CN115074065B - Epoxy adhesive for chip packaging and preparation process thereof - Google Patents

Epoxy adhesive for chip packaging and preparation process thereof Download PDF

Info

Publication number
CN115074065B
CN115074065B CN202210620003.XA CN202210620003A CN115074065B CN 115074065 B CN115074065 B CN 115074065B CN 202210620003 A CN202210620003 A CN 202210620003A CN 115074065 B CN115074065 B CN 115074065B
Authority
CN
China
Prior art keywords
boron nitride
epoxy adhesive
mixing
mixed material
epoxy
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202210620003.XA
Other languages
Chinese (zh)
Other versions
CN115074065A (en
Inventor
黄道生
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Doyle Huacheng Electronic Materials Shanghai Co ltd
Original Assignee
Doyle Huacheng Electronic Materials Shanghai Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Doyle Huacheng Electronic Materials Shanghai Co ltd filed Critical Doyle Huacheng Electronic Materials Shanghai Co ltd
Priority to CN202210620003.XA priority Critical patent/CN115074065B/en
Publication of CN115074065A publication Critical patent/CN115074065A/en
Application granted granted Critical
Publication of CN115074065B publication Critical patent/CN115074065B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/5033—Amines aromatic
    • 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
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C08K2003/382—Boron-containing compounds and nitrogen
    • C08K2003/385—Binary compounds of nitrogen with boron
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Epoxy Resins (AREA)

Abstract

The invention provides an epoxy adhesive for chip encapsulation and a preparation process thereof, wherein self-made bisphenol epoxy resin is selected, semi-aromatic polyamide, namely poly-p-dodecylene diamine is introduced, and the prepared bisphenol epoxy monomer simultaneously contains allyl and epoxy groups, so that two times of curing reaction under different temperature conditions are required for complete curing; hexagonal boron nitride and carbon nano tubes are used as heat-conducting fillers, and meanwhile, the toughness of the epoxy adhesive is improved; by functionalizing the boron nitride nanosheet, cumene oxyl groups are successfully and covalently grafted on the surface of the boron nitride, so that the cumene oxyl functionalized boron nitride nanosheet is obtained, and the dispersibility of the cumene oxyl functionalized boron nitride nanosheet in epoxy adhesive is improved; the heat resistance of the epoxy adhesive is improved by limiting the content of allyl and benzene rings in the dibutylphenol-based epoxy resin and the cumyloxy-functionalized boron nitride nanosheet, controlling the proportion of each functional group.

Description

Epoxy adhesive for chip packaging and preparation process thereof
Technical Field
The invention relates to the technical field of bonding glue, in particular to epoxy bonding glue for chip packaging and a preparation process thereof.
Background
Under the background that electronic products develop towards high density and high performance, the size and the weight of a chip are smaller and smaller, the requirement on the density of three-dimensional chip packaging is higher and higher, and the heat dissipation problem of a heating component is more and more obvious. If the accumulated heat can not be dissipated in time, local high temperature is easily formed, and then components and parts can be damaged, so that the reliability and the normal working period of equipment are influenced, and the service life is directly influenced.
Because epoxy resin has good electrical insulation performance, the epoxy resin is the most commonly used chip packaging material matrix in the existing market, but the thermal conductivity coefficient of the epoxy resin is low, so that the development of the epoxy adhesive for chip packaging with high thermal conductivity coefficient becomes a hot problem at present.
Disclosure of Invention
The invention aims to provide an epoxy adhesive for chip packaging and a preparation process thereof, which aim to solve the problems in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme:
the epoxy adhesive for chip packaging comprises the following components in parts by mass: 15-20 parts of biseugenol epoxy resin, 5-10 parts of poly-p-phthaloyl dodecaamine, 1-5 parts of polythiol, 0.5-1.0 part of imidazole, 20-30 parts of cumyl oxy functionalized boron nitride nanosheet and 10-15 parts of carbon nano tube.
In order to adapt to the high-speed development of chips at the present stage and meet the higher and higher requirements on the epoxy adhesive for chip packaging, the invention prepares the epoxy adhesive for chip packaging with high heat conductivity coefficient, good heat resistance and high flame retardance.
The epoxy adhesive for chips in the existing market is multi-purpose bisphenol A epoxy resin which is petroleum-based epoxy resin, and the invention is based on a green sustainable development route, develops harmless bio-based epoxy resin and meets the dual requirements of environment and health; and solves the problems of low heat resistance, high inflammability and the like of the existing homemade bio-based epoxy resin.
The prepared bis-eugenol epoxy resin has rigid benzene rings, a plurality of easily-reacted derivative sites (hydroxyl, double bonds and benzene rings) and an o-methoxyphenol structure which contributes to carbon formation, so that the heat resistance and the flame retardance of the epoxy adhesive are improved.
Further, the preparation of the bis-eugenol epoxy resin comprises the following steps:
(1) Mixing honokiol, potassium carbonate, benzyltriethylammonium chloride and acetonitrile, stirring at 60-65 deg.C for 30-40min, adding bromopropylene, reacting at 65-70 deg.C for 10-12h, filtering, spin-drying the solvent, sequentially washing with ethyl acetate and deionized water, transferring to 200 deg.C, heating for 2h, and separating with chromatographic column to obtain 3, 3-diallyl magnolol;
(2) Mixing 3, 3-diallyl magnolol and epichlorohydrin, adding benzyltriethylammonium chloride, reacting for 3h at 80 ℃, adding sodium hydroxide and benzyltriethylammonium chloride, mixing and stirring for 30min, washing with deionized water and saturated sodium chloride aqueous solution for 2-5 times, drying with anhydrous magnesium sulfate, spin-drying the solvent, and drying to obtain the glycidyl etherate of 3, 3-diallyl magnolol;
(3) Mixing 3, 3-diallyl magnolol glycidyl etherate and diaminodiphenylmethane at 75-80 deg.C, pouring into a mold while hot, vacuum defoaming for 3-5min, and curing at different time periods to obtain the final product.
Further, the molar mass ratio of honokiol, potassium carbonate and benzyltriethylammonium chloride is 1moL:2.2moL:0.5g; the mol ratio of 3, 3-diallyl magnolol to epichlorohydrin is 1:20; the molar ratio of the glycidyl etherate of the 3, 3-diallyl magnolol to the diaminodiphenylmethane is 1:1.
further, the time-sharing curing is as follows: keeping the temperature at 105 ℃ for 1h, heating to 145 ℃ for 1h, heating to 185 ℃ for 2h, heating to 200 ℃ for 2h.
Further, the honokiol is honokiol of Changsha Shanhe biological technology.
The viscosity of the epoxy monomer has a large influence on the processability. By regulating and controlling the low viscosity of the low-epoxy monomer, the mixture of the monomer and the curing agent has better fluidity before curing, and the film cavity is easily filled; the low-viscosity epoxy monomer is beneficial to infiltrating the filler; and the low-viscosity monomer can be pre-polymerized partially to reach the required high viscosity.
According to the invention, two allyl groups are introduced to the benzene ring of honokiol at the same time to obtain 3, 3-diallyl magnolol, so that the viscosity of the bis-eugenol epoxy monomer is reduced, and the allyl groups are longer alkyl flexible chains and have a lubricating effect among molecules; and the number and the position of allyl in the molecule are regulated and controlled, and the curing reaction rate of the system is slowed down by matching with the time-phased curing, so that the implosion in the curing process is reduced, the generation of bubbles and stress concentration is avoided, and the performance of the epoxy adhesive is regulated, controlled and improved.
The prepared bis-eugenol epoxy monomer contains allyl and epoxy groups at the same time, so that two curing reactions at different temperatures are required for complete curing. The first cure is a ring-opening reaction of the amino group of the curing agent and the glycidyl ether group to form an epoxy cross-linked network.
The second curing is a cross-linking reaction with the ingredient of the epoxy adhesive, which generates allyl groups.
The glass transition temperature of the epoxy adhesive increases along with the increase of the allyl content, and because the allyl content increases, the number of chemical cross-linking points in the adhesive increases, the activity of resin chain segments is reduced, and the glass transition temperature is improved; however, the longer the bridging bond between benzene rings, the lower the glass transition temperature, because the introduction of the bridging bond not only increases the molecular weight between the cross-linking points, but also increases the freedom of movement between two benzene rings, so the ratio of each functional group is controlled by limiting the content of allyl groups and benzene rings in the dibutylphenol-based epoxy resin and cumyloxy-functionalized boron nitride nanosheets, and the heat resistance of the epoxy adhesive is improved.
The heat conductivity of the epoxy adhesive is improved by introducing the heat-conducting filler into the epoxy resin, and the hexagonal boron nitride and the carbon nano tube are used as the heat-conducting filler, so that the toughness of the epoxy adhesive is improved; hexagonal boron nitride, however, has surface inertness, which greatly limits its applications.
By functionalizing the boron nitride nanosheets, few-layer or even single-layer boron nitride nanosheets are obtained, and the dispersibility of the boron nitride nanosheets in the epoxy adhesive is improved.
Further, the preparation of the cumyl oxy-functionalized boron nitride nanosheet comprises the following steps:
1) Dispersing hexagonal boron nitride in N-methylpyrrolidone, ultrasonically stirring, centrifuging, standing, filtering the supernatant after standing through a polytetrafluoroethylene microporous filter membrane with the aperture of 0.1pm, washing with absolute ethyl alcohol, and drying to obtain solvent-stripped hexagonal boron nitride;
2) Under the anhydrous and anaerobic conditions, mixing hexagonal boron nitride stripped by a solvent with liquid ammonia, stirring for 1h at-78 ℃, adding metal lithium particles, continuously stirring for 1-2h, adding dicumyl peroxide, reacting for 12h, adding ethanol and deionized water, adjusting the pH of the mixed solution after reaction to be neutral by hydrochloric acid, centrifuging, washing by deionized water, filtering by a polytetrafluoroethylene microporous filter membrane with the aperture of 0.1pm, washing by tetrahydrofuran, chloroform and ethanol in sequence, and drying to obtain the isopropylbenzene oxyl functionalized boron nitride nanosheet.
Further, the molar volume ratio of the hexagonal boron nitride stripped by the solvent, the dicumyl peroxide and the liquid ammonia is 1.6mmoL:12.8mmoL:60mL.
Further, a preparation process of the epoxy adhesive for chip packaging comprises the following steps:
s1: stirring and mixing the dibutyranyl epoxy resin and the poly-terephthaloyl dodecane diamine at the rotating speed of 800-1000r/min of a mixer to obtain a mixed material A; stirring and mixing cumyloxy functionalized boron nitride nanosheets and carbon nanotubes at the rotating speed of 800-1000r/min of a mixer to obtain a mixed material B; preparing the mixed material A and the mixed material B according to the mass ratio to obtain a mixed material C;
s2: and (2) mixing absolute ethyl alcohol, l,1, 2-tetrachloroethane, polythiol and imidazole to obtain a mixed solvent, dispersing the mixed material C in the mixed solvent, stirring and mixing at the rotating speed of a mixer of 1200-1400r/min, and carrying out heat preservation and solidification to obtain the epoxy adhesive for chip packaging.
Further, the mass ratio of the mixed material A to the mixed material B is 3:2.
further, the volume ratio of the absolute ethyl alcohol to the 1, 2-tetrachloroethane is 46:34.
further, the mass volume ratio of the mixed material C to the l,1, 2-tetrachloroethane is 30g:34mL.
Further, the conditions of heat preservation and solidification are as follows: keeping the temperature for 5-6h at 280-285 ℃.
The invention has the beneficial effects that:
the invention provides an epoxy adhesive glue for chip packaging and a preparation process thereof, solves the problems of poor heat conductivity, poor flame retardance and the like of the conventional epoxy adhesive glue for chip packaging, and meets the requirements of the field of electronic chips.
The self-made dibutylphenol-based epoxy resin is selected to replace bisphenol A-type epoxy resin commonly used in the existing market as an epoxy raw material, so that the epoxy resin is green, healthy and environment-friendly, and conforms to the sustainable development strategy; semi-aromatic polyamide, namely poly (dodeca-poly (phenyleneterephthalamide)) is introduced into the epoxy adhesive, and the longer aliphatic chain structure improves the low water absorption rate and the dimensional stability of the epoxy adhesive;
the prepared bis-eugenol epoxy monomer contains allyl and epoxy groups at the same time, so that two curing reactions at different temperatures are required for complete curing; the first curing is that the ring-opening reaction of the amino group and the glycidyl ether group of the curing agent generates an epoxy cross-linked network; the second curing is a cross-linking reaction of allyl with the ingredient in the epoxy adhesive;
hexagonal boron nitride and carbon nano tubes are used as heat-conducting fillers, and meanwhile, the toughness of the epoxy adhesive is improved; by functionalizing the boron nitride nanosheets, few-layer or even single-layer boron nitride nanosheets are obtained, and the dispersibility of the boron nitride nanosheets in the epoxy adhesive is improved;
stripping hexagonal boron nitride by adopting a liquid phase stripping method to prepare a solvent-stripped boron nitride nanosheet, functionalizing the boron nitride nanosheet in a lithium/ammonia system by using alkyl peroxide dicumyl peroxide, and successfully and covalently grafting a isopropylbenzene oxygen group on the surface of the boron nitride after the dicumyl peroxide reacts with the reduced boron nitride nanosheet so as to obtain a isopropylbenzene oxygen group functionalized boron nitride nanosheet;
the construction of the uniform dispersion state and the orientation structure of the cumyloxy functionalized boron nitride nanosheets and the carbon nanotubes is an important factor for improving the heat-conducting property and the mechanical property of the epoxy adhesive; however, the particle size and density of the carbon nano tube, the dibutylphenol epoxy resin and the poly-p-phthaloyl dodecaamine are different, and uniform mixing of a single solvent is difficult to realize;
the invention selects the material with the volume ratio of 46:34, wherein tetrachloroethane (density is 1.6 g/mL) is used for improving the density of the solvent and reducing the sedimentation velocity of the large-particle-size powder, and ethanol can improve the suspension characteristic of the carbon nanotubes through the interaction with the carbon nanotubes, so that the dispersion state of the carbon nanotubes is more uniform and the carbon nanotubes tend to be oriented and arranged;
the heat resistance of the epoxy adhesive is improved by controlling the proportion of each functional group by limiting the content of allyl and benzene rings in the dibutylphenol-based epoxy resin and the cumyloxy-functionalized boron nitride nanosheet.
Detailed Description
The technical solutions in the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
It should be noted that, if the embodiment of the present invention relates to directional indications such as up, down, left, right, front, and back \8230, the directional indications are only used for explaining a specific posture such as relative positional relationship between components, motion situation, etc., and if the specific posture is changed, the directional indications are changed accordingly. In addition, technical solutions between various embodiments may be combined with each other, but must be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present invention.
The technical solutions of the present invention are further described in detail with reference to specific examples, which should be understood that the following examples are only illustrative of the present invention and are not intended to limit the present invention.
Example 1
A preparation process of epoxy adhesive glue for chip packaging comprises the following steps:
s1: stirring and mixing the dibutylphenol-based epoxy resin and the poly (dodecamethyleneterephthalamide) at the rotating speed of 800r/min of a mixer to obtain a mixed material A; stirring and mixing cumyloxy functionalized boron nitride nanosheets and carbon nanotubes at the rotating speed of a mixer of 800r/min to obtain a mixed material B; preparing the mixed material A and the mixed material B according to the mass ratio to obtain a mixed material C; the mass ratio of the mixed material A to the mixed material B is 2:3;
the epoxy adhesive comprises the following components in parts by mass: 15 parts of biseugenol epoxy resin, 5 parts of poly-p-phthaloyl dodecanediamine, 1 part of polythiol, 0.5 part of imidazole, 20 parts of cumyl oxy functionalized boron nitride nanosheet and 10 parts of carbon nanotube;
the preparation method of the eugenol epoxy resin comprises the following steps:
(1) Mixing 1moL of honokiol, 2.2moL of potassium carbonate, 0.5g of benzyltriethylammonium chloride and 200mL of acetonitrile, stirring at 60 ℃ for 40min, adding 26g of bromopropylene, reacting at 65 ℃ for 12h, filtering, spin-drying the solvent, washing with ethyl acetate and deionized water in sequence, transferring to 200 ℃ and heating for 2h, and obtaining 3, 3-diallyl magnolol by a chromatographic column method;
(2) Taking 1moL of 3, 3-diallyl magnolol and 20moL of epoxy chloropropane, mixing, adding 0.05mol of benzyltriethylammonium chloride, reacting for 3 hours at 80 ℃, adding 5moL/L of sodium hydroxide and 0.05moL of benzyltriethylammonium chloride, mixing and stirring for 30 minutes, washing for 2 times with deionized water and saturated NaCl aqueous solution, drying with anhydrous magnesium sulfate, spin-drying the solvent, and drying to obtain the glycidyl etherate of the 3, 3-diallyl magnolol;
(3) Uniformly mixing 1moL of glycidyl etherate of 3, 3-diallyl magnolol and 1moL of diaminodiphenylmethane at 80 ℃, pouring the mixture into a mould while the mixture is hot, defoaming the mixture in vacuum for 3min, and curing the mixture at different periods: keeping the temperature at 105 ℃ for 1h, heating to 145 ℃ for 1h, heating to 185 ℃ for 2h, heating to 200 ℃ for 2h to obtain the eugenol epoxy resin;
the preparation method of the cumyloxy functionalized boron nitride nanosheet comprises the following steps:
1) Dispersing hexagonal boron nitride in N-methylpyrrolidone at a concentration of 2mg/mL, ultrasonically stirring, centrifuging, standing, filtering supernatant after standing through a polytetrafluoroethylene microporous filter membrane with the aperture of 0.1pm, washing with absolute ethyl alcohol, and drying to obtain solvent-stripped hexagonal boron nitride;
2) Under the anhydrous and anaerobic conditions, 1.6mmoL of solvent stripped hexagonal boron nitride is mixed with 60mL of liquid ammonia, the mixture is stirred for 1h at minus 78 ℃, 116mg of metal lithium particles are added and continuously stirred for 1h, 12.8mmoL of dicumyl peroxide is added for reaction for 12h, ethanol and deionized water are added, the pH of the mixed solution after the reaction is regulated to be neutral by 12% hydrochloric acid, the mixed solution is centrifuged, washed by the deionized water, filtered by a polytetrafluoroethylene microporous filter membrane with the aperture of 0.1pm, washed by tetrahydrofuran, chloroform and ethanol in sequence, and dried to obtain a isopropylphenoxy functionalized boron nitride nanosheet;
s2: mixing 46mL of absolute ethyl alcohol, 34mL of 1, 2-tetrachloroethane, polythiol and imidazole to obtain a mixed solvent, dispersing 30g of the mixed material C in the mixed solvent, stirring and mixing at the rotating speed of 1200-1400r/min of a mixer, and preserving heat at 280 ℃ for 5 hours to obtain the epoxy adhesive for chip packaging.
Example 2
A preparation process of an epoxy adhesive for chip packaging comprises the following steps:
s1: stirring and mixing the dibutylphenol-based epoxy resin and the poly (dodecamethyleneterephthalamide) at the rotating speed of 900r/min of a mixer to obtain a mixed material A; stirring and mixing cumyloxy functionalized boron nitride nanosheets and carbon nanotubes at the rotating speed of 800-1000r/min in a mixer to obtain a mixed material B; preparing the mixed material A and the mixed material B according to the mass ratio to obtain a mixed material C; the mass ratio of the mixed material A to the mixed material B is 2:3;
the epoxy adhesive comprises the following components in parts by mass: 18 parts of bis-eugenol epoxy resin, 8 parts of poly-p-phthaloyl dodecanediamine, 3 parts of polythiol, 0.8 part of imidazole, 25 parts of cumyl oxy functionalized boron nitride nanosheet and 14 parts of carbon nanotube;
the preparation method of the eugenol epoxy resin comprises the following steps:
(1) Mixing 1moL of honokiol, 2.2moL of potassium carbonate, 0.5g of benzyltriethylammonium chloride and 200mL of acetonitrile, stirring at 62 ℃ for 35min, adding 26g of bromopropylene, reacting at 68 ℃ for 11h, filtering, spin-drying the solvent, washing with ethyl acetate and deionized water in sequence, transferring to 200 ℃ and heating for 2h, and obtaining 3, 3-diallyl magnolol by a chromatographic column method;
(2) Taking 1moL of 3, 3-diallyl magnolol and 20moL of epoxy chloropropane, mixing, adding 0.05mol of benzyltriethylammonium chloride, reacting for 3 hours at 80 ℃, adding 5moL/L of sodium hydroxide and 0.05moL of benzyltriethylammonium chloride, mixing and stirring for 30 minutes, washing with deionized water and a saturated NaCl aqueous solution for 4 times, drying with anhydrous magnesium sulfate, spin-drying the solvent, and drying to obtain the glycidyl etherate of the 3, 3-diallyl magnolol;
(3) Uniformly mixing 1moL of glycidyl etherate of 3, 3-diallyl magnolol and 1moL of diaminodiphenylmethane at 80 ℃, pouring the mixture into a mold while the mixture is hot, defoaming the mixture in vacuum for 4min, and curing the mixture at different time periods: preserving heat for 1h at 105 ℃, heating to 145 ℃, preserving heat for 1h, heating to 185 ℃, preserving heat for 2h, heating to 200 ℃, preserving heat for 2h, and obtaining the eugenol-based epoxy resin;
the preparation method of the cumyloxy functionalized boron nitride nanosheet comprises the following steps:
1) Dispersing hexagonal boron nitride in N-methyl pyrrolidone at the concentration of 2mg/mL, ultrasonically stirring, centrifuging, standing, filtering the supernatant after standing through a polytetrafluoroethylene microporous filter membrane with the aperture of 0.1pm, washing with absolute ethyl alcohol, and drying to obtain solvent-stripped hexagonal boron nitride;
2) Under the anhydrous and anaerobic conditions, 1.6mmoL of solvent-stripped hexagonal boron nitride is mixed with 60mL of liquid ammonia, the mixture is stirred for 1h at minus 78 ℃, 116mg of metal lithium particles are added and continuously stirred for 1.5h, 12.8mmoL of dicumyl peroxide is added for reaction for 12h, ethanol and deionized water are added, the pH of the mixed solution after the reaction is regulated to be neutral by 12% hydrochloric acid, the mixed solution is centrifuged, washed by the deionized water, filtered by a polytetrafluoroethylene microporous filter membrane with the aperture of 0.1pm, washed by tetrahydrofuran, chloroform and ethanol in sequence, and dried to obtain a isopropylbenzene oxyl functionalized boron nitride nanosheet;
s2: mixing 46mL of absolute ethyl alcohol, 34mL of 1, 2-tetrachloroethane, polythiol and imidazole to obtain a mixed solvent, dispersing 30g of the mixed material C in the mixed solvent, stirring and mixing at the rotating speed of 1300r/min of a mixer, and preserving heat at 281 ℃ for 5.5 hours to obtain the epoxy adhesive for chip packaging.
Example 3
A preparation process of epoxy adhesive glue for chip packaging comprises the following steps:
s1: stirring and mixing the dibutylphenol-based epoxy resin and the poly (dodecamethyleneterephthalamide) at the rotating speed of 800-1000r/min of a mixer to obtain a mixed material A; stirring and mixing cumyloxy functionalized boron nitride nanosheets and carbon nanotubes at the rotating speed of 800-1000r/min of a mixer to obtain a mixed material B; preparing the mixed material A and the mixed material B according to the mass ratio to obtain a mixed material C; the mass ratio of the mixed material A to the mixed material B is 2:3;
the epoxy adhesive comprises the following components in parts by mass: 20 parts of biseugenol epoxy resin, 8 parts of poly-p-phthaloyl dodecanediamine, 5 parts of polythiol, 1 part of imidazole, 30 parts of cumyl oxy functionalized boron nitride nanosheet and 12 parts of carbon nano tube;
the preparation method of the eugenol epoxy resin comprises the following steps:
(1) Mixing 1moL of honokiol, 2.2moL of potassium carbonate, 0.5g of benzyltriethylammonium chloride and 200mL of acetonitrile, stirring at 65 ℃ for 30min, adding 26g of bromopropylene, reacting at 70 ℃ for 10h, filtering, spin-drying the solvent, sequentially washing with ethyl acetate and deionized water, transferring to 200 ℃ and heating for 2h, and then obtaining 3, 3-diallyl-magnolol by a chromatographic column method;
(2) Taking 1moL of 3, 3-diallyl magnolol and 20moL of epoxy chloropropane, mixing, adding 0.05mol of benzyltriethylammonium chloride, reacting for 3 hours at 80 ℃, adding 5moL/L of sodium hydroxide and 0.05moL of benzyltriethylammonium chloride, mixing and stirring for 30 minutes, washing with deionized water and saturated NaCl aqueous solution for 5 times, drying with anhydrous magnesium sulfate, spin-drying the solvent, and drying to obtain the glycidyl etherate of the 3, 3-diallyl magnolol;
(3) Uniformly mixing 1moL of glycidyl etherate of 3, 3-diallyl magnolol and 1moL of diaminodiphenylmethane at 80 ℃, pouring the mixture into a mold while the mixture is hot, defoaming the mixture in vacuum for 5min, and curing the mixture at different time periods: keeping the temperature at 105 ℃ for 1h, heating to 145 ℃ for 1h, heating to 185 ℃ for 2h, heating to 200 ℃ for 2h to obtain the eugenol epoxy resin;
the preparation method of the cumyloxy functionalized boron nitride nanosheet comprises the following steps:
1) Dispersing hexagonal boron nitride in N-methyl pyrrolidone at the concentration of 2mg/mL, ultrasonically stirring, centrifuging, standing, filtering the supernatant after standing through a polytetrafluoroethylene microporous filter membrane with the aperture of 0.1pm, washing with absolute ethyl alcohol, and drying to obtain solvent-stripped hexagonal boron nitride;
2) Under the anhydrous and anaerobic conditions, 1.6mmoL of solvent stripped hexagonal boron nitride is mixed with 60mL of liquid ammonia, the mixture is stirred for 1h at minus 78 ℃, 116mg of metal lithium particles are added and continuously stirred for 2h, 12.8mmoL of dicumyl peroxide is added for reaction for 12h, ethanol and deionized water are added, the pH of the mixed solution after the reaction is regulated to be neutral by 12% hydrochloric acid, the mixed solution is centrifuged, washed by the deionized water, filtered by a polytetrafluoroethylene microporous filter membrane with the aperture of 0.1pm, washed by tetrahydrofuran, chloroform and ethanol in sequence, and dried to obtain a isopropylphenoxy functionalized boron nitride nanosheet;
s2: mixing 46mL of absolute ethyl alcohol, 34mL of 1, 2-tetrachloroethane, polythiol and imidazole to obtain a mixed solvent, dispersing 30g of the mixed material C in the mixed solvent, stirring and mixing at the rotating speed of 1400r/min of a mixer, and preserving heat at 285 ℃ for 5 hours to obtain the epoxy adhesive for chip packaging.
Comparative example 1
Using example 2 as a control, the bisphenol A epoxy resin was used in place of the bisphenol epoxy resin, and the other steps were normal.
Comparative example 2
The control group of example 2 was used, and eugenol was used to replace honokiol, and other procedures were normal.
Comparative example 3
With example 2 as a control, cumyloxy-functionalized boron nitride nanosheets were replaced with hexagonal boron nitride nanosheets, and the other procedures were normal.
Comparative example 4
Taking the example 2 as a control group, the mass ratio of the mixed material A to the mixed material B is 2:4, 18 parts of dibutylphenol epoxy resin, 8 parts of poly-p-phthaloyl dodecaamine, 30 parts of cumyl oxy functionalized boron nitride nanosheets and 22 parts of carbon nanotubes, and other working procedures are normal.
Comparative example 5
Taking the example 2 as a control group, the mass ratio of the mixed material A to the mixed material B is 2:2, 18 parts of dibutylphenol epoxy resin, 8 parts of poly-p-phthaloyl dodecaamine, 20 parts of cumyl oxy functionalized boron nitride nanosheets and 6 parts of carbon nanotubes, and other working procedures are normal.
Comparative example 6
The sample of example 2 was used as a control, and the second curing was not performed, i.e., the sample was not kept at 281 ℃ for 5.5 hours, and the other steps were normal.
Comparative example 7
Example 2 was used as a control, and the other steps were normal without using absolute ethanol and l,1, 2-tetrachloroethane.
Limiting oxygen index test: performing a test with reference to IOS4589-2, wherein the temperature of the mixed gas is 22 ℃, the contact time of the flame and the top surface is shorter than 30s, the mixed gas is removed every 5s, whether the mixed gas is combusted is observed, and the minimum oxygen concentration just required for maintaining the combustion is the oxygen index;
thermal conductivity: the thermal conductivity was tested with reference to ASTM D5470;
and (3) performance testing: the adhesive glues prepared in examples 1 to 3 and comparative examples 1 to 7 were tested for thickness, tensile strength, thermal conductivity, and flame retardancy, and the test results are shown in table 1;
TABLE 1
Thickness, μm Tensile strength, mpa Thermal conductivity W/(m.K) Limiting oxygen index
Example 1 15 11.1 11.91 50
Example 2 15 12.6 12.42 52
Example 3 15 11.7 12.05 49
Comparative example 1 15 9.1 9.52 31
Comparative example 2 15 8.3 8.21 33
Comparative example 3 15 7.9 8.04 38
Comparative example 4 15 8.1 9.25 36
Comparative example 5 15 8.2 9.38 37
Comparative example 6 15 7.2 9.43 35
Comparative example 7 15 7.7 8.06 42
TABLE 1
Comparing the example 2 with the comparative example 1, the self-made bisphenol epoxy resin is selected to replace bisphenol A epoxy resin commonly used in the existing market as an epoxy raw material, so that the epoxy resin is green, healthy and environment-friendly, and accords with the sustainable development strategy; semi-aromatic polyamide, namely poly (dodeca-poly (phenyleneterephthalamide)) is introduced into the epoxy adhesive, and the longer aliphatic chain structure improves the low water absorption rate and the dimensional stability of the epoxy adhesive, and improves the tensile strength, the thermal conductivity and the flame retardance of the epoxy adhesive;
comparing the example 2 with the comparative example 2, the invention obtains 3, 3-diallyl magnolol by simultaneously introducing two allyl groups on the benzene ring of honokiol, reduces the viscosity of the bis-eugenol epoxy monomer, and has lubricating effect among molecules because the allyl groups are longer alkyl flexible chains; the number and the position of allyl in the molecule are regulated and controlled, and the curing reaction rate of the system is slowed down by matching with the time-phased curing, so that the implosion in the curing process is reduced, the generation of bubbles and stress concentration is avoided, the performance of the epoxy adhesive is regulated and controlled, and the tensile strength, the thermal conductivity and the flame retardance of the epoxy adhesive are effectively improved;
comparing the example 2 with the comparative example 3, the hexagonal boron nitride and the carbon nano tube are used as heat-conducting fillers, and meanwhile, the toughness of the epoxy adhesive is improved; by functionalizing the boron nitride nanosheets, few-layer or even single-layer boron nitride nanosheets are obtained, and the dispersibility of the boron nitride nanosheets in the epoxy adhesive is improved;
stripping hexagonal boron nitride by adopting a liquid phase stripping method to prepare a solvent-stripped boron nitride nanosheet, functionalizing the boron nitride nanosheet in a lithium/ammonia system by using alkyl peroxide dicumyl peroxide, and successfully and covalently grafting a isopropylbenzene oxygen group on the surface of the boron nitride after the dicumyl peroxide reacts with the reduced boron nitride nanosheet so as to obtain a isopropylbenzene oxygen group functionalized boron nitride nanosheet; the construction of the uniform dispersion state and the orientation structure of the cumyloxy functionalized boron nitride nanosheets and the carbon nanotubes is an important factor for improving the heat-conducting property and the mechanical property of the epoxy adhesive;
comparing the example 2 with the comparative examples 4 and 5, controlling the proportion of each functional group to improve the thermal conductivity of the epoxy adhesive by limiting the content of allyl groups and benzene rings in the biseugenol-based epoxy resin and the cumeneoxy-functionalized boron nitride nanosheets;
comparing example 2 with comparative example 6, the prepared bis-eugenol epoxy monomer contains allyl and epoxy at the same time, so that two curing reactions under different temperature conditions are required for complete curing; the first curing is that the ring-opening reaction of the amino group of the curing agent and the glycidyl ether group generates an epoxy cross-linked network; the second curing is a cross-linking reaction of allyl with the ingredient in the epoxy adhesive; the mechanical property and the flame retardance of the adhesive are effectively improved through twice curing;
example 2 is compared with comparative example 7, and the volume ratio of 46:34, wherein tetrachloroethane (density is 1.6 g/mL) is used for improving the density of the solvent and reducing the sedimentation velocity of the large-particle-size powder, and ethanol can improve the suspension characteristic of the carbon nanotubes through the interaction with the carbon nanotubes, so that the dispersion state of the carbon nanotubes is more uniform, the carbon nanotubes are prone to an orientation arrangement structure, and the thermal conductivity of the carbon nanotubes is effectively improved.
The above description is only an example of the present invention, and is not intended to limit the scope of the present invention, and all modifications, equivalents and applications made by the present invention or directly/indirectly applied to other related technical fields within the spirit of the present invention are included in the scope of the present invention.

Claims (7)

1. The epoxy adhesive for chip packaging is characterized by comprising the following components in parts by mass: 15-20 parts of biseugenol epoxy resin, 5-10 parts of poly-p-phthaloyl dodecaamine, 1-5 parts of polythiol, 0.5-1.0 part of imidazole, 20-30 parts of cumyl oxy functionalized boron nitride nanosheet and 10-15 parts of carbon nanotube;
the preparation method of the eugenol epoxy resin comprises the following steps:
(1) Mixing honokiol, potassium carbonate, benzyltriethylammonium chloride and acetonitrile, stirring at 60-65 deg.C for 30-40min, adding bromopropylene, reacting at 65-70 deg.C for 10-12h, filtering, spin-drying the solvent, sequentially washing with ethyl acetate and deionized water, keeping the temperature at 200 deg.C for 2h, and separating with chromatographic column to obtain 3, 3-diallyl-magnolol;
(2) Mixing 3, 3-diallyl magnolol and epichlorohydrin, adding benzyltriethylammonium chloride, reacting at 80 ℃ for 3h, adding sodium hydroxide and benzyltriethylammonium chloride, mixing and stirring for 30min, washing with deionized water and saturated NaCl aqueous solution for 2-5 times, drying with anhydrous magnesium sulfate, spin-drying the solvent, and drying to obtain the glycidyl etherate of 3, 3-diallyl magnolol;
(3) Uniformly mixing the glycidyl etherate of 3, 3-diallyl magnolol and diaminodiphenylmethane at 75-80 ℃, pouring the mixture into a mold while the mixture is hot, defoaming the mixture in vacuum for 3-5min, and curing the mixture at different time intervals to obtain the bis-eugenol epoxy resin;
the preparation process of the epoxy adhesive for chip packaging comprises the following steps:
s1: stirring and mixing the dibutylphenol-based epoxy resin and the poly (dodecamethyleneterephthalamide) at the rotating speed of 800-1000r/min of a mixer to obtain a mixed material A; stirring and mixing cumyloxy functionalized boron nitride nanosheets and carbon nanotubes at the rotating speed of 800-1000r/min of a mixer to obtain a mixed material B; preparing the mixed material A and the mixed material B according to the mass ratio to obtain a mixed material C;
s2: mixing absolute ethyl alcohol, l,1, 2-tetrachloroethane, polythiol and imidazole to obtain a mixed solvent, dispersing the mixed material C in the mixed solvent, stirring and mixing at the rotating speed of a mixer of 1200-1400r/min, and carrying out heat preservation and solidification to obtain the epoxy adhesive for chip packaging;
the mass ratio of the mixed material A to the mixed material B is 2:3.
2. the epoxy adhesive for chip packaging according to claim 1, wherein the molar mass ratio of honokiol, potassium carbonate and benzyltriethylammonium chloride is 1moL:2.2moL:0.5g; the mol ratio of 3, 3-diallyl magnolol to epichlorohydrin is 1:20; the molar ratio of the glycidyl etherate of the 3, 3-diallyl magnolol to the diaminodiphenylmethane is 1:1.
3. the epoxy adhesive glue for chip packaging according to claim 1, wherein the curing conditions in time-sharing are as follows: keeping the temperature at 105 ℃ for 1h, heating to 145 ℃ for 1h, heating to 185 ℃ for 2h, heating to 200 ℃ for 2h.
4. The epoxy adhesive glue for chip packaging, according to claim 1, wherein the preparation of the cumyloxy functionalized boron nitride nanosheets comprises the following steps:
1) Dispersing hexagonal boron nitride in N-methylpyrrolidone, ultrasonically stirring, centrifuging, standing, filtering the supernatant after standing through a polytetrafluoroethylene microporous filter membrane with the aperture of 0.1pm, washing with absolute ethyl alcohol, and drying to obtain solvent-stripped hexagonal boron nitride;
2) Under the anhydrous and anaerobic conditions, mixing hexagonal boron nitride stripped by a solvent with liquid ammonia, stirring for 1h at-78 ℃, adding metal lithium particles, continuously stirring for 1-2h, adding dicumyl peroxide, reacting for 12h, adding ethanol and deionized water, adjusting the pH of the mixed solution after reaction to be neutral by hydrochloric acid, centrifuging, washing by deionized water, filtering by a polytetrafluoroethylene microporous filter membrane with the aperture of 0.1pm, washing by tetrahydrofuran, chloroform and ethanol in sequence, and drying to obtain the isopropylbenzene oxyl functionalized boron nitride nanosheet.
5. The epoxy adhesive paste for chip packaging according to claim 4, wherein the molar volume ratio of the solvent-exfoliated hexagonal boron nitride to the dicumyl peroxide to the liquid ammonia is 1.6mmoL:12.8mmoL:60mL.
6. The epoxy adhesive glue for chip packaging, according to claim 1, wherein the volume ratio of absolute ethyl alcohol to l,1, 2-tetrachloroethane is 46:34; the mass volume ratio of the mixed material C to the l,1, 2-tetrachloroethane is 30g:34mL.
7. The epoxy adhesive glue for chip packaging according to claim 1, wherein the conditions of heat preservation and curing are as follows: keeping the temperature for 5-6h at 280-285 ℃.
CN202210620003.XA 2022-06-01 2022-06-01 Epoxy adhesive for chip packaging and preparation process thereof Active CN115074065B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210620003.XA CN115074065B (en) 2022-06-01 2022-06-01 Epoxy adhesive for chip packaging and preparation process thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210620003.XA CN115074065B (en) 2022-06-01 2022-06-01 Epoxy adhesive for chip packaging and preparation process thereof

Publications (2)

Publication Number Publication Date
CN115074065A CN115074065A (en) 2022-09-20
CN115074065B true CN115074065B (en) 2023-03-24

Family

ID=83248334

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210620003.XA Active CN115074065B (en) 2022-06-01 2022-06-01 Epoxy adhesive for chip packaging and preparation process thereof

Country Status (1)

Country Link
CN (1) CN115074065B (en)

Also Published As

Publication number Publication date
CN115074065A (en) 2022-09-20

Similar Documents

Publication Publication Date Title
CN106543647B (en) A kind of high tenacity, low temperature resistant resin matrix and preparation method thereof
CN103361018B (en) A kind of LED of high-seal
CN111440417A (en) Toughening epoxy resin system for low temperature and preparation method and application thereof
CN103694637B (en) A kind of High-tenacity vacuum slow epoxy resin for wind power blade and preparation method thereof
CN113201207B (en) Preparation method of high-toughness and high-strength carbon nanotube/epoxy resin composite material
CN115386066B (en) High-performance bio-based thermosetting epoxy resin and preparation method thereof
CN102977556A (en) High-performance epoxy resin composition for vacuum infusion molding and preparation method thereof
CN112142953A (en) Dielectric and heat conduction enhanced bio-based high-temperature-resistant epoxy resin and preparation method and application thereof
CN113943473A (en) High-toughness epoxy resin composition and preparation process thereof
CN113292819A (en) Epoxy resin composition capable of being rapidly cured at medium and low temperature, epoxy resin-based composite material and preparation method thereof
CN103146058B (en) Toughened polypropylene composite material and preparation method thereof
CN109836557B (en) Toughened hydrophobic epoxy resin and preparation method thereof
CN103435978A (en) PET composite material and preparation method thereof
CN105400134B (en) A kind of heat conductive electronic material compositions
CN101891936A (en) Preparation method of composite material based on epoxy resin and phosphazene nanotubes
CN115074065B (en) Epoxy adhesive for chip packaging and preparation process thereof
CN113801431B (en) High-toughness high-strength phenolic resin material and preparation method thereof
CN111253712A (en) Matrix resin material for wet winding of carbon fiber composite high-pressure container
CN115594943B (en) Modified carbon nano tube flame-retardant reinforced epoxy resin and preparation method thereof
CN116606621A (en) Epoxy pouring sealant and preparation method and application thereof
CN115449211A (en) Flexible corrosion-resistant PPO resin-based copper-clad plate and preparation method thereof
CN113831732A (en) Low-water-absorption high-toughness high-temperature nylon composite material and preparation method thereof
CN111234181A (en) High-toughness insulating epoxy resin condensate and preparation method and application thereof
CN117304687B (en) Modified carbon fiber composite material and preparation method thereof
CN114907291B (en) Modified reactive diluent and preparation method thereof, and epoxy resin for carbon fiber and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant