CN104356603B - A kind of for semi-conductor adhesive membrane material preparing anti-lightning strike shunt bar and preparation method thereof - Google Patents

Abstract

A semiconductor adhesive film material for preparing a lightning protection shunt strip and a preparation method thereof. The invention relates to a semiconductor adhesive film material and a preparation method thereof. The present invention aims to solve the technical problems of complex process, incompatibility and mismatch caused by co-bonding with other adhesives or secondary bonding and forming in the existing technology. The material consists of 75-100 parts by weight of epoxy resin, 15-30 parts of thermoplastic resin, 6-12 parts of rubber elastic body, 15-25 parts of curing agent, 2-6 parts of accelerator, 6-12 parts The non-metallic conductive filler and 10-20 parts of non-metallic semiconductor filler; method: 1. weighing; 2. preparing resin mixture; 3. blending and discharging; 4. calendering to form a film. The semiconductor adhesive film material prepared by the invention not only has the characteristics of the structural adhesive film, but also has the resistance value characteristic of the semiconductor adhesive material. The semiconductor film material of the present invention is used for the preparation of lightning protection shunt strips.

Description

A semiconductor adhesive film material for preparing lightning protection shunt strips and its preparation method

technical field

The invention relates to a semiconductor adhesive film material and a preparation method thereof.

Background technique

The aircraft radome is generally located at the front of the aircraft. It is required that the radome not only ensures the smooth passage of radar electromagnetic waves, but also protects the radar antenna from the harmful effects of external loads (such as wind, rain, sand, dust, lightning, etc.). important part of the body. In order to ensure that electromagnetic waves pass through the radomes smoothly, most radomes are made of dielectric materials. Dielectric materials are poor conductors of electricity, and the aircraft radome is located on the most vulnerable position on the aircraft to be attacked by lightning, so the industry generally uses lightning shunt strips for protection.

The radome lightning protection system is generally composed of conductive or semi-conductive materials, such as compounding metal foil and composite material base strips with adhesives to prepare conductive lightning shunt strips, and another kind is filled with metal particles into the resin system. A semiconductor material is formed to make a shunt bar. Conductor shunt strips made of metal foil cannot achieve special functions such as stealth and wave penetration due to the reflection of metal on radar waves; although semiconductor shunt strips made of metal particles have stealth and wave penetration functions, due to the large proportion of metal particles, It is difficult to disperse uniformly in the system, which will lead to the problem of poor uniformity of resistance value during the blending and curing process. In addition, metal particles filled in the resin system will accelerate the corrosion and oxidation of metals under acid, alkali and humid heat aging, especially The metal particles on the surface have an impact on the overall performance of the entire system.

Contents of the invention

The present invention aims to solve the technical problems of complex process, incompatibility and mismatch caused by co-bonding or secondary bonding of other adhesives in the existing technology, and provides a kind of method for preparing lightning protection shunt Strip semiconductor adhesive film material and preparation method thereof.

A semiconductor film material used for preparing lightning protection shunt strips consists of 75-100 parts by weight of epoxy resin, 15-30 parts of thermoplastic resin, 6-12 parts of rubber elastic body, 15-25 parts It consists of curing agent, 2-6 accelerators, 6-12 parts of non-metallic conductive filler and 10-20 parts of non-metallic semiconductor filler.

A method for preparing a semiconductor film material for lightning protection shunt strips, specifically carried out in accordance with the following steps:

1. Weigh 75-100 parts of epoxy resin, 15-30 parts of thermoplastic resin, 6-12 parts of rubber elastomer, 15-25 parts of curing agent, 2-6 parts of accelerator, 6-12 parts according to parts by weight. Parts of non-metallic conductive filler and 10 to 20 parts of non-metallic semiconductor filler;

2. Divide the epoxy resin taken in step 1 into three equal parts by mass, the first part is hot-melted with a thermoplastic resin to prepare a polymer alloy; the second part is ground and blended with the rubber elastic body using a three-roll grinder; the second part Dissolve three parts in ethyl acetate, then add non-metallic conductive filler and non-metallic semiconductor filler, carry out ultrasonic dispersion, and then use a scraper type thin film evaporator to remove the solvent;

3. Blend the three resins obtained in step 2 with a vacuum kneader, add the curing agent and accelerator weighed in step 1, mix evenly, then use a double-roller mixer to mix and thin pass 3 times, and the material;

4. Calendering and forming a film by using a double-roller hot calendering method to obtain a semiconductor adhesive film material for preparing a lightning protection shunt strip.

The semiconductor adhesive film material of the present invention uses non-metallic conductive fillers and semiconductive fillers similar to the resin specific gravity as fillers in the resin system, and will not occur during the entire adhesive film preparation, adhesive film laying process, and curing/co-curing process. The problem of subsidence, the stability and uniformity of the resistance value are good; its semiconductor characteristics have stealth and wave-transmitting functions; the invention uses non-metallic fillers, and there will be no problems caused by the use of metal particle fillers under acid, alkali or hot and humid conditions. Corrosion and oxidation problems greatly increase the stability of the resistance value and the service life of the shunt strip; in addition, because the semiconductor adhesive film material itself has adhesive properties, it can be directly bonded and solidified with the composite material base strip, eliminating the need to use Problems of complex process, incompatibility and mismatch caused by additional co-bonding or secondary bonding of other adhesives.

The beneficial effects of the present invention are:

1. The present invention has obvious advantages in using non-metallic conductive fillers and semiconductor fillers instead of metal particle fillers. ① Overcome the uneven dispersion of metal particle fillers in the resin system blending and curing process. Using a non-metallic filler (graphene microflakes, carbon black and boron powder) system with a similar specific gravity to the resin as a filler, no sedimentation will occur during the entire film preparation, film laying process, and curing/co-curing process And other problems, the resistance value uniformity is good; ② Overcome the defects of metal particle filler in stealth. During the high-speed flight of the aircraft, the radar radome and other components need to consider the stealth performance such as wave penetration. The stealth aircraft has higher requirements for stealth performance, which puts forward higher requirements for materials. The use of metal particle filling will affect the wave transmission performance, etc. It has a great impact, and the present invention uses flake graphite/carbon black/boron powder system filling, which will greatly improve the dielectric properties and make it have better application prospects; ③ overcome the corrosion resistance and oxidation of metal particle fillers ability. Metal particles filled in the resin system will accelerate the corrosion and oxidation of metals, especially the surface metals, under acid, alkali and humid heat aging, which will affect the overall performance of the entire system; using flake graphite/carbon black/boron Powder filled resins do not face this risk.

2. The composite technology of non-metallic conductive fillers (graphene microflakes and conductive carbon black) and semiconductor fillers (boron powder) is used to solve the problem that the resistance value changes too much in the narrow mutation zone of the percolation curve when carbon-based conductive fillers are used alone. problem, thereby solving the stability of the resistance value, its volume resistivity can be stabilized at 6～8×10 ⁷ Ω·m, and its surface resistivity can be stabilized at 0.8～1.6×10 ⁹ Ω, endowing the semiconductor adhesive film material of the present invention The resistance value characteristic is suitable for the preparation of lightning protection shunt strips.

3. The present invention jointly adopts rubber elastomer and thermoplastic resin as the toughening material of the semiconductor adhesive film material, which gives the adhesive film better mechanical properties, heat resistance, toughness and durability, and the semiconductor adhesive film material of the present invention has both structure The characteristics of the adhesive film, its shear strength at room temperature reaches 19.1MPa, shear strength at 160°C reaches 14.8MPa, peel strength of aluminum honeycomb roller reaches 54.2N mm/mm, and the flexibility passes through R50 arc bending for 10 times without breaking. Good durability, the normal temperature shear strength retention rate after damp heat aging is 92.1% (55°C, RH=98-100% after damp heat aging for 1000h). Its adhesiveness, flexibility and durability meet the performance requirements of semiconductor adhesive film materials used in the preparation of lightning protection shunt strips, and avoid the complicated process and compatibility caused by co-bonding or secondary bonding of additional adhesives. and compatibility problems.

Test methods: GB/T 7124-2008 Determination of Tensile Shear Strength of Adhesives; GJB444-1988 Test Method for High Temperature Tensile Shear Strength of Adhesives; GJB130.7-1986 Test Method for Roller Peeling of Bonded Aluminum Honeycomb Sandwich Structure; HB5164 Putty Film Determination of flexibility; GJB150.9 Military equipment environmental test method damp heat test.

4. The semiconductor adhesive film material of the present invention has better viscosity-temperature characteristics, as can be seen from the viscosity-temperature curve of the semiconductor adhesive film material: the adhesive film material enters the low-viscosity zone at 80°C, and the viscosity at the lowest point remains at 9000Pa .s or more, which effectively guarantees that the adhesive film material will not flow and deform severely during the entire curing process, so that the shape of the cured high-resistance layer adhesive film material is maintained; the viscosity increases rapidly at 130-135 °C, The temperature is used as the curing temperature parameter of the material, and the actual curing process is: 130°C╳3h under 0.1MPa vacuum pressure.

The semiconductor film material of the present invention is used for the preparation of lightning protection shunt strips.

Description of drawings

Fig. 1 is the viscosity-temperature curve diagram of the semiconductor adhesive film material prepared in Example 1.

detailed description

The technical solution of the present invention is not limited to the specific embodiments listed below, but also includes any combination of the specific embodiments.

Specific Embodiment 1: In this embodiment, a semiconductor film material used to prepare lightning protection shunt strips consists of 75 to 100 parts by weight of epoxy resin, 15 to 30 parts of thermoplastic resin, and 6 to 12 parts It consists of rubber elastic body, 15-25 parts of curing agent, 2-6 parts of accelerator, 6-12 parts of non-metallic conductive filler and 10-20 parts of non-metallic semiconductor filler.

Specific embodiment 2: The difference between this embodiment and specific embodiment 1 is: a semiconductor adhesive film material used to prepare lightning protection shunt strips, in terms of parts by weight, consists of 80-90 parts of epoxy resin, 20-25 parts It consists of 8-10 parts of thermoplastic resin, 8-10 parts of rubber elastic body, 18-22 parts of curing agent, 2.5-3 parts of accelerator, 7-10 parts of non-metallic conductive filler and 14-16 parts of non-metallic semiconductor filler. Others are the same as in the first embodiment.

Specific embodiment three: the difference between this embodiment and specific embodiment one or two is that: the epoxy resin is composed of bisphenol A epoxy resin and tetrafunctional epoxy resin, and bisphenol A epoxy resin and tetrafunctional epoxy resin The mass ratio of functional epoxy resin is 4:1. Others are the same as in the first or second embodiment.

Embodiment 4: The difference between this embodiment and Embodiment 1 or 2 is that the thermoplastic resin is composed of one or more of polysulfone, phenolphthalein-based polyethersulfone, and phenolphthalein-based polyaryletherketone, and the rubber is elastic The body is composed of one or more of core-shell rubber particles, epoxy-based nitrile rubber and carboxylated nitrile rubber. Others are the same as in the first or second embodiment.

Embodiment 5: The difference between this embodiment and Embodiment 1 or 2 is that the curing agent is composed of dicyandiamide and 4,4'-diaminodiphenyl sulfone, and dicyandiamide and 4,4'- The mass ratio of diaminodiphenylsulfone is (6-9):(6-15), and the accelerator is urea, thiourea or imidazole compound. Others are the same as in the first or second embodiment.

Ureas in this embodiment are N-(2-hydroxyphenyl)-N', N'-dimethylurea or N-(5-chloro-2-hydroxybenzene)-N', N'-dimethyl Urea, thioureas are thiourea or thiourea derivatives ethylene thiourea, allyl thiourea, and imidazoles are 2,4-imidazole or 2-methylimidazole.

Specific embodiment six: what this embodiment is different from specific embodiment one or two is: described non-metallic conductive filler is made up of graphene microchip and conductive carbon black, and the mass ratio of graphene microchip and conductive carbon black is ( 2-4): (2-10), the non-metallic semiconductor filler is boron powder. Others are the same as in the first or second embodiment.

Embodiment 7: A method for preparing a semiconductor adhesive film material for lightning protection shunt strips described in Embodiment 1 is specifically carried out in accordance with the following steps:

1. Weigh 75-100 parts of epoxy resin, 15-30 parts of thermoplastic resin, 6-12 parts of rubber elastomer, 15-25 parts of curing agent, 2-6 parts of accelerator, 6-12 parts according to parts by weight. Parts of non-metallic conductive filler and 10 to 20 parts of non-metallic semiconductor filler;

2. Divide the epoxy resin taken in step 1 into three equal parts by mass, the first part is hot-melted with a thermoplastic resin to prepare a polymer alloy; the second part is ground and blended with the rubber elastic body using a three-roll grinder; the second part Dissolve three parts in ethyl acetate, then add non-metallic conductive filler and non-metallic semiconductor filler, carry out ultrasonic dispersion, and then use a scraper type thin film evaporator to remove the solvent;

3. Blend the three resins obtained in step 2 with a vacuum kneader, add the curing agent and accelerator weighed in step 1, mix evenly, then use a double-roller mixer to mix and thin pass 3 times, and the material;

4. Calendering and forming a film by using a double-roller hot calendering method to obtain a semiconductor adhesive film material for preparing a lightning protection shunt strip.

Embodiment 8: The difference between this embodiment and Embodiment 7 is that the epoxy resin in step 1 is composed of bisphenol A epoxy resin and tetrafunctional epoxy resin, and bisphenol A epoxy resin and tetrafunctional epoxy resin The mass ratio of epoxy resin is 4:1; the thermoplastic resin is composed of one or more of polysulfone, phenolphthalein-based polyethersulfone and phenolphthalein-based polyaryletherketone; the curing agent is composed of dicyandiamide and 4,4'- Composed of diaminodiphenylsulfone, and the mass ratio of dicyandiamide to 4,4'-diaminodiphenylsulfone is (6~9):(6~15), and the accelerator is urea, thiourea or imidazole The compound; the non-metallic conductive filler is composed of graphene microchips and conductive carbon black, and the mass ratio of graphene microchips to conductive carbon black is (2-4): (2-10), and the non-metallic semiconductor filler is boron powder. Others are the same as in the seventh embodiment.

Embodiment 9: This embodiment differs from Embodiment 7 in that: in step 1, the rubber elastic body is core-shell rubber particles. Others are the same as in the seventh embodiment.

Embodiment 10: This embodiment is different from Embodiment 7 in that: the film forming temperature in step 4 is 75-85°C. Others are the same as in the seventh embodiment.

Adopt the following examples to verify the beneficial effects of the present invention:

Embodiment one:

In this embodiment, a method for preparing a semiconductor film material for lightning protection shunt strips is specifically carried out according to the following steps:

1. Take 90 parts by weight of epoxy resin, 25 parts of thermoplastic resin, 9 parts of rubber elastomer, 18 parts of curing agent, 4 parts of accelerator, 8 parts of non-metallic conductive filler and 15 parts of non-metallic semiconductor filler;

2. Divide the epoxy resin taken in step 1 into three equal parts by mass, the first part is hot-melted with a thermoplastic resin to prepare a polymer alloy; the second part is ground and blended with the rubber elastic body using a three-roll grinder; the second part Dissolve three parts in ethyl acetate, then add non-metallic conductive filler and non-metallic semiconductor filler, carry out ultrasonic dispersion, and then use a scraper type thin film evaporator to remove the solvent;

3. Blend the three resins obtained in step 2 with a vacuum kneader, add the curing agent and accelerator weighed in step 1, mix evenly, then use a double-roller mixer to mix and thin pass 3 times, and the material;

4. Calendering and forming a film by using a double-roller hot calendering method to obtain a semiconductor adhesive film material for preparing a lightning protection shunt strip.

Wherein, the epoxy resin in step 1 of this embodiment is composed of bisphenol A epoxy resin and tetrafunctional epoxy resin, and the mass ratio of bisphenol A epoxy resin and tetrafunctional epoxy resin is 4:1; thermoplastic The resin is polysulfone; the curing agent is composed of dicyandiamide and 4,4'-diaminodiphenylsulfone, and the mass ratio of dicyandiamide to 4,4'-diaminodiphenylsulfone is 7:11, and the accelerator is Urea, ethylene thiourea; the non-metallic conductive filler is composed of graphene micro flakes and conductive carbon black, and the mass ratio of graphene micro flakes to conductive carbon black is 3:5, and the non-metallic semiconductor filler is boron powder, rubber The elastomer is core-shell rubber particles; the film-forming temperature in step 4 is 80°C.

The viscosity-temperature curve of the semiconductor adhesive film material prepared in this example is shown in Figure 1. It can be seen from Figure 1 that the adhesive film material enters the low viscosity region at 80°C, and the viscosity at the lowest point remains above 9000Pa.s , which effectively guarantees that the adhesive film material will not flow and deform severely during the entire curing process, so that the shape of the cured high-resistance layer adhesive film material is maintained; the viscosity increases rapidly at 130-135 °C, and the temperature As the curing temperature parameter of the material, the actual curing process is: 130°C╳3h under 0.1MPa vacuum pressure.

Test the semiconductor adhesive film material prepared in this embodiment:

Test methods: GB/T 7124-2008 Determination of Tensile Shear Strength of Adhesives; GJB444-1988 Test Method for High Temperature Tensile Shear Strength of Adhesives; GJB130.7-1986 Test Method for Roller Peeling of Bonded Aluminum Honeycomb Sandwich Structure; HB5164 Putty Film Determination of flexibility; GJB150.9 Military equipment environmental test method damp heat test.

The normal temperature shear strength of the semiconductor adhesive film material prepared in this example reached 19.1MPa, the shear strength at 160°C reached 14.8MPa, the peel strength of the aluminum honeycomb roller reached 54.2N mm/mm, and the flexibility passed 10 times of R50 arc bending No fracture, good durability, and the shear strength retention rate at room temperature after damp heat aging is 92.1% (55°C, RH=98-100% after damp heat aging for 1000h). Its adhesiveness, flexibility and durability meet the performance requirements of semiconductor adhesive film materials used in the preparation of lightning protection shunt strips, and avoid the complicated process and compatibility caused by co-bonding or secondary bonding of additional adhesives. and compatibility problems.

Claims (10)

1. A semiconductor adhesive film material for preparing lightning protection shunt strips, characterized in that the material consists of 75 to 100 parts of epoxy resin, 15 to 30 parts of thermoplastic resin, 6 to 12 parts of It consists of rubber elastic body, 15-25 parts of curing agent, 2-6 parts of accelerator, 6-12 parts of non-metallic conductive filler and 10-20 parts of non-metallic semiconductor filler. 2. A kind of semiconductor film material for preparing lightning protection shunt strips according to claim 1, characterized in that the material consists of 80 to 90 parts of epoxy resin, 20 to 25 parts of thermoplastic It consists of resin, 8-10 parts of rubber elastic body, 18-22 parts of curing agent, 2.5-3 parts of accelerator, 7-10 parts of non-metallic conductive filler and 14-16 parts of non-metallic semiconductor filler. 3. according to claim 1 or 2, a kind of semi-conductor adhesive film material for preparing lightning protection shunt strip is characterized in that said epoxy resin is made up of bisphenol A type epoxy resin and tetrafunctional epoxy resin , and the mass ratio of bisphenol A epoxy resin to tetrafunctional epoxy resin is 4:1. 4. according to claim 1 or 2, a kind of semi-conductor film material for preparing lightning protection shunt strip is characterized in that said thermoplastic resin is made of polysulfone, phenolphthalein-based polyethersulfone and phenolphthalein-based polyaryletherketone The rubber elastomer is composed of one or more of the core-shell rubber particles, epoxy-based nitrile rubber and carboxylated nitrile rubber. 5. according to claim 1 or 2, a kind of semiconductor adhesive film material for preparing lightning protection shunt strips is characterized in that the curing agent is composed of dicyandiamide and 4,4'-diaminodiphenyl sulfone , and the mass ratio of dicyandiamide to 4,4'-diaminodiphenylsulfone is (6-9): (6-15), and the accelerator is urea, thiourea or imidazole compound. 6. according to claim 1 and 2, a kind of semi-conductor adhesive film material for preparing lightning protection shunt strip is characterized in that said non-metallic conductive filler is made up of graphene microplate and conductive carbon black, and graphene The mass ratio of the microchips to the conductive carbon black is (2-4):(2-10), and the non-metal semiconductor filler is boron powder. 7. a kind of preparation method that is used to prepare the semiconducting film material of lightning protection shunt strip as claimed in claim 1, it is characterized in that the method is specifically carried out according to the following steps: 1. Weigh 75-100 parts of epoxy resin, 15-30 parts of thermoplastic resin, 6-12 parts of rubber elastomer, 15-25 parts of curing agent, 2-6 parts of accelerator, 6-12 parts according to parts by weight. Parts of non-metallic conductive filler and 10 to 20 parts of non-metallic semiconductor filler; 2. Divide the epoxy resin taken in step 1 into three equal parts by mass, the first part is hot-melted with a thermoplastic resin to prepare a polymer alloy; the second part is ground and blended with the rubber elastic body using a three-roll grinder; the second part Dissolve three parts in ethyl acetate, then add non-metallic conductive filler and non-metallic semiconductor filler, carry out ultrasonic dispersion, and then use a scraper type thin film evaporator to remove the solvent; 3. Blend the three resins obtained in step 2 with a vacuum kneader, add the curing agent and accelerator weighed in step 1, mix evenly, then use a double-roller mixer to mix and thin pass 3 times, and the material; 4. Calendering and forming a film by using a double-roller hot calendering method to obtain a semiconductor adhesive film material for preparing a lightning protection shunt strip. 8. a kind of preparation method that is used to prepare the semiconducting film material of lightning protection shunt strip according to claim 7, it is characterized in that epoxy resin is made of bisphenol A type epoxy resin and tetrafunctional epoxy resin in step 1 Composition of resin, and the mass ratio of bisphenol A type epoxy resin and tetrafunctional epoxy resin is 4:1; thermoplastic resin is composed of one or more of polysulfone, phenolphthalein-based polyethersulfone and phenolphthalein-based polyaryletherketone Composition; curing agent is made up of dicyandiamide and 4,4'-diaminodiphenylsulfone, and the mass ratio of dicyandiamide and 4,4'-diaminodiphenylsulfone is (6～9):(6～15 ), the promotor is urea, thiourea or imidazole compound; the non-metallic conductive filler is made up of graphene microplate and conductive carbon black, and the mass ratio of graphene microplate and conductive carbon black is (2～4): (2-10), the non-metallic semiconductor filler is boron powder. 9. A method for preparing a semiconductor film material for lightning protection shunt strips according to claim 7, wherein the rubber elastic body in step 1 is core-shell rubber particles. 10. A method for preparing a semiconductor film material for lightning protection shunt strips according to claim 7, characterized in that the film forming temperature in step 4 is 75-85°C.