TWI503351B - Ad type polyimide resin and method - Google Patents

Description

AD type polyimine resin and method

The present invention relates to an AR type polyimine resin and a method, and more particularly to a copolymer of a polyamidoximine resin.

In recent years, the industry has created a lot of consumer electronic products, computers, communications, industrial control panels and medical equipment and equipment based on the need for laminated composite materials, the former used polyether imide film but not high temperature heat, so The film obtained by the polyimine resin has improved heat resistance, and many of the modified polytree imine resin film and copper foil are processed and combined with each other, so heat resistance, mechanical properties and electrical properties are required. Very high, the use of composite materials to increase the adhesion between the copper foil, but often causes the processing load and cost increase, therefore, often in order to improve the above-mentioned lack of seeking a replacement base as an improvement is currently very difficult work.

The main object of the present invention is to provide a patent application for an AD type polyimine resin and a method thereof, since the product of the present invention is an adhesive having high heat resistance, excellent physical properties, and workability, mainly utilizing (TPA, IPA). , OBBA, BTDA, MDI and other monomers are polymerized into AD type polyimine resin (modified polyimine resin) in an appropriate ratio, and the indoleamine (-CONH-) group is implanted in the molecular structure chain, mainly Can be divided into: 1. MDI + BTDA + TPA → PAI-1. 2. MDI + BTDA + IPA → PAI-2. 3. MDI + BTDA + OBBA → PAI-3. The above three types of resins can improve the melt flowability, heat resistance, adhesion and flexibility of the polymer, and the heat resistance is also higher than that of the epoxy resin. When the AD type polyimide film is prepared, it is bonded by thermocompression bonding. A copper foil laminated circuit board having a two-layer structure is formed, so that the product to which the present invention is applied has a simple process (primary coating process), excellent physical properties, and stable quality.

The invention relates to an AD type polyimine resin and a method thereof. Please refer to FIG. 1 as an AD type polyimine resin with the following chemical structural formula as a repeating unit: Where n: a positive integer

R:

R':

R":

The preparation method of the invention for manufacturing AD type polyimine resin:

(1). The present invention utilizes a dianhydride and a diisocyanate to form a polyamidimide prepolymer such as the chemical structural formula - (I) as shown in Figure 2: Where X: a positive integer

R:

R':

(2) In the present invention, the formula (I) is further copolymerized with a diacid monomer to obtain a (Π) formula, that is, a brown transparent AD type polyimine resin having a high viscosity value (polyamidiamine copolymerization) Fitted as shown in Figure 3: Where R:

R':

R":

Example:

(1). Synthesis of polyimine prepolymer: 1 to 5 molar dianhydride (3.3', 4.4'-benzophenone tetracarboxylic dianhydride, BTDA) was placed in a four-neck reaction flask, and N-methyl- The 2-pyrrolidine (NMP) solvent was stirred at 50 ° C for 30 minutes, and the flask was kept under vacuum, and then 2 to 6 moles of diisocyanate (4.4'-diphenylmethane diisocyanate, MDI) was added. ), and maintain the solid content of 15%, after reacting at 50 ° C for 4 hours, the end group NCO content is determined by reverse titration in the synthesis process to obtain -NCO-terminated prepolymerized imine prepolymer.... ....(I'), the reaction formula is as follows: Where R':

(2). AD type polyimine resin: continue to polyimine imide prepolymer ... (I) down to room temperature, add 1 mole of diacid monomer, while adding dibutyl tin dilaurate ( a few drops of dibutyltin dilaurate (DBTDL), after 0.5 hours of reaction, gradually increase the temperature to 80 ° C for 1 hr, and then raise the temperature to 120 ° C for 2 hours. At this time, a brown solution of AD type polyimine resin with a relatively high viscosity can be obtained. ... (Π'). Among them, the reaction formula of the (Π') type AD type polyimine resin:

R:

R':

R":

The present invention is an AD type polyimine resin which can be classified into the following resin types:

1. PAI-1: MDI+BTDA+TPA

2. PAI-2: MDI+BTDA+IPA

3. PAI-3: MDI+BTDA+OBBA

Among them, the above three types of resins are used to prepare a film by dissolving the solid polyamidoximine using NMP, the solid content is maintained at 15%, and then the dissolved resin is poured onto a glass plate, and the resin is poured with a glass rod. Evenly coated on a glass plate and controlled to a thickness of about 25 μm, and then placed in a 50 ° C oven for vacuum drying for 12 hours, and then heated in multiple stages to completely remove the solvent.

The film (PAI-1, PAI-2, PAI-3) prepared by the above three AD type polyimine resins is listed as a ratio The test results of the more heat resistant properties are as follows:

(1). TGA analysis: When comparing the TGA patterns of the above three AD type polyimine films (PAI-1, PAI-2, PAI-3), the heat resistance of the present invention is known: From the above, it was found that the film synthesized by the AD type polyimine resin of the present invention has good heat resistance, and the heat resistance loss range is known from the above-mentioned thermogravimetric loss temperature range: PAI-3>PAI-1>PAI-2.

(2). DMA analysis: The material is deformed by sinusoidal or other periodic stress, and the glass transition point (Tg) of the material to be tested is sought. When analyzing three AD type polyimine films (PAI-1, PAI) of the present invention. The glass temperature transition point (Tg) shown by -2, PAI-3) is as follows: From the above TGA analysis and DMA analysis, the film prepared by the AD type polyimine resin of the present invention has a thickness of 25.4 μm, and it has been found through tests that the heat resistance is excellent, the tensile strength is 70 to 85 MPa, and the dielectric constant is 2.7. Between ~2.9, the water absorption rate is between 1.4 and 3.0, and the viscosity of the AD type polyimine resin ranges from 0.8 to 1 dl/g.

The invention relates to an AD type polyimine resin and a method thereof, which have met the patent requirements, and the patent application is filed according to law.

Fig. 1 is a chemical structural formula of the AD type polyimine resin of the present invention.

Fig. 2 is a chemical structural formula of the method (I) of the method for producing an AD type polyimine resin of the present invention.

Fig. 3 is a chemical structural formula of the method for producing an AD type polyimine resin of the present invention.

Figure 4 is a TGA diagram of the AD type polyimine film - PAI-1 of the present invention.

Figure 5 is a TGA diagram of the AD type polyimine film - PAI-2 of the present invention.

Fig. 6 is a TGA diagram of the AD type polyimine film-PAI-3 of the present invention.

Figure 7 is a DMA diagram of the AD type polyimine film - PAI-1 of the present invention.

Figure 8 is a DMA diagram of the AD type polyimine film - PAI-2 of the present invention.

Figure 9 is a DMA diagram of the AD type polyimine film - PAI-3 of the present invention.

Claims (10)

An AD type polyimine resin, which is a polyamidoximine copolymer having the following formula (重) as a repeating unit: n: positive integer R: or R': or R": or, or The glass transition temperature of the film (25.4 μm) was 230-300 ° C, and the thermal cracking temperature of the film (25.4 μm) was above 500 ° C. The AD type polyimine resin according to claim 1, wherein the heat resistant temperature is 300 ° C or higher. The AD type polyimine resin described in claim 1 has a viscosity in the range of 0.8 to 1 dl/g. The AD type polyimine resin described in claim 1 is prepared from an AD type polyimine resin. A film shape. The AD type polyimine resin as described in claim 1 is characterized in that it is prepared into a film (25.4 μm) having a thermal cracking temperature of 500 ° C or higher. The AD type polyimine resin as described in claim 1 is characterized in that the glass transition temperature of the film (25.4 μm) is 230 to 300 ° C. The AD type polyimine resin described in claim 1 is characterized in that it has a tensile strength of 70 to 85 MPa prepared as a film (25.4 μm). The AD type polyimine resin described in claim 1 is characterized in that it is prepared into a film (25.4 μm) having a dielectric constant of between 2.7 and 2.9. The AD type polyimine resin as described in claim 1 is characterized in that the water absorption rate of the film (25.4 μm) is between 1.4 and 3.0. The AD type polyimine resin according to claim 1, wherein the resin is applied to a flexible circuit board, and is also used for a high temperature resistant adhesive.