CN115537160A - Insulating adhesive film material for preparing fine circuit and preparation method thereof - Google Patents

Insulating adhesive film material for preparing fine circuit and preparation method thereof Download PDF

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CN115537160A
CN115537160A CN202211088067.6A CN202211088067A CN115537160A CN 115537160 A CN115537160 A CN 115537160A CN 202211088067 A CN202211088067 A CN 202211088067A CN 115537160 A CN115537160 A CN 115537160A
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protective film
film
resin
polymer
polymer protective
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孙蓉
于均益
罗遂斌
于淑会
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Shenzhen Institute of Advanced Electronic Materials
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Shenzhen Institute of Advanced Electronic Materials
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/52—Encapsulations
    • H01L33/56—Materials, e.g. epoxy or silicone resin
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Power Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention discloses an insulating glue film material for preparing a fine circuit and a preparation method thereof, and particularly comprises a polymer compound consisting of a glue film layer and a carrier film and a polymer protective film covering the surface of the glue film layer by hot pressing or rolling; the roughness Ra of the polymer protective film is 5 nm-1 mu m; the thermal expansion coefficient is 10ppm/K to 300ppm/K; the softening temperature point is 40-350 ℃; the elongation at break is 10-1000%. According to the invention, the polymer protective film has proper thermal expansion coefficient, softening point and elongation at break, so that the processing performance of the insulating adhesive film can be ensured.

Description

Insulating adhesive film material for preparing fine circuit and preparation method thereof
Technical Field
The invention belongs to the technical field of electronic packaging materials, and particularly relates to an insulating adhesive film material applied to semiconductor system-level packaging.
Technical Field
With the development of electronic information technology, especially the rapid development mainly based on wearable electronics, smart phones, ultra-thin computers, unmanned driving, internet of things technology and 5G communication technology in recent years, increasingly high requirements are put forward on the aspects of miniaturization, lightness, thinness, multiple functions, high performance and the like of electronic systems. For this reason, the number of layers of integrated circuits is increasing, and line widths are decreasing to increase wiring density. With the improvement of chip processing capability, the trend of high line density of the substrate is also developing towards multi-layer. The insulating adhesive film is required to have better line filling capability and reliability.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a laminated insulating adhesive film material which can be used for conductor packaging and is suitable for preparing fine circuits by an additive method or a semi-additive method.
In order to achieve the purpose of the invention, the invention adopts the following technical scheme.
One aspect of the invention provides an insulating glue film material, which consists of a polymer compound consisting of a glue film layer and a carrier film and a polymer protective film covered on the surface of the glue film layer by hot pressing or rolling; the surface of the polymer protective film is subjected to release treatment; the adhesive film layer is made of slurry containing a resin composition, filler particles, a resin curing agent, other auxiliaries and a solvent;
the roughness Ra of the polymer protective film is 5 nm-1 mu m;
the polymer protective film has a Coefficient of Thermal Expansion (CTE) of 10ppm/K to 300ppm/K;
the softening temperature point of the polymer protective film is 40-350 ℃;
the elongation at break of the polymer protective film is 10-1000%.
Further, the polymer protective film comprises a molecular structure
Figure RE-GDA0003901475080000011
Figure RE-GDA0003901475080000012
Figure RE-GDA0003901475080000021
One or more of (a).
Further, the release treatment method is release treatment by one or more methods of silicon-containing release agent, silicon-free release agent, fluoroplastic release agent, corona, sanding and polishing.
Further, the polymer protective film has a thickness of 5 to 200. Mu.m, preferably 20 to 100. Mu.m, and more preferably 20 to 40 μm.
Further, the Coefficient of Thermal Expansion (CTE) of the polymer protective film is preferably 15ppm/K to 200ppm/K, more preferably 35ppm/K to 160ppm/K.
Further, the softening temperature point of the polymer protective film is preferably 50 to 250 ℃, and more preferably 60 to 200 ℃.
Further, the roughness Ra of the polymer protective film is preferably 10nm to 0.8 μm, and more preferably 10nm to 200nm.
Further, the tensile strength of the polymer protective film is 50 to 150MPa, preferably 70 to 130MPa.
Further, the elongation at break of the polymer protective film is more than 120-1000%, preferably 150-500%.
Further, the polymer composite has a coefficient of thermal expansion CTE of 5ppm/K to 200ppm/K, preferably 30ppm/K to 150ppm/K, and more preferably 40ppm/K to 100ppm/K.
Further, the polymer composite has an elongation at break before curing of 1% to 300%, preferably 30% to 200%, more preferably 50% to 160%.
Further, the resin composition is selected from one or more of epoxy resin, rubber resin, phenolic resin, polyester resin, polyamide resin, urea resin, melamine formaldehyde resin, furan resin, organic silicon resin, polyester resin, acrylic resin, cyanate resin, vinyl resin, hydrocarbon resin and polyether resin. Wherein the epoxy resin is selected from one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, phenolic aldehyde epoxy resin, o-cresol formaldehyde epoxy resin, polyfunctional epoxy resin, alicyclic epoxy resin, resorcinol epoxy resin, rubber modified epoxy resin, polyurethane modified epoxy resin, biphenyl epoxy resin, dicyclopentadiene epoxy resin and epoxy resin. The rubber resin is selected from one or more of styrene-butadiene rubber, isoprene rubber, ethylene propylene rubber, chloroprene rubber, nitrile rubber, chloroprene rubber, chlorine-based rubber, fluorine rubber, epichlorohydrin rubber, silicone rubber, polyurethane rubber, polysulfide rubber and acrylate rubber. The phenolic resin comprises one or more of linear phenol formaldehyde resin, linear bisphenol A formaldehyde resin, linear o-cresol formaldehyde resin, phenol aralkyl phenolic resin, nitrogen-containing phenolic resin, dicyclopentadiene phenolic resin, biphenyl type phenolic resin, tetraphenol ethane phenolic resin and naphthalene type phenolic resin. The polyester resin comprises one or more of bisphenol A polyester resin, bisphenol F polyester resin, dicyclopentadiene polyester resin, biphenyl polyester resin and naphthalene polyester resin. The acrylic resin comprises one or more of monofunctional polyurethane acrylic resin, difunctional aliphatic acrylic resin, trifunctional aliphatic acrylic resin, tetrafunctional aliphatic acrylic resin, polyester acrylic resin, bisphenol A epoxy acrylic resin, novolac epoxy acrylic resin, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate and di-trimethylolpropane tetraacrylate. The polyester resin comprises one or more of bisphenol A polyester resin, bisphenol F polyester resin, dicyclopentadiene polyester resin, biphenyl polyester resin and naphthalene polyester resin.
Further, the resin curing agent is selected from aliphatic polyamine curing agents, alicyclic polyamine curing agents, latent curing agents, acid anhydride curing agents, aromatic amine curing agents, polyamide curing agents, and synthetic resin curing agents. Still further, the aliphatic polyamine-type curing agent is selected from ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenetriamine, dimethylaminopropylamine, diethylaminopropylamine, trimethylhexamethylenediamine, dihexyltriamine, trimethylhexamethylenediamine, polyether diamine, etc.; the alicyclic polyamine type curing agent is selected from diaminomethylcyclohexane, menthane diamine, aminoethyl guazine, hexahydropyridine, diaminocyclohexane, diaminomethylcyclohexylmethane, diaminocyclohexylmethane and the like; the latent curing agent is selected from dicyandiamide, boron trifluoride monoethylamine, boron trifluoride phenethylamine, boron trifluoride o-methylbenzylamine, boron trifluoride benzylamine, boron trifluoride dimethylaniline, boron trifluoride ethylaniline, boron trifluoride pyridine, MS-1 microcapsule, MS-2 microcapsule, sebacic acid trihydrazide and the like; the acid anhydride curing agent is selected from benzophenonetetracarboxylic dianhydride, methyl endomethyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, glutaric anhydride, polyazelaic anhydride, dichloromaleic anhydride, methylhexahydrophthalic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, benzophenonetetracarboxylic anhydride, maleic anhydride, dodecylmaleic anhydride, succinic anhydride, hexahydrophthalic anhydride, cyclopentanetetracarboxylic anhydride, difaleic anhydride methyl ethyl benzene, etc.; the aromatic amine curing agent is selected from m-phenylenediamine, m-xylylenediamine, diaminodiphenylmethane, dicyclo-fluorene diamine, diaminodiphenyl sulfone, 4-chloro-o-phenylenediamine and the like; the synthetic resin curing agent is selected from one or more of aniline formaldehyde resin, phenol formaldehyde resin, linear phenolic resin, etc.
Further, the inorganic filler is one or more of silicon dioxide, aluminum oxide, boron nitride, titanium dioxide, zinc oxide, zirconium oxide, magnesium oxide, calcium carbonate, barium titanate, strontium titanate, barium strontium titanate, lead zirconate titanate, copper calcium titanate and the like. The size of the inorganic filler is 20nm to 10 μm, preferably 50nm to 3 μm, more preferably 200nm to 1 μm, or a mixture of multiple scales. The shape of the inorganic filler particles is mainly spherical or spheroidal particles, and particles of other shapes such as rods, wires, flakes, etc. may also be present in part. The inorganic filler particles account for 20% to 80%, preferably 30% to 60%, more preferably 45% to 55% of the mass of the volatile components such as solvent-free solid components of the composite.
Further, the carrier film is selected from a polymer film material and a paper base film material, and further selected from a polyester film (PET), a polyether ether ketone film (PEEK), a polyetherimide film (PEI), a polyimide film (PI), a polycarbonate film (PC), a release paper, a coated paper, and the like. The carrier film is selected from carrier films with release films, and the release films are selected from silicon-containing release films, silicon-free release films, fluoroplastic release films, corona release films, frosted release films, polished release films and matte release films. The thickness of the supporting carrier film is 10 to 300 μm, preferably 20 to 100 μm, and more preferably 30 to 60 μm.
The solvent is selected from one or more of volatile solvents including aromatic solvents, halogenated hydrocarbon solvents, aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents, alcohol solvents, ester solvents, ketone solvents and amide solvents; more preferably, the aromatic solvent comprises one or more of xylene, o-xylene, m-xylene, p-xylene, hexamethylbenzene, ethylbenzene; more preferably, the halogenated hydrocarbon solvent comprises one or more of chlorobenzene, dichlorobenzene, dichloromethane; more preferably, the aliphatic hydrocarbon solvent comprises one or more of pentane, hexane, octane; more preferably, the alicyclic hydrocarbon solvent comprises one or more of cyclohexane, cyclohexanone, toluene cyclohexanone; more preferably, the alcoholic solvent comprises one or more of methanol, ethanol, isopropanol; more preferably, the ester solvent comprises one or more of methyl acetate, ethyl acetate and propyl acetate; more preferably, the ketone solvent comprises one or more of acetone, butanone, methyl isobutyl ketone; more preferably, the amide solvent comprises one or more of dimethylformamide, hexamethylphosphoramide, N-dimethylformamide, and dimethylacetamide.
Further, the auxiliary agent is selected from one or more of epoxy resin curing accelerator, dispersing agent, defoaming agent, leveling agent and coupling agent.
The epoxy resin curing accelerator comprises phenol, bisphenol A, resorcinol, 2,4,6-tri (dimethylamino methylene) phenol, benzyl dimethylamine, acyl guanidine, benzoyl peroxide, copper acetylacetonate, aluminum acetylacetonate, zirconium acetylacetonate and imidazoles, wherein the imidazoles are selected from one or more of 2-methylimidazole, 2-ethylimidazole, 2,4-diethylimidazole, 2-methyl-4-ethylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole and the like.
The dispersing agent is selected from fatty acids, such as polyethylene glycol fatty acid ester, sodium fatty acid methyl ester sulfonate, sucrose fatty acid ester, polyglycerol fatty acid ester, fatty acid polyoxyethylene ether, nonylphenol polyoxyethylene ether, polyoxyethylene sorbitan fatty acid ester, polyvinylpyrrolidone K30, polyvinylpyrrolidone K90, sodium lignosulfonate, polyacrylamide, sodium dodecylbenzene sulfonate, sodium methylene bis-methylnaphthalene sulfonate, and one or more of esters and fatty amides.
The defoaming agent is selected from one or more of organic silicon defoaming agents, polyether defoaming agents and polyether modified polysiloxane defoaming agents.
The leveling agent is selected from one or more of polydimethylsiloxane, polyether polyester modified organic siloxane, alkyl modified organic siloxane, end group modified organic silicon, organic modified polysiloxane acrylic leveling agent and acrylate leveling agent.
The coupling agent is preferably a silane coupling agent with the general formula of RSiX3, wherein R represents amino, sulfydryl, vinyl, epoxy, cyano, methacryloxy and other groups, and X represents a hydrolyzable alkoxy (such as methoxy, ethoxy and the like). Such as KH550, KH560, KH570, KH792, DL602, DL 171.
The polymer composite suitable for the protective film has a Coefficient of Thermal Expansion (CTE) of 5ppm/K to 200ppm/K; the elongation at break before curing is 1% -300%;
the invention also provides application of the insulating glue film material in preparing packaging materials for Printed Circuit Boards (PCBs), substrates, carrier plates and semiconductor electronics.
In another aspect, the present invention provides a method for preparing the above insulating adhesive film material, which comprises the following steps:
s1) weighing raw materials for preparing slurry;
s2) mixing the raw materials for preparing the slurry, and coating the mixture on the surface of a carrier membrane to form a polymer composite;
and S3) attaching the polymer protective film to the surface of the polymer compound through hot pressing or rolling to prepare the insulating adhesive film material.
Further, the pressing temperature of hot pressing or rolling in S3) is 25-200 ℃, preferably 25-150 ℃, and more preferably 25-100 ℃.
In a further aspect, the present invention provides a use of a polymer protective film as a protective film for a packaging adhesive film for printed wiring boards (PCBs), substrates, carrier boards, semiconductor electronics;
the roughness Ra of the polymer protective film is 5 nm-1 mu m;
the polymer protective film has a Coefficient of Thermal Expansion (CTE) of 10ppm/K to 300ppm/K;
the softening temperature point of the polymer protective film is 40-350 ℃;
the elongation at break of the polymer protective film is 10-1000%.
Further, the Coefficient of Thermal Expansion (CTE) of the packaging adhesive film is 5 ppm/K-200 ppm/K; the elongation at break of the packaging adhesive film before curing is 1-300%; the thermal expansion coefficient of the packaging adhesive film is preferably 30ppm/k-150ppm/k, more preferably 40ppm/k-100ppm/k; the elongation at break before curing is preferably from 30% to 200%, more preferably from 50% to 160%.
Advantageous effects
The prepared adhesive film has good surface appearance, no holes, no defects, uniform thickness, good line filling capability and high reliability.
Drawings
FIG. 1 is a schematic structural diagram of an insulating adhesive film material, in which 1-1 is a polymer composite and 1-2 is a polymer protective film.
FIG. 2 is a photomicrograph of a filled cross-section of a line of insulating film material. 2-1 embodiment 1 insulating glue film material circuit filling cross section, 2-2 embodiment 2 insulating glue film material circuit filling cross section, 2-3 comparative example 1 insulating glue film material circuit filling cross section. 2-4 surface view of the insulation film material of comparative example 1 after peeling.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, specific embodiments accompanied with figures are described in detail below, but the present invention is not to be construed as limiting the implementable range thereof.
The embodiment provides an insulating glue film material which is suitable for being used for semiconductor packaging and is suitable for preparing fine lines by an additive method or a semi-additive method, and the insulating glue film material is prepared by the following steps:
the molecular structure of the polymer protective film is selected from
Figure RE-GDA0003901475080000061
Figure RE-GDA0003901475080000062
The polymer protective film has a Coefficient of Thermal Expansion (CTE) of 10ppm/K to 300ppm/K, preferably 15ppm/K to 200ppm/K, and more preferably 15ppm/K to 150ppm/K. The CTE is lower than 10ppm/K or higher than 300ppm/K, so that the difference between the elongation of the protective film and the elongation of the polymer composite is larger in the protective film attaching process, attaching dislocation is caused, defects are generated, and the quality of the adhesive film is influenced.
Because the polymer protective film needs to be attached by applying tension at a certain temperature, the softening temperature point of the polymer protective film is 40-350 ℃, preferably 50-250 ℃, and more preferably 60-200 ℃, the protective film is not influenced by the tension in the attaching process, and the excessive temperature in the attaching process can cause the curing of the polymer compound to influence the circuit filling, so that the excessive softening temperature point is not needed.
Stress with different degrees needs to be applied to the polymer protective film in the laminating process and in the rolling process after laminating is completed, so that the breaking elongation of the polymer protective film is 10% -1000%, preferably 50% -800%, more preferably 100% -500%, failure of the insulating adhesive film caused by breakage of the protective film is avoided, and the polymer composite is broken in the laminating process due to excessively high breaking elongation. The thickness of the polymer protective film is 5 to 200. Mu.m, preferably 20 to 100. Mu.m, and more preferably 20 to 40 μm. The roughness Ra of the polymer protective film is 5 nm-1 μm, preferably 10 nm-0.8 μm, more preferably 10 nm-0.5 μm, and when the Ra is less than 5nm, the excessively smooth surface is not favorable for the composite attachment of the protective film and the polymer, thereby causing defects such as bubbles and the like; when Ra is higher than 1 μm, it will affect the thickness error of the polymer composite, thereby causing a decrease in reliability thereof. The surface of the polymer protective film is subjected to release treatment by one or more methods of silicon-containing release agent, silicon-free release agent, fluoroplastic release agent, corona, sanding and polishing, so that the defect caused by transfer of the polymer compound to the polymer protective film during pressing is avoided.
Example 1
1. Weighing the following raw materials for preparing the slurry:
Figure RE-GDA0003901475080000063
Figure RE-GDA0003901475080000071
2. after ball milling for 12 hours at 600rpm, the obtained slurry is coated on the surface of a silicon-free release carrier film to form a polymer composite, the CTE of the prepared polymer composite is 50ppm/k, and the elongation at break before curing is 120%.
3. Drying at 120 deg.C for 5 min, and then at 60 deg.CAnd then, hot-pressing the polymer protective film on the surface of the polymer compound to prepare the insulating adhesive film material. The polymer protective film has a molecular structure comprising
Figure RE-GDA0003901475080000072
The surface is treated by a silicon-free release agent. The roughness Ra is 20nm, the breaking elongation is more than 360%, the tensile strength is 79MPa, the CTE is 109ppm/K, and the softening temperature point is 80 ℃.
4. And (3) carrying out vacuum hot pressing on the surface of the circuit by using the insulating adhesive film material at 100 ℃, and observing the filling capacity of the insulating adhesive film circuit. The lines fill well without holes (2-1 in fig. 2). The thickness error of the adhesive film is +/-4%.
Example 2
1. The following raw materials for preparing the slurry were weighed:
Figure RE-GDA0003901475080000073
2. after ball milling for 12 hours at 600rpm, the slurry is coated on the surface of a silicon-free release carrier membrane to form a polymer composite, the CTE of the prepared polymer composite is 40ppm/k, and the elongation at break before curing is 60%.
3. After drying at 120 ℃ for 5 minutes, hot pressing the polymer protective film on the surface of the polymer composite at 60 ℃ to prepare the insulating adhesive film material. The polymer protective film has a molecular structure comprising
Figure RE-GDA0003901475080000074
The surface is corona treated. The roughness Ra was 59nm, the elongation at break was 376%, the tensile strength was 90MPa, the CTE was 102ppm/K, and the softening point was 80 ℃.
4. And (3) carrying out vacuum hot pressing on the surface of the circuit by using the insulating adhesive film material at 100 ℃, and observing the filling capacity of the insulating adhesive film circuit. The lines fill well without holes (2-2 in fig. 2). The thickness error of the glue film is +/-6 percent.
Example 3
1. The following raw materials for preparing the slurry were weighed:
Figure RE-GDA0003901475080000081
2. after ball milling for 12 hours at 600rpm, the slurry is coated on the surface of a silicon-free release carrier membrane to form a polymer composite, the CTE of the prepared polymer composite is 45ppm/k, and the breaking elongation before curing is 120%.
3. After drying at 120 ℃ for 5 minutes, hot pressing the polymer protective film on the surface of the polymer composite at 60 ℃ to prepare the insulating adhesive film material. The polymer protective film has a molecular structure comprising
Figure RE-GDA0003901475080000082
The surface is treated by a parting agent. The roughness Ra is 100nm, the elongation at break is more than 150%, the tensile strength is 120MPa, the CTE is 40ppm/K, and the softening temperature point is 180 ℃.
4. And (3) carrying out vacuum hot pressing on the surface of the circuit by using the insulating adhesive film material at 105 ℃, and observing the filling capacity of the insulating adhesive film circuit. The lines are well filled and have no holes. The thickness error of the glue film is +/-5%.
Example 4
1. The following raw materials for preparing the slurry were weighed:
Figure RE-GDA0003901475080000083
Figure RE-GDA0003901475080000091
2. after ball milling for 12 hours at 600rpm, the slurry is coated on the surface of a silicon-free release carrier membrane to form a polymer composite, the CTE of the prepared polymer composite is 100ppm/k, and the elongation at break before curing is 150%.
3. After drying at 120 ℃ for 5 minutes, the polymer protective film is hot-pressed on the surface of the polymer composite at 60 ℃ to prepare the insulating adhesive film material. The polymer protective film has a molecular structure comprising
Figure RE-GDA0003901475080000092
The surface is corona treated. The roughness Ra is 190nm, the breaking elongation is more than 200%, the tensile strength is 100MPa, the CTE is 150ppm/K, and the softening temperature point is 160 ℃.
4. And (3) carrying out vacuum hot pressing on the surface of the circuit by using the insulating adhesive film material at 105 ℃, and observing the filling capacity of the insulating adhesive film circuit. The lines are well filled and have no holes. The thickness error of the glue film is +/-5%.
Comparative example 1
1. The following raw materials for preparing the slurry were weighed:
Figure RE-GDA0003901475080000093
2. ball milling is carried out for 12 hours at 600rpm, and the obtained slurry is coated on the surface of a fluoroplastic release carrier membrane to form a polymer composite.
3. After drying at 120 ℃ for 5 minutes, hot pressing the polymer protective film on the surface of the polymer composite at 60 ℃ to prepare the insulating adhesive film material. The polymer protective film has a molecular structure comprising
Figure RE-GDA0003901475080000094
The surface is corona treated. The roughness Ra was 2 μm, the elongation at break was 2.25%, the tensile strength was 99MPa, and the CTE was 9ppm/K.
4. And (3) carrying out vacuum hot pressing on the surface of the circuit by using the insulating adhesive film material at 100 ℃, and observing the filling capacity of the insulating adhesive film circuit. The lines are poorly filled with holes (2-3 in fig. 2). The thickness error of the adhesive film is more than +/-10 percent.
Comparative example 2
1. The following raw materials for preparing the slurry were weighed:
Figure RE-GDA0003901475080000101
2. ball milling is carried out for 12 hours at 600rpm, and the obtained slurry is coated on the surface of a fluoroplastic release carrier membrane to form a polymer composite.
3. After drying at 120 ℃ for 5 minutes, the polymer is dried at 60 DEGAnd (3) hot-pressing the compound protective film on the surface of the polymer composite to prepare the insulating adhesive film material. The polymer protective film has a molecular structure comprising
Figure RE-GDA0003901475080000102
The roughness Ra was 4nm, the tensile strength was 99MPa, and the CTE was 9ppm/K.
4. And (3) carrying out vacuum hot pressing on the surface of the circuit by using the insulating adhesive film material at 100 ℃, and observing the filling capacity of the insulating adhesive film circuit. The circuit is not filled well and has holes. And the protective film peels off to generate surface defects (2-4 in fig. 2).

Claims (10)

1. An insulating adhesive film material comprises a polymer compound consisting of an adhesive film layer and a carrier film and a polymer protective film covered on the surface of the adhesive film layer by hot pressing or rolling; the surface of the polymer protective film is subjected to release treatment; the adhesive film layer is made of slurry containing a resin composition, filler particles, a resin curing agent, other auxiliaries and a solvent; it is characterized in that the preparation method is characterized in that,
the roughness Ra of the polymer protective film is 5 nm-1 mu m;
the polymer protective film has a Coefficient of Thermal Expansion (CTE) of 10ppm/K to 300ppm/K;
the softening temperature point of the polymer protective film is 40-350 ℃;
the elongation at break of the polymer protective film is 10-1000%;
preferably, the polymer protective film comprises a molecular structure thereof
Figure FDA0003835987250000011
Figure FDA0003835987250000012
Figure FDA0003835987250000013
One or more structures of (a).
2. The adhesive insulating film material of claim 1, wherein the polymer protective film has a thermal expansion coefficient of 15ppm/K to 200ppm/K, a softening temperature point of 50 ℃ to 250 ℃, a roughness Ra of 10nm to 0.8 μm, a tensile strength of 50MPa to 150MPa, and an elongation at break of 120% to 1000% greater than the elongation at break;
preferably, the thermal expansion coefficient of the polymer protective film is 35ppm/K to 160ppm/K, the softening temperature point of the polymer protective film is 60 ℃ to 200 ℃, the roughness Ra of the polymer protective film is 10nm to 200nm, the tensile strength of the polymer protective film is 70MPa to 130MPa, and the elongation at break of the polymer protective film is 150% to 500%.
3. The insulating adhesive film material of claim 1, wherein the polymer composite has a thermal expansion coefficient of 5ppm/K to 200ppm/K, and a pre-curing elongation at break of 1% to 300%;
preferably, the polymer composite has a coefficient of thermal expansion of 30ppm/k to 150ppm/k, and the polymer composite has a pre-cure elongation at break of 30% to 200%;
more preferably, the polymer composite has a coefficient of thermal expansion of 40ppm/k to 100ppm/k and a pre-cure elongation at break of 50% to 160%.
4. The insulative adhesive film material of claim 1, wherein the thickness of the polymer protective film is 5 μm to 200 μm, preferably 20 μm to 100 μm, and more preferably 20 μm to 40 μm.
5. The adhesive insulating film material according to claim 1, wherein the resin composition is selected from one or more of epoxy resin, rubber resin, phenol resin, polyester resin, polyamide resin, urea resin, melamine resin, furan resin, silicone resin, polyester resin, acrylic resin, cyanate resin, vinyl resin, hydrocarbon resin, and polyether resin;
the resin curing agent is selected from aliphatic polyamine curing agent, alicyclic polyamine curing agent, latent curing agent, acid anhydride curing agent, aromatic amine curing agent, polyamide curing agent and synthetic resin curing agent;
the inorganic filler is one or a mixture of more of silicon dioxide, aluminum oxide, boron nitride, titanium dioxide, zinc oxide, zirconium oxide, magnesium oxide, calcium carbonate, barium titanate, strontium titanate, barium strontium titanate, lead zirconate titanate, copper calcium titanate and the like.
The solvent is selected from one or more of volatilizable solvents, including aromatic solvents, halogenated hydrocarbon solvents, aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents, alcohol solvents, ester solvents, ketone solvents and amide solvents;
the auxiliary agent is selected from one or a combination of more of epoxy resin curing accelerator, dispersant, defoamer, flatting agent and coupling agent;
preferably, the epoxy resin curing accelerator is selected from phenol, bisphenol A, resorcinol, 2,4,6-tris (dimethylaminomethylene) phenol, benzyl dimethylamine, acyl guanidine, benzoyl peroxide, copper acetylacetonate, aluminum acetylacetonate, zirconium acetylacetonate, imidazoles selected from one or more of 2-methylimidazole, 2-ethylimidazole, 2,4-diethylimidazole, 2-methyl-4-ethylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, and the like;
preferably, the dispersing agent is selected from polyethylene glycol fatty acid ester, sodium fatty acid methyl ester sulfonate, sucrose fatty acid ester, polyglycerol fatty acid ester, fatty acid polyoxyethylene ether, nonylphenol polyoxyethylene ether, polyoxyethylene sorbitan fatty acid ester, polyvinylpyrrolidone K30, polyvinylpyrrolidone K90, sodium lignin sulfonate, polyacrylamide, sodium dodecylbenzene sulfonate, sodium methylene bis-methyl naphthalene sulfonate and a combination of one or more of esters and fatty amides;
preferably, the defoaming agent is selected from one or more of organic silicon defoaming agents, polyether defoaming agents and polyether modified polysiloxane defoaming agents;
preferably, the leveling agent is selected from one or more of polydimethylsiloxane, polyether polyester modified organic siloxane, alkyl modified organic siloxane, end group modified organic silicon, organic modified polysiloxane acrylic leveling agent and acrylate leveling agent;
preferably, the coupling agent is a silane coupling agent.
6. The insulative film material of claim 1, further wherein the carrier film is selected from the group consisting of a polymer film material and a paper-based film material;
preferably, the polymer film material is selected from polyester film, polyetheretherketone film, polyetherimide film, polyimide film, polycarbonate film;
preferably, the paper-based film material is selected from release paper, laminating paper;
preferably, the carrier film is selected from carrier films with release films, more preferably, the release film is selected from silicon-containing release films, silicon-free release films, fluoroplastic release films, corona release films, frosted release films, polished release films, matte release films;
preferably, the thickness of the carrier film is from 10 μm to 300. Mu.m.
7. Use of the insulating adhesive film material of any one of claims 1 to 6 for the preparation of packaging materials for Printed Circuit Boards (PCB), substrates, carrier boards, semiconductor electronics.
8. The method for preparing an insulating adhesive film material of any one of claims 1 to 6, which comprises the steps of:
s1) weighing raw materials for preparing slurry;
s2) mixing the raw materials for preparing the slurry, and coating the mixture on the surface of a carrier membrane to form a polymer composite;
s3) attaching the polymer protective film to the surface of the polymer compound through hot pressing or rolling to prepare an insulating adhesive film material;
preferably, the pressing temperature of the hot pressing or rolling in S3) is 25 ℃ to 200 ℃, preferably 25 ℃ to 150 ℃, more preferably 25 ℃ to 100 ℃.
9. Use of a polymer protective film as a protective film for a packaging adhesive film for printed wiring boards (PCB), substrates, carrier boards, semiconductor electronics;
the roughness Ra of the polymer protective film is 5 nm-1 mu m;
the polymer protective film has a Coefficient of Thermal Expansion (CTE) of 10ppm/K to 300ppm/K;
the softening temperature point of the polymer protective film is 40-350 ℃;
the elongation at break of the polymer protective film is 10-1000%.
10. The use according to claim 9, wherein the encapsulating adhesive film has a coefficient of thermal expansion of 5ppm/K to 200ppm/K; the elongation at break of the packaging adhesive film before curing is 1-300%;
preferably, the thermal expansion coefficient of the packaging adhesive film is preferably 30ppm/k-150ppm/k, more preferably 40ppm/k-100ppm/k;
preferably, the elongation at break before curing is preferably from 30% to 200%, more preferably from 50% to 160%.
CN202211088067.6A 2022-09-07 2022-09-07 Insulating adhesive film material for preparing fine circuit and preparation method thereof Pending CN115537160A (en)

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CN112662334A (en) * 2020-12-07 2021-04-16 中国科学院深圳先进技术研究院 Low-thermal expansion coefficient insulating adhesive film and preparation method thereof
CN112724867A (en) * 2020-12-10 2021-04-30 深圳先进技术研究院 Insulating adhesive film material and preparation method and application thereof
CN112724868A (en) * 2020-12-10 2021-04-30 深圳先进技术研究院 Insulating dielectric composite film material and preparation method and application thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030052400A1 (en) * 2001-08-09 2003-03-20 Yasushi Okura Semiconductor device
JP2006220886A (en) * 2005-02-10 2006-08-24 Showa Denko Kk Photosensitive dry film for printed wiring board protective film, method for manufacturing the same, and printed wiring board
JP2014156515A (en) * 2013-02-14 2014-08-28 Ajinomoto Co Inc Curable resin composition
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