阅读说明：本技术 芯片封装专用低介电高导热底部填充胶 (Special low-dielectric high-thermal-conductivity underfill adhesive for chip packaging ) 是由 彭琦 刘锋 陈燕舞 吴嘉培 高仕旭 于 2020-03-27 设计创作，主要内容包括：本发明涉及一种芯片封装专用低介电高导热底部填充胶,芯片封装专用低介电高导热底部填充胶,其特征在于包括低分子量的含氟聚苯酚结构的环氧树脂、环氧树脂、稀释剂、增韧剂、固化剂、潜伏性促进剂、硅烷偶联剂、导热填料及消泡剂。其以该树脂降低基体树脂的介电常数,同时通过增加高导热的填料实现高导热性能,具有低介电、高导热、低CTE、高Tg和高模量的特性,适合在5G移动通讯芯片中作为底部填充胶使用。(The invention relates to a low-dielectric high-thermal-conductivity underfill adhesive special for chip packaging, which is characterized by comprising epoxy resin with a low molecular weight fluorine-containing polyphenol structure, epoxy resin, a diluent, a toughening agent, a curing agent, a latent accelerator, a silane coupling agent, a thermal conductive filler and a defoaming agent. The resin is used for reducing the dielectric constant of matrix resin, and simultaneously realizes high heat-conducting property by increasing high heat-conducting filler, has the characteristics of low dielectric, high heat-conducting property, low CTE, high Tg and high modulus, and is suitable for being used as underfill in a 5G mobile communication chip.)

1. The special low-dielectric high-heat-conductivity underfill adhesive for chip packaging is characterized by comprising epoxy resin, a diluent, a toughening agent, a curing agent, a latent accelerator, a silane coupling agent, a heat-conducting filler and a defoaming agent with a low molecular weight fluorine-containing polyphenol structure, wherein the weight ratio of the epoxy resin, the diluent, the toughening agent, the curing agent, the latent accelerator, the silane coupling agent, the heat-conducting filler and the defoaming agent with the low molecular weight fluorine-containing polyphenol structure is 100: 10-50: 20-100: 50-200: 20-50: 5-50: 0.1-1: 50-200: 0.5-3.

2. The special low-dielectric high-thermal-conductivity underfill adhesive for chip packaging according to claim 1, wherein the structural formula of the low-molecular-weight fluorine-containing polyphenol structured epoxy resin is as follows, and the synthesis method comprises: dissolving 2, 6-difluorophenol acrylate, 2, 6-dimethylphenol acrylate and an epoxy group-containing monomer in a solvent A, adding an initiator, reacting at the temperature of 40-80 ℃ for 2-5 hours, and purifying to obtain epoxy resin containing fluorinated polyphenol, wherein the epoxy resin containing fluorinated polyphenol is a low-molecular-weight low-dielectric random copolymer; the weight ratio of the 2, 6-difluorophenol acrylate, the 2, 6-dimethylphenol acrylate, the epoxy group-containing monomer, the solvent A and the initiator is as follows: 100: 20-50: 20-50: 500-2000: 10-20 parts of;

wherein R is₁Is CH₃Or H, x is 0-50, y is 1-40, z is 1-40, and n is 2-130.

3. The underfill with low dielectric constant and high thermal conductivity for chip packaging according to claim 2, wherein the structural formula of the 2, 6-difluorophenol acrylate is as follows, and the synthesis method comprises: dissolving 2, 6 difluorophenol in a solvent B, adding acryloyl chloride with double bonds, reacting at the temperature of 40-80 ℃ for 2-5 hours, and purifying by a precipitation method to obtain 2, 6 difluorophenol acrylate; the weight ratio of the 2, 6-difluorophenol to the solvent B to the acryloyl chloride is 100: 200-1000: 20-50 parts of;

。

4. the special low-dielectric high-thermal-conductivity underfill adhesive for chip packaging according to claim 2, wherein the structural formula of the 2, 6-dimethylphenol acrylate is as follows, and the synthesis method comprises: dissolving 2, 6-dimethylphenol in a solvent B, adding acryloyl chloride with double bonds, reacting at the temperature of 40-80 ℃ for 2-5 hours, and purifying by a precipitation method to obtain 2, 6-dimethylphenol acrylate; the weight ratio of the 2, 6-difluorophenol to the solvent B to the acryloyl chloride is 100: 200-1000: 20-50 parts of;

。

5. the underfill with low dielectric constant and high thermal conductivity for chip packaging as claimed in claim 1, wherein the epoxy resin is one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, novolac epoxy resin, alicyclic epoxy resin, biphenyl epoxy resin, naphthalene ring structure epoxy resin, hydrogenated epoxy resin, and silicone epoxy resin, and has a molecular weight of 1000-30000, a halogen content of 200ppm or less, and a metal ion content of 5ppm or less.

6. The special low-dielectric high-thermal-conductivity underfill adhesive for chip packaging according to claim 2, wherein the epoxy group-containing monomer is glycidyl methacrylate and glycidyl acrylate; the initiator is characterized by being one or a mixture of more of diisobutyryl peroxide, cumyl peroxyneodecanoate, bis (3-methoxybutyl) peroxydicarbonate, bis (ethoxyhexyl) peroxydicarbonate, tert-amyl peroxyneodecanoate, tert-butyl peroxyneodecanoate, bis (2, 4-dichlorobenzoyl) peroxide, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxyisobutyrate, tert-amyl peroxybenzoate, acetylacetone peroxide, tert-butyl hydroperoxide, tert-amyl hydroperoxide, tert-butyl cumyl peroxide, azobisisobutyronitrile, azobisisoheptonitrile and dimethyl azobisisobutyrate.

7. The underfill with low dielectric constant and high thermal conductivity for chip packaging according to claim 1, wherein the curing agent is one or a mixture of tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl succinic anhydride, octenyl succinic anhydride, dodecenyl succinic anhydride ‍, methyl nadic anhydride, methyl tetrahydrophthalic anhydride or methyl hexahydrophthalic anhydride.

8. The underfill with low dielectric constant and high thermal conductivity specially used for chip packaging according to claim 1, wherein the latent accelerator is one or a mixture of heptadecyl imidazole, 2-phenyl-4, 5-dihydroxyphenyl imidazole, 2-phenyl-4-methyl-5-hydroxymethyl imidazole, 2-phenyl-4-benzyl-5-hydroxymethyl imidazole, triphenylphosphine, aluminum acetylacetonate, cobalt naphthenate and salicyloyl hydrazide; commercial products such as 2MZ, C11Z, C17Z, 2E4MZ, 2PZ-PW, 2PZ, 2P4MZ, 1B2MZ, 1B2PZ, 12DMZ, 2MZ-CN, 2E4MZ-CN, C11Z-CN, 2PZ-CN, C11Z-CNS, 2PZCNS-PW, 2MZ-A, 2MZA-PW, 2MZ-A, C11Z-A, 2E4MZ-A, 2MA-OK, 2MAOK-PW, 2PZ-OK, 2PHZ or 2P4MHZ, all of which are manufactured in the four countries of Japan; PN-23, PN-40, PN-H, MY-24 or PN-50 from the company Aomoto Japan; EH-4337S, EH-3293S or EH-4357S from Aidicco, Japan; NOVACURE HX-372 or HX-3088 from Asahi Kasei corporation, Japan.

9. The underfill with low dielectric constant and high thermal conductivity for chip packaging according to claim 1, wherein the diluent is one or more selected from butyl glycidyl ether, phenyl glycidyl ether, benzyl glycidyl ether, dodecyl glycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane triglycidyl ether, 1, 6-hexanediol diglycidyl ether, glycidyl methacrylate, C12-C14 alkyl glycidyl ether, and 1, 2-cyclohexanediol diglycidyl ether.

10. The underfill as claimed in claim 1, wherein the thermal conductive filler is selected from the group consisting of spherical silicon nitride, spherical alumina, and mixtures of spherical silica and boron nitride, and has a particle size of 100-1000 nm.

11. The special low-dielectric high-thermal-conductivity underfill adhesive for chip packaging according to claim 1, wherein the toughening agent is: butadiene elastomer systems such as the commercial MX137, MX154 or MX533 series (KANEKA corporation, japan); of organosilicon-modified systems, such as MX965 (KANEKA, Japan) or KMP-605 (Beacon); rubber systems, such as ATBN or CTBN (of the Japan department of Japan).

12. The special low-dielectric high-thermal-conductivity underfill adhesive for chip packaging according to claim 1, wherein the silane coupling agent is bis- (γ -triethoxysilylpropyl) tetrasulfide, γ -aminopropyltriethoxysilane, γ - (2, 3-epoxypropoxy) propyltrimethoxysilane, γ -methacryloxypropyltrimethoxysilane, γ -mercaptopropyltrimethylsilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, isopropyl triisostearate isopropyl complex, isopropyldioleate acyloxy (dioctylphosphate) titanate, isopropyltris (dioctylphosphate) titanate, bis (dioctyloxypyrophosphate) ethylene titanate, or bis (dioctyloxypropylphosphate) ethylene titanate, One or a mixture of a plurality of bis (diethyl citrate) dipropoxy zirconium chelate compounds or organic zirconate coupling agents.

13. The special low-dielectric high-thermal-conductivity underfill for chip packaging as claimed in claim 1, wherein the defoaming agent is one or a mixture of several of hum 5400, hum 5500, hum 6800, hum 5300, BYK-051, BYK-052, BYK-053, BYK-054, BYK-056, BYK-057, BYK-065, BYK-066N, BYK-067A, BYK-070, BYK-077, BYK-085, BYK-077, BYK-088 and BYK-141 of an organosilicon system.

14. The underfill with low dielectric constant and high thermal conductivity for chip packaging according to claim 2, wherein the solvent a is one or a mixture of cyclohexanone, dioxane, nitromethane, nitroethane, nitrobenzene, chloroform, dimethyl sulfoxide, dimethylformamide, tetrahydrofuran, azomethylpyrrolidone, methyl ethyl ketone, propylene glycol monomethyl ether, dibutyl ether, or xylene.

15. The special low-dielectric high-thermal-conductivity underfill adhesive for chip packaging according to claim 3, wherein the solvent B is one or a mixture of tetrahydrofuran, cyclohexanone, chloroform, dioxane, ethyl acetate or toluene.

Technical Field

The invention relates to an epoxy resin with a low dielectric fluorophenol-containing structure, in particular to a low dielectric high heat conduction underfill special for chip packaging.

Background

For chip packaging, underfill is a very critical packaging material, and the material suppliers of chip-level underfill commonly used in the industry include nano, Hitach, Henkel, etc., and there are a lot of related technical patent inventions, and the companies such as chinese material suppliers like debapont science and technology, Youbang, Xinyou, etc. also have related patent applications, and related products are synchronously released.

With the development of communication technology, especially with the advent of the 5G era, the data volume of signal transmission is becoming larger, and the requirement of 5G low-delay characteristic is more demanding than the requirement of low-dielectric and high-thermal-conductivity packaging materials.

In order to further reduce the dielectric constant, the inventors modified the epoxy resin of underfill, for example, in the Chinese patent application having application No. 201710944980.4 entitled "Low dielectric constant Environment-friendly underfill and method for preparing the same", which uses epoxy resins from Nanjing Toxico medicine YS-HBPA1, Japanese ADEKA EP-4080E, Japanese DIC HP-4032D, Nippon Chemicals NC-7000L, Nippon Mitsubishi Y L6121H, and Nippon Chemicals NC-3000. in order to enhance the high thermal conductivity, the application No. 201910611768.5 entitled "underfill composition" is a Chinese patent application having application No. 201510355328.X, named "underfill", which uses Al as an invention₂O₃AlN, BN, SiC and Si₃N₄(ii) a The invention patent with application number 201510326082.3 and name underfill and preparation method thereof uses nano aluminum oxide, spherical nano boron nitride, spherical nano aluminum nitride, spherical nano silicon carbide, spherical nano silicon nitride and spherical nano diamond powder to realize high heat conduction effect. The underfill invented in the above patent is notwithstandingThe heat conductivity is improved, but the technical problems of low dielectric constant and high heat conductivity cannot be solved at the same time. With the demand of low dielectric and high thermal conductivity of chips, the underfill with low dielectric and high thermal conductivity needs to be developed.

Disclosure of Invention

In order to overcome the defects of the prior art, the invention aims to provide the special low-dielectric high-thermal-conductivity underfill for chip packaging, which has low dielectric and high thermal conductivity and can be used for the underfill and heat dissipation of high-end chips.

In order to achieve the above-mentioned primary object, the technical scheme of the present invention is implemented as follows, and the underfill is a low-dielectric high-thermal-conductivity underfill dedicated for chip packaging, and is characterized by comprising a low-molecular-weight epoxy resin with a fluorine-containing polyphenol structure, an epoxy resin, a diluent, a toughening agent, a curing agent, a latent accelerator, a silane coupling agent, a thermal conductive filler and an antifoaming agent, wherein the weight ratio of the low-molecular-weight epoxy resin with the fluorine-containing polyphenol structure, the epoxy resin, the diluent, the toughening agent, the curing agent, the latent accelerator, the silane coupling agent, the thermal conductive filler and the antifoaming agent is 100: 10-50: 20-100: 50-200: 20-50: 5-50: 0.1-1: 50-200: 0.5-3.

In the technical scheme, the structural formula of the low molecular weight fluorine-containing polyphenol structure-containing epoxy resin is shown as follows, and the synthesis method comprises the following steps: dissolving 2, 6-difluorophenol acrylate, 2, 6-dimethylphenol acrylate and acrylic glycidyl ether in a solvent A, adding an initiator, reacting at the temperature of 40-80 ℃ for 2-5 hours, and purifying to obtain epoxy resin containing fluorinated polyphenol, wherein the epoxy resin containing fluorinated polyphenol is a low-molecular-weight low-dielectric random copolymer; the weight ratio of the 2, 6-difluorophenol acrylate, the 2, 6-dimethylphenol acrylate, the epoxy group-containing monomer, the solvent A and the initiator is as follows: 100: 20-50: 20-50: 500-2000: 10-20 parts of;

wherein R is₁Is CH₃Or H, x is 0 to 50, y is 1-40, z is 1-40, and n is 2-130.

In the technical scheme, the structural formula of the 2, 6-difluorophenol acrylate is as follows, and the synthesis method comprises the following steps: dissolving 2, 6 difluorophenol in a solvent B, adding acryloyl chloride with double bonds, reacting at the temperature of 40-80 ℃ for 2-5 hours, and purifying by a precipitation method to obtain 2, 6 difluorophenol acrylate; the weight ratio of the 2, 6-difluorophenol to the solvent B to the acryloyl chloride is 100: 200-1000: 20-50 parts of;

。

in the technical scheme, the structural formula of the 2, 6-dimethylphenol acrylate is shown as follows, and the synthesis method comprises the following steps: dissolving 2, 6-dimethylphenol in a solvent B, adding acryloyl chloride with double bonds, reacting at the temperature of 40-80 ℃ for 2-5 hours, and purifying by a precipitation method to obtain 2, 6-dimethylphenol acrylate; the weight ratio of the 2, 6-difluorophenol to the solvent B to the acryloyl chloride is 100: 200-1000: 20-50 parts of;

in the technical scheme, the epoxy resin is one or a mixture of bisphenol A epoxy resin, bisphenol F epoxy resin, novolac epoxy resin, alicyclic epoxy resin, biphenyl epoxy resin, naphthalene ring structure epoxy resin, hydrogenated epoxy resin and organosilicon epoxy resin, the molecular weight of the epoxy resin is between 1000-30000, the halogen content is below 200ppm, and the metal ion content is below 5 ppm.

In the technical scheme, the epoxy group-containing monomer is glycidyl methacrylate and glycidyl acrylate.

In the technical scheme, the initiator is one or a mixture of more of diisobutyryl peroxide, cumyl peroxyneodecanoate, bis (3-methoxybutyl) peroxydicarbonate, bis (ethoxyhexyl) peroxydicarbonate, tert-amyl peroxyneodecanoate, tert-butyl peroxyneodecanoate, bis (2, 4-dichlorobenzoyl) peroxide, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxyisobutyrate, tert-amyl peroxybenzoate, acetylacetone peroxide, tert-butyl hydroperoxide, tert-amyl hydroperoxide, tert-butyl cumyl peroxide, azobisisobutyronitrile, azobisisoheptonitrile and dimethyl azobisisobutyrate.

In the technical scheme, the curing agent is one or a mixture of more of tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl succinic anhydride, octenyl succinic anhydride, dodecenyl succinic anhydride ‍, methyl nadic anhydride, methyl tetrahydrophthalic anhydride or methyl hexahydrophthalic anhydride.

In the technical scheme, the latent accelerator is one or a mixture of more of heptadecyl imidazole, 2-phenyl-4, 5-dihydroxyphenyl imidazole, 2-phenyl-4-methyl-5-hydroxymethyl imidazole, 2-phenyl-4-benzyl-5-hydroxymethyl imidazole, triphenylphosphine, aluminum acetylacetonate, cobalt naphthenate and salicyloyl hydrazine; commercial products such as 2MZ, C11Z, C17Z, 2E4MZ, 2PZ-PW, 2PZ, 2P4MZ, 1B2MZ, 1B2PZ, 12DMZ, 2MZ-CN, 2E4MZ-CN, C11Z-CN, 2PZ-CN, C11Z-CNS, 2PZCNS-PW, 2MZ-A, 2MZA-PW, 2MZ-A, C11Z-A, 2E4MZ-A, 2MA-OK, 2MAOK-PW, 2PZ-OK, 2PHZ or 2P4MHZ, all of which are manufactured in the four countries of Japan; PN-23, PN-40, PN-H, MY-24 or PN-50 from the company Aomoto Japan; EH-4337S, EH-3293S or EH-4357S from Aidicco, Japan; NOVACURE HX-372 or HX-3088 from Asahi Kasei corporation, Japan.

In the technical scheme, the diluent is one or a mixture of butyl glycidyl ether, phenyl glycidyl ether, benzyl glycidyl ether, dodecyl glycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane triglycidyl ether, 1, 6-hexanediol diglycidyl ether, glycidyl methacrylate, C12-14 alkyl glycidyl ether or 1, 2-cyclohexanediol diglycidyl ether.

In the technical scheme, the heat conducting filler is one or a mixture of spherical silicon nitride, spherical alumina, spherical silicon dioxide or boron nitride, and the particle size of the heat conducting filler is between 100 and 1000 nm.

In the technical scheme, the toughening agent is as follows: butadiene elastomer systems such as the commercial MX137, MX154 or MX533 series (KANEKA corporation, japan); of organosilicon-modified systems, such as MX965 (KANEKA, Japan) or KMP-605 (Beacon); rubber systems, such as ATBN or CTBN (of the Japan department of Japan);

in the technical scheme, the silane coupling agent is bis- (gamma-triethoxysilylpropyl) tetrasulfide, gamma-aminopropyltriethoxysilane, gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, gamma-mercaptopropyltrimethylsilane, vinyltriethoxysilane, one or a mixture of more of vinyl tri (2-methoxyethoxy) silane, isopropyl triisostearate, a compound of isopropyl triisostearate, isopropyl dioleate acyloxy (dioctyl phosphate acyloxy) titanate, isopropyl tri (dioctyl pyrophosphate acyloxy) titanate, bis (dioctyl pyrophosphate ester) ethylene titanate, bis (diethyl citrate) dipropoxy zirconium chelate or organic zirconate coupling agent.

In the technical scheme, the defoaming agent is one or a mixture of several of hum 5400, hum 5500, hum 6800, hum 5300, BYK-051, BYK-052, BYK-053, BYK-054, BYK-056, BYK-057, BYK-065, BYK-06 066N, BYK-06 067A, BYK-070, BYK-077, BYK-085, BYK-077, BYK-088 and BYK-141 of an organosilicon system.

In the technical scheme, the solvent A is one or a mixture of more of cyclohexanone, dioxane, nitromethane, nitroethane, nitrobenzene, chloroform, dimethyl sulfoxide, dimethylformamide, tetrahydrofuran, nitrogen methyl pyrrolidone, methyl ethyl ketone, propylene glycol monomethyl ether, dibutyl ether or xylene.

In the technical scheme, the solvent B is one or a mixture of more of tetrahydrofuran, cyclohexanone, chloroform, dioxane, ethyl acetate or toluene.

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

1. the invention discloses a multi-functional epoxy resin, which contains a low-dielectric fluorine-containing polyphenol structure and an epoxy resin structure, so that the resin has a low dielectric function and simultaneously contains a reactive epoxy group, and the resin is used as a main resin to carry out the formula design of underfill, so that the low dielectric property of the underfill can be realized.

2. According to the invention, spherical heat-conducting fillers such as boron nitride, aluminum trioxide and the like with high heat conductivity are added, so that on one hand, the high heat-conducting property of the underfill can be realized, and meanwhile, the fluidity of the underfill can be improved.

3. According to the application of the invention, the phenol structure is a fluorine-containing group, and the dielectric property and the water absorption performance can be further improved by the fluorine-containing group, so that the underfill prepared by taking the structure as a main body is suitable for large-size chips, and is beneficial to improving the mechanical and environmental reliability of the chips.

Detailed Description

The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.