thereof, wherein the layer-added adhesive film comprises the following components in parts by weight:

ext> 100ext> partsext> ofext> naphthaleneext> typeext> epoxyext> resinext> (ext> HPext> -ext> 6000ext>)ext>,ext> 40ext> partsext> ofext> sphericalext> siliconext> dioxideext> (ext> SOCext> 2ext>)ext>,ext> 45ext> partsext> ofext> DOPOext> modifiedext> cyanateext> esterext> (ext> compoundext> IIext>)ext>,ext> 35ext> partsext> ofext> siliconext> -ext> containingext> bismaleimideext> (ext> compoundext> 1ext>)ext>,ext> 3ext> partsext> ofext> MOFsext> materialext> (ext> SIFSIXext> -ext> 3ext> -ext> Niext>)ext>,ext> 5ext> partsext> ofext> acrylicext> resinext> (ext> DOGext> -ext> Aext>)ext>,ext> 10ext> partsext> ofext> phenoxyext> resinext> (ext> TERext> 240ext> Cext> 30ext>)ext>,ext> 1ext> partext> ofext> 2ext> -ext> ethylext> -ext> 4ext> -ext> methylimidazoleext> (ext> 2ext> Eext> 4ext> MIext>)ext> andext> 200ext> partsext> ofext> butanoneext>.ext>

Example 3

40 parts of biphenyl type epoxy resin (NC-3000-L), 10 parts of phenol type epoxy resin (WHR-991S), 20 parts of bisphenol A type liquid epoxy resin (jER 828 EL), 80 parts of spherical silicon dioxide (SOC 2), 35 parts of DOPO modified cyanate ester (compound III), 40 parts of silicon-containing bismaleimide (compound 2), 2 parts of MOFs material (SIFSIX-2-Cu-i), 8 parts of acrylic resin (XX-5598Z), 7 parts of phenoxy resin (YX 7553BH 30), 0.5 part of 2-phenyl-4-methyl-5-hydroxymethyl imidazole, 3 parts of organosilicon defoamer, 3 parts of flatting agent (BYK-333) and 300 parts of cyclohexanone.

And (3) uniformly mixing the components of the laminated adhesive film, coating the laminated adhesive film on a PET release film, drying the PET release film at 100 ℃ for 5min, and removing the PET release film to obtain the laminated adhesive film with the thickness of 80 mu m.

Example 4

50 parts of naphthalene-type epoxy resin (HP-6000), 30 parts of bisphenol A-type liquid epoxy resin (jER 828 EL), 870 parts of spherical silicon dioxide (SOC 2), 40 parts of DOPO modified cyanate ester (compound III), 50 parts of silicon-containing bismaleimide (compound 2), 2 parts of MOFs (SIFSIX-2-Cu-i), 7 parts of acrylic resin (XX-5598Z), 6 parts of phenoxy resin (YX 7553BH 30), 0.8 part of 2-ethyl-4-methylimidazole, 2 parts of organosilicon defoamer, 2 parts of flatting agent (BYK-333) and 200 parts of cyclohexanone.

And (3) uniformly mixing the components of the laminated adhesive film, coating the laminated adhesive film on a PET release film, drying the PET release film at 130 ℃ for 3min, and removing the PET release film to obtain the laminated adhesive film with the thickness of 50 mu m.

Example 5

The present embodiment provides a build-up adhesive film and a method for producing the same, which are different from example 2 only in that the silicon-containing bismaleimide (compound 1) is replaced with bismaleimide (BMI 5100), and the other conditions are the same as example 2.

Example 6

The present embodiment provides a laminated adhesive film and a method for preparing the same, which are different from example 2 only in that the DOPO modified cyanate ester is replaced by cyanate ester (BA 230S), and other conditions are the same as in example 2.

Example 7

The present embodiment provides a laminated adhesive film and a method for producing the same, which are different from example 1 only in that MOFs (SIFSIX-1-Cu) is replaced with MOFs (ZIF-8), and other conditions are the same as in example 2.

Example 8

The present example provides a build-up adhesive film and a method for preparing the same, which are different from example 1 in that bismaleimide (BMI 5100) is replaced by bismaleimide (compound 4) containing silicon, MOFs material (SIFSIX-3-Ni) is not contained in the build-up adhesive film, and other conditions are the same as in example 1.

Example 9

The difference between the embodiment and the embodiment 1 is that DOPO modified cyanate ester (compound I) is replaced by cyanate ester (BA 230S 75), and MOFs (SIFSIX-3-Ni) is not contained in the embodiment 1.

Example 10

The present example provides a build-up adhesive film and a method for preparing the same, which are different from example 1 in that bismaleimide (compound 4) containing silicon is replaced with bismaleimide (BMI 5100), DOPO modified cyanate ester (compound I) is replaced with cyanate ester (BA 230S 75), and other conditions are the same as in example 1.

Comparative example 1

This comparative example provides a laminated adhesive film and a method for preparing the same, which are different from example 2 in that bismaleimide (compound 4) containing silicon is replaced with bismaleimide (BMI 5100), DOPO modified cyanate ester (compound I) is replaced with cyanate ester (BA 230S 75), and MOFs (SIFSIX-3-Ni) is not contained in the laminated adhesive film, and other conditions are the same as in example 2.

The performance of the laminated adhesive films provided in the above examples and comparative examples was tested as follows:

dielectric constant and dielectric loss tangent: placing the laminating adhesive films provided in the examples and the comparative examples on a PET film, curing for 30min at 180 ℃, and then peeling off the PET film to obtain a pre-cured laminating adhesive film; the pre-cured build-up adhesive film was cut into test pieces (3 pieces) of 2mm×80mm, and then the dielectric constant and dielectric loss tangent of each test piece were measured using "HP8362B" of agilent technologies, inc. By means of cavity resonance perturbation method under the conditions of a measurement frequency of 5.8GHz and a measurement temperature of 23 ℃, and the average value of the dielectric constants and dielectric loss tangents of the 3 test pieces was calculated as the dielectric constant and dielectric loss tangents.

Flame retardancy: laminating the laminating adhesive films with PET release films provided in the examples and the comparative examples and a substrate (MCL-E-705G formed by Hitachi, japan) by a film laminating machine, and respectively laminating the laminating adhesive films (on the side without PET release film) on two sides of the substrate to obtain a laminated body; after the lamination was completed, the PET release film on the laminate was removed, and the build-up adhesive film was thermally cured (cured at 190 ℃ for 90 minutes) to form a cured product on both sides of the substrate. The laminate (thickness: about 380 μm) was cut into a sample having a size of 12.7mm.times.127 mm and an edge of 1.27mm, and the test was conducted in accordance with the UL-94V standard, and the test results were recorded.

The results of the performance test of the laminated adhesive films provided in the above examples and comparative examples are shown in table 1 below:

TABLE 1

As can be seen from the contents of Table 1, the invention further uses MOFs material and DOPO modified cyanate ester and/or silicon-containing bismaleimide to prepare the laminated adhesive film, which has excellent dielectric property and better flame retardance, can meet the application of the laminated adhesive film in an FC-BGA packaging carrier board, has a dielectric constant of 2.5-2.8, a dielectric loss tangent of 0.003-0.0038 and has a flame retardance grade of V-0 after being subjected to a flame retardance test by UL-94V standard.

As is clear from the data of examples 1-4, the dielectric properties of the laminated adhesive film are further improved by the common use of MOFs material, DOPO modified cyanate ester and silicon-containing bismaleimide, the dielectric constant is 2.5-2.6, and the dielectric loss tangent is 0.003-0.0032.

Compared with example 1, if the conventional MOFs (example 7) are selected, the dielectric properties of the prepared laminated adhesive film are poor. Therefore, the invention further improves the performance of the laminated adhesive film by selecting specific MOFs materials.

Compared with the embodiment 1, if the laminated adhesive film only contains any one of DOPO modified cyanate ester, silicon bismaleimide or MOFs (embodiments 8-10), the performance of the prepared laminated adhesive film is poor; if the laminated adhesive film does not contain DOPO modified cyanate ester, silicon-containing bismaleimide and MOFs (comparative example 1), the dielectric property and the flame retardance of the prepared laminated adhesive film are poor.

In summary, according to the invention, through the use of MOFs materials with specific structures and the synergistic effect of the MOFs materials and DOPO modified cyanate ester and/or silicon-containing bismaleimide, the build-up adhesive film with excellent dielectric property and better flame retardance is prepared, and the application of the build-up adhesive film in the FC-BGA packaging carrier plate is satisfied.

The applicant states that the detailed process flow of the present invention is illustrated by the above examples, but the present invention is not limited to the above detailed process flow, i.e. it does not mean that the present invention must be implemented depending on the above detailed process flow. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.

Claims

1. The low-dielectric build-up adhesive film for the FC-BGA packaging loading board is characterized by comprising the following components in parts by weight:

the cyanate adopts DOPO modified cyanate;

the bismaleimide is silicon-containing bismaleimide;

the DOPO modified cyanate is selected from any one of the following compounds I to III:

the silicon-containing bismaleimide is selected from any one of the following compounds 1 to 4:

2. the build-up adhesive film of claim 1, wherein the epoxy resin is selected from any one or a combination of at least two of bisphenol a type liquid epoxy resin, bisphenol F type liquid epoxy resin, bisphenol AF type liquid epoxy resin, biphenyl type epoxy resin, phenol type epoxy resin, naphthalene type epoxy resin, novolac type liquid epoxy resin, dicyclopentadiene type novolac epoxy resin, aralkyl biphenyl type novolac epoxy resin, or naphthol type novolac epoxy resin.

3. The laminated adhesive film according to claim 1, wherein the inorganic filler is selected from any one or a combination of at least two of silica, alumina, glass, cordierite, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate, calcium zirconate, or zirconium phosphate.

4. The laminated adhesive film according to claim 1, wherein the MOFs material is selected from any one or a combination of at least two of sifsiix-1-Cu, sifsifsix-2-Cu-i or sifsifsix-3-Ni;

5. The laminated adhesive film according to claim 1, further comprising 0.1 to 1 part of a curing accelerator.

6. The laminated adhesive film according to claim 5, wherein the curing accelerator is any one or a combination of at least two selected from 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl-4, 5-dimethylol imidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-ethyl-4-methylimidazole and 4-dimethylaminopyridine.

7. The laminated adhesive film according to claim 1, wherein 3-9 parts of other auxiliary agents are further included in the laminated adhesive film.

8. The laminated adhesive film according to claim 7, wherein the other auxiliary agent is selected from any one or a combination of at least two of a thickener, an antifoaming agent, and a leveling agent.

9. The laminated adhesive film according to claim 1, further comprising 200-300 parts of an organic solvent.

10. The laminated adhesive film according to claim 9, wherein the organic solvent is selected from any one or a combination of at least two of toluene, xylene, butanone, methyl ethyl ketone, cyclohexanone, ethyl acetate, and N, N-dimethylformamide.

11. The laminated adhesive film according to claim 1, wherein the thickness of the laminated adhesive film is 10 to 100 μm.

12. A method for preparing a laminated adhesive film according to any one of claims 1 to 11, comprising the steps of:

13. The method of claim 12, wherein the substrate has a thickness of 10 to 150 μm.

14. The method of claim 13, wherein the substrate has a thickness of 25 to 50 μm.

15. The method of claim 12, wherein the drying temperature is 80-130 ℃.

16. The method of claim 12, wherein the drying time is 3 to 10 minutes.

17. The method of claim 12, wherein the drying further comprises a post-treatment step.

18. The method of claim 17, wherein the post-treatment is removal of the substrate.

19. Use of a build-up film according to any one of claims 1 to 11 for packaging carrier boards.