CN110628179A - A kind of low dielectric constant flame retardant electronic packaging material and preparation method thereof - Google Patents

Abstract

The invention discloses a low dielectric constant flame-retardant electronic packaging material and a preparation method thereof, which comprises 50-99 wt% of a polymer matrix and 1-50 wt% of a phosphorus-fluorine flame retardant. The low dielectric constant flame-retardant electronic packaging material of the present invention contains two flame-retardant elements, phosphorus and fluorine. The phosphorus element can play the role of gas phase flame retardancy and condensed phase flame retardancy, and promote the system to catalyze into charcoal; the introduction of fluorine element can improve The thermal stability of the material; the two elements cooperate with each other to effectively improve the thermal stability and flame retardancy of the material.

Description

A kind of low dielectric constant flame retardant electronic packaging material and preparation method thereof

technical field

The invention belongs to the technical field of flame-retardant organic materials, and in particular relates to a low dielectric constant flame-retardant electronic packaging material and a preparation method thereof.

Background technique

Polymer materials such as epoxy resin, polycarbonate (PC) and acrylonitrile-butadiene-styrene terpolymer (ABS) have high transparency, good dimensional stability, excellent dielectric properties, and good electrical insulation And other advantages, are widely used in the field of electronic packaging. However, with the rapid development of electronic products, the processing and dissemination of digital information is gradually developing in the direction of high frequency and high speed. The electrical constant and dielectric loss are a necessary trend to deal with the development of electronic packaging materials. Introducing fluorine into the material is an important means of preparing low dielectric constant materials. The electron cloud density of fluorine atoms is high, the polarizability is low, and the volume of fluorine is large, which can reduce the packing density of polymers and increase the density of polymers. free volume, thereby reducing the dielectric constant of the polymer material, while the carbon-fluorine bond has a high binding energy, and the introduction of fluorine-containing compounds can also effectively improve the heat resistance of the polymer. Polymer materials are generally flammable, and there are fire hazards in their applications. Therefore, in the application of electronic packaging, the flame retardancy of materials is also essential.

Contents of the invention

The purpose of the present invention is to overcome the defects of the prior art and provide a low dielectric constant flame-retardant electronic packaging material.

Another object of the present invention is to provide a method for preparing the above-mentioned low dielectric constant flame-retardant electronic packaging material.

Technical scheme of the present invention is as follows:

A low dielectric constant flame-retardant electronic packaging material, comprising 50-99wt% of a polymer matrix and 1-50wt% of a phosphorus-fluorine flame retardant, wherein the polymer matrix includes epoxy resin, polycarbonate and acrylonitrile -Butadiene-styrene terpolymer, the structural formula of phosphorus-containing fluorine flame retardant is

In a preferred embodiment of the present invention, the synthesis route of the phosphorus-containing fluorine flame retardant is as follows:

Further preferably, the preparation method of the phosphorus-containing fluorine flame retardant comprises the following steps:

(1) Add 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), 3,5-bis(trifluoromethyl)benzyl alcohol, and The first solvent and the second solvent, under stirring in an ice bath, slowly drop triethylamine into the above reaction vessel using a constant pressure dropping funnel, and react at room temperature for 5-24 hours after the drop addition; the above first solvent is tetrahydrofuran, dichloro Methane or toluene, the above-mentioned second solvent is carbon tetrachloride or chloroform, and the first solvent and the second solvent are different from each other;

(2) Extract the material obtained in step (1) with water, take the organic layer and dry it with anhydrous magnesium sulfate and filter to obtain the filtrate;

(3) The above-mentioned filtrate is subjected to rotary evaporation to remove the first solvent and the second solvent, and the obtained white solid is fully vacuum-dried to obtain the phosphorus-containing fluorine flame retardant.

More preferably, the first solvent is 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 3,5-bis(trifluoromethyl)benzyl alcohol and triethylamine The molar ratio is 1:0.1-10:0.1-10.

More preferably, the mass ratio of the 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, the first solvent and the second solvent is 1:1-200:1-200 .

One of the preparation methods of the above-mentioned low dielectric constant flame-retardant electronic packaging material, the polymer matrix is epoxy resin, which specifically includes: weighing 50-99wt% of epoxy resin prepolymer, 1-50wt% of the Phosphorus-fluorine flame retardant and 5-15wt% of 4,4'-diaminodiphenylmethane (DDM); after the epoxy resin prepolymer is heated to 60-140°C, the phosphorus-fluorine flame retardant is added and stirred until transparent, then add 4,4'-diaminodiphenylmethane and stir until it is completely dissolved, then pour it into a mold, and heat it up for curing to obtain the low dielectric constant flame-retardant electronic packaging material; wherein, the above-mentioned temperature program is : Curing at 115-125°C for 3-5h, curing at 135-145°C for 1-3h, curing at 170-185°C for 1-3h.

In a preferred embodiment of the present invention, the epoxy resin prepolymer is E51 bisphenol A epoxy resin.

In a preferred embodiment of the present invention, the mass ratio of the epoxy resin prepolymer to 4,4'-diaminodiphenylmethane is 8:2.02.

In a preferred embodiment of the present invention, the temperature program is as follows: curing at 120° C. for 4 hours, curing at 140° C. for 2 hours, and curing at 180° C. for 2 hours.

The second preparation method of the above-mentioned low dielectric constant flame-retardant electronic packaging material, the polymer matrix is polycarbonate or acrylonitrile-butadiene-styrene terpolymer, specifically includes: after drying, the high Phosphorous and fluorine-containing flame retardants are added to the masterbatch of the molecular matrix, mixed and extruded by a twin-screw extruder, and further granulated and dried to obtain the low dielectric constant flame-retardant electronic packaging material.

The beneficial effects of the present invention are:

1. The low dielectric constant flame-retardant electronic packaging material of the present invention contains two flame-retardant elements, phosphorus and fluorine. The phosphorus element can play the role of gas-phase flame-retardant and condensed-phase flame-retardant, and promote the system to catalyze into charcoal; the introduction of fluorine element It can improve the thermal stability of the material; the two elements cooperate with each other, which can effectively improve the thermal stability and flame retardancy of the material.

2. The phosphorus- and fluorine-containing flame retardant in the present invention is a flame retardant with a polyphenyl ring structure. Compared with similar fatty phosphorus- and fluorine-containing flame retardants, it has better thermal stability, is not easy to decompose, and has a higher The high char formation rate further enhances the thermal stability and flame retardant performance of the system.

3. The phosphorous and fluorine flame retardant in the present invention contains DOPO at one end of the molecular structure, and DOPO has good solubility in the polymer matrix, which can improve the compatibility between the flame retardant and the polymer matrix, making the prepared High-quality flame-retardant electronic packaging materials can maintain good transparency and mechanical properties.

4. The low dielectric constant flame-retardant electronic packaging material of the present invention introduces fluorine element into the system. Fluorine is a special element, which has the characteristics of low polarizability, large molecular volume, and the binding energy of carbon-fluorine bond High, so fluorine can reduce the dielectric constant and dielectric loss of materials, expand and enhance the application and competitiveness of polymer materials in the field of electronic packaging.

Description of drawings

Fig. 1 is the infrared absorption spectrum of the low dielectric constant flame-retardant electronic packaging material prepared in Example 1 of the present invention.

Fig. 2 is the external view of pure epoxy resin (left) and the low dielectric constant flame-retardant electronic packaging material prepared in Example 1.

Fig. 3 is the carbon layer diagram of pure epoxy resin (left) and the low dielectric constant flame-retardant electronic packaging material prepared in Example 5 after the cone calorimeter test.

Detailed ways

The technical solutions of the present invention will be further illustrated and described below through specific embodiments in conjunction with the accompanying drawings.

Example 1

(1) Add 2g 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), 3.16g 3,5-bis(trifluoromethyl)benzyl to the reaction flask in turn Alcohol, 15mL of dichloromethane and 15mL of carbon tetrachloride, under stirring in an ice bath, slowly drop triethylamine into the reaction flask using a constant pressure dropping funnel, react at room temperature for 12 hours after the dropwise addition, and extract the obtained solution with water for 3 times , take the organic layer, dry it with anhydrous magnesium sulfate, filter it, remove the solvent by rotary evaporation of the filtrate, put the obtained white solid in a vacuum drying oven, and dry it at 60° C. for 24 hours to obtain the phosphorus-containing fluorine flame retardant.

(2) Weigh E51 bisphenol A type epoxy resin prepolymer and heat up to 90°C, add 1wt% phosphorus-containing fluorine flame retardant, stir until transparent, then add curing agent 4,4'-diaminodiphenyl in proportion Methane (DDM) was stirred until it was completely dissolved (the mass ratio of E51 bisphenol A type epoxy resin prepolymer to 4,4'-diaminodiphenylmethane was 8:2.02), then poured into an aluminum mold, and the temperature was raised Curing is carried out to obtain a low dielectric constant flame-retardant electronic packaging material; the temperature program is: 120° C. for 4 hours, 140° C. for 2 hours, and 180° C. for 2 hours.

Figure 2 is the appearance of pure epoxy (left) and the low dielectric constant flame-retardant electronic packaging material prepared in this example. It can be seen from the figure that the epoxy resin still maintains good transparency after adding the flame retardant.

Utilize oxygen index tester to measure the oxygen index value of this low dielectric constant flame retardant electronic packaging material 28.8% (pure epoxy is 26.0%), utilize LCR tester to measure this low dielectric constant flame retardant electronic packaging material in The dielectric constant at 200MHz is 6.3 (6.6 for pure epoxy), and the dielectric loss is 0.0275 (0.0295 for pure epoxy).

Example 2

(1) Add 3.36g 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), 3.16g 3,5-bis(trifluoromethyl) to the reaction flask in turn Benzyl alcohol, 15mL of dichloromethane and 15mL of carbon tetrachloride were stirred in an ice bath, and triethylamine was slowly dropped into the reaction flask using a constant pressure dropping funnel. Next, the organic layer was dried with anhydrous magnesium sulfate, filtered, the filtrate was rotary evaporated to remove the solvent, and the obtained white solid was placed in a vacuum drying oven and dried at 60° C. for 24 hours to obtain the phosphorus-containing fluorine flame retardant.

(2) Take the dried PC masterbatch, add 1wt% phosphorus-containing fluorine flame retardant, utilize a twin-screw extruder to mix and extrude, and then further pass through granulation and drying, and prepare the low-density compound with an injection molding machine Standard splines for dielectric constant flame retardant electronic packaging materials.

Utilize the oxygen index tester to record the oxygen index value of this standard sample bar to be 28.4% (25.0% for pure polycarbonate), utilize the LCR tester to record the dielectric constant of this standard sample bar at 200MHz to be 4.6 (pure polycarbonate Carbonate is 4.8), and the dielectric loss is 0.0154 (0.0189 for pure polycarbonate).

Example 3

(1) Add 2g 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), 3.16g 3,5-bis(trifluoromethyl)benzyl to the reaction flask in turn Alcohol, 15mL of dichloromethane and 15mL of carbon tetrachloride, under stirring in an ice bath, slowly drop triethylamine into the reaction flask using a constant pressure dropping funnel, react at room temperature for 18 hours after the dropwise addition, and extract the obtained solution with water for 3 times , take the organic layer, dry it with anhydrous magnesium sulfate, filter it, remove the solvent by rotary evaporation of the filtrate, put the obtained white solid in a vacuum drying oven, and dry it at 60° C. for 24 hours to obtain the phosphorus-containing fluorine flame retardant.

(2) Take the dried ABS masterbatch, add 1wt% phosphorus-containing fluorine flame retardant, utilize a twin-screw extruder to mix and extrude, and then further pass through granulation and drying, and prepare the low-density compound with an injection molding machine. Standard splines for dielectric constant flame retardant electronic packaging materials.

Utilize the oxygen index tester to measure the oxygen index value of this standard bar to be 21.5% (pure ABS is 18.0%), utilize the LCR tester to measure the dielectric constant of this standard bar at 200MHz 2.6 (pure ABS is 2.7) , The dielectric loss is 0.0115 (0.0121 for pure ABS).

Example 4

(1) Add 2g 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), 3.16g 3,5-bis(trifluoromethyl)benzyl to the reaction flask in turn Alcohol, 15mL of dichloromethane and 15mL of carbon tetrachloride, under stirring in an ice bath, slowly drop triethylamine into the reaction flask using a constant pressure dropping funnel, react at room temperature for 12 hours after the dropwise addition, and extract the obtained solution with water for 3 times , take the organic layer, dry it with anhydrous magnesium sulfate, filter it, remove the solvent by rotary evaporation of the filtrate, put the obtained white solid in a vacuum drying oven, and dry it at 60° C. for 24 hours to obtain the phosphorus-containing fluorine flame retardant.

(2) Weigh E51 bisphenol A type epoxy resin prepolymer and heat up to 90°C, add 5wt% phosphorus-containing fluorine flame retardant, stir until transparent, then add curing agent 4,4'-diaminodiphenyl in proportion Methane (DDM) was stirred until it was completely dissolved (the mass ratio of E51 bisphenol A type epoxy resin prepolymer to 4,4'-diaminodiphenylmethane was 8:2.02), then poured into an aluminum mold, and the temperature was raised Curing is carried out to obtain a low dielectric constant flame-retardant electronic packaging material; the temperature program is: 120° C. for 4 hours, 140° C. for 2 hours, and 180° C. for 2 hours.

Utilize the oxygen index tester to measure the oxygen index value of this low dielectric constant flame retardant electronic packaging material to be 35.1% (pure epoxy is 26.0%), utilize LCR tester to measure this low dielectric constant flame retardant electronic packaging material in The dielectric constant at 200MHz is 5.8 (6.6 for pure epoxy), and the dielectric loss is 0.0253 (0.0295 for pure epoxy).

Example 5

(1) Add 2g 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), 3.16g 3,5-bis(trifluoromethyl)benzyl to the reaction flask in turn Alcohol, 15mL of dichloromethane and 15mL of carbon tetrachloride, under stirring in an ice bath, slowly drop triethylamine into the reaction flask using a constant pressure dropping funnel, react at room temperature for 12 hours after the dropwise addition, and extract the obtained solution with water for 3 times , take the organic layer, dry it with anhydrous magnesium sulfate, filter it, remove the solvent by rotary evaporation of the filtrate, put the obtained white solid in a vacuum drying oven, and dry it at 60° C. for 24 hours to obtain the phosphorus-containing fluorine flame retardant.

(2) Weigh E51 bisphenol A type epoxy resin prepolymer and heat up to 90°C, add 10wt% phosphorus-containing fluorine flame retardant, stir until transparent, then add curing agent 4,4'-diaminodiphenyl in proportion Methane (DDM) was stirred until it was completely dissolved (the mass ratio of E51 bisphenol A type epoxy resin prepolymer to 4,4'-diaminodiphenylmethane was 8:2.02), then poured into an aluminum mold, and the temperature was raised Curing is carried out to obtain a low dielectric constant flame-retardant electronic packaging material; the temperature program is: 120° C. for 4 hours, 140° C. for 2 hours, and 180° C. for 2 hours.

Utilize the oxygen index tester to measure the oxygen index value of this low dielectric constant flame retardant electronic packaging material to be 35.1% (pure epoxy is 37.0%), utilize LCR tester to measure this low dielectric constant flame retardant electronic packaging material in The dielectric constant at 200MHz is 5.6 (6.6 for pure epoxy), and the dielectric loss is 0.0245 (0.0295 for pure epoxy).

Fig. 3 is pure epoxy (left) and the low dielectric constant flame-retardant electronic packaging material (right) that this embodiment makes after the carbon layer exterior view of cone calorimeter test, can see this embodiment from the figure The carbon layer of the low dielectric constant flame-retardant electronic packaging material prepared in the example has obvious expansion after burning. This is because the design of the polyphenyl ring structure in the phosphorus-containing fluorine flame retardant makes the material form a dense At the same time, the gas phase flame retardancy and condensed phase flame retardancy of the phosphorus and fluorine flame retardants together form an intumescent carbon layer.

Example 6

(1) Add 2g 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), 3.16g 3,5-bis(trifluoromethyl)benzyl to the reaction flask in turn Alcohol, 15mL toluene and 15mL trichloromethane were stirred in an ice bath, and triethylamine was slowly dropped into the reaction flask using a constant pressure dropping funnel. The layer was dried with anhydrous magnesium sulfate, filtered, the filtrate was rotary evaporated to remove the solvent, and the obtained white solid was placed in a vacuum drying oven and dried at 60° C. for 24 hours to obtain the phosphorus-fluorine flame retardant.

(2) Weigh E51 bisphenol A type epoxy resin prepolymer and heat up to 90°C, add 1wt% phosphorus-containing fluorine flame retardant, stir until transparent, then add curing agent 4,4'-diaminodiphenyl in proportion Methane (DDM) was stirred until it was completely dissolved (the mass ratio of E51 bisphenol A type epoxy resin prepolymer to 4,4'-diaminodiphenylmethane was 8:2.02), then poured into an aluminum mold, and the temperature was raised Curing is carried out to obtain a low dielectric constant flame-retardant electronic packaging material; the temperature program is: 120° C. for 4 hours, 140° C. for 2 hours, and 180° C. for 2 hours.

Utilize oxygen index tester to measure the oxygen index value of this low dielectric constant flame retardant electronic packaging material 28.8% (pure epoxy is 26.0%), utilize LCR tester to measure this low dielectric constant flame retardant electronic packaging material in The dielectric constant at 200MHz is 6.3 (6.6 for pure epoxy), and the dielectric loss is 0.0275 (0.0295 for pure epoxy).

The above is only a preferred embodiment of the present invention, so the scope of the present invention cannot be limited accordingly, that is, equivalent changes and modifications made according to the patent scope of the present invention and the content of the specification should still be covered by the present invention In the range.

Claims (10)

1. A low dielectric constant flame-retardant electronic packaging material, characterized in that: it comprises 50-99wt% polymer matrix and 1-50wt% phosphorus-containing fluorine flame retardant, wherein the polymer matrix comprises epoxy resin, Polycarbonate and acrylonitrile-butadiene-styrene terpolymer, the structural formula of phosphorus-containing fluorine flame retardant is 2. A low-dielectric constant flame-retardant electronic packaging material as claimed in claim 1, characterized in that: the synthesis route of the phosphorus- and fluorine-containing flame retardant is as follows: 3. A low dielectric constant flame-retardant electronic packaging material as claimed in claim 2, wherein the preparation method of the phosphorus-fluorine flame retardant comprises the following steps: (1) Add 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), 3,5-bis(trifluoromethyl)benzyl alcohol, and The first solvent and the second solvent, under stirring in an ice bath, slowly drop triethylamine into the above reaction vessel using a constant pressure dropping funnel, and react at room temperature for 5-24 hours after the drop addition; the above first solvent is tetrahydrofuran, dichloro Methane or toluene, the above-mentioned second solvent is carbon tetrachloride or chloroform, and the first solvent and the second solvent are different from each other; (2) Extract the material obtained in step (1) with water, take the organic layer and dry it with anhydrous magnesium sulfate and filter to obtain the filtrate; (3) The above-mentioned filtrate is subjected to rotary evaporation to remove the first solvent and the second solvent, and the obtained white solid is fully vacuum-dried to obtain the phosphorus-containing fluorine flame retardant. 4. A low dielectric constant flame retardant electronic packaging material as claimed in claim 3, characterized in that: the first solvent is 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10 The molar ratio of -oxide, 3,5-bis(trifluoromethyl)benzyl alcohol and triethylamine is 1:0.1-10:0.1-10. 5. A low dielectric constant flame-retardant electronic packaging material as claimed in claim 3, characterized in that: said 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, The mass ratio of the first solvent to the second solvent is 1:1-200:1-200. 6. A method for preparing a low-dielectric constant flame-retardant electronic packaging material according to any one of claims 1 to 5, characterized in that: the polymer matrix is epoxy resin, specifically comprising: weighing 50 -99wt% of epoxy resin prepolymer, 1-50wt% of the phosphorus-containing fluorine flame retardant and 5-15wt% of 4,4'-diaminodiphenylmethane (DDM); the epoxy resin prepolymer After the body is heated to 60-140°C, add phosphorus-containing fluorine flame retardant, stir until transparent, then add 4,4'-diaminodiphenylmethane and stir until completely dissolved, then pour it into the mold, and heat it up to cure, that is, The low dielectric constant flame-retardant electronic packaging material; wherein, the above-mentioned temperature program is: 115-125°C curing for 3-5 hours, 135-145°C curing for 1-3 hours, and 170-185°C curing for 1-3 hours. 7. The preparation method according to claim 6, characterized in that: the epoxy resin prepolymer is E51 bisphenol A type epoxy resin. 8. The preparation method according to claim 6 or 7, characterized in that: the mass ratio of the epoxy resin prepolymer to 4,4'-diaminodiphenylmethane is 8: 2.02. 9. The preparation method according to claim 6 or 7, characterized in that: the programmed temperature is: 120°C for 4 hours, 140°C for 2 hours, and 180°C for 2 hours. 10. A method for preparing a low-dielectric constant flame-retardant electronic packaging material according to any one of claims 1 to 5, wherein the polymer matrix is polycarbonate or acrylonitrile-butadiene- The styrene terpolymer specifically includes: adding a phosphorus-fluorine flame retardant to the masterbatch of the polymer matrix after drying, mixing and extruding with a twin-screw extruder, and further granulating and drying After that, the low dielectric constant flame-retardant electronic packaging material is obtained.