CN104892904A - Interlayer insulation material for multilayer printed circuit board and preparation process thereof - Google Patents

Abstract

The invention discloses an interlayer insulation material for a multilayer printed circuit board and a preparation process thereof; methoxy diphenyl ether as a raw material undergoes a reaction with acetyl aniline to obtain an amine terminated diphenyl ether oligomer containing a reactive end group, the amine terminated diphenyl ether oligomer is copolymerized with epoxy resin, no small molecule is released during copolymerization, and a curing material maintains advantages of polydiphenyl oxide resin; a thermal decomposition temperature of the copolymer reaches 365.25 DEG C, the temperature index is 187.14 DEG C, and the copolymer can be used as a high-temperature-resistant insulation material for being applied in the fields of motor and electric appliances.

Description

The interlayer dielectic of multilayer printed circuit board and manufacture craft thereof

Technical field

The invention belongs to printed wiring material field, be specifically related to interlayer dielectic and the manufacture craft thereof of multilayer printed circuit board.

Background technology

The title of circuit card has: wiring board, pcb board, aluminium base, high frequency plate, thick copper coin, impedance plate, PCB, ultra-thin wiring board, ultrathin circuit board, printing (copper lithographic technique) circuit card etc.Circuit card makes circuit miniaturization, visualize, for permanent circuit batch production and optimize electrical appliance layout and play an important role.

The words that wiring board divides by the number of plies are divided into single sided board, dual platen, and the classification that multilayer circuit board three is large.

First be single sided board, on the most basic PCB, part concentrates on wherein one side, and wire then concentrates on another side.Because wire only appears at wherein one side, so just claim this PCB to be called one-sided circuit board.Single sided board makes simply usually, and cost is low, but shortcoming cannot be applied on too complicated product.

Dual platen is the extension of single sided board, when individual layer wiring can not meet the needs of electronic product, will use dual platen.Two-sided have cover copper and have cabling, and can by via hole come conducting two-layer between circuit, the network made it required for being formed connects.

Multi-ply wood refers to that the conductive pattern layer with more than three layers forms with lamination of being separated by with insulating material therebetween, and the printed board that interconnects on request of conductive pattern therebetween.Multilayer circuit board is the product of electronic information technology to high-speed, multi-functional, Large Copacity, small volume, slimming, lightweight future development.The words that wiring board divides by characteristic are divided into soft board (FPC), hardboard (PCB), Rigid Flex (FPCB).

The sheet material of wiring board is divided into several:

FR-1: flame-proof cover copper foil ratio phenolic paper laminate.

FR-4:1) flame-proof cover copper foil epoxy E glass fabric laminates and bonding sheet material thereof.2) flame-proof cover copper foil modification or modified epoxy E glass fabric laminates and bonding sheet material thereof.3) flame-proof cover copper foil epoxy/PPO glass cloth laminated board and bonding sheet material thereof.4) flame-proof cover copper foil modification or modified epoxy glass cloth laminated board and bonding sheet material thereof.5) flame-proof cover copper foil epoxy E glass cloth laminated board (for catalytic addition method).

Also there is the insulating material adopting polydiphenyl ether as circuit card present stage, the thermosetting resin that polydiphenyl ether is is main chain with phenylene and oxygen-ether linkage, have high temperature resistant, corrosion-resistant, radiation resistance and excellent electrical insulation properties, be widely used in manufacturing and strengthened sheet material, tubing, use sub-electric insulation without matrix materials such as latitude bands, the aspects such as mechanical engineering material, Britain, the U.S., Japan etc. develops industrial application product in succession: resin raw material wide material sources, low price, but release small-molecule substance when solidifying, be difficult to obtain closely knit gapless cured article, because which limit its use.

Summary of the invention

Object of the present invention is just interlayer dielectic and the manufacture craft thereof of the multilayer printed circuit board provided to solve the problem.

The present invention is achieved through the following technical solutions above-mentioned purpose:

The interlayer dielectic of multilayer printed circuit board, comprises second phthalein aniline, methoxyl group diphenyl ether and E-51 epoxy resin, and the proportion of second phthalein aniline, methoxyl group diphenyl ether and E-51 epoxy resin is 3:3:4.

The manufacture craft of the interlayer dielectic of multilayer printed circuit board, comprises the following steps,

A, carry out the synthesis of aminodiphenylether resin: the small molecules first diphenyl ether of technical grade decompression removing contained in it;

Then be that the diphenyl ether of 1:1-1:2 and second phthalein aniline and the two total mass 2%-6% join in the reactor with agitator, nitrogen conduit and condenser by mol ratio;

After being warming up to the whole melt into homogeneous phase of mixture, constant temperature 125 DEG C, reacts to non-volatile thing is released;

The small molecules contained in decompression removing resin, obtains thick reddish-brown liquid Acetanilide diphenyl ether;

In aniline acetate diphenyl ether, add the HC1/ ethanolic soln that concentration is 8%-12%, the consumption of HC1/ ethanolic soln is 3-5 times of second phthalein Amineterminated diphenyl ethers resin quality;

Heat up and stir, after resin dissolves completely, back hydrolysis 4-6 hour;

Be neutralized to PH7-7.5 with saturated K0H/ ethanolic soln, underpressure distillation goes out ethanol, and product distilled water wash removes inorganics;

Through 85-90 DEG C of vacuum-drying, aminodiphenylether resin can be obtained;

B, by system aminodiphenylether resin mix according to mass ratio 1:1 with epoxy resin E-51, after heating and melting becomes homogeneous phase, pour into and scribble in the aluminium box of silicone grease.

In step B, heating and melting comprises and at 100 DEG C, to heat at 1 hour, 130 DEG C at heating 1 hour, 160 DEG C at heating 1 hour, 190 DEG C at heating 1 hour and 220 DEG C heating successively 2 hours.

In steps A, system aminodiphenylether resin need take the aminodiphenylether resin of about 0.2g with analytical balance, in the mixing solutions of molten sub-25ml Glacial acetic acid and 1,3-dioxane (1:1.3V/V);

The glacial acetic acid solution 2-3 instilling 1% Viola crystallina drips as indicating liquid;

Then be titrated to till solution becomes bright green by purple with perchloric acid-acetic acid solution that Potassium Hydrogen Phthalate is calibrated;

Standard as do not reached needs to repeat steps A.

Beneficial effect is: the present invention with methoxyl group phenyl ether for raw material, the obtained Amineterminated diphenyl ethers oligopolymer containing active end group is reacted with Acetanilide, and by it and epoxy resin copolymerization, release without small molecules during copolymerization, cured article maintains the advantage of polydiphenyl ether resin, the heat decomposition temperature of multipolymer reaches 365.25 DEG C, and humidity index is 187.14 DEG C, can be used as high-temperature insulation material and is applied to electrical equipment and electrical field.

Accompanying drawing explanation

Fig. 1 is aminodiphenylether resin and epoxy resin E-51 solidification process infrared spectrum in the present invention;

Fig. 2 is aminodiphenylether resin and epoxy resin E-51 cured resin TGA graphic representation in the present invention.

Embodiment

Below in conjunction with accompanying drawing, the invention will be further described:

The interlayer dielectic of multilayer printed circuit board, comprises second phthalein aniline, methoxyl group diphenyl ether and E-51 epoxy resin, and the proportion of second phthalein aniline, methoxyl group diphenyl ether and E-51 epoxy resin is 3:3:4.

The manufacture craft of the interlayer dielectic of multilayer printed circuit board, comprises the following steps,

B, carry out the synthesis of aminodiphenylether resin: the small molecules first diphenyl ether of technical grade decompression removing contained in it;

Then be that the diphenyl ether of 1:1-1:2 and second phthalein aniline and the two total mass 2%-6% join in the reactor with agitator, nitrogen conduit and condenser by mol ratio;

After being warming up to the whole melt into homogeneous phase of mixture, constant temperature 125 DEG C, reacts to non-volatile thing is released;

The small molecules contained in decompression removing resin, obtains thick reddish-brown liquid Acetanilide diphenyl ether;

In aniline acetate diphenyl ether, add the HC1/ ethanolic soln that concentration is 8%-12%, the consumption of HC1/ ethanolic soln is 3-5 times of second phthalein Amineterminated diphenyl ethers resin quality;

Heat up and stir, after resin dissolves completely, back hydrolysis 4-6 hour;

Be neutralized to PH7-7.5 with saturated K0H/ ethanolic soln, underpressure distillation goes out ethanol, and product distilled water wash removes inorganics;

Through 85-90 DEG C of vacuum-drying, aminodiphenylether resin can be obtained;

B, by system aminodiphenylether resin mix according to mass ratio 1:1 with epoxy resin E-51, after heating and melting becomes homogeneous phase, pour into and scribble in the aluminium box of silicone grease.

In step B, heating and melting comprises and at 100 DEG C, to heat at 1 hour, 130 DEG C at heating 1 hour, 160 DEG C at heating 1 hour, 190 DEG C at heating 1 hour and 220 DEG C heating successively 2 hours.

In steps A, system aminodiphenylether resin need take the aminodiphenylether resin of about 0.2g with analytical balance, in the mixing solutions of molten sub-25ml Glacial acetic acid and 1,3-dioxane (1:1.3V/V);

The glacial acetic acid solution 2-3 instilling 1% Viola crystallina drips as indicating liquid;

Then be titrated to till solution becomes bright green by purple with perchloric acid-acetic acid solution that Potassium Hydrogen Phthalate is calibrated;

Standard as do not reached needs to repeat steps A.

IR analyzes: the 983G type Bo Liye infrared spectrometer adopting Perkin-Elmer company.

TGA analyzes: the TGA7 type thermal weight loss rate analyser adopting Perkin-Elmer company, heat-up rate is 5 DEG C/min.

Below one or more embodiments of the present invention:

Measure in aminodiphenylether resin by method of the present invention, mole number amino in 100g aminodiphenylether resin is 0.3118.

Pouring in the process be cured in the aluminium box scribbling silicone grease; Adopt stair-stepping heating mode to be cured, the sample got respectively under differing temps carries out TR analysis, as shown in Figure 1 for the absorption peak of epoxy group(ing), weaken, after system solidifies 2 hours under the temperature condition of 220 DEG C along with the carrying out of reaction basic disappearance, illustrates that reaction completes substantially. for the absorption peak of secondary amide, along with the rising of temperature of reaction, the first grow of absorption peak after die down, grow is the result by a large amount of secondary amine and epoxy reaction, and to weaken be because of the result with epoxy reaction of secondary amide at relatively high temperatures.

3300-3500 be primary amine absorption peak before place's solidification, because epoxy addition in solidification process reacts generation great amount of hydroxy group, the absorption peak at this place is broadened grow.The analytical results of comprehensive infrared spectra, the solidification of aminodiphenylether resin and epoxy resin E-51 is the mainly reaction carried out of secondary amine and epoxy group(ing) at relatively high temperatures.

Aminodiphenylether resin is the oligopolymer with heat resistant structure, and when its fish epoxy resin copolymerization time, rate of weight loss analyser carries out TGA analysis to cured product, and Fig. 2 is TGA Qu County, the performance decomposition temperature of product and humidity index calculated by following formula respectively:

=(10C-3B)/7

=（ +B）/2X

In formula: temperature (435.71 DEG C) corresponding when B is weightless 50%; The temperature (386.39 DEG C) that C is corresponding when being weightless 15%; X is functional coefficient, X=2.14.Calculating the apparent decomposition temperature of this cured article according to the data of TGA is like this 365.25 DEG C, and humidity index is 187.14 DEG C, illustrates that the resistance toheat of this cured resin is very good.

More than show and describe ultimate principle of the present invention, principal character and advantage.The technician of the industry should understand; the present invention is not restricted to the described embodiments; what describe in above-described embodiment and specification sheets just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.Application claims protection domain is defined by appending claims and effect thing thereof.

Claims (4)

1. the interlayer dielectic of multilayer printed circuit board, is characterized in that: comprise second phthalein aniline, methoxyl group diphenyl ether and E-51 epoxy resin, and the proportion of second phthalein aniline, methoxyl group diphenyl ether and E-51 epoxy resin is 3:3:4.

2. a manufacture craft for the interlayer dielectic of multilayer printed circuit board as claimed in claim 1, is characterized in that: comprise the following steps,

Carry out the synthesis of aminodiphenylether resin: first the decompression of the diphenyl ether of technical grade is removed the small molecules contained in it;

Then be that the diphenyl ether of 1:1-1:2 and second phthalein aniline and the two total mass 2%-6% join in the reactor with agitator, nitrogen conduit and condenser by mol ratio;

After being warming up to the whole melt into homogeneous phase of mixture, constant temperature 125 DEG C, reacts to non-volatile thing is released;

The small molecules contained in decompression removing resin, obtains thick reddish-brown liquid Acetanilide diphenyl ether;

In aniline acetate diphenyl ether, add the HC1/ ethanolic soln that concentration is 8%-12%, the consumption of HC1/ ethanolic soln is 3-5 times of second phthalein Amineterminated diphenyl ethers resin quality;

Heat up and stir, after resin dissolves completely, back hydrolysis 4-6 hour;

Be neutralized to PH7-7.5 with saturated K0H/ ethanolic soln, underpressure distillation goes out ethanol, and product distilled water wash removes inorganics;

Through 85-90 DEG C of vacuum-drying, aminodiphenylether resin can be obtained;

B, by system aminodiphenylether resin mix according to mass ratio 1:1 with epoxy resin E-51, after heating and melting becomes homogeneous phase, pour into and scribble in the aluminium box of silicone grease.

3. the manufacture craft of the interlayer dielectic of multilayer printed circuit board according to claim 2, it is characterized in that: in step B, heating and melting comprises and at 100 DEG C, to heat at 1 hour, 130 DEG C at heating 1 hour, 160 DEG C at heating 1 hour, 190 DEG C at heating 1 hour and 220 DEG C heating successively 2 hours.

4. the manufacture craft of the interlayer dielectic of multilayer printed circuit board according to claim 2; it is characterized in that: in steps A; system aminodiphenylether resin need take the aminodiphenylether resin of about 0.2g with analytical balance; in the mixing solutions of molten sub-25ml Glacial acetic acid and 1,3-dioxane (1:1.3V/V);

The glacial acetic acid solution 2-3 instilling 1% Viola crystallina drips as indicating liquid;

Then be titrated to till solution becomes bright green by purple with perchloric acid-acetic acid solution that Potassium Hydrogen Phthalate is calibrated;

Standard as do not reached needs to repeat steps A.