WO2022120715A1

WO2022120715A1 - Insulating adhesive film material, preparation method therefor and application thereof

Info

Publication number: WO2022120715A1
Application number: PCT/CN2020/135258
Authority: WO
Inventors: 罗遂斌; 于均益; 于淑会; 徐鹏鹏; 刘捷; 孙蓉
Original assignee: 深圳先进技术研究院
Priority date: 2020-12-10
Filing date: 2020-12-10
Publication date: 2022-06-16

Abstract

Disclosed are an insulating adhesive film material, a preparation method therefor and an application thereof; the insulating adhesive film material comprises an insulating polymer composite layer, and the insulating polymer composite layer is made of an electronic paste. The electronic paste is made from the following raw material components: a resin polymer, a first curing agent, a curing accelerator, an inorganic filler material that uses a second curing agent for surface treatment, a dispersant, an additive, and a solvent; and the second curing agent is a liquid curing agent or a curing agent solution, the mass of a solute in the liquid curing agent or the curing agent solution being 0.01-5% of the mass of the inorganic filler material. The insulating adhesive film material of the present invention can be applied to a semiconductor electronic package such as a printed circuit board (PCB), a substrate, a carrier board, achieving the fabrication of a fine electronic circuit.

Description

A kind of insulating film material, preparation method and application thereof

technical field

The invention belongs to the technical field of electronic packaging materials, and in particular relates to an insulating adhesive film material and a preparation method and application thereof.

Background technique

With the development of electronic information technology, especially the rapid development of wearable electronics, smart phones, ultra-thin computers, unmanned driving, Internet of Things technology and 5G communication technology in recent years, the miniaturization and thinning of electronic systems , multi-function, high performance and other aspects put forward higher and higher requirements. The line width of integrated circuits has developed from 3μm in 1997 to 0.05μm in 2010, and now is 0.01um, or even smaller. The matching PCB circuit size requirements have dropped from 300 μm in 1997 to 30 μm today, or even lower. It is very difficult to fabricate circuits smaller than 30 μm using conventional subtractive methods, and there are many limitations.

In addition, in the prior art, fillers are generally added directly into the resin system, or a coupling agent is introduced to enhance the dispersibility in the resin system. The bonding force between the filler particles and the resin matrix is poor, and fillers are prone to appear during the application process. The phenomenon of separation and cracking from the resin affects the processability and reliability of the circuit board.

SUMMARY OF THE INVENTION

In order to solve the problems raised in the above-mentioned background art, the purpose of the present invention is to provide an insulating film material suitable for the preparation of fine circuits by additive method or semi-additive method, and its preparation method and application, which can be used in semiconductor packaging.

In order to achieve the above purpose, the technical scheme adopted in the present invention is: on the one hand, the present invention provides a kind of electronic paste, which is made from the following raw material components:

Resin polymer, first curing agent, curing accelerator, inorganic filler, dispersant, additive, solvent for surface treatment with second curing agent;

The second curing agent is a liquid curing agent or a curing agent solution, and the mass of the solute in the liquid curing agent or curing agent solution is 0.01-5% of the mass of the inorganic filler. When the surface treatment amount of the curing agent is higher than 5%, the curing speed of the resin system is easy to be too fast, the curing is uneven, and problems such as cracking and easy peeling are caused. When the surface treatment amount of the curing agent is less than 0.01%, it has little effect on the performance of the resin system, and it is difficult to achieve the expected effect.

Further, the mass of the resin polymer is 5-65% of the mass of the electronic paste, the mass of the first curing agent is 2%-120% of the mass of the resin polymer, and the mass of the curing accelerator is the resin 0-1.5% of the mass of the polymer, the mass of the inorganic filler material treated with the second curing agent is 10%-70% of the mass of the electronic paste, and the mass of the dispersant is the mass of the second curing agent. The mass of the surface-treated inorganic filler material is 0-5%, the mass of the additive is 0-15% of the mass of the electronic paste, and the mass of the solvent is 15%-55% of the mass of the electronic paste.

Further, the mass of the solute in the liquid curing agent or curing agent solution is 0.1-3% of the mass of the inorganic filler;

Preferably, the mass of the solute in the liquid curing agent or curing agent solution is 0.2%-2% of the mass of the inorganic filler.

Further, the method of using the second curing agent for surface treatment of the inorganic filler is a heating coating method or a solution dispersion method;

Preferably, the heating coating method specifically comprises placing the inorganic filler material in a container, and the temperature in the container is 10°C-200°C, preferably 20°C-150°C, more preferably 20°C-100°C, Then the second curing agent is slowly and gradually added, and at the same time, it is rapidly stirred for 20min-24h, preferably 1h-20h, more preferably 4h-15h, so as to obtain the inorganic filler which is surface-treated with the second curing agent;

Preferably, in the solution dispersion method, the second curing agent is placed in a container, and the inorganic filler is slowly and gradually added while ultrasonically stirring. 24h, preferably 1h-20h, more preferably 4h-15h, and then perform ball milling for 1h-48h, preferably 5h-30h, wherein the ball mill rotating speed is 50rpm-5000rpm, preferably 100rpm-1000rpm, to obtain the surface using the second curing agent. Processed inorganic filler materials.

Further, the inorganic filler material includes silicon dioxide, aluminum oxide, boron nitride, titanium dioxide, zinc oxide, zirconium oxide, magnesium oxide, calcium carbonate, barium titanate, strontium titanate, barium strontium titanate, zirconium titanate One or more of lead, calcium copper titanate, etc.; preferably, the particle size of the inorganic filler material is 0.02-10 μm, preferably 0.05-3 μm, more preferably 0.2-1 μm, or a multi-scale mixture; Preferably, the shape of the inorganic filler is mainly spherical or quasi-spherical particles, and there may also be some particles of other shapes such as rods, wires, sheets, etc.;

Preferably, the liquid curing agent includes ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, aliphatic amines (such as Baxxodur EC280, Baxxodur EC130 produced by BASF), alicyclic amines (such as Baxxodur EC201, Baxxodur EC210), aromatic amines (eg Ethacure 200 from Albemarle), polyetheramines (eg Baxxodur EC301 from BASF, Baxxodur EC302, Baxxodur EC303, Baxxodur EC310, Baxxodur EC311), polyamides (eg Versamid 115 from Gabriel) , Versamid 125, Versamid 140, Versamid 150), one or more of the liquid acid anhydride curing agent; more preferably, the liquid acid anhydride curing agent comprises methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride One or more of diformic anhydride and methyl nadic anhydride;

Preferably, the solute in the curing agent solution includes one or more of dicyandiamide, boron trifluoride phenethylamine, and phenolic resin; One or more of phenol A formaldehyde resin, linear o-cresol formaldehyde resin, XYLOK phenolic resin, nitrogen-containing phenolic resin, dicyclopentadiene phenolic resin, biphenyl phenolic resin; the solvent in the curing agent solution is selected from Volatile solvents, including one or more of aromatic solvents, halogenated hydrocarbon solvents, aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents, alcohol solvents, ester solvents, ketone solvents, and amide solvents; more preferably Preferably, the aromatic solvent includes one or more of xylene, o-xylene, m-xylene, p-xylene, hexamethylbenzene, and ethylbenzene; more preferably, the halogenated hydrocarbon solvent includes chlorine One or more of benzene, dichlorobenzene, and dichloromethane; more preferably, the aliphatic hydrocarbon solvent includes one or more of pentane, hexane, and octane; more preferably, the Alicyclic hydrocarbon solvents include one or more of cyclohexane, cyclohexanone, and toluene cyclohexanone; more preferably, the alcohol solvent includes one or more of methanol, ethanol, and isopropanol more preferably, the ester solvent includes one or more of methyl acetate, ethyl acetate and propyl acetate; more preferably, the ketone solvent includes acetone, 2-butanone, methyl isopropyl acetate One or more of butyl ketone; more preferably, the amide solvent includes one of dimethylformamide, hexamethylphosphoramide, N,N-dimethylformamide and dimethylacetamide one or more; more preferably, the solid content of the curing agent solution is 0.01%-100%, preferably 0.1%-50%, more preferably 0.1%-10%;

Preferably, the viscosity of the liquid curing agent or curing agent solution at 25°C is 0.01Pa·s～1Pa·s, preferably 0.02Pa·s～0.5Pa·s, more preferably 0.05Pa·s～0.2Pa·s s.

Further, the resin polymer includes epoxy resin and one or more of cyanate resin, phenolic resin, acrylic resin, benzoxazine resin, polyester resin; preferably, the epoxy resin includes Bisphenol A epoxy resin (such as Nanya NPEL-128, NPEL-127, NPEL-144, NPES-609, NPES-901, NPES-902, NPES-903, NPES-904, NPES-907, NPES-909, Guodu Chemical YD-001, YD-012, YD-013k, YD-014, YD-134, YD-134D, YD-134L, YD-136, YD-128, YD-127, produced by Huntsman

GY 2600,

GY 6010,

GY 6020,

MY 790-1,

LY 1556,

GY 507, etc.), bisphenol F epoxy resin (such as NPEF-170 produced by Nanya, EPALLOY 8220, EPALLOY 8220E, EPALLOY 8230 produced by CVC, and EPALLOY 8230 produced by Huntsman

GY 281,

GY 282,

GY 285,

PY306,

PY 302-2,

PY 313, etc.), novolac epoxy resin (such as NPPN-638S, NPPN-631 produced by Nanya, EPALLOY 8240, EPALLOY 8240, EPALLOY 8250, EPALLOY 8330, etc. produced by CVC), o-cresol epoxy resin (such as Nanya NPCN-701, NPCN-702, NPCN-703, NPCN-704, NPCN-704L, NPCN-704K80, etc.), multifunctional epoxy resins (such as NPPN-431A70 produced by Nanya, ERISYS GA-240 produced by CVC, etc.) ), cycloaliphatic epoxy resins (such as EPALLOY 5000, EPALLOY 5200, JE-8421, etc. produced by CVC), resorcinol epoxy resins (such as ERISYS RDGE produced by CVC), rubber-modified epoxy resins (such as CVC HyPox RA 95, HyPox RA 840, HyPox RA 1340, HyPox RF 928, HyPox RM 20, HyPox RM 22, HyPox RK 84L, HyPox RK 820, etc.), biphenyl epoxy resin (such as YX4000 produced by Mitsui Chemicals, Japan, etc.) YX4000K, YX4000H, YX4000HK, YL6121H, YL6121HN), dicyclopentadiene epoxy resin (such as CYDB-500, CYDB-700, CYDB-900, CYDB-400, CYDB-450A80, etc. produced by Yueyang Baling Petrochemical) one or more; preferably, the cyanate resin includes bisphenol A-type cyanate, bisphenol F-type cyanate, bisphenol E-type cyanate, bisphenol M-type cyanate, dicyclopentadiene One or more of alkene-type cyanate ester, novolac-type cyanate ester, tetramethyl bisphenol F-type cyanate ester; preferably, the phenolic resin includes linear phenol formaldehyde resin, linear bisphenol A formaldehyde resin, One or more of linear o-cresol formaldehyde resin, phenol aralkyl phenolic resin, nitrogen-containing phenolic resin, dicyclopentadiene phenolic resin, biphenyl phenolic resin, tetraphenolic ethane phenolic resin, and naphthenic phenolic resin Preferably, the acrylic resin includes monofunctional urethane acrylic resin, bifunctional aliphatic acrylic resin, trifunctional aliphatic acrylic resin, tetrafunctional aliphatic acrylic resin, polyester acrylic resin, bisphenol A epoxy acrylic resin, One or more of novolac epoxy acrylic resin, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, di-trimethylolpropane tetraacrylate; The oxazine resin includes bisphenol A type benzoxazine resin, bisphenol F type benzoxazine resin, bisphenol S type benzoxazine resin, dicyclopentadiene benzoxazine resin, biphenyl type benzoxazine resin One or more of resins, tetraphenolic ethane benzoxazine resins, and naphthenic benzoxazine resins; preferably, the The polyester resin includes one or more of bisphenol A type polyester resin, bisphenol F type polyester resin, dicyclopentadiene polyester resin, biphenyl type polyester resin, and naphthalene type polyester resin;

Preferably, the first curing agent includes aliphatic polyamine curing agent, alicyclic polyamine curing agent, aromatic amine curing agent, acid anhydride curing agent, polyamide curing agent, latent curing agent, synthetic resin curing agent One or more of; more preferably, the aliphatic polyamine type curing agent includes ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenetriamine, dimethylaminopropylamine , one or more of diethylaminopropylamine, trimethylhexamethylenediamine, dihexyltriamine, trimethylhexamethylenediamine, polyetherdiamine; more preferably, the alicyclic polyvalent Amine type curing agents include one of diaminomethylcyclohexane, montanediamine, aminoethyl oxazine, hexahydropyridine, diaminocyclohexane, diaminomethylcyclohexylmethane, and diaminocyclohexylmethane. one or more; more preferably, the aromatic amine curing agent includes m-phenylenediamine, m-xylylenediamine, diaminodiphenylmethane, bicyclic fluorene diamine, diaminodiphenylsulfone, 4-chlorine One or more of o-phenylenediamine; more preferably, the acid anhydride curing agent includes benzophenone tetracarboxylic dianhydride, methylendometyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride Formic anhydride, methyltetrahydrophthalic anhydride, glutaric anhydride, polyazelaic anhydride, dichloromaleic anhydride, methylhexahydrophthalic anhydride, phthalic anhydride, trimellitic anhydride, homogenous phthalic anhydride, trimellitic dianhydride, benzophenone tetracarboxylic dianhydride, maleic anhydride, dodecyl maleic anhydride, succinic anhydride, hexahydrophthalic anhydride, cyclopentane One or more of tetracarboxylic dianhydride and dimaleic anhydride methylethylbenzene; more preferably, the latent curing agent includes dicyandiamide, boron trifluoride monoethylamine, boron trifluoride styrene ethyl amine Amine, boron trifluoride o-methylaniline, boron trifluoride bisamine, boron trifluoride dimethylaniline, boron trifluoride ethylaniline, boron trifluoride pyridine, MS-1 microcapsules, MS-2 One or more of microcapsules and sebacic acid trihydrazide; more preferably, the synthetic resin curing agent includes aniline formaldehyde resin, active ester, acid anhydride modified polybutadiene, phenol formaldehyde resin, novolac one or more of the resins.

Preferably, the curing accelerator includes imidazoles, phenol, bisphenol A, resorcinol, 2,4,6-tris(dimethylaminomethylene)phenol, benyldimethylamine, acylguanidine, One or more of benzoyl oxide, copper acetylacetonate, aluminum acetylacetonate, zirconium acetylacetonate; more preferably, the imidazoles include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-Undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2 -Phenylimidazole, 1,2-dimethylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2 -Undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole trimellitate, 1-cyanoethyl-2-undecylimidazole trimellitic acid salt, 1-cyanoethyl-2-phenylimidazole trimellitic acid salt, 1-cyanoethyl-2-ethyl-4-methylimidazole trimellitic acid salt, 2,4-diamino -6(2'-methylimidazole-(1'))ethyl-S-triazine, 2,4-diamino-6(2'-ethyl-4'-methylimidazole-(1')) Ethyl-S-triazine, 2,4-diamino-6(2'-undecylimidazole-(1'))ethyl-S-triazine, 2-methylimidazole-trimeric isocyanate salt, 2-phenylimidazole-trimeric isocyanate, 2,4-diamino-6(2'-methylimidazole-(1'))ethyl-S-triazine trimeric isocyanate, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-cyanoethyl-2-phenyl-4,5-dicyanoethyl In 1-β-aminoethyl-2-methylimidazole, 1-β-aminoethyl-2-ethylimidazole, 2-phenyl-4-benzyl-5-hydroxymethylimidazole one or more of;

Preferably, the additives include flame retardants, leveling agents, and defoaming agents;

Preferably, the solvent is selected from volatile solvents, including aromatic solvents, halogenated hydrocarbon solvents, aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents, alcohol solvents, ester solvents, ketone solvents, and amide solvents. one or more; more preferably, the aromatic solvent includes one or more of xylene, ortho-xylene, meta-xylene, para-xylene, hexamethylbenzene, ethylbenzene; more preferably, The halogenated hydrocarbon solvent includes one or more of chlorobenzene, dichlorobenzene, and dichloromethane; more preferably, the aliphatic hydrocarbon solvent includes one or more of pentane, hexane, and octane. more preferably, the alicyclic hydrocarbon solvent includes one or more of cyclohexane, cyclohexanone, and toluene cyclohexanone; more preferably, the alcohol solvent includes methanol, ethanol, isopropyl one or more of alcohols; more preferably, the ester solvent includes one or more of methyl acetate, ethyl acetate, and propyl acetate; more preferably, the ketone solvent includes acetone, One or more of 2-butanone and methyl isobutyl ketone; more preferably, the amide solvents include dimethylformamide, hexamethylphosphoramide, N,N-dimethylformamide, One or more of dimethylacetamide.

In another aspect, the present invention provides an insulating adhesive film material, characterized in that, the insulating adhesive film material is composed of a three-layer structure, and the three-layer structure includes an insulating polymer composite layer, a thin film material and a protective film, and the The insulating polymer composite layer is supported by a film material, and the surface of the insulating polymer composite layer is covered with a protective film;

The insulating polymer composite layer is made of any one of the electronic pastes described above.

Further, the film material is selected from polymer film material or paper-based film material; preferably, the polymer film material includes polyester film (PET), polyetheretherketone film (PEEK), polyetherimide film (PEI), polyimide film (PI), polycarbonate film (PC); preferably, the paper-based film material includes release paper and coated paper;

Preferably, the protective film is selected from polymer film materials; more preferably, the polymer film materials include polyester film (PET), polypropylene film (OPP), and polyethylene film (PE);

Preferably, the thickness of the insulating polymer composite layer is 1 μm˜100 μm, preferably 10 μm˜50 μm, more preferably 15 μm˜30 μm;

Preferably, the thickness of the thin film material is 10 μm to 300 μm, preferably 20 μm to 100 μm, more preferably 30 μm to 60 μm; the insulating polymer composite electronic paste can form a uniform and smooth film on the surface of the supporting film material;

Preferably, the protective film has a thickness of 10 μm to 300 μm, preferably 20 μm to 100 μm, and more preferably 30 μm to 60 μm.

In another aspect, the present invention provides a method for preparing the above-mentioned insulating adhesive film material, comprising the following steps:

1) coating the electronic paste for preparing the insulating polymer composite layer on the surface of the film material, and then drying;

2) After drying, it is attached to the protective film to form the insulating adhesive film material.

Preferably, the coating method of the electronic paste includes gravure printing, micro gravure printing, comma doctor blade, slit extrusion;

Preferably, the drying temperature is 50-150° C., and the drying time is 1-10 min;

Preferably, the bonding temperature is 25-150°C, and the bonding time is 1-10 min;

Preferably, the preparation method of the electronic paste is to mix the raw material components of the electronic paste, and achieve uniform dispersion among the components through stirring, ball milling, sand milling or ultrasonic dispersion to form the electronic paste.

In another aspect, the present invention provides an application of the above-mentioned insulating adhesive film material in semiconductor electronic packaging.

The beneficial effects of the present invention are: after the second curing agent is used to treat the surface of the inorganic filler material, the second curing agent will coat the surface of the inorganic filler material, and the filler will be introduced into the polymer matrix to make the resin in the filler material The surface solidifies rapidly, making the filler material and the polymer matrix more closely combined and reducing pores, thereby increasing the glass transition temperature of the insulating polymer composite (usually after the filler is introduced into the polymer matrix, due to the filler surface and the polymer matrix) The interface, pores, etc. formed by poor contact between the two will cause the glass transition temperature of the polymer composite to further decrease), and the glass transition temperature of the insulating polymer composite after coating, drying and curing of the electronic paste of the present invention is high. At 120°C (if the glass transition temperature of the cured product is lower than 120°C, the electronic device prepared by using this material will easily fail during use, which is not conducive to the long-term stable operation of the device). In addition, this method will also improve the insulating properties and mechanical properties of the polymer composites to a certain extent.

The insulating adhesive film material of the invention can be applied to semiconductor electronic packages such as printed circuit boards (PCBs), substrates, carrier boards, etc., to realize the manufacture of fine electronic circuits.

Description of drawings

Fig. 1 is a schematic structural diagram of an inorganic filler material for surface treatment with a second curing agent according to the present invention, wherein 1-a is the second curing agent, and 1-b is the inorganic filler.

2 is a schematic structural diagram of an insulating polymer composite layer containing an inorganic filler material surface-treated with a second curing agent, wherein 2-1 is an inorganic filler material surface-treated with a second curing agent, 2-2 For resin polymer.

3 is a cross-sectional scanning electron microscope image of the insulating polymer composite in Example 1 of the present invention.

4 is a cross-sectional scanning electron microscope image of the insulating polymer composite in Example 2 of the present invention.

5 is a cross-sectional scanning electron microscope image of the insulating polymer composite in Example 3 of the present invention.

6 is a cross-sectional scanning electron microscope image of the insulating polymer composite in Comparative Example 1. FIG.

FIG. 7 is a cross-sectional scanning electron microscope image of the insulating polymer composite in Comparative Example 2. FIG.

Detailed ways

In order to make the above objects, features and advantages of the present invention more clearly understood, the specific embodiments of the present invention are described in detail below with reference to the accompanying drawings, but should not be construed as limiting the scope of implementation of the present invention.

The schematic structural diagram of the inorganic filler material surface-treated with the second curing agent is shown in FIG. 1 , wherein 1-a is the second curing agent, and 1-b is the inorganic filler material. The schematic diagram of the structure of the insulating polymer composite layer containing the inorganic filler material surface-treated with the second curing agent is shown in Figure 2, wherein 2-1 is the inorganic filler material surface-treated with the second curing agent, 2-2 For resin polymer.

Example 1

Preparation of Inorganic Filling Material Surface-treated with the Second Curing Agent: Dissolve 0.02g of dicyandiamide in 10g of N,N-dimethylformamide to prepare N,N-dimethylformamide of dicyandiamide The formamide solution was slowly added with 10 g of spherical alumina while ultrasonically stirred at 40 kHz for 4 hours, and then ball-milled at 600 rpm for 12 hours to obtain alumina particles modified with a curing agent.

Preparation of electronic paste: 5g epoxy resin EPALLOY 8220, 8g cyanate ester resin CE05CS, 0.3g dicyandiamide, 0.01g 2-ethyl-4-methylimidazole, 3g using the second curing agent for surface treatment. Inorganic fillers, 0.3 g of nonylphenol polyoxyethylene ether, 10 g of N,N-dimethylformamide, and 10 g of butanone were mixed, and the electronic slurry was obtained after ball milling at 600 rpm for 12 hours.

Preparation of insulating film material: 1) The electronic paste prepared for insulating polymer composite layer was coated on the surface of PET film with a thickness of 50 μm using comma blade coating method, and then dried. After drying, the thickness of insulating polymer composite layer was obtained. Controlled to 20μm, the drying process uses a segmented oven, and the temperature of the oven is increased in stages, starting from the coating end, the temperature of the oven is set to 60°C, 80°C, 100°C, 110°C, 120°C; 2) Insulation after drying The polymer composite film and the OPP film with a thickness of 20 μm were hot-pressed and compounded. During the hot-pressing process, the temperature of the heating roller was set to 70° C. After hot-pressing, an insulating adhesive film material with a three-layer structure was obtained.

Performance measurement: peel off the OPP protective film, solidify the insulating film material, and the curing heating curve is that the temperature rises from room temperature to 120 ° C for 30 minutes, peels off the PET film, then heats up to 200 ° C for 60 minutes, and determines the glass transition temperature of the insulating polymer composite. is 200℃;

The cross-section of the insulating polymer composite was scanned by electron microscope, and the results are shown in Figure 3. It can be seen from the figure that the alumina particles are well combined with the resin polymer, without pores and cracks.

Example 2

Preparation of Inorganic Filling Material Surface-treated with Second Curing Agent: Dissolve 0.2 g of dicyandiamide in 10 g of N,N-dimethylformamide to prepare N,N-dimethylformamide of dicyandiamide Formamide solution was slowly added with 10 g spherical silica while ultrasonically stirred at 40 kHz for 4 hours, and then ball-milled at 600 rpm for 12 hours to obtain spherical silica modified with curing agent.

Preparation of electronic paste: 2g epoxy resin HyPox RK 84, 10g epoxy resin NPES-902, 8g cyanate ester resin CE05CS, 0.8g dicyandiamide, 0.03g 2-ethyl-4-methylimidazole, 5g The inorganic fillers surface-treated with the second curing agent, 0.3g of nonylphenol polyoxyethylene ether, 10g of N,N-dimethylformamide, and 10g of methyl ethyl ketone were mixed, and the electronic paste was obtained after ball milling at 600rpm for 12 hours .

Performance measurement: peel off the OPP protective film, solidify the insulating film material, the curing heating curve is the temperature rise from room temperature to 120 ℃ for 30 minutes, peel off the PET film, then heat up to 200 ℃ for 60 minutes, and measure the glass transition temperature of the insulating polymer compound is 185℃;

The cross section of the insulating polymer composite was scanned by electron microscope, and the results are shown in Figure 4. It can be seen from the figure that the silica particles are well combined with the resin polymer, with no pores and less cracking.

Example 3

Preparation of Inorganic Filling Material Surface-treated with Second Curing Agent: Dissolve 0.3 g of boron trifluoride phenethylamine in 10 g of butanone to prepare a butanone solution of boron trifluoride phenethylamine. 10 g of spherical silica inorganic filler material was placed in a warming container and heated to 80° C., and then the boron trifluoride acetophenone solution was slowly and gradually added, while stirring rapidly for 4 h to obtain spherical silica modified with a curing agent.

Preparation of electronic paste: 2g epoxy resin HyPox RK 84, 15g epoxy resin NPES-902, 5g cyanate ester resin CE05CS, 0.5g dicyandiamide, 0.03g 2-ethyl-4-methylimidazole, 8g The inorganic fillers surface-treated with the second curing agent, 0.3g of nonylphenol polyoxyethylene ether, 10g of N,N-dimethylformamide, and 10g of methyl ethyl ketone were mixed, and the electronic paste was obtained after ball milling at 600rpm for 12 hours .

Performance measurement: peel off the OPP protective film, solidify the insulating film material, the curing heating curve is the temperature rise from room temperature to 120 ℃ for 30 minutes, peel off the PET film, then heat up to 200 ℃ for 60 minutes, and measure the glass transition temperature of the insulating polymer compound is 165℃;

The cross section of the insulating polymer composite was scanned by electron microscope, and the results are shown in Figure 5. It can be seen from the figure that the silica particles are well combined with the resin polymer, with no pores and less cracking.

Comparative Example 1

Preparation of electronic paste: 2g epoxy resin HyPox RK 84, 15g epoxy resin NPES-902, 5g cyanate resin CE05CS, 1g dicyandiamide, 0.03g 2-ethyl-4-methylimidazole, 10g spherical Silica (without surface treatment), 0.3 g of nonylphenol polyoxyethylene ether, 10 g of N,N-dimethylformamide, and 20 g of methyl ethyl ketone were mixed, and the electronic slurry was obtained after ball milling at 600 rpm for 12 hours.

Performance measurement: peel off the OPP protective film, solidify the insulating film material, the curing heating curve is as follows: the temperature rises from room temperature to 120 °C for 30 minutes, peels off the PET film, then heats up to 200 °C for 60 minutes, and determines the glass transition temperature of the insulating polymer composite. is 136℃;

The cross-section of the insulating polymer composite was scanned by electron microscope, and the results are shown in Figure 6. It can be seen from the figure that the silica particles are poorly combined with the resin polymer, and there are many pores.

Comparative Example 2

Preparation of Inorganic Filling Material Surface-treated with Second Curing Agent: Dissolve 1.0 g of dicyandiamide in 10 g of N,N-dimethylformamide to prepare N,N-dimethylformamide of dicyandiamide The amide solution was slowly added with 10 g of spherical silica while ultrasonically stirred at 40 kHz for 4 h, and then ball-milled at 600 rpm for 12 hours to obtain spherical silica modified with a curing agent.

Performance measurement: peel off the OPP protective film, solidify the insulating film material, the curing heating curve is as follows: the temperature rises from room temperature to 120 °C for 30 minutes, peels off the PET film, then heats up to 200 °C for 60 minutes, and determines the glass transition temperature of the insulating polymer composite. is 139℃;

The cross section of the insulating polymer composite was scanned by electron microscope, and the result is shown in Figure 7. It can be seen from the figure that the silica particles are poorly bonded to the resin polymer, and there are many pores.

The above descriptions are only specific embodiments of the present invention, not all of the embodiments. Any equivalent transformations to the technical solutions of the present invention that are taken by those of ordinary skill in the art by reading the description of the present invention are covered by the claims of the present invention. .

Claims

An electronic paste is characterized in that, it is made from the following raw material components:

Resin polymer, first curing agent, curing accelerator, inorganic filler, dispersant, additive, solvent for surface treatment with second curing agent;

The second curing agent is a liquid curing agent or a curing agent solution, and the mass of the solute in the liquid curing agent or curing agent solution is 0.01-5% of the mass of the inorganic filler.
The electronic paste according to claim 1, wherein the mass of the resin polymer is 5-65% of the mass of the electronic paste, and the mass of the first curing agent is 2%- 120%, the mass of the curing accelerator is 0-1.5% of the mass of the resin polymer, and the mass of the inorganic filler that is surface-treated with the second curing agent is 10%-70% of the mass of the electronic paste, so The mass of the dispersant is 0-5% of the mass of the inorganic filler that is surface-treated with the second curing agent, the mass of the additive is 0-15% of the mass of the electronic paste, and the mass of the solvent is the mass of the electronic paste 15%-55% of the mass.
The electronic paste according to claim 1 or 2, wherein the mass of the solute in the liquid curing agent or curing agent solution is 0.1-3% of the mass of the inorganic filler;

Preferably, the mass of the solute in the liquid curing agent or curing agent solution is 0.2%-2% of the mass of the inorganic filler.
The electronic paste according to claim 1 or 2, wherein the method for surface treatment of the inorganic filler material with the second curing agent is a heating coating method or a solution dispersion method;

Preferably, the heating coating method specifically comprises placing the inorganic filler material in a container, and the temperature in the container is 10°C-200°C, preferably 20°C-150°C, more preferably 20°C-100°C, Then the second curing agent is slowly and gradually added, and at the same time, it is rapidly stirred for 20min-24h, preferably 1h-20h, more preferably 4h-15h, so as to obtain the inorganic filler which is surface-treated with the second curing agent;

Preferably, in the solution dispersion method, the second curing agent is placed in a container, and the inorganic filler is slowly and gradually added while ultrasonically stirring. 24h, preferably 1h-20h, more preferably 4h-15h, and then perform ball milling for 1h-48h, preferably 5h-30h, wherein the ball mill rotating speed is 50rpm-5000rpm, preferably 100rpm-1000rpm, to obtain the surface using the second curing agent. Processed inorganic filler materials.
The electronic paste according to claim 1 or 2, wherein the inorganic filler material comprises silicon dioxide, aluminum oxide, boron nitride, titanium dioxide, zinc oxide, zirconium oxide, magnesium oxide, calcium carbonate, titanic acid One or more of barium, strontium titanate, barium strontium titanate, lead zirconate titanate, calcium copper titanate, etc.; preferably, the particle size of the inorganic filler is 0.02-10 μm, preferably 0.05-3 μm , more preferably 0.2 to 1 μm;

Preferably, the liquid curing agent includes ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, aliphatic amine, alicyclic amine, aromatic amine, polyetheramine, polyamide, and liquid acid anhydride curing agent. one or more; more preferably, the liquid acid anhydride curing agent includes one or more of methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, and methylnadic anhydride ;

Preferably, the solute in the curing agent solution includes one or more of dicyandiamide, boron trifluoride phenethylamine, and phenolic resin; One or more of phenol A formaldehyde resin, linear o-cresol formaldehyde resin, XYLOK phenolic resin, nitrogen-containing phenolic resin, dicyclopentadiene phenolic resin, biphenyl phenolic resin; the solvent in the curing agent solution is selected from Volatile solvents, including one or more of aromatic solvents, halogenated hydrocarbon solvents, aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents, alcohol solvents, ester solvents, ketone solvents, and amide solvents; more preferably Preferably, the aromatic solvent includes one or more of xylene, o-xylene, m-xylene, p-xylene, hexamethylbenzene, and ethylbenzene; more preferably, the halogenated hydrocarbon solvent includes chlorine One or more of benzene, dichlorobenzene, and dichloromethane; more preferably, the aliphatic hydrocarbon solvent includes one or more of pentane, hexane, and octane; more preferably, the Alicyclic hydrocarbon solvents include one or more of cyclohexane, cyclohexanone, and toluene cyclohexanone; more preferably, the alcohol solvent includes one or more of methanol, ethanol, and isopropanol more preferably, the ester solvent includes one or more of methyl acetate, ethyl acetate and propyl acetate; more preferably, the ketone solvent includes acetone, 2-butanone, methyl isopropyl acetate One or more of butyl ketone; more preferably, the amide solvent includes one of dimethylformamide, hexamethylphosphoramide, N,N-dimethylformamide and dimethylacetamide one or more; more preferably, the solid content of the curing agent solution is 0.01%-100%, preferably 0.1%-50%, more preferably 0.1%-10%;

Preferably, the viscosity of the liquid curing agent or curing agent solution at 25°C is 0.01Pa·s～1Pa·s, preferably 0.02Pa·s～0.5Pa·s, more preferably 0.05Pa·s～0.2Pa·s s.
The electronic paste according to claim 1 or 2, wherein the resin polymer comprises epoxy resin and one of cyanate resin, phenolic resin, acrylic resin, benzoxazine resin and polyester resin one or more; preferably, the epoxy resin includes bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, o-cresol type epoxy resin, multifunctional epoxy resin, Alicyclic epoxy resin, resorcinol epoxy resin, rubber modified epoxy resin, polyurethane modified epoxy resin, biphenyl epoxy resin, dicyclopentadiene epoxy resin, naphthalene epoxy resin, anthracene One or more of epoxy resins; preferably, the cyanate resin includes bisphenol A-type cyanate ester, bisphenol F-type cyanate ester, bisphenol E-type cyanate ester, bisphenol M-type cyanate ester One or more of cyanate ester, dicyclopentadiene-type cyanate ester, novolac-type cyanate ester, tetramethylbisphenol F-type cyanate ester; preferably, the phenolic resin includes linear phenol-formaldehyde resin, Linear bisphenol A formaldehyde resin, linear ortho-cresol formaldehyde resin, phenol aralkyl phenolic resin, nitrogen-containing phenolic resin, dicyclopentadiene phenolic resin, biphenyl phenolic resin, tetraphenolic ethane phenolic resin, naphthenic phenolic resin One or more of resins; preferably, the acrylic resin includes monofunctional urethane acrylic resin, bifunctional aliphatic acrylic resin, trifunctional aliphatic acrylic resin, tetrafunctional aliphatic acrylic resin, polyester acrylic resin, difunctional aliphatic acrylic resin One or more of phenol A epoxy acrylic resin, novolac epoxy acrylic resin, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, di-trimethylolpropane tetraacrylate; preferably Preferably, the benzoxazine resin includes bisphenol A type benzoxazine resin, bisphenol F type benzoxazine resin, bisphenol S type benzoxazine resin, dicyclopentadiene benzoxazine resin, One or more of biphenyl benzoxazine resin, tetraphenol ethane benzoxazine resin, and naphthenic benzoxazine resin; preferably, the polyester resin includes bisphenol A type polyester One or more of resin, bisphenol F type polyester resin, dicyclopentadiene polyester resin, biphenyl type polyester resin and naphthalene type polyester resin;

Preferably, the first curing agent includes aliphatic polyamine curing agent, alicyclic polyamine curing agent, aromatic amine curing agent, acid anhydride curing agent, polyamide curing agent, latent curing agent, synthetic resin curing agent One or more of; more preferably, the aliphatic polyamine type curing agent includes ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenetriamine, dimethylaminopropylamine , one or more of diethylaminopropylamine, trimethylhexamethylenediamine, dihexyltriamine, trimethylhexamethylenediamine, polyetherdiamine; more preferably, the alicyclic polyvalent Amine type curing agents include one of diaminomethylcyclohexane, montanediamine, aminoethyloxazine, hexahydropyridine, diaminocyclohexane, diaminomethylcyclohexylmethane, and diaminocyclohexylmethane. one or more; more preferably, the aromatic amine curing agent includes m-phenylenediamine, m-xylylenediamine, diaminodiphenylmethane, bicyclic fluorene diamine, diaminodiphenylsulfone, 4-chlorine One or more of o-phenylenediamines; more preferably, the acid anhydride curing agent includes benzophenone tetracarboxylic dianhydride, methyl endomethylene tetrahydrophthalic anhydride, tetrahydrophthalic anhydride Formic anhydride, methyltetrahydrophthalic anhydride, glutaric anhydride, polyazelaic anhydride, dichloromaleic anhydride, methylhexahydrophthalic anhydride, phthalic anhydride, trimellitic anhydride, homogenous phthalic anhydride, trimellitic dianhydride, benzophenone tetracarboxylic dianhydride, maleic anhydride, dodecyl maleic anhydride, succinic anhydride, hexahydrophthalic anhydride, cyclopentane One or more of tetracarboxylic dianhydride and dimaleic anhydride methylethylbenzene; more preferably, the latent curing agent includes dicyandiamide, boron trifluoride monoethylamine, boron trifluoride styrene Amine, boron trifluoride o-methylaniline, boron trifluoride bisamine, boron trifluoride dimethylaniline, boron trifluoride ethylaniline, boron trifluoride pyridine, MS-1 microcapsules, MS-2 One or more of microcapsules and sebacic acid trihydrazide; more preferably, the synthetic resin curing agent includes aniline formaldehyde resin, active ester, acid anhydride modified polybutadiene, phenol formaldehyde resin, novolac one or more of resins;

Preferably, the curing accelerator includes imidazoles, phenol, bisphenol A, resorcinol, 2,4,6-tris(dimethylaminomethylene)phenol, benyldimethylamine, acylguanidine, One or more of benzoyl oxide, copper acetylacetonate, aluminum acetylacetonate, zirconium acetylacetonate; more preferably, the imidazoles include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-Undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2 -Phenylimidazole, 1,2-dimethylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2 -Undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole trimellitate, 1-cyanoethyl-2-undecylimidazole trimellitic acid salt, 1-cyanoethyl-2-phenylimidazole trimellitic acid salt, 1-cyanoethyl-2-ethyl-4-methylimidazole trimellitic acid salt, 2,4-diamino -6(2'-methylimidazole-(1'))ethyl-S-triazine, 2,4-diamino-6(2'-ethyl-4'-methylimidazole-(1')) Ethyl-S-triazine, 2,4-diamino-6(2'-undecylimidazole-(1'))ethyl-S-triazine, 2-methylimidazole-trimeric isocyanate salt, 2-phenylimidazole-trimeric isocyanate, 2,4-diamino-6(2'-methylimidazole-(1'))ethyl-S-triazine trimeric isocyanate, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-cyanoethyl-2-phenyl-4,5-dicyanoethyl In 1-β-aminoethyl-2-methylimidazole, 1-β-aminoethyl-2-ethylimidazole, 2-phenyl-4-benzyl-5-hydroxymethylimidazole one or more of;

Preferably, the additives include flame retardants, leveling agents, and defoaming agents;

Preferably, the solvent is selected from volatile solvents, including aromatic solvents, halogenated hydrocarbon solvents, aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents, alcohol solvents, ester solvents, ketone solvents, and amide solvents. one or more; more preferably, the aromatic solvent includes one or more of xylene, ortho-xylene, meta-xylene, para-xylene, hexamethylbenzene, ethylbenzene; more preferably, The halogenated hydrocarbon solvent includes one or more of chlorobenzene, dichlorobenzene, and dichloromethane; more preferably, the aliphatic hydrocarbon solvent includes one or more of pentane, hexane, and octane. more preferably, the alicyclic hydrocarbon solvent includes one or more of cyclohexane, cyclohexanone, and toluene cyclohexanone; more preferably, the alcohol solvent includes methanol, ethanol, isopropyl one or more of alcohols; more preferably, the ester solvent includes one or more of methyl acetate, ethyl acetate, and propyl acetate; more preferably, the ketone solvent includes acetone, One or more of 2-butanone and methyl isobutyl ketone; more preferably, the amide solvents include dimethylformamide, hexamethylphosphoramide, N,N-dimethylformamide, One or more of dimethylacetamide.
An insulating adhesive film material, characterized in that the insulating adhesive film material is composed of a three-layer structure, the three-layer structure includes an insulating polymer compound layer, a film material and a protective film, and the insulating polymer compound layer is composed of a film Material support, the surface of the insulating polymer composite layer is covered with a protective film;

The insulating polymer composite layer is made of the electronic paste of any one of claims 1-6.
The insulating adhesive film material according to claim 7, wherein the film material is selected from polymer film material or paper-based film material; preferably, the polymer film material comprises polyester film (PET), polyester film Ether ether ketone film (PEEK), polyetherimide film (PEI), polyimide film (PI), polycarbonate film (PC); film paper;

Preferably, the protective film is selected from polymer film materials; more preferably, the polymer film materials include polyester film (PET), polypropylene film (OPP), and polyethylene film (PE);

Preferably, the thickness of the insulating polymer composite layer is 1 μm˜100 μm, preferably 10 μm˜50 μm, more preferably 15 μm˜30 μm;

Preferably, the thickness of the thin film material is 10 μm˜300 μm, preferably 20 μm˜100 μm, more preferably 30 μm˜60 μm;

Preferably, the protective film has a thickness of 10 μm to 300 μm, preferably 20 μm to 100 μm, and more preferably 30 μm to 60 μm.
The preparation method of the insulating adhesive film material according to claim 7 or 8, characterized in that, comprising the following steps:

1) coating the electronic paste for preparing the insulating polymer composite layer on the surface of the film material, and then drying;

2) After drying, it is bonded with a protective film to form the insulating film material;

Preferably, the coating method of the electronic paste includes gravure printing, micro gravure printing, comma doctor blade, slit extrusion;

Preferably, the drying temperature is 50-150° C., and the drying time is 1-10 min;

Preferably, the bonding temperature is 25-150°C, and the bonding time is 1-10 min;

Preferably, the preparation method of the electronic paste is to mix the raw material components of the electronic paste, and achieve uniform dispersion among the components through stirring, ball milling, sand milling or ultrasonic dispersion to form the electronic paste.
Application of the insulating adhesive film material according to claim 7 or 8 in semiconductor electronic packaging.