CN101121819A - Modified maleimide-terminated polyimide resin composition and its application - Google Patents

Abstract

The invention relates to a modified maleimide-terminated polyimide resin composition and its application. The composition is mainly composed of maleimide-terminated polyimide resin, allyl compound and inorganic filling material. The maleimide-terminated polyimide resin used is synthesized by using N-methyl-2-pyrrolidone as a solvent and adopting a variable temperature solution imidization method. The appropriate amount of inorganic filler added to the modified resin composition obviously improves the allowable range of the difference in coefficient of thermal expansion between the polyimide film layer and the copper foil. The adhesive-free two-layer flexible copper-clad laminate prepared with the modified end-capped polyimide resin composition has excellent heat resistance, is suitable for lead-free soldering, has small curling, no pores on the surface, and has good Excellent dimensional stability, good mechanical strength, high peel strength and folding resistance, as well as low thermal expansion coefficient, dielectric constant and water absorption.

Description

Modified maleimide-terminated polyimide resin composition and its application

Technical field:

The invention relates to the field of flexible copper-clad laminate substrates for flexible printed circuits and their composite materials, and relates to the synthesis method of maleimide-terminated polyimide resin and the preparation of its modified resin composition and its application in the field. The application of an adhesive-free two-layer flexible copper clad laminate.

technical background:

As stated in the description of the Chinese invention patent application number 200710053151.3 submitted by the inventor, at present, with the rapid development of the electronics industry, the appearance and performance requirements of electronic products are getting higher and higher, short, small, light, thin, beautiful Electronic products with excellent comprehensive performance have become the first choice of manufacturers and consumers, so the base material of flexible printed circuit boards inevitably changes from the adhesive-type three-layer method to the lighter and thinner adhesive-free two-layer method product development.

Adhesive-free two-layer flexible copper-clad laminate is to directly bond the matrix resin to the surface of the copper foil to form a matrix resin layer that is tightly bonded to the copper foil, because there is no traditional epoxy or acrylic resin as the adhesive layer , compared with the traditional glue-type three-layer method products, its comprehensive performance is more excellent. According to bibliographical reports, this type of non-adhesive type two-layer method product mainly obtains by three kinds of methods: one as reported in CN1114821, forms copper conductive layer by the method for chemical deposition and electroplating on polyimide film surface; As reported by CN13273617, copper is deposited on the insulating film by vacuum sputtering technology or evaporation deposition technology, thereby forming a flexible copper clad laminate; the third is to directly coat the matrix resin or its precursor solution on the surface of the copper foil, and then At a certain temperature, after a certain process, a polyimide film layer bonded to the surface of the copper foil is formed. In the third method mentioned above, the most reported one is to directly coat the polyamic acid solution as the precursor of polyimide on the surface of copper foil, and then carry out gradient temperature rise, and finally make it complete imide at a high temperature above 350°C. Amination to form polyimide coated on copper foil, thereby obtaining a flexible two-layer copper clad laminate without glue (as reported in CN1575092A and CN1410471A). The biggest advantage of this method is that the production cost is low and the process is relatively simple . However, because the polyimide precursor solution used - polyamic acid is easily degraded and the storage period is too short, it cannot well meet the needs of large-scale industrial production, and the condition control in the thermal imidization process is extremely harsh. The requirements for equipment and environmental conditions are too high. In response to this problem, the present inventor synthesized a fully imidized maleic acid soluble in polar solvents (such as N-methyl-2-pyrrolidone) in the description of Chinese patent application number 200710053151.3. Imine-terminated polyimide resin, mix it with allyl compound, make a matrix resin homogeneous solution, apply it directly on the surface of copper foil, remove the solvent, at a relatively low temperature (within 260°C) cross-linking and curing to form a polyimide film layer covered with copper foil. The main advantages of this method are: the matrix resin used is easy to store, easy to process, and can be taken at any time. The curing temperature is much lower than the commonly used precursor solution of polyimide - polyamic acid. Therefore, in the production process The requirements for equipment and environmental conditions are greatly reduced; when the resin is cross-linked and cured, no small molecule volatiles are emitted, so an adhesive-free two-layer flexible copper clad laminate substrate with almost no pores and excellent comprehensive performance can be obtained.

For the increasingly miniaturized printed circuits, the dimensional stability of flexible copper clad laminates is an extremely important parameter. Flexible copper clad laminates with good dimensional stability will not curl significantly during processing. In addition to the adhesiveness, high temperature resistance and mechanical properties of the matrix resin of the glue-type two-layer flexible copper-clad laminate must meet the requirements, the difference in thermal expansion coefficient between it and the copper foil must also be controlled within a certain range, so that The prepared flexible copper clad laminate has better dimensional stability. There are two ways to solve the problem of dimensional stability of adhesive-free two-layer flexible copper-clad laminates: first, by optimizing the formula, a material with a thermal expansion coefficient close to that of copper foil can be selected as the matrix resin; second, by An appropriate amount of inorganic filler is added to increase the allowable range of the thermal expansion coefficient difference between the matrix resin and the copper foil, so as to achieve the purpose of improving the dimensional stability of the flexible copper clad laminate.

Regarding the problems referred to above, on the basis of the Chinese invention patent application number of 200710053151.3, the present invention adds mica, talcum powder, barium sulfate, calcium hydrogen phosphate, Different inorganic filler materials such as silicon dioxide or its mixture, after testing the dimensional stability parameters of each copper clad laminate, it is found that adding a certain amount of inorganic filler materials can significantly improve the thermal expansion coefficient between the polyimide film layer and the copper foil The tolerance range for the difference value. As shown in Examples 2 and 3 in Table 1 of this manual, their thermal expansion coefficients reach 27ppm/°C and 30ppm/°C respectively, which are much higher than the 17ppm/°C of copper foil, but their dimensional stability is still good (use IPC-TM-650, NO.2.2.4 standard detection, MD, TD values are less than 0.05%).

Invention content:

The object of the present invention is to provide a modified maleimide-terminated polyimide resin composition and a preparation method for the production of adhesive-free two-layer flexible copper-clad laminates. The resin composition has excellent heat resistance, dimensional stability, bending resistance, processability, low dielectric constant, and low dielectric loss factor.

Another object of the invention is to provide a new method for synthesizing the maleimide-terminated polyimide resin as one of the components of the composition.

Another object of the present invention is to provide an application method of a modified maleimide-terminated polyimide resin composition on an adhesive-free two-layer flexible copper clad laminate.

The technical scheme that reaches the above-mentioned purpose of the present invention is:

The composition and the weight proportion of a kind of modified maleimide capped polyimide resin composition are:

Maleimide-terminated polyimide resin 100 parts

Allyl compound 4-50 parts

Inorganic filler material 10-35 parts

Wherein, the allyl compound is one or a blend of diallyl bisphenol A and diallyl bisphenol S;

The inorganic filler is one or more blends of mica, talcum powder, barium sulfate, calcium hydrogen phosphate, and silicon dioxide, and the particle size is less than 1 micron. It must be added in a certain amount enough to have an effect. Taking mica and talcum powder as an example, the added amount reaches more than 10% of the amount of maleimide-terminated polyimide resin to have a better effect.

In the formulation of the modified resin system, the amount of allyl compound is selected as 4% to 50% of the amount of maleimide-terminated polyimide resin. If the amount of allyl compound is less than 4%, The toughness of the system is poor, and if the amount is greater than 50%, the heat resistance and dielectric properties of the system will be greatly reduced.

The preparation method of the above-mentioned maleimide-terminated polyimide resin is characterized in that, taking aromatic tetraacid dianhydride, diamine and maleic anhydride as raw materials, aromatic tetraacid dianhydride, diamine and maleic anhydride The ratio of the amount of substance of butenedioic anhydride is n: (n+1): 2, and the synthesis process is:

a) Aromatic tetra-acid dianhydride is made into a reaction solution with a low-boiling-point alcohol solvent, and 1 g of aromatic tetra-acid dianhydride is mixed with 7 to 10 ml of solvent, under the protection of nitrogen, and refluxed for 1 to 5 hours to obtain the corresponding diacid dianhydride Ester, the alcoholic solvent is distilled off, and the remaining alcoholic solvent is removed under reduced pressure;

b) Dissolve the diamine in a mixed solvent of chlorobenzene and N-methyl-2-pyrrolidone, the volume ratio of chlorobenzene and N-methyl-2-pyrrolidone is 1:4-8, and add the resulting solution to step a ) in the obtained diacid diester, after fully stirring, at a temperature of 160° C. to 180° C., reflux reaction for 6 to 30 hours to generate an amino-terminated polyimide resin solution, and cool naturally;

c) Add maleic anhydride to the solution obtained in step b), react at room temperature for 3 to 24 hours, then add chlorobenzene to make the volume ratio of chlorobenzene to N-methyl-2-pyrrolidone 2 to 3 : 1, at 130°C to 132°C, reflux and divide water for 24 to 36 hours, after cooling, pour the reaction solution into high-speed agitated absolute ethanol to obtain a precipitate, which is successively washed with absolute ethanol and anhydrous ether After fully washing, vacuum drying is obtained to obtain the maleimide-terminated polyimide resin.

The reaction process is shown in formula (1),

In the formula; n is the degree of polymerization of the resin, 1≤n≤20; the aromatic tetra-acid dianhydride is O(CO) ₂ R ₁ (CO) ₂ ; the diamine is H ₂ NR ₂ -NH ₂ ;

The aromatic tetraacid dianhydride monomer O(CO) ₂ R ₁ (CO) ₂ selected in the above step a) is suitable for R ₁ as shown in formula (2). wherein X is O, S, SO ₂ , CO, CH ₂ , C(CH ₃ ) ₃ , CF ₂ , C(CF ₃ ) ₂ or does not exist. R ₁ may have a substituent, but preferably has no substituent, or is C ₁ -C ₆ lower alkyl or lower alkoxy. When synthesizing maleimide-terminated polyimide resin, a single aromatic tetra-acid dianhydride can be used, or a mixture of two or more aromatic tetra-acid dianhydrides can be used. Preferred aromatic tetra-acid dianhydrides are: 3,3',4,4'-biphenyl tetra-acid dianhydride (BPDA), 3,3',4,4'-benzophenone tetra-acid dianhydride (BTDA) , 3,3',4,4'-diphenyl ether tetra-acid dianhydride (ODPA), 2,2'-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane tetra-acid dianhydride (BPADA), 2,2'-bis(3,4-dicarboxyphenyl)hexafluoropropane tetraacid dianhydride (6FDA). The amount of the five cannot be zero at the same time, and the amount fraction of any one of them accounting for the aromatic tetraacid dianhydride blend is 0% to 100%;

For the diamine H ₂ NR ₂ —NH ₂ selected in the above step b), the applicable ones include R ₂ as shown in formula (3). Where Z is O, S, SO ₂ , CO, CH ₂ , C(CH ₃ ) ₃ , CF ₂ , C(CF ₃ ) ₂ or nonexistent; R ₂ is C ₁ ~ C ₆ lower alkyl or lower alkoxy R ₃ is C ₁ ~ C ₁₂ hydrocarbon group or alkoxy group; R ₄ is methyl, ethyl or tert-butyl; when synthesizing maleimide-terminated polyimide resin, one of them can be selected One, two or more diamine monomer mixtures. Preferred diamines are: 1,3-bis(3-aminopropyl)tetramethyldisiloxane, 1,3-bis(4-aminophenoxymethane)-1,1,3,3- Tetramethyldisiloxane, 4,4'-diaminodiphenylsulfone, 2,2-bis[(4-aminophenoxy)phenyl]propane, 3,3',5,5'-tetramethyl Base-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)-2-tert Butylbenzene, 1,4-bis(4-aminophenoxy)-2,5-di-tert-butylbenzene, the amount of the eight cannot be zero at the same time, and any one of them accounts for the substance of the diamine blend The amount fraction is from 0% to 100%.

The low-boiling alcohol solvent described in the reaction is one of anhydrous methanol, anhydrous ethanol or a blend of the two.

The application of the modified maleimide-terminated polyimide resin composition of the present invention on the adhesive-free two-layer flexible copper-clad laminate is characterized in that:

Weigh the raw materials according to the above-mentioned maleimide-terminated polyimide resin, allyl compound and inorganic filler material by weight, and mix them to obtain the modified maleimide-terminated polyimide resin. Polyimide resin composition, which is dissolved in a polar solvent and fully stirred to form a homogeneous solution with a solid content of 10% to 50%, and this solution is coated on a copper foil with a thickness of 5 microns to 35 microns , control the thickness of the liquid film to be 10 microns to 30 microns after the solvent evaporates, and carry out gradient temperature rise and solidification in a high-temperature oven under the protection of nitrogen to obtain an adhesive-free two-layer flexible copper clad laminate.

The polar solvent of the above-mentioned dissolved modified maleimide-terminated polyimide resin composition is N-methyl-2-pyrrolidone (NMP), N, N'-dimethylformamide (DMF), N,N'-dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), m-cresol, dimethyl sulfate, sulfolane, butyrolactone, tetrahydrofuran, etc. Among them, N-methyl-2-pyrrolidone (NMP), N, N'-dimethylformamide (DMF), N, N'-dimethylacetamide (DMAc), dimethylsulfoxide (DMSO) are preferred one or a mixture of several.

The above gradient temperature curing process is: 80°C×1 hour, 120°C×1 hour, 180°C×1 hour, 260°C×1 hour.

The bonding surface (the surface coated with the homogeneous solution) of the copper foil used above has been chemically or physically roughened.

The main advantages of the present invention are:

Using N-methyl-2-pyrrolidone as a solvent, a fully imidized maleimide-terminated polyimide resin was synthesized by a variable temperature solution imidization method. The solid powder is easy to store and can be dissolved in the selected In polar solvents, it is easy to process and can be taken at any time. The homogeneous solution prepared with the modified resin composition has good stability at room temperature, wherein the appropriate amount of inorganic filler material added to the modified resin composition significantly improves the difference in thermal expansion coefficient between the polyimide film layer and the copper foil Allowable range of values. It is used on the non-adhesive two-layer method flexible copper clad laminate, and the production cost is low and the process is simple. Its curing temperature is much lower than polyamic acid, the precursor solution of commonly used polyimide, so the requirements for equipment and environmental conditions are greatly reduced in the production process. When the resin is cured, no small molecule volatiles are released, so an adhesive-free two-layer flexible copper-clad laminate substrate with almost no pores and excellent comprehensive performance can be obtained.

Detailed ways:

The invention is further illustrated by the following examples, but the invention is not limited to these examples.

Example 1

Under nitrogen protection, 32.265 grams (0.10 moles) of 3,3', 4,4'-benzophenone tetraacid dianhydride were refluxed in 250 milliliters of methanol for 1 to 5 hours to obtain the corresponding diacid diester. Evaporate, remove residual methanol under reduced pressure, 27.338 grams (0.11 moles) of 1,3-bis(3-aminopropyl) tetramethyldisiloxane, with 31 milliliters of chlorobenzene and 123 milliliters of N- Methyl-2-pyrrolidone is dissolved and added to the diacid diester. After fully stirring, react at 164°C for 6 hours to form an amino-terminated polyimide resin solution. After cooling naturally, add maleic acid 1.961 g (0.02 mol) of dianhydride, after reacting at room temperature for 8 hours, add 205 ml of chlorobenzene, at 132°C, reflux and divide water for 32 hours, after cooling, pour the reaction solution into high-speed stirring absolute ethanol to obtain a precipitate The resulting precipitate was thoroughly washed successively with absolute ethanol and absolute ether, and vacuum-dried to obtain 51.80 grams of maleimide-terminated polyimide resin.

Weigh 50 grams of the above-mentioned maleimide-terminated polyimide resin, 2.5 grams of diallyl bisphenol A and 5 grams of mica, mix the three, dissolve in 190 milliliters of NMP, and stir fully to form homogeneous solution. Coat this solution on a copper foil with a thickness of 35 microns that has been physically roughened, and control the thickness of the liquid film to 10 microns to 30 microns after the solvent evaporates. The process is: 80°C x 1 hour, 120°C x 1 hour, 180°C x 1 hour, 260°C x 1 hour. Cool slowly to room temperature to obtain the adhesive-free two-layer flexible copper clad laminate.

Example 2

Under nitrogen protection, 24.851 grams (0.08 moles) of 3,3', 4,4'-diphenyl ether tetra-acid dianhydride were refluxed in 174 milliliters of ethanol for 1 to 5 hours to obtain the corresponding diacid diester, and the ethanol was distilled 20.369 grams (0.09 moles) of 3,3'-dimethyl-4,4'-diaminodiphenylmethane were mixed with 20 milliliters of chlorobenzene and 98 milliliters of N-methyl After the base-2-pyrrolidone is dissolved, add it to the diacid diester, stir it well, and react it at 168°C for 10 hours to form an amino-terminated polyimide resin solution. After it is naturally cooled, add maleic acid 1.961 grams (0.02 moles) of dianhydride, after reacting at room temperature for 12 hours, add 274 milliliters of chlorobenzene, at 130°C, reflux and divide water for 36 hours, after cooling, pour the reaction solution into high-speed stirring absolute ethanol to obtain a precipitate The resulting precipitate was thoroughly washed successively with absolute ethanol and absolute ether, and vacuum-dried to obtain 41.50 grams of maleimide-terminated polyimide resin.

Weigh 30 grams of the above-mentioned maleimide-terminated polyimide resin, 5.0 grams of diallyl bisphenol A and 6 grams of talcum powder, mix the three, dissolve in 140 milliliters of DMAc, and stir thoroughly into a homogeneous solution. Coat this solution on a copper foil with a thickness of 35 microns, control the thickness of the liquid film to be 10 microns to 30 microns after the solvent evaporates, and carry out gradient heating in a high-temperature oven under the protection of nitrogen. The heating process is: 80 ° C × 1 hour, 120°C x 1 hour, 180°C x 1 hour, 260°C x 1 hour. Cool slowly to room temperature to obtain the adhesive-free two-layer flexible copper clad laminate.

Example 3

Under nitrogen protection, 8.827 grams (0.03 moles) of 3,3', 4,4'-biphenyltetraacid dianhydride and 19.359 grams (0.03 moles) of 3,3', 4,4'-benzophenone tetraacid dianhydride ( 0.06 mol) in 230 milliliters of methanol and refluxed for 1 to 5 hours to obtain the corresponding diacid diester, the methanol was distilled off, and the remaining methanol was removed under reduced pressure, and 1.4-bis(4-aminophenoxy)-2 - 13.938 grams (0.04 moles) of tert-butylbenzene, 24.273 grams (0.06 moles) of 1.4-bis(4-aminophenoxy)-2.5-di-tert-butylbenzene, with 25 milliliters of chlorobenzene and 150 milliliters of N-methyl - After 2-pyrrolidone is dissolved, add it to the diacid diester, stir it well, and react at 172°C for 16 hours to form an amino-terminated polyimide resin solution. Acid anhydride 1.961 g (0.02 mol), after reacting at room temperature for 24 hours, add 425 milliliters of chlorobenzene, at 130 ° C, reflux and divide water for 29 hours, after cooling, pour the reaction solution into high-speed stirring absolute ethanol to obtain a precipitate , the obtained precipitate was washed thoroughly with anhydrous ethanol and anhydrous ether successively, and vacuum-dried to obtain 61.05 grams of maleimide-terminated polyimide resin.

Weigh 50 grams of the above-mentioned maleimide-terminated polyimide resin, 7.5 grams of diallyl bisphenol A and 10 grams of barium sulfate, mix the three, dissolve them in 230 milliliters of DMF, and stir them fully to form homogeneous solution. Coat this solution on a copper foil with a thickness of 35 microns that has been physically roughened, and control the thickness of the liquid film to 10 microns to 30 microns after the solvent evaporates. The process is: 80°C x 1 hour, 120°C x 1 hour, 180°C x 1 hour, 260°C x 1 hour. Cool slowly to room temperature to obtain the adhesive-free two-layer flexible copper clad laminate.

Example 4

Under the protection of nitrogen, 52.049 grams (0.10 moles) of 2,2'-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane tetraacid dianhydride and 2,2'-bis(3, 22.212 g (0.05 moles) of 4-dicarboxyphenyl) hexafluoropropane tetraacid dianhydride was refluxed in 590 ml of ethanol for 1 to 5 hours to obtain the corresponding diacid diester, the ethanol was distilled off, and the residual ethanol was decompressed After exhaustion, 4.966 grams (0.02 moles) of 4,4'-diaminodiphenylsulfone, 34.845 grams (0.10 moles) of 1.4-bis(4-aminophenoxy)-2-tert-butylbenzene, and 1,3 - Bis(4-aminophenoxymethane)-1,1,3,3-tetramethyldisiloxane 15.064 (0.04 mol), dissolved in 47 ml of chlorobenzene and 285 ml of N-methyl-2-pyrrolidone Afterwards, add it to the diacid diester, after fully stirring, react at 172°C for 12 hours to generate an amino-terminated polyimide resin solution, after it cools naturally, add 1.961 grams of maleic anhydride ( 0.02 moles), after reacting at room temperature for 14 hours, add 665 milliliters of chlorobenzene, at 131°C, reflux and divide water for 28 hours, after cooling, pour the reaction solution into high-speed stirring absolute ethanol to obtain a precipitate, the resulting precipitate After fully washing successively with absolute ethanol and anhydrous ether, vacuum drying was performed to obtain 100.14 g of maleimide-terminated polyimide resin.

Weigh 60 grams of the above-mentioned maleimide-terminated polyimide resin, 18 grams of diallyl bisphenol A and 15 grams of calcium hydrogen phosphate, mix the three, dissolve in 300 milliliters of DMSO, and stir thoroughly into a homogeneous solution. Coat this solution on a copper foil with a thickness of 35 microns, control the thickness of the liquid film to be 10 microns to 30 microns after the solvent evaporates, and carry out gradient heating in a high-temperature oven under the protection of nitrogen. The heating process is: 80 ° C × 1 hour, 120°C x 1 hour, 180°C x 1 hour, 260°C x 1 hour. Cool slowly to room temperature to obtain the adhesive-free two-layer flexible copper clad laminate.

Example 5

Under nitrogen protection, 9.680 g (0.03 moles) of 3,3',4,4'-benzophenone tetraacid dianhydride, 2,2'-bis[4-(3,4-dicarboxyphenoxy ) phenyl] propane tetraacid dianhydride 15.615 (0.03 mol) and 3,3 ', 4, 4'-biphenyl tetraacid dianhydride 8.827 grams (0.03 mol) in 240 milliliters of ethanol and refluxed 1～5 hour to obtain corresponding Di-acid diester, ethanol was distilled off, and the remaining ethanol was removed under reduced pressure, and 3,3'-dimethyl-4 dissolved in 24 ml of chlorobenzene and 134 ml of N-methyl-2-pyrrolidone , 11.316 grams (0.05 moles) of 4'-diaminodiphenylmethane, 6.969 grams (0.02 moles) of 1.4-bis(4-aminophenoxy)-2-tert-butylbenzene, and 1,3-bis(4- Aminophenoxymethane)-1,1,3,3-tetramethyldisiloxane 9.415 (0.025 mol) was added to the diacid diester, after stirring well, it was reacted at 170°C for 18 hours to generate amino After the end-capped polyimide resin solution was naturally cooled, 0.981 g (0.01 mol) of maleic anhydride was added, and after reacting at room temperature for 12 hours, 350 ml of chlorobenzene was added, and at 130° C., refluxed for water separation for 33 hours, after cooling, pour the reaction solution into dehydrated ethanol stirred at high speed to obtain a precipitate, which was washed thoroughly with dehydrated ethanol and anhydrous ether successively, and vacuum-dried to obtain the maleimide-terminated poly Imide resin 58.51 grams.

Weigh 50 grams of the above-mentioned maleimide-terminated polyimide resin, 4 grams of diallyl bisphenol A and 8 grams of silicon dioxide, mix the three, dissolve in 210 milliliters of DMAc, and stir thoroughly into a homogeneous solution. Coat this solution on a copper foil with a thickness of 35 microns, control the thickness of the liquid film to be 10 microns to 30 microns after the solvent evaporates, and carry out gradient heating in a high-temperature oven under the protection of nitrogen. The heating process is: 80 ° C × 1 hour, 120°C x 1 hour, 180°C x 1 hour, 260°C x 1 hour. Cool slowly to room temperature to obtain the adhesive-free two-layer flexible copper clad laminate.

The test performance of the adhesive-free two-layer flexible copper-clad laminate prepared in the above example is shown in Table 1.

Table 1 Test performance of adhesive-free two-layer flexible copper clad laminate

Test items Test Conditions unit Example 1 Example 2 Example 3 Example 4 Example 5 Test Methods Thermal expansion coefficient   100-200°C ppm 15 27 30 16 20 TMA glass transition temperature A ℃ 286 292 288 289 298 DSC Flame resistance A - V-0 V-0 V-0 V-0 V-0 UL94 Dimensional stability MD % ＜0.05 ＜0.05 ＜0.05 ＜0.05 ＜0.05   IPC-TM-650, NO.2.2.4 TD ＜0.05 ＜0.05 ＜0.05 ＜0.05 ＜0.05 Solder resistance 300℃/60s - qualified qualified qualified qualified qualified   IPC-TM-650, NO.2.4.13 Bending resistance MD Second-rate ＞4000 ＞4000 ＞4000 ＞4000 ＞4000 JIS6471, (0.8R, 0.5kg) TD ＞4000 ＞4000 ＞4000 ＞4000 ＞4000 surface resistance A Ω >10 ¹⁴ >10 ¹⁴ >10 ¹⁴ >10 ¹⁴ >10 ¹⁴   IPC-TM-650, NO.2.5.17 volume resistance A Ωcm >10 ¹⁴ >10 ¹⁴ >10 ¹⁴ >10 ¹⁴ >10 ¹⁴   IPC-TM-650, NO.2.5.17 water absorption A % <1.0 <1.0 <1.0 <1.0 <1.0   IPC-TM-650, NO.2.6.2 Dielectric constant A - <3.5 <3.5 <3.5 <3.5 <3.5   IPC-TM-650, NO.2.5.5.3 tensile strength A MPa >400 >400 >400 >400 >400 IPC～TM-650, NO.2.4.19 Peel strength A Kgf/cm >1.0 >1.0 >1.0 >1.0 >1.0   IPC-TM-650, NO.2.4.9

Claims (8)

1. modified maleimide end-sealed type polyimide resin combination, it is characterized in that: the composition of described composition and weight proportion are:

100 parts of maleimide end-sealed type polyimide resins

4～50 parts of allylic cpds

10～35 parts of inorganic filling materials;

Described allylic cpd is a kind of or the two blend in diallyl bisphenol and the diallyl bisphenol S;

Described inorganic filling material is one or more blends in mica, talcum powder, barium sulfate, secondary calcium phosphate, the silicon-dioxide, and its particle diameter is less than 1 micron.

2. the preparation method of a maleimide end-sealed type polyimide resin, it is characterized in that, with aromatic tetrahydric dianhydride, diamine and MALEIC ANHYDRIDE is raw material, and the ratio of the amount of substance of aromatic tetrahydric dianhydride, diamine and MALEIC ANHYDRIDE is n: (n+1): 2, and building-up process is:

A) aromatic tetrahydric dianhydride is used low-boiling point alcohol kind solvent wiring solution-forming, 1 gram aromatic tetrahydric dianhydride is with 7～10 milliliters of solvents, under nitrogen protection, refluxed 1～5 hour, obtain corresponding two acid diesters, alcoholic solvent is steamed, residual alcoholic solvent under reduced pressure eliminates;

B) with the mixed solvent dissolving of diamine with chlorobenzene and N-N-methyl-2-2-pyrrolidone N-, chlorobenzene and N-N-methyl-2-2-pyrrolidone N-volume ratio are 1: 4～8, gained solution is joined in two acid diesters that step a) obtains, after fully stirring, under 160 ℃～180 ℃ temperature, back flow reaction 6～30 hours generates amino-terminated polyimide resin solution, naturally cooling;

C) in the solution that step b) obtains, add MALEIC ANHYDRIDE, after reacting 3～24 hours under the room temperature, add chlorobenzene, make the volume ratio of chlorobenzene and N-N-methyl-2-2-pyrrolidone N-become 2～3: 1, under 130 ℃～132 ℃, reflux water-dividing 24～36 hours, after the cooling reaction solution is poured in the dehydrated alcohol of high-speed stirring, obtain throw out, after the gained throw out was successively used dehydrated alcohol and anhydrous diethyl ether thorough washing, vacuum-drying promptly got the maleimide end-sealed type polyimide resin;

Wherein, the described aromatic tetrahydric dianhydride of step a) be 3,3 ', 4,4 '-BPDA, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-phenyl ether tetracarboxylic dianhydride, 2,2 '-it is two that [4-(3,4-dicarboxyl phenoxy group) phenyl] propane tetracarboxylic dianhydride, 2,2 '-two (3,4-two carboxyphenyls) HFC-236fa tetracarboxylic dianhydride, five amount can not be zero simultaneously, and wherein any one amount of substance mark that accounts for the aromatic tetrahydric dianhydride blend is 0%～100%;

The described diamine of step b) is 1, two (the 3-aminopropane base) tetramethyl disiloxanes of 3-, 1, two (the 4-amino-benzene oxygen methane)-1,1,3 of 3-, the 3-tetramethyl disiloxane, 4,4 '-diaminodiphenylsulfone(DDS), 2, two [(4-amino-benzene oxygen) phenyl] propane of 2-, 3,3 ', 5,5 '-tetramethyl--4,4 '-diaminodiphenylmethane, 3,3 '-dimethyl-4,4 '-diaminodiphenylmethane, 1, two (4-the amino-benzene oxygen)-2-tert.-butylbenzenes of 4-, 1, two (the 4-amino-benzene oxygens)-2 of 4-, 5-di-tert-butyl, eight amount can not be zero simultaneously, and wherein any one amount of substance mark that accounts for the diamine blend is 0%～100%.

3. the preparation method of maleimide end-sealed type polyimide resin according to claim 2 is characterized in that: described low-boiling point alcohol kind solvent is a kind of or the two blend in anhydrous methanol, the dehydrated alcohol.

4. the application of the described modified maleimide end-sealed type polyimide resin combination of claim 1; it is characterized in that: be applied on the gum-free two-layer method flexibility coat copper plate; usage is according to described maleimide end-sealed type polyimide resin; allylic cpd and inorganic filling material ratio of weight and number take by weighing raw material; after three's mixing; be dissolved in the polar solvent; fully stir; the formation solid content is 10%～50% homogeneous phase solution; this solution is coated on the Copper Foil of 5 microns～35 micron thickness; control liquid film thickness after solvent evaporates is 10 microns～30 microns; in high temperature oven, under nitrogen protection, carry out gradient increased temperature curing and get final product.

5. the application of modified maleimide end-sealed type polyimide resin combination according to claim 4, it is characterized in that: described polar solvent is N-N-methyl-2-2-pyrrolidone N-, N, N '-dimethyl formamide, N, a kind of or several mixtures in N '-N,N-DIMETHYLACETAMIDE, the dimethyl sulfoxide (DMSO).

6. the application of modified maleimide end-sealed type polyimide resin combination according to claim 4 is characterized in that: the solid content of described homogeneous phase solution is 10%～50%.

7. the application of modified maleimide end-sealed type polyimide resin combination according to claim 4 is characterized in that: described gradient increased temperature curing process is: 80 ℃ * 1 hour, and 120 ℃ * 1 hour, 180 ℃ * 1 hour, 260 ℃ * 1 hour.

8. the application of modified maleimide end-sealed type polyimide resin combination according to claim 4 is characterized in that: used Copper Foil applies the one side of homogeneous phase solution and has carried out chemistry or physics roughened.