HIGH-TEMPERATURE-RESISTANT INSULATING COATING MATERIAL AND PREPARATION METHOD THEREOF

Abstract

A high-temperature-resistant insulating polymer composite is provided, including the following components in parts by mass: 3-12 parts of cyanate ester resin, 3-20 parts of epoxy resin, 5-15 parts of an inorganic filler, 0.1-2 parts of an epoxy resin curing agent, 0.0001-0.005 parts of a curing accelerant, and 0.1-2 parts of a dispersant. A glass transition temperature of the cured high-temperature-resistant insulating polymer composite is higher than 120° C.

Claims

1. A high-temperature-resistant insulating polymer composite, wherein the high-temperature-resistant insulating polymer composite is prepared from the following raw materials in parts by mass: 3-12 parts of a cyanate ester resin, 3-20 parts of an epoxy resin, 5-15 parts of an inorganic filler, 0.1-2 parts of an epoxy resin curing agent, 0.0001-0.005 parts of a curing accelerant, and 0.1-2 parts of a first dispersant.

2. The high-temperature-resistant insulating polymer composite according to claim 1, wherein a mass of the cyanate ester resin accounts for 5%-85% of a total mass of the cyanate ester resin and the epoxy resin.

3. The high-temperature-resistant insulating polymer composite according to claim 1, wherein a glass transition temperature of the high-temperature-resistant insulating polymer composite is higher than 120° C.

4. The high-temperature-resistant insulating polymer composite according to claim 1, wherein the high-temperature-resistant insulating polymer composite is a laminate with a thickness of 1 μm to 300 μm.

5. The high-temperature-resistant insulating polymer composite according to claim 1, wherein the cyanate ester resin is at least one selected from the group consisting of bisphenol A cyanate ester, bisphenol F cyanate ester, bisphenol E cyanate ester, bisphenol M cyanate ester, dicyclopentadiene cyanate ester, phenolic cyanate ester, and tetramethyl bisphenol F cyanate ester; , the epoxy resin is selected from the group consisting of bisphenol A epoxy resin, bisphenol F epoxy resin, phenolic epoxy resin, o-methyl phenolic epoxy resin, polyfunctional epoxy resin, alicyclic epoxy resin, resorcinol epoxy resin, rubber modified epoxy resin, polyurethane modified epoxy resin, biphenyl epoxy resin, and brominated epoxy resin; , the epoxy resin curing agent is selected from the group consisting of a fatty polyamine curing agent, an alicyclic polyamine curing agent, an aromatic amine curing agent, an anhydride curing agent, a polyamide curing agent, a latent curing agent, and a synthetic resin curing agent, and, the latent curing agent is selected from the group consisting of cyanoguanidine, boron trifluoride monoethylamine, boron trifluoride phenylethylamine, boron trifluoride o-toluidine, boron trifluoride bianamine, boron trifluoride dimethylaniline, boron trifluoride ethylaniline, boron trifluoride pyridine, an MS-1 microcapsule, an MS-2 microcapsule, and triacylhydrazine maleate; the curing accelerant is at least one selected from the group consisting of an imidazole epoxy resin curing accelerant, phenol, bisphenol A, resorcinol, 2,4,6-tri (dimethylamino methylene) phenol, benzyl dimethylamine, acyl guanidine, benzoyl peroxide, copper acetylacetone, aluminum acetylacetonate, and zirconium acetylacetonate; , the inorganic filler is at least one selected from the group consisting 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, and calcium copper titanate; dimensions of inorganic filler particles are 20 nm-10 μm or the inorganic filler particles are a multi-scale mixture; the inorganic filler particles are selected from the group consisting of spherical particles, spheroidal particles, rodlike particles, linear particles, and flaky particles; the inorganic filler particles account for 20%-80% by mass of solid components of the high-temperature-resistant insulating polymer composite, the solid components of the high-temperature-resistant insulating polymer composite are nonvolatile; the first dispersant is selected from the group consisting of an anionic emulsifier, a cationic emulsifier, and a non-ionic emulsifier, and the non-ionic emulsifier is selected from the group consisting of nonylphenol polyoxyethylene ether, alkyl phenol polyoxyethylene ether, high-carbon fatty alcohol polyoxyethylene ether, fatty acid polyoxyethylene ether, fatty acid methyl ester ethoxylate, and a high-molecular polymer; the anionic emulsifier is selected from the group consisting of cis-9-sodium octadecenoate, sodium oleate, sodium oleate, sodium laurate, C13-C18 sodium alkyl benzene sulfinate; and sulfate; and the cationic emulsifier is an alkyl ammonium salt emulsifier, the alkyl ammonium salt emulsifier is at least one selected from the group consisting of dodecyl ammonium chloride and a quaternary ammonium salt, and the quaternary ammonium salt is cetyl trimethyl ammonium bromide and cetyl brominated pyridine pyran.

6. The high-temperature-resistant insulating polymer composite according to claim 1, wherein the high-temperature-resistant insulating polymer composite is obtained by mixing the raw materials with a solvent to prepare an electronic slurry and then drying the electronic slurry when the high-temperature-resistant insulating polymer composite is prepared, wherein the solvent used is a volatile solvent selected from the group consisting of an aromatic solvent, a halogenated hydrocarbon solvent, a fatty hydrocarbon solvent, an alicyclic hydrocarbon solvent, an alcohol solvent, an ester solvent, a ketone solvent, and an amide solvent.

7. The high-temperature-resistant insulating polymer composite according to claim 1, further comprising an auxiliary agent, wherein the auxiliary agent is at least one selected from the group consisting of a second dispersant, a defoamer, a coupling agent, an anti-settling agent, a leveling agent, a rheological agent, and a flame retardant.

8. A preparation method of the high-temperature-resistant insulating polymer composite according to claim 1, comprising steps of: 1) uniformly dispersing the cyanate ester resin, the epoxy resin, the inorganic filler, the epoxy resin curing agent, the curing accelerant, the dispersant, and a solvent to obtain an electronic slurry of the high-temperature-resistant insulating polymer composite; and 2) coating the electronic slurry of the high-temperature-resistant insulating polymer composite to a surface of a film material layer, attaching the electronic slurry of the high-temperature-resistant insulating polymer composite to a protective film layer after being dried by an oven to form an insulating coating material; wherein, a coating mode of the electronic slurry of the high-temperature-resistant insulating polymer composite is selected from the group consisting of gravure printing, micro-gravure printing, comma scrapers, and slit extrusion, and a drying temperature of the solvent is 50° C.-150° C., and, drying is a sectional temperature rise baking.

9. A method of preparing a high-temperature-resistant insulating coating material, comprising a step of using the high-temperature-resistant insulating polymer composite according to claim 1 in preparing the high-temperature-resistant insulating coating material.

10. A high-temperature-resistant insulating coating material, wherein the high-temperature-resistant insulating coating material is a three-layered structure composed of a protective film layer, a layer of the high-temperature-resistant insulating polymer composite according to claim L and a film material layer, wherein the layer of the high-temperature-resistant insulating polymer composite is supported by the film material layer, and a surface of the layer of the high-temperature-resistant insulating polymer composite is covered with the protective film layer; the film material layer is a first polymer film material or a paper-based film material, the first polymer film material is selected from the group consisting of a polyester (PET) film, a polyether-ether-ketone (PEEK) film, a polyetherimide (PEI) film, a polyimide (PI) film, and a polycarbonate (PC) film, and the paper-based film material is selected from the group consisting of a release paper and a coated paper; a thickness of the film material layer is 10 μm-300 μm; the layer of the high-temperature-resistant insulating polymer composite is formed by an electronic slurry of the high-temperature-resistant insulating polymer composite and on a surface of the film material layer; a material of the protective film layer is second polymer film material, and the second polymer film material is selected from the group consisting of a polyester film, a polypropylene film, and a polyethylene film; a thickness of the protective film layer is 10 μm-300 μm; a thickness of the layer of the high-temperature-resistant insulating polymer composite between the film material layer and the protective film layer is 1 μm-100 μm.

11. A preparation method of the high-temperature-resistant insulating coating material according to claim 10, comprising steps of: 1) uniformly dispersing the cyanate ester resin, the epoxy resin, the inorganic filler, the aepoxy resin curing agent, the curing accelerant, the dispersant, and a solvent to form the electronic slurry of the high-temperature-resistant insulating polymer composite; and 2) coating the electronic slurry of the high-temperature-resistant insulating polymer composite to the surface of the film material layer, attaching the electronic slurry of the high-temperature-resistant insulating polymer composite to the protective film layer after being dried by an oven to form the high-temperature-resistant insulating coating material; wherein a coating mode of the electronic slurry of the high-temperature-resistant insulating polymer composite is selected from the group consisting of gravure printing, micro-gravure printing, comma scrapers, and slit extrusion, a drying temperature of the solvent is 50° C.−150° C., and drying is a sectional temperature rise baking; after the solvent is baked and dried, attaching the protective film layer and obtaining the high-temperature-resistant insulating coating material with the three-layered structure in a hot-pressing mode at a temperature of 50° C.-100° C.

12. A method of preparing a semiconductor electronic package, comprising a step of using the high-temperature-resistant insulating coating material according to claim 10 for the semiconductor electronic package, wherein the semiconductor electronic package is a fine circuit package or a package of a printed circuit board, a substrate and a carrier board made by an addition process or a semi-addition process.

13. The high-temperature-resistant insulating polymer composite according to claim 6, wherein the aromatic solvent is selected from the group consisting of xylene, o-xylene, m-xylene, p-xylene, hexamethyl benzene, and ethylbenzene; the halogenated hydrocarbon solvent is selected from the group consisting of chlorobenzene, dichlorobenzene, and dichloromethane; the fatty hydrocarbon solvent is selected from the group consisting of pentane, pentane, and pentane; the alicyclic hydrocarbon solvent is selected from the group consisting of cyclohexane, cyclohexanone, and toluene cyclohexanone; the alcohol solvent is selected from the group consisting of methanol, ethanol, and isopropanol; the ester solvent is selected from the group consisting of methyl acetate, acetic ether, and propyl acetate; the ketone solvent is selected from the group consisting of acetone, 2-butanone, and methyl isobutyl ketone; and the amide solvent is at least one selected from the group consisting of dimethylformamide, hexamethyl phosphamide, N-methyl formamide, and dimethylacetamide.

14. The preparation method according to claim 8, wherein in step 1), an auxiliary agent is further added to obtain the electronic slurry of the high-temperature-resistant insulating polymer composite, and the auxiliary agent is selected from the group consisting of a second defoamer, a coupling agent, an anti-settling agent, a leveling agent, a rheological agent, and a flame retardant.

15. The preparation method according to claim 11, wherein in step 1), an auxiliary agent is further added to form the electronic slurry of the high-temperature-resistant insulating polymer composite, wherein the auxiliary agent is selected from the group consisting of a second defoamer, a coupling agent, an anti-settling agent, a leveling agent, a rheological agent, and a flame retardant.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0043] FIG. 1 is a schematic structural diagram of an insulating coating material, wherein 1-1 is a protective film layer, 1-2 is a layer of the insulating polymer composite, and 1-3 is a supporting film material layer.

[0044] FIG. 2 is a schematic structural diagram of an insulating polymer composite in the insulating coating material, wherein 2-1 are inorganic filler particles and 2-2 is a high molecular polymer.

[0045] FIG. 3 is a schematic flow diagram of the insulating coating material prepared by the present invention.

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0046] In order to make purposes, features and advantages of the present invention more obvious and understandable, detailed description on specific embodiments of the present invention will be made below in combination with the drawings, but cannot be understood as limitation to the applicable scope of the present invention.

[0047] The embodiment provides a high-temperature-resistant insulating coating material usable for semiconductor package and suitable for an addition process or a semi-addition process of fine circuit, the material being prepared by the following steps:

Example 1

[0048] 1. The components are weighed according to a formula below:

[0049] 10 g of spherical aluminum oxide, 5 g of epoxy resin EPALLOY 8220, 8 g of cyanate ester resin CEO5CS, 0.4 g of cyanoguanidine, 0.01 g of 2-methyl-4-ethyl imidazole, 0.3 g of nonylphenol polyoxyethylene ether, 10 g of N,N-dimethyl formamide and 10 g of butanone.

[0050] 2. The components are subjected to ball-milling for 12 hours at 600 rpm to obtain electronic slurry of an insulating polymer composite.

[0051] 3. The electronic slurry of the insulating polymer composite is coated to the surface of a PET thin film with a thickness of 50 μm by a comma scraper coating manner.

[0052] 4. The thickness of the insulating polymer composite film is controlled according to a solid content of the electronic slurry and a separation distance between the scraper and the PET thin film, the thickness of the dried thin film is controlled to be 20 μm, the segmented oven is used in the drying process, the temperature of the oven is raised stage by stage, and started from the coating end, the temperature of the oven is set at 60° C., 80° C., 100° C., 110° C. and 120° C.

[0053] 5. The dried insulating polymer composite film and the OPP film with the thickness of 20 μm are subjected to hot pressing compounding, and in the hot pressing process, a temperature of a heating roller is set at 70° C. Hot pressing is carried out to obtain the insulating coating material with the three-layered structure.

[0054] 6. The glass transition temperature of the cured insulating coating material of Example 1 is 202° C.

Example 2

[0055] 1. The components are weighed according to a formula below:

[0056] 10 g of spherical silicon dioxide, 2 g of epoxy resin HyPox PK 84, 10 g of epoxy resin NPES-902, 8 g of cyanate ester resin CEO5CS, 1 g of cyanoguanidine, 0.03 g of 2-methyl-4-ethyl imidazole, 0.3 g of nonylphenol polyoxyethylene ether, 10 g of N,N-dimethyl formamide and 20 g of butanone.

[0057] 2. The components are subjected to ball-milling for 12 hours at 600 rpm to obtain electronic slurry of an insulating polymer composite.

[0058] 3. The electronic slurry of the insulating polymer composite is coated to the surface of a PET thin film with a thickness of 50 μm by a comma scraper coating manner.

[0059] 4. The thickness of the insulating polymer composite film is controlled according to a solid content of the electronic slurry and a separation distance between the scraper and the PET thin film, the thickness of the dried thin film is controlled to be 20 μm, the segmented oven is used in the drying process, the temperature of the oven is raised stage by stage, and started from the coating end, the temperature of the oven is set at 60° C., 80° C., 100° C., 110° C. and 120° C.

[0060] 5. The dried insulating polymer composite film and the OPP film with the thickness of 20 μm are subjected to hot pressing compounding, and in the hot pressing process, a temperature of a heating roller is set at 70° C. Hot pressing is carried out to obtain the insulating coating material with the three-layered structure.

[0061] 6. The glass transition temperature of the cured insulating coating material of Example 2 is 185° C.

Example 3

[0062] 1. The components are weighed according to a formula below: 10 g of spherical silicon dioxide, 2 g of epoxy resin HyPox PK 84, 15 g of epoxy resin NPES-902, 5 g of cyanate ester resin CEO5CS, 1 g of cyanoguanidine, 0.03 g of 2-methyl-4-ethyl imidazole, 0.3 g of nonylphenol polyoxyethylene ether, 10 g of N,N-dimethyl formamide and 20 g of butanone.

[0063] 2. The components are subjected to ball-milling for 12 hours at 600 rpm to obtain electronic slurry of an insulating polymer composite.

[0064] 3. The electronic slurry of the insulating polymer composite is coated to the surface of a PET thin film with a thickness of 50 μm by a comma scraper coating manner.

[0065] 4. The thickness of the insulating polymer composite film is controlled according to a solid content of the electronic slurry and a separation distance between the scraper and the PET thin film, the thickness of the dried thin film is controlled to be 20 μm, the segmented oven is used in the drying process, the temperature of the oven is raised stage by stage, and started from the coating end, the temperature of the oven is set at 60° C., 80° C., 100° C., 110° C. and 120° C.

[0066] 5. The dried insulating polymer composite film and the OPP film with a thickness of 20 μm are subjected to hot pressing compounding, and in the hot pressing process, a temperature of a heating roller is set at 70° C. Hot pressing is carried out to obtain the insulating coating material with the three-layered structure.

[0067] 6. The glass transition temperature of the cured insulating coating material of Example 3 is 165° C.

Comparative Example 4

[0068] 1. The components are weighed according to a formula below: 10 g of spherical aluminum oxide, 13 g of epoxy resin EPALLOY 8220, 1 g of cyanoguanidine, 0.1 g of 2-methyl-4-ethyl imidazole, 0.3 g of nonylphenol polyoxyethylene ether, 10 g of N,N-dimethyl formamide and 10 g of butanone.

[0069] 2. The components are subjected to ball-milling for 12 hours at 600 rpm to obtain electronic slurry of an insulating polymer composite.

[0070] 3. The electronic slurry of the insulating polymer composite is coated to the surface of a PET thin film with the thickness of 50 μm by a comma scraper coating manner.

[0071] 4. The thickness of the insulating polymer composite thin film is controlled according to a solid content of the electronic slurry and a separation distance between the scraper and the PET thin film, the thickness of the dried thin film is controlled to be 20 μm, the segmented oven is used in the drying process, the temperature of the oven is raised stage by stage, and started from the coating end, the temperature of the oven is set at 60° C., 80° C., 100° C., 110° C. and 120° C.

[0072] 5. The dried insulating polymer composite film and the OPP film with the thickness of 20 μm are subjected to hot pressing compounding, and in the hot pressing process, a temperature of a heating roller is set at 70° C. Hot pressing is carried out to obtain the insulating coating material with the three-layered structure.

[0073] 6. The glass transition temperature of the cured insulating coating material of Comparative example 4 is 105° C.

Comparative Example 5

[0074] 1. The Components are Weighed According to a Formula Below:

[0075] 10 g of spherical silicon dioxide, 10 g of epoxy resin HyPox PK 84, 10 g of epoxy resin NPES-902, 1 g of cyanoguanidine, 0.3 g of 2-methyl-4-ethyl imidazole, 0.3 g of nonylphenol polyoxyethylene ether, 10 g of N,N-dimethyl formamide and 20 g of butanone.

[0076] 2. The components are subjected to ball-milling for 12 hours at 600 rpm to obtain electronic slurry of an insulating polymer composite.

[0077] 3. The electronic slurry of the insulating polymer composite is coated to the surface of a PET thin film with the thickness of 50 μm by a comma scraper coating manner.

[0078] 4. The thickness of the insulating polymer composite thin film is controlled according to a solid content of the electronic slurry and a separation distance between the scraper and the PET thin film, the thickness of the dried thin film is controlled to be 20 μm, the segmented oven is used in the drying process, the temperature of the oven is raised stage by stage, and started from the coating end, the temperature of the oven is set at 60° C., 80° C., 100° C., 110° C. and 120° C.

[0079] 5. The dried insulating polymer composite film and the OPP film with the thickness of 20 μm are subjected to hot pressing compounding, and in the hot pressing process, a temperature of a heating roller is set at 70° C. Hot pressing is carried out to obtain the insulating coating material with the three-layered structure.

[0080] 6. The glass transition temperature of the cured insulating coating material of Comparative example 5 is 115° C.

Comparative Example 6

[0081] 1. The components are weighed according to a formula below: 10 g of spherical silicon dioxide, 7 g of epoxy resin HyPox PK 84, 15 g of epoxy resin NPES-902, 1 g of cyanoguanidine, 0.03 g of 2-methyl-4-ethyl imidazole, 0.3 g of nonylphenol polyoxyethylene ether, 10 g of N,N-dimethyl formamide and 20 g of butanone.

[0082] 2. The components are subjected to ball-milling for 12 hours at 600 rpm to obtain electronic slurry of an insulating polymer composite.

[0083] 3. The electronic slurry of the insulating polymer composite is coated to the surface of a PET thin film with the thickness of 50 μm by a comma scraper coating manner.

[0084] 4. The thickness of the insulating polymer composite thin film is controlled according to a solid content of the electronic slurry and a separation distance between the scraper and the PET thin film, the thickness of the dried thin film is controlled at 20 μm, the segmented oven is used in the drying process, the temperature of the oven is raised stage by stage, and started from the coating end, the temperature of the oven is set at 60° C., 80° C., 100° C., 110° C. and 120° C.

[0085] 5. The dried insulating polymer composite thin film and the OPP thin film with the thickness of 20 μm are subjected to hot pressing compounding, and in the hot pressing process, a temperature of a heating roller is set at 70° C. Hot pressing is carried out to obtain the insulating coating material with the three-layered structure.

[0086] 6. The glass transition temperature of the cured insulating coating material of Comparative example 6 is 115° C.