阅读说明：本技术 一种半导体封装用耐高温胶带及其制备方法 (High-temperature-resistant adhesive tape for semiconductor packaging and preparation method thereof ) 是由 刘杰 梁龙 万中梁 汪峰 李鑫 朱润雨 方超超 于 2021-09-06 设计创作，主要内容包括：本发明公开了一种半导体封装用耐高温胶带及其制备方法,该耐高温胶带包括如下重量份原料：90-110份耐高温丙烯酸压敏胶、40-60份乙酸乙酯、1-3份环氧固化剂、1-3份碳纳米管、15-20份改性环氧树脂；使用耐高温丙烯酸压敏胶体系,使得胶带具有很好的耐高温效果,且胶层耐高温剥离力变化小,封装过程后胶带易移除,且无环氧塑封料泄露的风险,同时该耐高温胶带不易发生热氧老化出现脱落,并在胶层内同步进行防静电处理,胶层剥离电压＜100V,有效地避免了因静电吸附灰尘污染半导体芯片。(The invention discloses a high-temperature-resistant adhesive tape for semiconductor packaging and a preparation method thereof, wherein the high-temperature-resistant adhesive tape comprises the following raw materials in parts by weight: 90-110 parts of high-temperature-resistant acrylic pressure-sensitive adhesive, 40-60 parts of ethyl acetate, 1-3 parts of epoxy curing agent, 1-3 parts of carbon nano tube and 15-20 parts of modified epoxy resin; the high-temperature-resistant acrylic pressure-sensitive adhesive system is used, so that the adhesive tape has a good high-temperature-resistant effect, the change of the high-temperature-resistant peeling force of the adhesive layer is small, the adhesive tape is easy to remove after the packaging process, the risk of leakage of epoxy plastic packaging materials does not exist, meanwhile, the high-temperature-resistant adhesive tape is not easy to generate thermal oxidation aging and fall off, the antistatic treatment is synchronously performed in the adhesive layer, the peeling voltage of the adhesive layer is less than 100V, and the semiconductor chip is effectively prevented from being polluted by electrostatic adsorption dust.)

1. A high temperature resistant adhesive tape for semiconductor packaging is characterized in that: the feed comprises the following raw materials in parts by weight: 90-110 parts of high-temperature-resistant acrylic pressure-sensitive adhesive, 40-60 parts of ethyl acetate, 1-3 parts of epoxy curing agent, 1-3 parts of carbon nano tube and 15-20 parts of modified epoxy resin;

the high-temperature-resistant acrylic pressure-sensitive adhesive is prepared by the following steps:

step A1: adding monomer mixed liquid with the mass of 1/2 and mixed solvent with the mass of 1/3 into a reaction kettle, introducing nitrogen to remove oxygen, dropwise adding initiator diluent with the mass of 1/2, and carrying out heat preservation reaction;

step A2: and dropwise adding the residual monomer mixed solution and 2/5 mass initiator diluent into the reaction kettle, after heat preservation reaction, adding the residual initiator solution, continuing heat preservation reaction, adding the residual solvent, and uniformly mixing to obtain the high-temperature-resistant acrylic pressure-sensitive adhesive.

2. The high temperature resistant adhesive tape for semiconductor packaging according to claim 1, wherein: the monomer mixed liquid is one of acrylic acid, isooctyl acrylate, butyl acrylate, methyl acrylate, hydroxyethyl acrylate and a viscosity stabilizer which are mixed according to the mass ratio of 2:150:50:30:1.5:3 or acrylamide, isooctyl acrylate, ethyl acrylate, vinyl acetate, hydroxypropyl acrylate and the viscosity stabilizer which are mixed according to the mass ratio of 2:160:40: 1.5:2 or methyl ethyl acetoacetate, isooctyl acrylate, ethyl acrylate, methyl methacrylate, hydroxypropyl acrylate and the viscosity stabilizer which are mixed according to the mass ratio of 2:120:80:30:1.5: 4.

3. The high temperature resistant adhesive tape for semiconductor packaging according to claim 1, wherein: the mixed solvent is formed by mixing methyl acetate, ethyl acetate and toluene according to the mass ratio of 3-7:8-18:15-23, the initiator diluent drops are formed by dissolving azodiisoamyl nitrile in toluene, and the mass fraction of the initiator diluent drops is 5%.

4. The high temperature resistant adhesive tape for semiconductor packaging according to claim 1, wherein: the modified epoxy resin is prepared by the following steps:

step B1: stirring epoxy resin E-44, pyromellitic dianhydride, toluene and acetone, adding tetrabutylammonium bromide, reacting to obtain an intermediate 1, adding 2, 6-di-tert-butylphenol, potassium hydroxide and tetrahydrofuran into a reaction kettle, refluxing, dropwise adding methyl acrylate, reacting to obtain an intermediate 2, adding the intermediate 2, lithium aluminum hydride and tetrahydrofuran into the reaction kettle, refluxing, adding methanol, reacting to obtain an intermediate 3;

step B2: dissolving the intermediate 1 in N, N-dimethylformamide, adding the intermediate 3 and 4-dimethylaminopyridine, reacting to obtain an intermediate 4, dissolving ethyl benzoate in acetone, stirring, dropwise adding concentrated sulfuric acid, heating for reaction to obtain an intermediate 5, adding the intermediate 5, N-bromosuccinimide, benzoyl peroxide and carbon tetrachloride into a reaction kettle, reacting to obtain an intermediate 6, adding the intermediate 6, potassium carbonate, deionized water and tetraethylammonium bromide into the reaction kettle, and performing reflux reaction to obtain an intermediate 7;

step B3: adding 2, 4-di-tert-butylphenol, deionized water, concentrated sulfuric acid and paraformaldehyde into a reaction kettle, reacting, filtering, mixing a filter cake, petroleum ether and triethylamine, adding phosphorus trichloride, reacting to obtain an intermediate 8, adding the intermediate 7, the intermediate 8, tetrahydrofuran and sodium carbonate into the reaction kettle, reacting to obtain an intermediate 9, adding the intermediate 9, the intermediate 3, tetrahydrofuran and sodium methoxide into the reaction kettle, and performing reflux reaction to obtain the modified epoxy resin.

5. The high temperature resistant adhesive tape for semiconductor packaging according to claim 4, wherein: the molar ratio of the epoxy resin E-44 to the pyromellitic dianhydride in the step B1 is 2:1, and the molar ratio of the epoxy resin E-44 to the pyromellitic dianhydride is 5:1:6, and the molar ratio of the intermediate 2 to the lithium aluminum hydride to the methanol is 1:8: 2.

6. The high temperature resistant adhesive tape for semiconductor packaging according to claim 4, wherein: the molar ratio of the intermediate 1, the intermediate 3 and the 4-dimethylaminopyridine in the step B2 is 1:1.2:1, the molar ratio of the ethyl benzoate, the acetone and the concentrated sulfuric acid is 5g:2mL:3mL, the molar ratio of the intermediate 5, the N-bromosuccinimide, the benzoyl peroxide and the carbon tetrachloride is 0.1mol:0.1mol:0.15g:200mL, and the molar ratio of the intermediate 6, the potassium carbonate, the deionized water and the tetraethylammonium bromide is 3.5g:8g:100mL:3 mL.

7. The high temperature resistant adhesive tape for semiconductor packaging according to claim 4, wherein: the dosage ratio of the 2, 4-di-tert-butylphenol, the paraformaldehyde, the triethylamine and the phosphorus trichloride in the step B3 is 1:1:2.2:1.3, the dosage molar ratio of the intermediate 7, the intermediate 8 and the sodium carbonate is 1:2:2, and the dosage ratio of the intermediate 9, the intermediate 3, the tetrahydrofuran and the sodium methoxide is 3mmol:1mmol:10mL:0.025 g.

8. The method for preparing the high temperature resistant adhesive tape for semiconductor packaging according to claim 1, wherein the method comprises the following steps: the method specifically comprises the following steps:

the high temperature resistant acrylic pressure sensitive adhesive, ethyl acetate, an epoxy curing agent, the carbon nano tube and modified epoxy resin are mixed and stirred uniformly, then coated on a 20-30 mu mPI original film, the thickness of the dry adhesive is 4-6 mu m, a 20-30 mu m antistatic release film is attached, and the high temperature resistant adhesive tape for semiconductor packaging is prepared after curing for 45-50h at the temperature of 45-55 ℃.

Technical Field

The invention relates to the technical field of semiconductor preparation, in particular to a high-temperature-resistant adhesive tape for semiconductor packaging and a preparation method thereof.

Background

QFN is a quad or quad no-lead package that provides excellent electrical performance because it does not have chicken-wing leads as in conventional SOIC and TSOP packages, has short electrical conduction paths between internal leads and pads, low self-inductance and low wiring resistance within the package, and provides excellent thermal dissipation through exposed leadframe pads with direct thermal vias for dissipating heat within the package, and has an area (5mmx5mm) reduced by 84%, a thickness reduced by 80%, a weight reduced by 95%, and an electronic package parasitic effect reduced by 50% as compared to conventional 28-lead PLCC packages, and is well suited for use on high density PCBs for cell phones, digital cameras, PDAs, and other portable electronic devices, and involves Gold Wire, Wire Bonding, Molding, MoldingCure, Gold Wire Bonding, and other processes, A series of working procedures such as De-flash and the like and a long-time high-temperature and high-pressure process, the traditional adhesive tape cannot meet the requirement of long-time high-temperature resistance, and the product after the packaging process is poor;

the invention relates to an acrylic pressure-sensitive adhesive tape which is used for semiconductor packaging under high temperature and high pressure and has temperature-resistant reliability, the adhesive tape is suitable for being pasted on the back of a semiconductor lead frame, the adhesive tape plays a shielding effect in a molding process, so that resin is prevented from permeating into a shielding area, and no residual adhesive exists on the surface after the adhesive tape is removed at high temperature;

the prior patent is as follows: the adhesive with enhanced reliability under high pressure and the adhesive tape (CN103571412B) using the adhesive for semiconductor packaging are hot melt adhesive tapes, the adhesive tape has no viscosity at normal temperature, can be attached to the back of a semiconductor lead frame at a certain temperature and pressure, and a heating and pressurizing device needs to be additionally arranged in the attaching process, so that the operation is complicated. The adhesive tape has no antistatic function, and semiconductor components are often polluted due to electrostatic adsorption dust in the transportation and unreeling processes;

a solution is now proposed to address the technical drawback in this respect.

Disclosure of Invention

The invention aims to provide a high-temperature-resistant adhesive tape for semiconductor packaging and a preparation method thereof, and solves the problems that the semiconductor packaging adhesive tape in the prior art is a silica gel system pressure-sensitive adhesive tape and a hot-melt adhesive tape, the hot-melt adhesive tape is non-adhesive at normal temperature, needs to be heated and pressurized in the laminating process, has high energy consumption, needs to use a fluorine release film with high price in the silica gel pressure-sensitive adhesive tape, and has silicon transfer in the high-temperature packaging process through a high-temperature-resistant acrylic pressure-sensitive adhesive system.

The purpose of the invention can be realized by the following technical scheme:

a high-temperature-resistant adhesive tape for semiconductor packaging comprises the following raw materials in parts by weight: 90-110 parts of high-temperature-resistant acrylic pressure-sensitive adhesive, 40-60 parts of ethyl acetate, 1-3 parts of epoxy curing agent, 1-3 parts of carbon nano tube and 15-20 parts of modified epoxy resin;

the high-temperature resistant adhesive tape is prepared by the following steps:

the high temperature resistant acrylic pressure sensitive adhesive, ethyl acetate, an epoxy curing agent, the carbon nano tube and modified epoxy resin are mixed and stirred uniformly, then coated on a 20-30 mu mPI original film, the thickness of the dry adhesive is 4-6 mu m, a 20-30 mu m antistatic release film is attached, and the high temperature resistant adhesive tape for semiconductor packaging is prepared after curing for 45-50h at the temperature of 45-55 ℃.

Furthermore, the epoxy curing agent is one or two of diethylenetriamine and triethylene tetramine mixed in any proportion.

Further, the high-temperature-resistant acrylic pressure-sensitive adhesive is prepared by the following steps:

step A1: adding monomer mixed liquid with the mass of 1/2 and mixed solvent with the mass of 1/3 into a reaction kettle, introducing nitrogen to remove oxygen, dropwise adding initiator diluent with the mass of 1/2 at the rotation speed of 150 plus 200r/min and the temperature of 70-80 ℃, wherein the dropwise adding time is 1-2h, and preserving heat for 0.5-1.5h after the dropwise adding is finished;

step A2: and dropwise adding the residual monomer mixed solution and 2/5 mass initiator diluent into the reaction kettle for 1.5-2.5h, after the dropwise addition is finished, keeping the temperature for 0.5-1.5h, adding the residual initiator solution within 0.5-1h, continuously keeping the temperature until the viscosity of the polymer reaches 4500-5500mpa.s, adding the residual solvent, and uniformly mixing to obtain the high-temperature-resistant acrylic pressure-sensitive adhesive.

Further, the monomer mixed liquid is one of acrylic acid, isooctyl acrylate, butyl acrylate, methyl acrylate, hydroxyethyl acrylate and a viscosity stabilizer which are mixed according to the mass ratio of 2:150:50:30:1.5:3 or acrylamide, isooctyl acrylate, ethyl acrylate, vinyl acetate, hydroxypropyl acrylate and the viscosity stabilizer which are mixed according to the mass ratio of 2:160:40:30:1.5:2 or ethyl acetoacetate methacrylate, isooctyl acrylate, ethyl acrylate, methyl methacrylate, hydroxypropyl acrylate and the viscosity stabilizer which are mixed according to the mass ratio of 2:120:80:30:1.5: 4.

Furthermore, the viscosity stabilizer is one or two of GH viscosity stabilizer and SC viscosity stabilizer mixed in any proportion.

Further, the mixed solvent is formed by mixing methyl acetate, ethyl acetate and toluene according to the mass ratio of 3-7:8-18:15-23, the initiator diluent drops are formed by dissolving azodiisoamyl nitrile in toluene, and the mass fraction of the initiator diluent drops is 5%.

Further, the modified epoxy resin is prepared by the following steps:

step B1: adding epoxy resin E-44, pyromellitic dianhydride, toluene and acetone into a reaction kettle, stirring and adding tetrabutylammonium bromide under the conditions that the rotation speed is 200-300r/min and the temperature is 80-90 ℃ to react for 5-7h to prepare an intermediate 1, adding 2, 6-di-tert-butylphenol, potassium hydroxide and tetrahydrofuran into the reaction kettle, refluxing and dropwise adding methyl acrylate under the condition that the temperature is 70-80 ℃ to react for 6-8h to prepare an intermediate 2, adding the intermediate 2, lithium aluminum hydride and tetrahydrofuran into the reaction kettle, refluxing and adding methanol under the condition that the temperature is 70-75 ℃ to react for 1-1.5h to prepare an intermediate 3;

the reaction process is as follows:

step B2: dissolving the intermediate 1 in N, N-dimethylformamide, adding the intermediate 3 and 4-dimethylaminopyridine, reacting for 8-10h at the rotation speed of 200-300r/min and the temperature of 90-95 ℃ to obtain an intermediate 4, dissolving ethyl benzoate in acetone, stirring and dropwise adding concentrated sulfuric acid at the rotation speed of 150-200r/min and the temperature of 10-15 ℃, heating to the temperature of 15-20 ℃, reacting for 2-3h to obtain an intermediate 5, adding the intermediate 5, N-bromosuccinimide, benzoyl peroxide and carbon tetrachloride into a reaction kettle, reacting for 8-10h at the temperature of 80-90 ℃ to obtain an intermediate 6, adding the intermediate 6, potassium carbonate, deionized water and tetraethylammonium bromide into the reaction kettle, carrying out reflux reaction for 2-3h to obtain an intermediate 7;

the reaction process is as follows:

step B3: adding 2, 4-di-tert-butylphenol, deionized water, concentrated sulfuric acid and paraformaldehyde into a reaction kettle, reacting for 6-8h at the rotation speed of 120-150r/min and the temperature of 70-75 ℃, filtering, mixing a filter cake, petroleum ether and triethylamine, adding phosphorus trichloride at the temperature of 40-50 ℃ to react for 10-15h to obtain an intermediate 8, adding the intermediate 7, the intermediate 8, tetrahydrofuran and sodium carbonate into the reaction kettle, reacting for 3-4h at the temperature of 50-60 ℃ to obtain an intermediate 9, adding the intermediate 9, the intermediate 3, tetrahydrofuran and sodium methoxide into the reaction kettle, and performing reflux reaction for 10-15h at the temperature of 150-160 ℃ to obtain the modified epoxy resin.

The reaction process is as follows:

further, the molar ratio of the epoxy resin E-44 to the pyromellitic anhydride in the step B1 is 2:1, the amount of tetrabutylammonium bromide is 2% of the sum of the epoxy resin E-44 and the pyromellitic anhydride, the molar ratio of the 2, 6-di-tert-butylphenol, the potassium hydroxide and the methyl acrylate is 5:1:6, and the molar ratio of the intermediate 2, the lithium aluminum hydride and the methanol is 1:8: 2.

Further, the molar ratio of the intermediate 1, the intermediate 3 and the 4-dimethylaminopyridine in the step B2 is 1:1.2:1, the molar ratio of the ethyl benzoate, the acetone and the concentrated sulfuric acid is 5g:2mL:3mL, the mass fraction of the concentrated sulfuric acid is 98%, the molar ratio of the intermediate 5, the N-bromosuccinimide, the benzoyl peroxide and the carbon tetrachloride is 0.1mol:0.1mol:0.15g:200mL, and the molar ratio of the intermediate 6, the potassium carbonate, the deionized water and the tetraethylammonium bromide is 3.5g:8g:100mL:3 mL.

Further, the dosage ratio of the 2, 4-di-tert-butylphenol, the paraformaldehyde, the triethylamine and the phosphorus trichloride in the step B3 is 1:1:2.2:1.3, the dosage of the concentrated sulfuric acid is 1.5% of the mass of the 2, 4-di-tert-butylphenol, the mass fraction of the concentrated sulfuric acid is 95%, the dosage molar ratio of the intermediate 7, the intermediate 8 and the sodium carbonate is 1:2:2, and the dosage ratio of the intermediate 9, the intermediate 3, the tetrahydrofuran and the sodium methoxide is 3mmol:1mmol:10mL:0.025 g.

The invention has the beneficial effects that:

the invention prepares a high temperature resistant acrylic pressure-sensitive adhesive in the process of preparing a high temperature resistant adhesive tape for semiconductor packaging, the high temperature resistant acrylic pressure-sensitive adhesive is prepared by polymerizing monomer mixed liquid, the adhesive tape is prepared by using a high temperature resistant acrylic pressure-sensitive adhesive system, the adhesive tape has good high temperature resistant effect, the change of the high temperature resistant stripping force of the adhesive layer is small, the adhesive tape is easy to remove after the packaging process, and no risk of leakage of epoxy plastic packaging material exists, meanwhile, a modified epoxy resin is prepared, the modified epoxy resin takes epoxy resin E-44 as a raw material and is modified by pyromellitic dianhydride to prepare an intermediate 1, 2, 6-di-tert-butylphenol is reacted with methyl acrylate to prepare an intermediate 2, the intermediate 2 is reacted with lithium aluminum hydride to prepare an intermediate 3, the intermediate 3 and the intermediate 1 are subjected to esterification reaction to prepare an intermediate 4, ethyl benzoate is reacted with acetone to prepare an intermediate 5, treating the intermediate 5 with N-bromosuccinimide to obtain an intermediate 6, further treating the intermediate 6 to obtain an intermediate 7, reacting 2, 4-di-tert-butylphenol with paraformaldehyde, reacting with phosphorus trichloride to obtain an intermediate 8, reacting the intermediate 8 with the intermediate 7 to obtain an intermediate 9, reacting the intermediate 9 with the intermediate 3, so that the intermediate 9 and the alcoholic hydroxyl on the intermediate 3 generate ester exchange reaction to prepare the modified epoxy resin, the molecular chain of the modified epoxy resin contains a large amount of hindered and phosphite ester structures, has good aging resistant effect, ensures that the high temperature resistant adhesive tape is not easy to fall off due to thermal oxidation aging, meanwhile, the antistatic treatment is synchronously carried out in the adhesive layer, the peeling voltage of the adhesive layer is less than 100V, and the semiconductor chip is effectively prevented from being polluted by electrostatic adsorption dust.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

A high-temperature-resistant adhesive tape for semiconductor packaging comprises the following raw materials in parts by weight: 90 parts of high-temperature-resistant acrylic pressure-sensitive adhesive, 40 parts of ethyl acetate, 1 part of diethylenetriamine, 1 part of carbon nanotube and 15 parts of modified epoxy resin;

the high-temperature resistant adhesive tape is prepared by the following steps:

the high-temperature-resistant acrylic pressure-sensitive adhesive, ethyl acetate, diethylenetriamine, carbon nanotubes and modified epoxy resin are uniformly mixed and stirred, then coated on a 20 mu mPI original film, the thickness of the dry adhesive is 4 mu m, a 20 mu m antistatic release film is attached, and the high-temperature-resistant adhesive tape for semiconductor packaging is prepared after curing for 45 hours at the temperature of 45 ℃.

The high-temperature-resistant acrylic pressure-sensitive adhesive is prepared by the following steps:

weighing 2g of acrylic acid, 150g of isooctyl acrylate, 50g of butyl acrylate, 30g of methyl acrylate, 1.5g of hydroxyethyl acrylate and 3g of GH (GH) viscosity stabilizer, and uniformly mixing to obtain a monomer mixed solution for later use;

weighing 1.2g of azodiisoamyl nitrile, and dissolving in 22.8g of toluene to obtain initiator diluent with the mass fraction of 5% for later use;

weighing 50g of methyl acetate, 80g of ethyl acetate and 230g of toluene, and uniformly mixing to obtain a mixed solvent for later use;

step A1: adding monomer mixed liquid with the mass of 1/2 and mixed solvent with the mass of 1/3 into a reaction kettle, introducing nitrogen to remove oxygen, dropwise adding initiator diluent with the mass of 1/2 at the rotation speed of 150r/min and the temperature of 75 ℃, wherein the dropwise adding time is 1.5h, and preserving heat for 1h after the dropwise adding is finished;

step A2: and dropwise adding the residual monomer mixed solution and 2/5 mass initiator diluent into the reaction kettle for 2h, keeping the temperature for 1h after the dropwise addition is finished, adding the residual initiator solution within 1h, keeping the temperature until the viscosity of the polymer reaches 4500mpa.s, adding the residual solvent, and uniformly mixing to obtain the high-temperature-resistant acrylic pressure-sensitive adhesive.

The modified epoxy resin is prepared by the following steps:

step B1: adding epoxy resin E-44, pyromellitic dianhydride, toluene and acetone into a reaction kettle, stirring and adding tetrabutylammonium bromide under the conditions of the rotating speed of 200r/min and the temperature of 80 ℃, reacting for 5 hours to obtain an intermediate 1, adding 2, 6-di-tert-butylphenol, potassium hydroxide and tetrahydrofuran into the reaction kettle, refluxing and dropwise adding methyl acrylate under the condition of the temperature of 70 ℃, reacting for 6 hours to obtain an intermediate 2, adding the intermediate 2, lithium aluminum hydride and tetrahydrofuran into the reaction kettle, refluxing and adding methanol under the condition of the temperature of 70 ℃, reacting for 1 hour to obtain an intermediate 3;

step B2: dissolving the intermediate 1 in N, N-dimethylformamide, adding the intermediate 3 and 4-dimethylaminopyridine, reacting for 8 hours at the rotation speed of 200r/min and the temperature of 90 ℃ to obtain an intermediate 4, dissolving ethyl benzoate in acetone, stirring and dropwise adding concentrated sulfuric acid at the rotation speed of 150r/min and the temperature of 10 ℃, heating to 15 ℃ to react for 2 hours to obtain an intermediate 5, adding the intermediate 5, N-bromosuccinimide, benzoyl peroxide and carbon tetrachloride into a reaction kettle, reacting for 8 hours at the temperature of 80 ℃ to obtain an intermediate 6, adding the intermediate 6, potassium carbonate, deionized water and tetraethylammonium bromide into the reaction kettle, and performing reflux reaction for 2 hours to obtain an intermediate 7;

step B3: adding 2, 4-di-tert-butylphenol, deionized water, concentrated sulfuric acid and paraformaldehyde into a reaction kettle, reacting for 6 hours at the rotation speed of 120r/min and the temperature of 70 ℃, filtering, mixing a filter cake, petroleum ether and triethylamine, adding phosphorus trichloride into the reaction kettle at the temperature of 40 ℃ to react for 10 hours to obtain an intermediate 8, adding the intermediate 7, the intermediate 8, tetrahydrofuran and sodium carbonate into the reaction kettle, reacting for 3 hours at the temperature of 50 ℃ to obtain an intermediate 9, adding the intermediate 9, the intermediate 3, tetrahydrofuran and sodium methoxide into the reaction kettle, and performing reflux reaction for 10 hours at the temperature of 150 ℃ to obtain the modified epoxy resin.

Example 2

A high-temperature-resistant adhesive tape for semiconductor packaging comprises the following raw materials in parts by weight: 100 parts of high-temperature-resistant acrylic pressure-sensitive adhesive, 50 parts of ethyl acetate, 2 parts of triethylene tetramine, 2 parts of carbon nano tube and 18 parts of modified epoxy resin;

the high-temperature resistant adhesive tape is prepared by the following steps:

the high-temperature-resistant acrylic pressure-sensitive adhesive, ethyl acetate, triethylene tetramine, the carbon nano tube and the modified epoxy resin are uniformly mixed and stirred, then coated on a 25 mu mPI original film, the thickness of the dry adhesive is 5 mu m, a 25 mu m antistatic release film is attached, and the high-temperature-resistant adhesive tape for semiconductor packaging is prepared by curing for 48 hours at the temperature of 50 ℃.

The high-temperature-resistant acrylic pressure-sensitive adhesive is prepared by the following steps:

weighing 2g of acrylamide, 160g of isooctyl acrylate, 40g of ethyl acrylate, 30g of vinyl acetate, 1.5g of hydroxypropyl acrylate and 2g of SC (styrene-butadiene-styrene) viscosity stabilizer, and uniformly mixing to obtain a monomer mixed solution for later use;

weighing 1.5g of azodiisoamyl nitrile, and dissolving in 28.5g of toluene to obtain initiator diluent with the mass fraction of 5% for later use;

weighing 70g of methyl acetate, 120g of ethyl acetate and 170g of toluene, and uniformly mixing to obtain a mixed solvent for later use;

step A1: adding monomer mixed liquid with the mass of 1/2 and mixed solvent with the mass of 1/3 into a reaction kettle, introducing nitrogen to remove oxygen, dropwise adding initiator diluent with the mass of 1/2 at the rotation speed of 180r/min and the temperature of 75 ℃, wherein the dropwise adding time is 1.5h, and preserving heat for 1h after the dropwise adding is finished;

step A2: and dropwise adding the residual monomer mixed solution and 2/5 mass initiator diluent into the reaction kettle for 2h, keeping the temperature for 1h after the dropwise addition is finished, adding the residual initiator solution within 1h, keeping the temperature until the viscosity of the polymer reaches 5000mpa.s, adding the residual solvent, and uniformly mixing to obtain the high-temperature-resistant acrylic pressure-sensitive adhesive.

The modified epoxy resin is prepared by the following steps:

step B1: adding epoxy resin E-44, pyromellitic dianhydride, toluene and acetone into a reaction kettle, stirring and adding tetrabutylammonium bromide under the conditions that the rotating speed is 300r/min and the temperature is 85 ℃, reacting for 6 hours to obtain an intermediate 1, adding 2, 6-di-tert-butylphenol, potassium hydroxide and tetrahydrofuran into the reaction kettle, refluxing and dropwise adding methyl acrylate under the condition that the temperature is 75 ℃, reacting for 7 hours to obtain an intermediate 2, adding the intermediate 2, lithium aluminum hydride and tetrahydrofuran into the reaction kettle, refluxing and adding methanol under the condition that the temperature is 73 ℃, reacting for 1.3 hours to obtain an intermediate 3;

step B2: dissolving the intermediate 1 in N, N-dimethylformamide, adding the intermediate 3 and 4-dimethylaminopyridine, reacting for 9 hours at the rotation speed of 300r/min and the temperature of 93 ℃ to obtain an intermediate 4, dissolving ethyl benzoate in acetone, stirring and dropwise adding concentrated sulfuric acid at the rotation speed of 180r/min and the temperature of 10-15 ℃, heating to 18 ℃ to react for 2.5 hours to obtain an intermediate 5, adding the intermediate 5, N-bromosuccinimide, benzoyl peroxide and carbon tetrachloride into a reaction kettle, reacting for 9 hours at the temperature of 85 ℃ to obtain an intermediate 6, adding the intermediate 6, potassium carbonate, deionized water and tetraethylammonium bromide into the reaction kettle, and performing reflux reaction for 2.5 hours to obtain an intermediate 7;

step B3: adding 2, 4-di-tert-butylphenol, deionized water, concentrated sulfuric acid and paraformaldehyde into a reaction kettle, reacting for 7 hours at 73 ℃ at the rotation speed of 120r/min, filtering, mixing a filter cake, petroleum ether and triethylamine, adding phosphorus trichloride into the reaction kettle at 45 ℃ to react for 13 hours to obtain an intermediate 8, adding the intermediate 7, the intermediate 8, tetrahydrofuran and sodium carbonate into the reaction kettle, reacting for 3.5 hours at 55 ℃ to obtain an intermediate 9, adding the intermediate 9, the intermediate 3, tetrahydrofuran and sodium methoxide into the reaction kettle, and performing reflux reaction for 13 hours at 155 ℃ to obtain the modified epoxy resin.

Example 3

A high-temperature-resistant adhesive tape for semiconductor packaging comprises the following raw materials in parts by weight: 110 parts of high-temperature-resistant acrylic pressure-sensitive adhesive, 60 parts of ethyl acetate, 3 parts of diethylenetriamine, 3 parts of carbon nanotubes and 20 parts of modified epoxy resin;

the high-temperature resistant adhesive tape is prepared by the following steps:

the high-temperature-resistant acrylic pressure-sensitive adhesive, ethyl acetate, diethylenetriamine, carbon nanotubes and modified epoxy resin are uniformly mixed and stirred, then coated on a 30 mu mPI original film, the thickness of the dry adhesive is 6 mu m, a 30 mu m antistatic release film is attached, and the high-temperature-resistant adhesive tape for semiconductor packaging is prepared after curing for 50 hours at the temperature of 55 ℃.

The high-temperature-resistant acrylic pressure-sensitive adhesive is prepared by the following steps:

weighing 2g of ethyl acetoacetate methacrylate, 120g of isooctyl acrylate, 80g of ethyl acrylate, 30g of methyl methacrylate, 1.5g of hydroxypropyl acrylate and 4g of GH stabilizing agent, and uniformly mixing to obtain a monomer mixed solution for later use;

weighing 0.95g of azodiisoamyl nitrile, and dissolving in 18.05g of toluene to obtain initiator diluent with the mass fraction of 5% for later use;

weighing 30g of methyl acetate, 180g of ethyl acetate and 150g of toluene, and uniformly mixing to obtain a mixed solvent for later use;

step A1: adding monomer mixed liquid with the mass of 1/2 and mixed solvent with the mass of 1/3 into a reaction kettle, introducing nitrogen to remove oxygen, dropwise adding initiator diluent with the mass of 1/2 at the rotation speed of 200r/min and the temperature of 80 ℃, wherein the dropwise adding time is 2 hours, and preserving heat for 1.5 hours after the dropwise adding is finished;

step A2: and dropwise adding the residual monomer mixed solution and 2/5 mass initiator diluent into the reaction kettle for 2.5h, after dropwise adding, keeping the temperature for 1.5h, adding the residual initiator solution within 1h, keeping the temperature until the viscosity of the polymer reaches 5500mpa.s, adding the residual solvent, and uniformly mixing to obtain the high-temperature-resistant acrylic pressure-sensitive adhesive.

The modified epoxy resin is prepared by the following steps:

step B1: adding epoxy resin E-44, pyromellitic dianhydride, toluene and acetone into a reaction kettle, stirring and adding tetrabutylammonium bromide under the conditions that the rotating speed is 300r/min and the temperature is 90 ℃, reacting for 7 hours to obtain an intermediate 1, adding 2, 6-di-tert-butylphenol, potassium hydroxide and tetrahydrofuran into the reaction kettle, refluxing and dropwise adding methyl acrylate under the condition that the temperature is 80 ℃, reacting for 8 hours to obtain an intermediate 2, adding the intermediate 2, lithium aluminum hydride and tetrahydrofuran into the reaction kettle, refluxing and adding methanol under the condition that the temperature is 75 ℃, reacting for 1.5 hours to obtain an intermediate 3;

step B2: dissolving the intermediate 1 in N, N-dimethylformamide, adding the intermediate 3 and 4-dimethylaminopyridine, reacting for 10 hours at the rotation speed of 300r/min and the temperature of 95 ℃ to obtain an intermediate 4, dissolving ethyl benzoate in acetone, stirring and dropwise adding concentrated sulfuric acid at the rotation speed of 200r/min and the temperature of 15 ℃, heating to 20 ℃ to react for 3 hours to obtain an intermediate 5, adding the intermediate 5, N-bromosuccinimide, benzoyl peroxide and carbon tetrachloride into a reaction kettle, reacting for 10 hours at the temperature of 90 ℃ to obtain an intermediate 6, adding the intermediate 6, potassium carbonate, deionized water and tetraethylammonium bromide into the reaction kettle, and performing reflux reaction for 3 hours to obtain an intermediate 7;

step B3: adding 2, 4-di-tert-butylphenol, deionized water, concentrated sulfuric acid and paraformaldehyde into a reaction kettle, reacting for 8 hours at the rotation speed of 150r/min and the temperature of 75 ℃, filtering, mixing a filter cake, petroleum ether and triethylamine, adding phosphorus trichloride at the temperature of 50 ℃ to react for 15 hours to obtain an intermediate 8, adding the intermediate 7, the intermediate 8, tetrahydrofuran and sodium carbonate into the reaction kettle, reacting for 4 hours at the temperature of 60 ℃ to obtain an intermediate 9, adding the intermediate 9, the intermediate 3, tetrahydrofuran and sodium methoxide into the reaction kettle, and performing reflux reaction for 15 hours at the temperature of 160 ℃ to obtain the modified epoxy resin.

Comparative example 1

Compared with example 1, the high temperature resistant acrylic pressure sensitive adhesive is not added in the comparative example, and the rest steps are the same.

Comparative example 2

This comparative example is an adhesive tape for semiconductor processing disclosed in chinese patent CN 104272437A.

Comparative example 3

This comparative example is the adhesive tape for semiconductor package disclosed in chinese patent CN 103571412A.

The measurement was carried out using a tack tester TAC-II manufactured by Rhesca corporation, and in the measurement mode, a ConstantLoad in which a probe was pressed to a set pressure value and the pressure value was kept continuously controlled until the set time was completed was used, after the separator was peeled off, a probe made of SUS304 having a diameter of 3.0mm was brought into contact with the adhesive layer of the adhesive tape for semiconductor processing from the upper side with the adhesive layer facing upward, the probe was brought into contact with the measurement sample at a speed of 30mm/min, a contact load of 100gf and a contact time of 1 second, and then the probe was lifted upward at a peeling speed of 600mm/min, the force required for the lift-off was measured, the peak was read, the probe temperature was 23 ℃ and the plate temperature was set to 23 ℃, and the measurement was continued in an environment having a temperature of 80 ℃, and the results were shown in the following table:

from the above table, it can be seen that the adhesive strength of the high temperature resistant adhesive tape prepared in the embodiments 1-3 is 728-776kPa, meanwhile, the adhesive strength does not decrease greatly under high temperature conditions, and the antistatic treatment is synchronously performed in the adhesive layer, the peeling voltage of the adhesive layer is less than 100V, so as to effectively avoid the contamination of the semiconductor chip due to the electrostatic adsorption dust.

The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.