Adhesive film with high-temperature-resistant semi-conductive property and preparation method of adhesive film

Abstract

The invention discloses a high-temperature-resistant semiconductive adhesive film and a preparation method thereof, and relates to the field of high-temperature-resistant semiconductive adhesive films, the adhesive film is composed of epoxy resin, an arylamine curing agent, thermoplastic resin, a block copolymer, a conductive filler and an antioxidant; wherein the thermoplastic resin is dinitrogen bisphenol fluorene epoxy resin. The preparation method comprises the following steps: adding the epoxy resin into a reaction kettle, adding the thermoplastic resin and the block copolymer while heating and stirring, continuously heating, primarily mixing with the arylamine curing agent, the conductive filler and the antioxidant by adopting a kneading machine, further mixing by adopting a double-screw extruder, and carrying out double-roller hot rolling and film forming by adopting a film coating machine, thereby obtaining the conductive film. According to the invention, the adhesive film has good mechanical properties and stable electrical properties after thermal oxidation examination under the condition of 150 DEG C * 2000h.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of high-temperature-resistant semiconductive film, in particular to a method for preparing high-temperature-resistant semiconductive film from epoxy resin, thermoplastic resin, block copolymer, conductive filler, curing agent and antioxidant. BACKGROUND

[0002] With the rapid development of high-speed aircraft, higher temperature resistance requirements for materials used to manufacture aircraft are inevitably put forward. Especially in the field of civil aviation, its service time far exceeds that of military aircraft, and it needs to withstand dynamic load for a long time, so higher requirements for the high-temperature-resistant properties of materials are put forward. High-molecular conductive materials can be used for lightning protection on the surface of aircraft composite materials, which has good conductivity and can dissipate the current generated by lightning, thereby achieving the purpose of lightning protection.

[0003] The shunt used for preparing the film is mainly used on the radar cover of the aircraft. With the increase of flight speed and the change of environment, its use temperature may occasionally reach 150℃, which exceeds the existing use temperature range of semiconductive film. The performance of the film may change under this high-temperature condition, especially the electrical conductivity, which affects the lightning protection characteristics of the radar cover and brings great safety hazards to the flight of the aircraft. Therefore, it is imperative to invent a film with stable electrical conductivity under high-temperature conditions.

[0004] CN106189081B, the invention name "a surface film with conductive properties and its preparation method" discloses a surface film with conductive properties composed of epoxy resin, polyarylene ether nitrile ketone, core-shell rubber particles, flowability control agent, curing agent and conductive graphene. The preparation method is: a small amount of graphene is doped in the epoxy resin, the resin is specially toughened, and a composite material surface film with conductive properties is prepared by mechanical calendering. Then, the film is pressed, cut, placed in the groove of the composite plate, compacted, and cured under pressure. Finally, the resistivity of the cured plate sample is measured and calculated when the distance between the samples is 50mm. The surface film of the patent is weak in resisting long-term thermal oxidation at 150℃. SUMMARY

[0005] The present application is to solve the problem of poor mechanical properties and stable electrical properties of the existing semiconductive film under long-term thermal oxidation at 150℃, and to provide a high-temperature-resistant semiconductive film and a preparation method thereof.

[0006] The present application relates to a kind of high-temperature-resistant semiconductive characteristics adhesive film, the adhesive film is by epoxy resin 75~100 parts, aromatic amine curing agent 20~35 parts, thermoplastic resin 40~60 parts, block copolymer 6~15 parts, conductive filler 3~9 parts and antioxidant 3~9 parts according to weight fraction composition;Wherein, the epoxy resin is by bisphenol A type epoxy resin 1~4 parts, TGDDE epoxy resin 1~3 parts, di-azobisphenol fluorene epoxy resin 1~2 parts and brominated epoxy resin 1 part according to weight fraction composition.

[0007] Further, the adhesive film is by epoxy resin 80~90 parts, aromatic amine curing agent 20~30 parts, thermoplastic resin 40~50 parts, block copolymer 6~10 parts, conductive filler 3~6 parts and antioxidant 3~6 parts according to weight fraction composition.

[0008] Further, the adhesive film is by epoxy resin 75~85 parts, aromatic amine curing agent 25~30 parts, thermoplastic resin 45~55 parts, block copolymer 8~12 parts, conductive filler 4~8 parts and antioxidant 4~8 parts according to weight fraction composition.

[0009] Further, the epoxy resin is by bisphenol A type epoxy resin, TGDDE epoxy resin, di-azobisphenol fluorene epoxy resin and brominated epoxy resin according to weight ratio (1~3) :(1~2) :(1~2) :1 ratio composition.

[0010] Further, the bisphenol A type epoxy resin is bisphenol A type epoxy resin of E-51 or E-44 type.

[0011] Further, the aromatic amine curing agent is by 4,4'-diamino diphenyl sulfone, 1,2-bis (4-aminophenyl) -1,2-dicarboxy- close to twelve boranes according to weight ratio (1~4) :(1~3) :1 composition.

[0012] Further, the block copolymer is by poly (methyl methacrylate) -polybutyl methacrylate-poly (methyl methacrylate) triblock copolymer, polyethylene glycol-polypropylene glycol-polyethylene glycol triblock copolymer, polycaprolactone-polybutadiene-poly caprolactone triblock copolymer one or several compositions.

[0013] Further, the conductive filler in the adhesive film is by one or several of graphene, carbon nanotube, conductive carbon black.

[0014] Further, the antioxidant in the adhesive film is by one or several of 1,1'-di (2-methyl-4-hydroxy-5-tert-butyl phenyl) butane, tetra [beta- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid] pentaerythritol ester, 1,3,5-tri (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid.

[0015] The application discloses a preparation method of a high-temperature-resistant semiconductive adhesive film.

[0016] A1, epoxy resin 75-100 parts by weight, aromatic amine curing agent 20-35 parts by weight, thermoplastic resin 40-60 parts by weight, block copolymer 6-15 parts by weight, conductive filler 3-9 parts by weight and antioxidant 3-9 parts by weight are weighed;

[0017] A2, the epoxy resin weighed in step A1 is added into a reaction kettle, heated and warmed to 210-220 DEG C, the thermoplastic resin and the block copolymer are added at one time under stirring, and the homogeneous blending resin is prepared by keeping at 200-205 DEG C for 50-60 min;

[0018] A3, the homogeneous blending resin prepared in step A2 is mixed with the aromatic amine curing agent, the conductive filler and the antioxidant by using a kneader for preliminary mixing, and then further mixed by using a double-screw extruder to prepare the adhesive;

[0019] A4, the adhesive prepared in step A3 is formed into a film by double-roller hot calendering through an adhesive film machine to prepare the high-temperature-resistant semiconductive adhesive film.

[0020] The application comprises the following beneficial effects:

[0021] The application adopts epoxy resin, aromatic amine curing agent, thermoplastic resin, block copolymer, conductive filler and antioxidant to prepare a high-temperature-resistant semiconductive adhesive film by melt blending and mechanical blending, wherein the high-temperature-resistant diphenylolpropane fluorene epoxy resin (DEPFS), brominated epoxy resin and antioxidant components jointly act to realize that the adhesive film has good mechanical properties and stable electrical properties after heat and oxygen test at 150 DEG C for 2000 h. DETAILED DESCRIPTION

[0022] In order to make the purpose, technical scheme and advantages of the embodiments of the application more clear, the spirit of the disclosed content will be described in detail below, and any person skilled in the art can make changes and modifications to the technology taught by the disclosed content without departing from the spirit and scope of the disclosed content.

[0023] The illustrative embodiments of the application and the description thereof are used to explain the application, but not as a limitation of the application.

[0024] Embodiment 1

[0025] The high-temperature-resistant semiconductive adhesive film and the preparation method thereof are prepared according to the following steps:

[0026] A1, epoxy resin 75 parts by weight, aromatic amine curing agent 20 parts by weight, thermoplastic resin 40 parts by weight, block copolymer 6 parts by weight, conductive filler 3 parts by weight and antioxidant 3 parts by weight are weighed;

[0027] A2, the epoxy resin weighed in step A1 is added to the reaction kettle, heated to 210-220℃, and the thermoplastic resin and block copolymer are added at one time under stirring, and the homogeneous blend resin is prepared by keeping at 200-205℃ for 50-60min;

[0028] A3, the homogeneous blend resin prepared in step A2 is mixed with aromatic amine curing agent, conductive filler and antioxidant by mechanical blending method, and then further mixed by double screw extruder to prepare the rubber compound;

[0029] A4, the rubber compound prepared in step A3 is stretched into film by double roller hot press of film machine to prepare high temperature resistant semi-conductive adhesive film.

[0030] The epoxy resin is composed of bisphenol A type epoxy resin, TGDDE epoxy resin, di-azobisphenol fluorene epoxy resin and brominated epoxy resin in a weight ratio of 3:2:2:1. The bisphenol A type epoxy resin is bisphenol A type epoxy resin of E-51 type. The aromatic amine curing agent is composed of 4,4'-diamino diphenyl sulfone, 1,2-bis(4-aminophenyl)-1,2-dicarboxy-clo dodecaborane in a weight ratio of 3:2:1; the block copolymer is poly(methyl methacrylate)-poly(butyl acrylate)-poly(methyl methacrylate) triblock copolymer. The conductive filler in the adhesive film is graphene. The antioxidant in the adhesive film is 1,1'-bis(2-methyl-4-hydroxy-5-tert-butylphenyl) butane.

[0031] The di-azobisphenol fluorene epoxy resin (DEPFS) has the chemical structural formula:

[0032] .

[0033] Example 2

[0034] The difference between this example and example 1 is that epoxy resin 100 parts by weight, aromatic amine curing agent 30 parts by weight, thermoplastic resin 55 parts by weight, block copolymer 12 parts by weight, conductive filler 8 parts by weight and antioxidant 8 parts by weight are weighed; the others are the same as example 1.

[0035] Example 3

[0036] The difference between this embodiment and embodiment 1 is that: epoxy resin 100 parts by weight, aromatic amine curing agent 35 parts by weight, thermoplastic resin 60 parts by weight, block copolymer 15 parts by weight, conductive filler 9 parts by weight and antioxidant 9 parts by weight; antioxidant is 1,1'-di(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid according to the mass ratio of 1:1. The same as embodiment 1.

[0037] Example 4

[0038] The difference between this embodiment and embodiment 1 is that: epoxy resin 100 parts by weight, aromatic amine curing agent 30 parts by weight, thermoplastic resin 50 parts by weight, block copolymer 10 parts by weight, conductive filler 5 parts by weight and antioxidant 5 parts by weight; antioxidant is 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid. The same as embodiment 1.

[0039] Example 5

[0040] The difference between this embodiment and embodiment 1 is that: epoxy resin 100 parts by weight, aromatic amine curing agent 35 parts by weight, thermoplastic resin 55 parts by weight, block copolymer 12 parts by weight, conductive filler 6 parts by weight and antioxidant 6 parts by weight; antioxidant is 1,1'-di(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]pentaerythritol ester, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid according to the mass ratio of 1:1:1. The same as embodiment 1.

[0041] Example 6

[0042] The difference between this embodiment and embodiment 1 is that: epoxy resin 100 parts by weight, aromatic amine curing agent 25 parts by weight, thermoplastic resin 45 parts by weight, block copolymer 8 parts by weight, conductive filler 4 parts by weight and antioxidant 4 parts by weight; antioxidant is tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]pentaerythritol ester. The same as embodiment 1.

[0043] Example 7

[0044] The difference between this embodiment and embodiment 1 is that: the epoxy resin is composed of bisphenol A type epoxy resin and TGDDE epoxy resin according to the weight ratio of 3:2; the same as embodiment 1.

[0045] Table 1 Comparison of mechanical properties and electrical properties test results of different embodiments

[0046]

[0047] Examples 1 through 6 present test results for combinations of components of the present invention. The thermoplastic resin in Example 7 differs from that in Examples 1 through 6. The test data demonstrates that the blank shear strength (at 23°C and 177°C) and the shear strength after aging (150°C x 2000h) of Examples 1 through 6 are significantly higher than those of Example 7, demonstrating that the chemical compositions of Examples 1 through 6 exhibit superior thermal aging properties. Furthermore, the volume resistivity of the strips of Examples 1 through 6 exhibits minimal change after thermal aging (150°C x 2000h), while the volume resistivity of the strips of Example 7 exhibits a significant change. In summary, the chemical compositions of Examples 1 through 6 exhibit significantly superior mechanical and electrical stability compared to those of Example 7.

Claims

1. A high temperature resistant semi-conductive adhesive film, characterized in that The adhesive film is composed of 75-100 parts of epoxy resin, 20-35 parts of aromatic amine curing agent, 40-60 parts of thermoplastic resin, 6-15 parts of block copolymer, 3-9 parts of conductive filler and 3-9 parts of antioxidant in parts by weight; wherein, the epoxy resin is composed of 1-4 parts of bisphenol A epoxy resin, 1-3 parts of TGDDE epoxy resin, 1-2 parts of diazolidinone fluorene epoxy resin and 1 part of brominated epoxy resin in parts by weight.

2. The adhesive film having high temperature resistance and semi-conductive properties according to claim 1, characterized in that The adhesive film is composed of 80-90 parts of epoxy resin, 20-30 parts of aromatic amine curing agent, 40-50 parts of thermoplastic resin, 6-10 parts of block copolymer, 3-6 parts of conductive filler and 3-6 parts of antioxidant in parts by weight.

3. The adhesive film having high temperature resistance and semi-conductive properties according to claim 1, characterized in that The adhesive film is composed of 75-85 parts of epoxy resin, 25-30 parts of aromatic amine curing agent, 45-55 parts of thermoplastic resin, 8-12 parts of block copolymer, 4-8 parts of conductive filler and 4-8 parts of antioxidant in parts by weight.

4. The adhesive film having high temperature resistant semi-conductive properties according to claim 1, 2 or 3, characterized in that The epoxy resin is composed of bisphenol A epoxy resin, TGDDE epoxy resin, diazobisthenol fluorene epoxy resin and brominated epoxy resin in a weight ratio of (1-3): (1-2): (1-2):

1.

5. The adhesive film having high temperature resistance and semi-conductive properties according to claim 4, characterized in that The bisphenol A epoxy resin is E-51 or E-44 type bisphenol A epoxy resin.

6. The adhesive film having high temperature resistance and semi-conductive properties according to claim 1, 2 or 3, characterized in that The aromatic amine curing agent is composed of 4,4'-diaminodiphenyl sulfone and 1,2-bis(4-aminophenyl)-1,2-dicarboxyl-near dodecaborane in a weight ratio of (1-4):(1-3):

1.

7. The adhesive film having high temperature resistant semi-conductive properties according to claim 1, 2 or 3, characterized in that The block copolymer is composed of one or more of poly(methyl methacrylate)-polybutyl acrylate-poly(methyl methacrylate) triblock copolymer, polyethylene glycol-polypropylene glycol-polyethylene glycol triblock copolymer, and polycaprolactone-polybutadiene-polycaprolactone triblock copolymer.

8. The adhesive film having high temperature resistance and semi-conductive properties according to claim 1, 2 or 3, characterized in that The conductive filler in the adhesive film is composed of one or more of graphene, carbon nanotubes, and conductive carbon black.

9. The adhesive film having high temperature resistant semi-conductive properties according to claim 1, 2 or 3, characterized in that The antioxidant in the adhesive film is composed of one or more of 1,1'-bis(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanuric acid.

10. The method for preparing the high-temperature resistant semi-conductive adhesive film according to claim 1, characterized in that The preparation method is as follows: A1. Weigh 75-100 parts of epoxy resin, 20-35 parts of aromatic amine curing agent, 40-60 parts of thermoplastic resin, 6-15 parts of block copolymer, 3-9 parts of conductive filler and 3-9 parts of antioxidant by weight; A2. Add the epoxy resin weighed in step A1 to a reaction kettle, heat to 210-220°C, add the thermoplastic resin and block copolymer at once while stirring, and keep the mixture at 200-205°C for 50-60 minutes to obtain a homogeneous blended resin; A3, using a mechanical blending method to initially mix the homogeneous blended resin prepared in step A2 with an aromatic amine curing agent, a conductive filler, and an antioxidant using a kneader, and then further mixing using a twin-screw extruder to prepare a rubber compound; A4. The rubber compound obtained in step A3 is formed into a film by double-roll hot rolling using a film forming machine to obtain a high-temperature resistant semi-conductive film.

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