CN117165212A

CN117165212A - Insulating and laminating adhesive film and preparation method thereof

Info

Publication number: CN117165212A
Application number: CN202311211543.3A
Authority: CN
Inventors: 刘飞; 许伟鸿; 杨柳; 何岳山; 范梓琳; 陈航; 付永生; 陈凤林
Original assignee: Kunshan Newfield New Materials Technology Co ltd
Current assignee: Kunshan Newfield New Materials Technology Co ltd
Priority date: 2023-09-19
Filing date: 2023-09-19
Publication date: 2023-12-05

Abstract

The invention discloses an insulating laminated adhesive film and a preparation method thereof, wherein the raw materials of the insulating laminated adhesive film comprise the following components in parts by mass: 20-30 parts of epoxy resin, 20-30 parts of curing agent, 3-5 parts of phenoxy resin, 2-4 parts of polymer-based core-shell particles and 80-100 parts of filler; the curing agent includes a phosphorus-containing active ester. The phosphorus-containing active ester contains active ester groups, and can form a wide network structure when undergoing a curing reaction with epoxy resin, so that the thermal expansion coefficient of the laminated adhesive film is reduced; meanwhile, after the phosphorus-containing active ester reacts with the epoxy group, hydroxyl is not formed on the side chain, but ester groups with smaller polarity and larger volume are generated, the side group is changed into ester groups from hydroxyl, the polarity of alkyl ester groups is smaller, and the dielectric constant and dielectric loss of the reinforced adhesive film are effectively reduced.

Description

Insulating and laminating adhesive film and preparation method thereof

Technical Field

The invention relates to the technical field of resin materials, in particular to an insulating and laminating adhesive film and a preparation method thereof.

Background

The Flip Chip Ball Grid Array (FCBGA) package carrier is a development direction of a future semiconductor package carrier, has wide application and broad market prospect, is a high-density package carrier capable of realizing high speed and multifunction of chips, and is one of key core materials of SAP (super-functional application) in a manufacturing process of the FCBGA package carrier by a half-additive method. However, the existing laminated adhesive film has the following defects: the thermal expansion coefficient of the resin system in the build-up adhesive film is larger, the generated thermal expansion phenomenon can cause thermal stress, if the thermal stress is too large, the reliability of the FCBGA package loading board and the packaging system thereof can be damaged, and meanwhile, the thermal expansion coefficient mismatch easily causes through hole cracks and layering failure; meanwhile, as the wiring density of the circuit increases, the resistance of metal interconnection wires in electronic components and the capacitance of interlayer dielectrics easily form RC (resistance-capacitance delay) delay effect, thereby causing adverse effects such as signal transmission delay, power loss and the like; the existing laminated adhesive film material has insufficient dielectric property and larger dielectric constant, and seriously affects the application of the laminated adhesive film material in an integrated circuit.

Accordingly, the prior art is still in need of improvement and development.

Disclosure of Invention

In view of the shortcomings of the prior art, the invention aims to provide an insulation laminated adhesive film and a preparation method thereof, and aims to solve the problems of larger thermal expansion coefficient and larger dielectric constant of the existing laminated adhesive film material.

The technical scheme of the invention is as follows:

the invention provides an insulating laminated adhesive film, which comprises the following raw materials in parts by mass:

20-30 parts of epoxy resin, 20-30 parts of curing agent, 3-5 parts of phenoxy resin, 2-4 parts of polymer-based core-shell particles and 80-100 parts of filler;

the curing agent includes a phosphorus-containing active ester.

Optionally, the phosphorus-containing active ester comprises at least one of phosphorus-containing active ester I, phosphorus-containing active ester II and phosphorus-containing active ester III;

wherein, the structural formula of the phosphorus-containing active ester I is as follows:

the structural formula of the phosphorus-containing active ester II is as follows:

the structural formula of the phosphorus-containing active ester III is as follows:

each n in the three structural formulas is independently selected from integers between 1 and 5.

Optionally, the curing agent further comprises at least one of a maleimide curing agent, a phenolic curing agent, a carbodiimide curing agent, a phenolic curing agent, a naphthol curing agent, a cyanate curing agent, and a benzoxazine curing agent.

Optionally, the raw materials of the insulating laminated adhesive film further comprise 0.02-0.1 part of curing accelerator by mass.

Optionally, the curing accelerator comprises at least one of 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl-4, 5-dimethylol imidazole, 2-phenyl-4-methyl-5-hydroxymethyl imidazole, 2-ethyl-4-methylimidazole, 4-dimethylaminopyridine, and 2-phenyl imidazole.

Optionally, the filler comprises at least one of silica, clay, alumina, glass, cordierite, aluminum hydroxide, magnesium hydroxide, boron nitride, aluminum nitride, graphene.

Optionally, the filler comprises silica and/or graphene; the graphene comprises aminated graphene; the silica comprises mercaptosilica.

The second aspect of the invention provides a preparation method of an insulation laminated adhesive film, which comprises the following steps:

providing a substrate;

mixing 20-30 parts of epoxy resin, 20-30 parts of curing agent, 3-5 parts of phenoxy resin, 2-4 parts of polymer-based core-shell particles, 80-100 parts of filler and 200-300 parts of organic solvent according to parts by mass to obtain slurry; the curing agent comprises a phosphorus-containing active ester;

and transferring the slurry onto the base material, and drying to obtain the insulating laminated adhesive film.

Optionally, the filler comprises silica and/or graphene, the graphene comprising aminated graphene, the silica comprising mercapto silica;

the preparation method of the aminated graphene comprises the following steps:

adding graphene into water, and performing ultrasonic dispersion to obtain graphene dispersion;

adding diaminoguanidine hydrochloride aqueous solution and glutaraldehyde into the graphene dispersion liquid, adjusting the pH value to a preset value by using sodium hydroxide solution, and reacting at a preset temperature to obtain the aminated graphene;

the preparation method of the sulfhydryl silicon dioxide comprises the following steps:

ethanol, water and ammonia water are mixed, then silicon dioxide and a sulfhydrylation reagent are added, and after the reaction, the sulfhydrylation silicon dioxide is obtained.

In a third aspect of the present invention, an application of the laminated adhesive film of the present invention and/or the laminated adhesive film prepared by the preparation method of the present invention in packaging carrier boards is provided.

The beneficial effects are that: the phosphorus-containing active ester contains active ester groups, and can form a wide network structure when undergoing a curing reaction with epoxy resin, so that the thermal expansion coefficient of the laminated adhesive film is reduced; meanwhile, after the phosphorus-containing active ester reacts with the epoxy group, hydroxyl is not formed on the side chain, but ester groups with smaller polarity and larger volume are generated, the side group is changed into ester groups from hydroxyl, the polarity of alkyl ester groups is smaller, and the dielectric constant and dielectric loss of the reinforced adhesive film are effectively reduced.

Drawings

FIG. 1 is a graph showing the results of the thermal expansion coefficient test in example 1 of the present invention.

FIG. 2 is a graph showing the results of the thermal expansion coefficient test in example 6 of the present invention.

FIG. 3 shows the results of the thermal expansion coefficient test of comparative example 2 of the present invention.

Detailed Description

The invention provides an insulating laminated adhesive film, a preparation method and application thereof, and aims to make the purposes, technical schemes and effects of the invention clearer and more definite, and the invention is further described in detail below. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

The embodiment of the invention provides an insulating laminated adhesive film, wherein the raw materials of the insulating laminated adhesive film comprise the following components in parts by mass:

the curing agent includes a phosphorus-containing active ester.

The phosphorus-containing active ester contains active ester groups, and can form a wide network structure when undergoing a curing reaction with epoxy resin, so that the thermal expansion coefficient of the laminated adhesive film is reduced; meanwhile, after the phosphorus-containing active ester reacts with the epoxy group, hydroxyl is not formed on the side chain, but ester groups with smaller polarity and larger volume are generated, the side group is changed into ester groups from hydroxyl, the polarity of alkyl ester groups is smaller, and the dielectric constant and dielectric loss of the reinforced adhesive film are effectively reduced.

The present invention is not limited to a specific type of epoxy resin, and the epoxy resin may be at least one selected from bisphenol type epoxy resin, biphenyl type epoxy resin, phenol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, novolac type epoxy resin, dicyclopentadiene type epoxy resin, aralkyl type novolac epoxy resin, biphenyl aralkyl type novolac epoxy resin, naphthol type novolac epoxy resin, by way of example, but not limited thereto.

The present invention is not limited to a specific type of phenoxy resin either, and the phenoxy resin may be selected from at least one of FX280 (japan new japanese iron corporation), FX293 (japan new japanese iron corporation), YX8100 (mitsubishi chemical corporation, japan), YX7553BH30 (mitsubishi chemical corporation, japan), YX7200B35 (mitsubishi chemical corporation), TER240C30 (guangdong homogyu), by way of example, but not limited thereto.

In the practice of the present invention, the polymer-based core-shell particles comprise a core and a shell, and the core and shell are composed of different polymers, and in general, the core material may be a rubber elastomer; the rubber elastomer includes at least one of styrene-butadiene rubber, polybutadiene rubber, polyurethane rubber and organic silicon rubber; the shell material may be polymethyl methacrylate (PMMA). By way of example, the polymer-based core-shell particles may be selected from "XER-91" of Japanese synthetic rubber Co., ltd. "AC3601", "AC3355", "AC4030" of AICA Industrial Co., ltd. "EXL2655", "EXL2602" of American Dow chemical Co., ltd.

The addition of the polymer-based core-shell particles is beneficial to the improvement of the overall fracture toughness of the laminated adhesive film, and meanwhile, the adhesive force between the laminated adhesive film and other materials can be improved.

In the prior art, the main component of the laminated adhesive film is a flammable polymer material, a large amount of dense smoke and toxic gas can be generated in the combustion process, and the flame retardant property of the polymer material is improved, so that the laminated adhesive film needs to be in a key overcoming direction, therefore, in one embodiment of the invention, the phosphorus-containing active ester comprises at least one of phosphorus-containing active ester I, phosphorus-containing active ester II and phosphorus-containing active ester III;

each n in the three formulae is independently selected from integers between 1 and 5, and may be, for example, 1, 2, 3, 4 or 5.

In this embodiment, the phosphorus-containing active ester of the structure contains a plurality of active ester groups, can form a wider network structure when undergoing a curing reaction with epoxy resin, effectively reduces the thermal expansion coefficient of the build-up adhesive film, and meanwhile, the phosphorus-containing active ester of the structure does not form hydroxyl groups on side chains after reacting with the epoxy groups, but generates ester groups with smaller polarity and larger volume, the side groups are changed into ester groups from the hydroxyl groups, and the polarity of the alkyl ester groups is smaller, thereby being beneficial to reducing dielectric constants and dielectric losses. In addition, the phosphorus group in the active ester can generate phosphine-hetero-phenanthrene group in gas phase, can capture free radical of gas phase cracking gas, form a stable structure, play a role in quenching free radical, and improve the flame retardance of the laminated adhesive film.

The curing agent in the invention can be only phosphorus-containing active ester, and can also comprise other curing agents besides phosphorus-containing active ester. As an example, the curing agent may include, but is not limited to, at least one of a maleimide curing agent, a phenolic curing agent, a carbodiimide curing agent, a phenol curing agent, a naphthol curing agent, a cyanate curing agent, a benzoxazine curing agent, in addition to the phosphorus-containing active ester.

In some embodiments, the raw materials of the insulation layer-increasing adhesive film further include 0.02-0.1 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. by mass.

In some specific embodiments, the cure accelerator includes, but is not limited to, at least one of 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl-4, 5-dimethylol imidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-ethyl-4-methylimidazole, 4-dimethylaminopyridine, 2-phenylimidazole.

In some embodiments, the filler includes, but is not limited to, at least one of silica, clay, alumina, glass, cordierite, aluminum hydroxide, magnesium hydroxide, boron nitride, aluminum nitride, graphene.

In some embodiments, the filler comprises silica and/or graphene; the graphene comprises aminated graphene; the silica comprises mercaptosilica. In this embodiment, the filler includes an aminated graphene, or the filler includes a mercapto silica, or the filler includes an aminated graphene and a mercapto silica.

The space network structure formed by mutually overlapping and crosslinking the lamellar layers in the amino graphene has strong mechanical constraint on the thermal deformation of the epoxy resin, so that the lower thermal expansion rate and the lower thermal expansion coefficient are obtained; and simultaneously, carbon atoms in the graphene can expand outside the two-dimensional structure of the graphene, and become a three-dimensional structure under microcosmic, so that surface wrinkles are formed, a certain thermal contraction phenomenon is generated, and the thermal expansion phenomenon is further reduced. In addition, the aminated graphene can form a compact and ordered carbon layer to block flue gas exchange, plays a role in inhibiting flue gas release, and meanwhile, the carbon layer is high in structural strength and strong in continuity, and the compact carbon layer isolates CO and CO2 and other toxic and harmful gases, so that gas exchange is prevented, and the release amount of CO and CO2 is obviously reduced; the nitrogen-containing structure in the graphene is a hindered amine structure with quenching effect, so that nonflammable gas can be formed, and the gas-phase dilution effect is exerted;

in addition, the inner space of the carbon layer is larger, and gas exchange and heat exchange can be better prevented, so that combustion is inhibited, and the flame retardance is further improved.

The sulfhydrylation silicon dioxide can form mercaptan ions under the action of amino compounds (such as aminated graphene, 4-dimethyl aminopyridine and the like) in the raw materials, so that the reaction of epoxy groups and sulfhydryl groups is promoted, secondary hydroxyl groups and thioether bonds are generated, the stacking density of molecular chains and silicon dioxide is improved, the more compact the stacking is, the smaller the free volume is, the movement space of the molecular chain segments of the epoxy resin is limited, and good thermal expansion performance is obtained. The silicon element in the silicon dioxide has lower surface energy, is easy to migrate to the surface of the material to form a silicon-containing protective layer, improves the thermal stability of a carbon layer on the surface of the material, and can realize synergistic flame retardance through phosphorus, nitrogen and silicon to ensure the flame retardance of the laminated adhesive film.

In one embodiment, the raw materials of the insulation laminated adhesive film further comprise 3-9 parts of other auxiliary agents according to parts by weight. For example, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, or the like may be used.

In some embodiments, the thickener includes, but is not limited to, at least one of an inorganic salt thickener, a fatty thickener, an alkanolamide thickener, an ether thickener.

In some embodiments, the defoamer includes, but is not limited to, at least one of silicone-based defoamers, fluorine-based defoamers.

In some embodiments, the leveling agent includes, but is not limited to, at least one of a silicone-based leveling agent, an acrylic polymer-based leveling agent.

In some embodiments, the leveling agent includes, but is not limited to, at least one of a polyoxyethylene alkyl ether leveling agent, a polyoxyethylene alkyl phenyl ether leveling agent, a polyethylene glycol diester leveling agent, a sorbitan fatty acid ester leveling agent.

In some embodiments, the adhesion imparting agent includes, but is not limited to, at least one of vinyl trimethoxysilane, vinyl triethoxysilane, 3-aminopropyl triethoxysilane, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl methyldimethoxysilane.

In some embodiments, the colorant includes, but is not limited to, at least one of phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, carbon black.

In one embodiment, the thickness of the insulating and laminating adhesive film is 10-100 μm, for example, 10, 20, 30, 40, 50, 60, 70, 80, 90 or 100 μm.

The embodiment of the invention also provides a preparation method of the insulating laminated adhesive film, which comprises the following steps:

s1, providing a substrate;

s2, mixing 20-30 parts of epoxy resin, 20-30 parts of curing agent, 3-5 parts of phenoxy resin, 2-4 parts of polymer-based core-shell particles, 80-100 parts of filler and 200-300 parts of organic solvent according to mass parts to obtain slurry; the curing agent comprises a phosphorus-containing active ester;

s3, transferring the slurry to the base material, and drying to obtain the insulating laminated adhesive film.

The preparation method provided by the embodiment of the invention is simple and efficient, and the phosphorus-containing active ester is introduced into the raw materials for preparing the insulating laminated adhesive film, contains an active ester group, and can form a wide network structure when undergoing a curing reaction with epoxy resin, so that the thermal expansion coefficient of the laminated adhesive film is reduced; meanwhile, after the phosphorus-containing active ester reacts with the epoxy group, hydroxyl is not formed on a side chain, but ester groups with smaller polarity and larger volume are generated, the side group is changed into ester groups from hydroxyl groups, the polarity of alkyl ester groups is smaller, and the dielectric constant and dielectric loss of the laminated adhesive film are effectively reduced. In addition, the polymer-based core-shell particles are beneficial to improving the overall fracture toughness of the laminated adhesive film, and can also improve the adhesive force between the laminated adhesive film and other materials.

The choice of substrate in the embodiments of the present invention is not particularly limited, and substrates commonly used in the art may be used, and examples include, but are not limited to, polyethylene terephthalate (PET) release film, polyethylene film, polypropylene film, or polyvinyl chloride film. Meanwhile, in order to facilitate the subsequent removal of the base material, the polyethylene film, the polypropylene film or the polyvinyl chloride film can be subjected to corona treatment in advance before use.

In one embodiment, the thickness of the substrate is 10 to 150. Mu.m, for example, 10 μm, 20 μm, 25 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 110 μm, 120 μm, 130 μm, 140 μm, 150 μm, etc., and more preferably 25 to 50 μm.

In step S2, in some embodiments, the organic solvent includes at least one of toluene, xylene, butanone, methyl ethyl ketone, cyclohexanone, ethyl acetate, N-dimethylformamide, but is not limited thereto.

In one embodiment, the filler comprises silica and/or graphene, the graphene comprising aminated graphene, the silica comprising mercapto silica.

The preparation method of the aminated graphene comprises the following steps:

and adding diaminoguanidine hydrochloride aqueous solution and glutaraldehyde into the graphene dispersion liquid, regulating the pH value to a preset value by using sodium hydroxide solution, and reacting at a preset temperature to obtain the aminated graphene.

In some embodiments, the pH is adjusted to 9.5 to 10 with sodium hydroxide solution.

In some embodiments, the preset temperature is 30 to 35 ℃.

In some embodiments, the thiolating agent comprises at least one of 3-mercaptopropyl trimethoxysilane, 3-mercaptopropyl triethoxysilane.

In step S3, in some embodiments, the transferring means includes, but is not limited to, coating.

In some embodiments, the drying temperature is 80-130 ℃, for example, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, or the like. The drying time is 3-10 min, for example, 3min, 4min, 5min, 6min, 7min, 8min, 9min or 10 min.

In one embodiment, the drying further comprises a post-treatment step, wherein the post-treatment method is to remove the substrate.

The embodiment of the invention also provides an application of the build-up adhesive film in the packaging carrier plate, or an application of the build-up adhesive film prepared by the preparation method in the embodiment in the packaging carrier plate, or an application of the build-up adhesive film in the embodiment in the packaging carrier plate and the build-up adhesive film prepared by the preparation method in the embodiment in the invention. Wherein the package carrier may be a flip chip ball grid array package carrier. The laminated adhesive film provided by the invention has lower thermal expansion coefficient, excellent dielectric property and flame retardant property, and is very suitable for packaging carrier plates.

The following is a detailed description of specific examples.

Some sources of raw materials in the following examples and comparative examples are as follows:

epoxy resin: bisphenol type epoxy resin (NC-3000H, manufactured by Japanese chemical Co., ltd.), bisphenol type epoxy resin (ZX-1059, manufactured by Nissan iron chemical Co., ltd.), naphthalene type epoxy resin (HP-4032 SS, manufactured by DIC Co.);

curing agent: an active ester curing agent (HPC-8150-62T, manufactured by DIC Co., ltd.), and a cyanate ester curing agent (BA 230S7, manufactured by Lonza Japan Co., ltd.);

phenoxy resin: "YX7553BH30" manufactured by Mitsubishi chemical corporation, and "TER240C30" manufactured by Guangdong Coyu corporation;

polymer-based core-shell particles: "AC3816N", "AC3355" manufactured by AICA Industrial Co., ltd;

and (3) filling: silica (CAS number 7631-86-9).

The preparation method of the aminated graphene in the following embodiment comprises the following steps:

adding 0.3g of graphene into 75mL of deionized water, and magnetically stirring for 30min after ultrasonic dispersion to form a homogeneous graphene dispersion;

1.5g of diaminoguanidine hydrochloride was dissolved in 75mL of deionized water to give an aqueous diaminoguanidine hydrochloride solution;

and adding the diaminoguanidine hydrochloride aqueous solution into the graphene dispersion liquid, adding 300 mu L of glutaraldehyde, adjusting the pH=10 by using a sodium hydroxide solution, then heating at the temperature of 35 ℃ for 2.5 hours, filtering the product after the mixed solution is cooled to room temperature, and finally carrying out vacuum freeze drying on the product for 48 hours to obtain the aminated graphene.

mixing 100mL of absolute ethyl alcohol, 20mL of deionized water and 8mL of ammonia water, and stirring in a constant-temperature water bath at 40 ℃ for 15min to uniformly mix the components to obtain a mixed solution;

adding 5mg of silicon dioxide into the mixed solution, continuously stirring at a constant speed in a constant temperature water bath kettle at 40 ℃, adding 0.04g of a sulfhydrylation reagent (specifically, 3-mercaptopropyl trimethoxy silane), taking out after reacting for 30 hours, centrifuging for 5 minutes at a rotating speed of 100000r/min, leaving solid, washing and centrifuging twice with 50% ethanol solution, washing and centrifuging twice with absolute ethanol, and drying to obtain the sulfhydrylation silicon dioxide.

When the aminated graphene and the sulfhydrylated silica are specifically used, the dosage of each raw material in the preparation method is scaled up or scaled down in equal proportion according to the specific dosage.

Example 1

The embodiment provides an insulating layer-added adhesive film, which comprises the following raw materials in parts by mass:

5 parts of bisphenol epoxy resin (NC-3000H), 5 parts of bisphenol epoxy resin (ZX-1059), 10 parts of naphthalene epoxy resin (HP-4032 SS), 30 parts of phosphorus-containing active ester I, 3 parts of phenoxy resin (YX 7553BH 30), 4 parts of polymer-based core-shell particles (AC 3816N), 0.02 part of 4-Dimethylaminopyridine (DMAP), 100 parts of silicon dioxide (CAS No. 7631-86-9) and 300 parts of cyclohexanone.

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

and uniformly mixing the raw material components of the insulating laminated adhesive film according to the proportion, coating the mixture on a PET release film, drying the PET release film at 80 ℃ for 10min, and removing the PET release film to obtain the insulating laminated adhesive film with the thickness of 100 mu m.

Example 2

8 parts of bisphenol epoxy resin (NC-3000H), 8 parts of bisphenol epoxy resin (ZX-1059), 14 parts of naphthalene epoxy resin (HP-4032 SS), 20 parts of phosphorus-containing active ester II, 5 parts of phenoxy resin (TER 240C 30), 2 parts of polymer-based core-shell particles (AC 3355), 0.1 part of 4-Dimethylaminopyridine (DMAP), 80 parts of silicon dioxide and 200 parts of cyclohexanone.

and uniformly mixing the raw material components of the insulating laminated adhesive film according to the proportion, coating the mixture on a PET release film, drying the PET release film at 130 ℃ for 3min, and removing the PET release film to obtain the insulating laminated adhesive film with the thickness of 10 mu m.

Example 3

7 parts of bisphenol epoxy resin (NC-3000H), 7 parts of bisphenol epoxy resin (ZX-1059), 13 parts of naphthalene epoxy resin (HP-4032 SS), 25 parts of phosphorus-containing active ester III, 5 parts of phenoxy resin (YX 7553BH 30), 3 parts of core-shell particles (AC 3816N), 0.05 part of 4-Dimethylaminopyridine (DMAP), 90 parts of silicon dioxide and 250 parts of cyclohexanone.

and uniformly mixing the raw material components of the insulating laminated adhesive film according to the proportion, coating the mixture on a PET release film, drying the PET release film at 110 ℃ for 5min, and removing the PET release film to obtain the insulating laminated adhesive film with the thickness of 40 mu m.

Example 4

5 parts of bisphenol epoxy resin (NC-3000H), 5 parts of bisphenol epoxy resin (ZX-1059), 10 parts of naphthalene epoxy resin (HP-4032 SS), 30 parts of phosphorus-containing active ester I, 3 parts of phenoxy resin (YX 7553BH 30), 4 parts of polymer-based core-shell particles (AC 3816N), 0.02 part of 4-Dimethylaminopyridine (DMAP), 90 parts of silicon dioxide, 10 parts of aminated graphene and 300 parts of cyclohexanone.

Example 5

5 parts of bisphenol epoxy resin (NC-3000H), 5 parts of bisphenol epoxy resin (ZX-1059), 10 parts of naphthalene epoxy resin (HP-4032 SS), 30 parts of phosphorus-containing active ester I, 3 parts of phenoxy resin (YX 7553BH 30), 4 parts of polymer core-shell particles (AC 3816N), 0.02 part of 4-Dimethylaminopyridine (DMAP), 90 parts of silicon dioxide, 10 parts of mercapto silicon dioxide and 300 parts of cyclohexanone.

Example 6

5 parts of bisphenol epoxy resin (NC-3000H), 5 parts of bisphenol epoxy resin (ZX-1059), 10 parts of naphthalene epoxy resin (HP-4032 SS), 30 parts of phosphorus-containing active ester I, 3 parts of phenoxy resin (YX 7553BH 30), 4 parts of core-shell particles (AC 3816N), 0.02 part of 4-Dimethylaminopyridine (DMAP), 90 parts of silicon dioxide, 5 parts of aminated graphene, 5 parts of mercapto silicon dioxide and 300 parts of cyclohexanone.

Comparative example 1

This comparative example provides an insulation laminated adhesive film and a method for producing the same, which are different from example 1 only in that 30 parts of phosphorus-containing active ester I is replaced with 30 parts of cyanate ester curing agent (BA 230S 75), and the other conditions are the same as example 1.

Comparative example 2

This comparative example provides an insulation laminated adhesive film and a method for producing the same, which are different from example 1 only in that 30 parts of phosphorus-containing active ester I is replaced with 30 parts of active ester curing agent (HPC-8150-62T), and the other conditions are the same as in example 1.

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

coefficient of thermal expansion: curing the insulating and laminating adhesive films with the PET release films provided in the examples and the comparative examples at 100 ℃ for 30min and at 190 ℃ for 90min, and then peeling off the release films to obtain test samples; the test specimen was cut into test pieces having a width of about 3mm and a length of about 120mm, and the test pieces were subjected to thermomechanical analysis using a thermomechanical analysis apparatus ("TMA 450" from TA company, USA) under a preload force of 0.02N at a temperature rise range of 25℃to 260℃and a temperature rise rate of 10℃per minute, to obtain a thermal expansion coefficient in the range of 25℃to 150 ℃.

Dielectric loss tangent: curing the insulating laminated adhesive film with the PET release film provided in the examples and the comparative examples at 180 ℃ for 30min, and then peeling off the release film to obtain a pre-cured laminated adhesive film; the pre-cured insulating laminated 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 by a cavity resonance perturbation method under the conditions of a measurement frequency of 5.8GHz and a measurement temperature of 23 ℃ using "HP8362B" of agilent technologies, and the average value of the dielectric loss tangents of the 3 test pieces was calculated to be the dielectric loss tangent.

Flame retardancy: laminating the insulating laminated 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 insulating laminated 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, and the test results are shown in Table 1 and FIGS. 1 to 3 below.

Table 1 test results

	Coefficient of thermal expansion (ppm K) ^-1 )	Dielectric loss tangent	Flame retardancy
				Example 1	26	0.0044	V-1
Example 2	26	0.0046	V-1
				Example 3	25	0.0045	V-1
Example 4	21	0.0044	V-0
				Example 5	20	0.0044	V-1
Example 6	15	0.0042	V-0
				Comparative example 1	35	0.0061	V-1
Comparative example 2	31	0.0054	V-1

In summary, the invention provides an insulating laminated adhesive film, a preparation method and application thereof, and the low thermal expansion coefficient and the excellent dielectric property are obtained by means of phosphorus-containing active ester, so that RC delay effect is reduced, signal transmission speed and efficiency are improved, flame retardant effect of the laminated adhesive film is ensured by synergistic flame retardance of phosphorus, nitrogen and silicon, reliability of products in practical application is improved, and application of the laminated adhesive film in packaging carrier boards is satisfied. Specifically, a wide network structure is formed when the phosphorus-containing active ester and the epoxy resin are subjected to curing reaction, so that the thermal expansion coefficient of the system is reduced; the phosphorus-containing active ester does not form hydroxyl groups on side chains after reacting with epoxy groups, but generates ester groups with smaller polarity and larger volume, the side groups are changed from hydroxyl groups to ester groups, and the polarity of alkyl ester groups is smaller, so that the dielectric constant and dielectric loss are reduced. The dense and ordered carbon layer formed by the aminated graphene can block the flue gas exchange, plays a role in inhibiting the release of the flue gas, and has high structural strength and high continuity, and the dense carbon layer can separate CO and CO ₂ And other toxic and harmful gases are isolated, gas exchange is prevented, and CO are generated ₂ The release amount is obviously reduced; in addition, the inner space of the carbon layer is larger, and gas exchange and heat exchange can be better prevented, so that combustion is inhibited, and the flame retardance is effectively improved. The phosphorus group in the active ester can generate phosphine hetero-phenanthrene groups in a gas phase, can capture free radicals of gas phase cracking gas, form a stable structure and play a role in quenching the free radicals; the nitrogen-containing structure in the graphene has a hindered amine structure with a quenching effect, so that nonflammable gas is formed, a gas-phase dilution effect is exerted, the surface energy of silicon element in silicon dioxide is low, the silicon element can be easily migrated to the surface of a material to form a silicon-containing protective layer, the thermal stability of a carbon layer on the surface of the material is improved, and the flame retardant effect of a build-up adhesive film is ensured through synergistic flame retardance of phosphorus, nitrogen and silicon.

It is to be understood that the invention is not limited in its application to the examples described above, but is capable of modification and variation in light of the above teachings by those skilled in the art, and that all such modifications and variations are intended to be included within the scope of the appended claims.

Claims

1. The insulating laminated adhesive film is characterized by comprising the following raw materials in parts by mass:

the curing agent includes a phosphorus-containing active ester.

2. The insulation laminated adhesive film according to claim 1, wherein the phosphorus-containing active ester comprises at least one of phosphorus-containing active ester i, phosphorus-containing active ester ii, and phosphorus-containing active ester iii;

3. The insulation laminated adhesive film according to claim 1, wherein the curing agent further comprises at least one of a maleimide curing agent, a phenolic curing agent, a carbodiimide curing agent, a phenolic curing agent, a naphthol curing agent, a cyanate curing agent, and a benzoxazine curing agent.

4. The insulating and laminating adhesive film according to claim 1, wherein the raw materials of the insulating and laminating adhesive film further comprise 0.02-0.1 part by mass of a curing accelerator.

5. The insulation laminated adhesive film according to claim 4, wherein the curing accelerator comprises at least one of 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl-4, 5-dimethylol imidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-ethyl-4-methylimidazole, 4-dimethylaminopyridine, and 2-phenylimidazole.

6. The insulation laminated adhesive film according to claim 1, wherein the filler comprises at least one of silica, clay, alumina, glass, cordierite, aluminum hydroxide, magnesium hydroxide, boron nitride, aluminum nitride, graphene.

7. The insulation laminated adhesive film according to claim 6, wherein the filler comprises silica and/or graphene; the graphene comprises aminated graphene; the silica comprises mercaptosilica.

8. The preparation method of the insulating laminated adhesive film is characterized by comprising the following steps:

providing a substrate;

9. The method of preparation of claim 8, wherein the filler comprises silica and/or graphene, the graphene comprises aminated graphene, and the silica comprises mercapto silica;

the preparation method of the aminated graphene comprises the following steps:

10. Use of an insulation laminated film according to any one of claims 1 to 7 and/or prepared by a preparation method according to any one of claims 8 to 9 in packaging carrier boards.