CN102850726A - Composite material, high-frequency circuit substrate made therefrom and method for making same - Google Patents

Abstract

The invention relates to a composite material, a high-frequency circuit substrate made of the composite material and a manufacturing method of the high-frequency circuit substrate, wherein the composite material comprises the following components in percentage by volume: 10-90% of polyetherimide reinforcing material and 10-90% of thermosetting resin composition. A high-frequency circuit board manufactured by using the composite material comprises: the composite material comprises a plurality of layers of mutually overlapped prepregs and copper foils pressed on one side or two sides of the overlapped prepregs, wherein at least one prepreg in the plurality of layers of prepregs is made of the composite material. The composite material has lower dielectric constant and dielectric loss tangent, high heat resistance and good process processability by adopting the polyetherimide reinforced material, and is suitable for the field of high-frequency high-speed printed circuit boards.

Description

Composite material, high-frequency circuit substrate made therefrom and method for making same

technical field

The invention relates to a composite material, a high-frequency circuit substrate made with it and a manufacturing method thereof, in particular to a thermosetting resin composite material, a high-frequency circuit substrate made with it and a manufacturing method thereof.

Background technique

In recent years, with the development of information technology, communication equipment is becoming more and more high-performance, multi-functional and networked, and the frequency of electronic signal transmission is getting higher and higher. In order to achieve high-speed transmission and process large-capacity information, high-frequency is already an unstoppable trend. The frequency of use of electronic products continues to increase, and the requirements for the dielectric properties of substrate materials used as circuit boards are getting higher and higher. The main performance is Low dielectric constant and dielectric loss tangent.

At present, a lot of technical work has been done to realize the low dielectric constant and dielectric loss tangent of high-frequency circuit substrates, mainly including resins and reinforcing materials. First of all, epoxy is the most common resin used as a circuit substrate, because it has good heat resistance, manufacturability and adhesion, but its high dielectric constant limits its use on high-frequency circuit substrates. Resins such as cyanate ester, polyphenylene ether, bismaleimide, polyimide, and polytetrafluoroethylene are much superior to epoxy resin in terms of dielectric properties, but due to the poor heat resistance of cyanate ester , It often needs to be modified before it can be used, which greatly sacrifices its excellent dielectric properties. Polyphenylene ether resin itself has good heat resistance and node performance, but due to its too large molecular weight, resulting in poor technology and has not been able to achieve good applications; polytetrafluoroethylene itself has the best dielectric properties among existing materials However, because it is a thermoplastic material, its glass transition temperature is too low, which makes the processing difficult. In addition, because of its strong chemical resistance, it makes subsequent circuit board processing difficult. In terms of reinforcement materials, electronic grade glass fiber cloth is currently the most widely used in circuit substrates, which has good reinforcement effect, heat resistance and chemical resistance, but due to its own composition, its dielectric constant is very high , up to 6.6; in order to further improve its dielectric properties, a low dielectric constant NE cloth appears, and by adjusting its composition, its dielectric constant can be reduced to a certain extent, generally around 4.6. However, its dielectric constant value is still much higher than that of the resin system, which brings great restrictions to the reduction of the dielectric constant of the copper clad laminate material.

Contents of the invention

The purpose of the present invention is to provide a composite material, which has lower dielectric constant and dielectric loss tangent, high heat resistance and good processability by using polyetherimide reinforced material, suitable for high frequency High-speed printed circuit board field.

Another object of the present invention is to provide a high-frequency circuit substrate made of the above-mentioned composite material, which has a lower dielectric constant, good heat resistance and flame retardancy.

Another object of the present invention is to provide a method for manufacturing the above-mentioned high-frequency substrate, which is simple in operation and convenient in process.

In order to achieve the above object, the present invention provides a composite material, which includes components and their volume percentages as follows: 10-90% of polyetherimide reinforcing material and 10-90% of thermosetting resin composition;

The structural formula of the polyetherimide of the polyetherimide reinforcement material is as follows:

或—（CH₂）_m—，m为2~10的整数。Among them, R1 and R2 are

or —(CH ₂ ) _m —, m is an integer of 2-10.

The volume percentage of the polyimide reinforcing material is preferably 25-80%, more preferably 30-60%.

The polyetherimide reinforcing material is polyetherimide fiber woven cloth, polyetherimide non-woven fabric or polyetherimide glass fiber paper.

The thermosetting resin composition includes a thermosetting resin, the thermosetting resin is epoxy resin, phenolic resin, benzoxazine resin, polyphenylene ether resin, cyanate resin, polyimide resin, bismaleimide One or more combinations of resin, hydrocarbon resin, polysiloxane resin, polytetrafluoroethylene resin, polyethersulfone resin, polyetherketone resin, and modified resins of the aforementioned thermosetting resins.

The thermosetting resin composition also includes a curing agent and a curing accelerator. The curing agent is one or more mixtures of dicyandiamide, aromatic amine, phenolic resin, and acid anhydride compound. The curing accelerator is an imidazole compound and its derivatives. One or more mixtures of compounds, piperidine compounds, Lewis acids, triphenylphosphine and organometallic complexes.

The thermosetting resin composition also includes a flame retardant, and the flame retardant adopts a bromine-containing or halogen-free flame retardant, and the bromine-containing flame retardant is decabromodiphenyl ether, decabromodiphenylethane, brominated benzene Ethylene or ethylene bis-tetrabromophthalimide; the halogen-free flame retardants are tris(2,6-dimethylphenyl)phosphine, 10-(2,5-dihydroxyphenyl)- 9,10-dihydro-9-oxa-10-phosphinophenanthrene-10-oxide, 2,6-bis(2,6-dimethylphenyl)phosphinobenzene or 10-phenyl-9,10 - dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, phenoxyphosphacyanine compound, phosphoric acid ester, phosphoric acid ester salt compound or hydrated metal compound.

The thermosetting resin composition also includes an inorganic filler or an organic filler, and the inorganic filler is selected from crystalline silica, fused silica, spherical silica, hollow silica, glass powder, aluminum nitride, boron nitride , silicon carbide, aluminum hydroxide, magnesium hydroxide, titanium dioxide, strontium titanate, barium titanate, aluminum oxide, barium sulfate, talcum powder, calcium silicate, calcium carbonate, boehmite, zinc borate and mica or more; the organic filler is selected from one or more of polytetrafluoroethylene powder, polyphenylene sulfide and polyethersulfone powder.

The present invention also provides a high-frequency circuit substrate made of the above-mentioned composite material, which includes: several layers of prepregs laminated with each other and copper foil pressed on one side or both sides of the laminated prepregs, the several layers of prepregs At least one of the prepregs is made of the composite material.

Further, the present invention also provides a method for manufacturing the above-mentioned high-frequency circuit substrate, including the following steps:

Step 1. Provide the components of the composite material by volume percentage: 10-90% of the polyetherimide reinforcing material and 10-90% of the thermosetting resin composition;

Step 2, preparing the thermosetting resin composition into glue;

Step 3, impregnating the polyetherimide reinforcing material with the above-mentioned glue solution, and baking to obtain a prepreg;

Step 4: Take several sheets of the above-mentioned prepregs and laminate them, cover one or both sides of the laminated prepregs with copper foil, and cure them in a press to obtain the high-frequency circuit substrate. The curing temperature is 150~300°C , curing pressure 5~50Kg/cm ² .

The polyetherimide reinforcing material is polyetherimide fiber woven cloth, polyetherimide non-woven fabric or polyetherimide glass fiber paper.

Beneficial effects of the present invention: firstly, using polyetherimide reinforced material, its dielectric constant is 3.0, compared with traditional glass fiber reinforced material, can effectively reduce the dielectric constant of the circuit substrate;

Secondly, the present invention adopts polyetherimide reinforcement material, which has high heat resistance, glass transition temperature greater than 200°C, and intrinsic flame retardancy, which is higher than that of existing organic fibers such as polyethylene fibers. Excellent heat resistance and flame retardancy, more suitable for use in circuit substrates;

In a word, the composite material of the present invention is easy to manufacture, and the high-frequency circuit substrate made of it has low dielectric constant, good heat resistance, easy processing of the circuit board, and good flame retardancy.

Detailed ways

The invention provides a composite material, which includes components and their volume percentages (calculated according to the total volume percentage ratio of the composite material) as follows: 10-90% of a polyetherimide reinforcing material and 10-90% of a thermosetting resin composition.

The structural formula of the polyetherimide of the polyetherimide reinforcement material is as follows:

或—（CH₂）_m—，m为2~10的整数。Wherein R1 and R2 represent a group with an aromatic residue or an alkylene group, R1 and R2 may be the same or different, as

or —(CH ₂ ) _m —, m is an integer of 2-10.

The volume percentage of the polyimide reinforcing material is preferably 25-80%, more preferably 30-60%.

The polyetherimide reinforcing material can be polyetherimide fiber woven cloth, polyetherimide non-woven fabric or polyetherimide glass fiber paper. The present invention adopts polyetherimide reinforced material, such as polyetherimide fiber cloth, whose dielectric constant is 3.0, which has a lower dielectric constant than traditional glass fiber reinforced material, and can effectively reduce the dielectric constant of the material. electrical constant.

The thermosetting resin composition contains a thermosetting resin. The present invention is not particularly limited to the thermosetting resin, which may be epoxy resin, phenolic resin, benzoxazine resin, polyphenylene ether resin, cyanate resin, polyimide One of the modified resins of amine resin, bismaleimide resin, hydrocarbon resin, polysiloxane resin, polytetrafluoroethylene resin, polyethersulfone resin, polyetherketone resin, and the aforementioned thermosetting resins or multiple combinations. From the perspective of better dielectric properties, the thermosetting resin is preferably one of cyanate resin, bismaleimide resin, polyolefin resin, modified polyolefin resin, polytetrafluoroethylene resin and polyphenylene ether resin. one or more species. The epoxy resin can be bisphenol A type brominated epoxy resin, bromine-free bisphenol A type epoxy resin, phenol novolac resin, cresol novolac resin, bisphenol A novolac epoxy resin, DCPC type ring Oxygen resin, biphenyl type epoxy resin, naphthol type epoxy resin, alkylphenol type epoxy resin, aliphatic epoxy resin, trifunctional epoxy resin or nitrogen-containing epoxy resin; said cyanate ester resin Can be bisphenol A type cyanate resin, DCPD type cyanate resin, bisphenol M type cyanate resin, bisphenol F type cyanate resin, novolak type cyanate resin, alkylphenol type cyanate resin Resin or naphthol type cyanate; Described maleimide resin can be selected as DDM type bismaleimide resin, diamine modified bismaleimide resin or allyl modified bismaleimide resin Laimide resin; described benzoxazine resin can be selected as aniline type benzoxazine resin, bisphenol A type benzoxazine resin, bisphenol F type benzoxazine resin, naphthol type benzoxazine resin Oxazine resin or phenolphthalein type benzoxazine resin; the polyphenylene ether resin can be selected from hydroxylated polyphenylene ether resin, epoxy modified polyphenylene ether resin, vinylated modified polyphenylene ether resin or Acylation modified polyphenylene ether resin; the unsaturated resin can be polybutadiene resin, butadiene-styrene copolymer resin, maleimide modified polybutadiene resin, epoxy Modified polybutadiene resin, hydroxyl-terminated polybutadiene resin, styrene resin, methylstyrene resin, ethylstyrene resin, divinylbenzene resin, isopentene resin, acrylate, acrylonitrile resin or Benzocyclobutene resin. Based on 100 parts by weight of the thermosetting resin composition, the above thermosetting resin accounts for 50-99% by weight of the thermosetting resin composition.

The thermosetting resin composition may also contain a curing agent and a curing accelerator as required, and the selection of the curing agent is not particularly limited, mainly to increase the crosslinking density. It can be one or a mixture of dicyandiamide, aromatic amine, phenolic resin, acid anhydride compound, etc. The aromatic amine can be diaminodiphenyl sulfone, diaminodiphenyl ether diphenyl sulfone, diaminodiphenyl ether diphenyl ether, diaminodiphenyl ether bisphenol A, diaminodiphenyl ether-6F-bisphenol A or fluorenamine compound; the phenolic resin can be bisphenol A type phenolic resin, phenol phenolic resin, cresol phenolic resin, dicyclopentadiene type phenolic resin, biphenyl phenolic resin, naphthol phenolic resin, alkyl Phenol-formaldehyde resin or triphenol novolac resin; the anhydride compound may be methyl tetrahydro-acid anhydride, methyl hexahydro-acid anhydride or styrene bismaleic anhydride; calculated with 100 parts by weight of thermosetting resin composition, the curing agent It accounts for 1-50% by weight of the thermosetting resin composition.

The curing accelerator is not particularly limited, as long as it can catalyze the reaction of the thermosetting resin composition and reduce the reaction temperature of the curing system, preferably imidazole compounds and derivatives thereof, piperidine compounds, Lewis acid, triphenylphosphine , One or more mixtures of organometallic complexes. Described imidazole compound can enumerate 2-methylimidazole, 2-phenylimidazole and 2-ethyl-4-methylimidazole, and described piperidine compound can enumerate 2,3-diaminopiperidine, 2,5-diaminopiperidine 2,6-diaminopiperidine, 2,5-diamino, 2-amino-3-methylpiperidine, 2-amino-4-4-methylpiperidine, 2-amino -3-nitropiperidine, 2-amino-5-nitropiperidine and 4-dimethylaminopiperidine; the Lewis acid catalyst can be boron trifluoride monoethylamine; the organometallic The complex may be copper acetylacetonate, cobalt acetylacetonate, zinc octoate or vanadium naphthenate. Based on 100 parts by weight of the thermosetting resin composition, the amount of the curing accelerator added is 0.05-3 parts by weight, preferably 0.1-2.5 parts by weight, more preferably 0.15-2.0 parts by weight, especially preferably 0.15-1.0 parts by weight .

The thermosetting resin composition of the present invention can optionally add a flame retardant, and there is no special limitation on the optional flame retardant. It is better to use a non-reactive flame retardant so as not to affect the dielectric properties. Bromine-containing or halogen-free flame retardants can be used, and the bromine-containing flame retardants can be decabromodiphenyl ether, decabromodiphenylethane, brominated styrene or ethylene bis-tetrabromophthaloyl Amines; the halogen-free flame retardants are tris(2,6-dimethylphenyl)phosphine, 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa- 10-Phosphinanthrene-10-oxide, 2,6-bis(2,6-dimethylphenyl)phosphinobenzene or 10-phenyl-9,10-dihydro-9-oxa-10-phosphine Phenanthrene-10-oxide, phenoxyphosphacyanine compound, phosphoric acid ester, phosphoric acid ester salt compound or hydrated metal compound. Calculated relative to 100 parts by weight of the thermosetting resin composition, the added amount of the flame retardant is preferably 5-100 parts by weight, more preferably 5-90 parts by weight, and especially preferably 5-80 parts by weight.

If necessary, the thermosetting resin composition of the present invention may further contain fillers, which are organic fillers or inorganic fillers. There are no special restrictions on the fillers added as needed, and the inorganic fillers can be selected from crystalline silica, fused silica, spherical silica, hollow silica, glass powder, aluminum nitride, boron nitride, carbide One or more of silicon, aluminum hydroxide, magnesium hydroxide, titanium dioxide, strontium titanate, barium titanate, aluminum oxide, barium sulfate, talc, calcium silicate, calcium carbonate, boehmite, zinc borate and mica Various; the organic filler can be selected from one or more of polytetrafluoroethylene powder, polyphenylene sulfide and polyethersulfone powder. In addition, the shape and particle size of the inorganic filler are not particularly limited, and the particle size is usually 0.01-50 μm, preferably 0.01-20 μm, and particularly preferably 0.1-10 μm. Inorganic fillers in this particle size range are easier to disperse in the resin solution . Furthermore, the amount of filler added is not particularly limited, and calculated relative to 100 parts by weight of the thermosetting resin composition, the amount of filler added is 5-1000 parts by weight, preferably 5-300 parts by weight, more preferably 5-200 parts by weight. Parts by weight, particularly preferably 15-100 parts by weight.

The high-frequency circuit substrate made of the above-mentioned composite material includes several layers of prepregs laminated to each other and copper foils respectively covered on one or both sides, at least one or all of the several layers of prepregs are made of the composite material.

The manufacturing method of the above-mentioned high-frequency circuit substrate includes the following steps:

Step 1: Provide the components of the composite material by volume percentage: 10-90% of the polyetherimide reinforcing material and 10-90% of the thermosetting resin composition.

Step 2, preparing the thermosetting resin composition into a glue solution: using an appropriate solvent to prepare the thermosetting resin composition into a glue solution with a certain solid content in a certain proportion.

Step 3. Impregnate the polyetherimide reinforcing material with the above-mentioned glue, and control the appropriate thickness, that is, control the thickness of the glue on the polyetherimide reinforcing material to a suitable thickness range, and then bake Bake to remove the solvent to obtain a prepreg;

Step 4: Take several sheets of the above-mentioned prepregs and laminate them, cover one or both sides of the laminated prepregs with copper foil, and cure them in a press to obtain the high-frequency circuit substrate. The curing temperature is 150~300°C , curing pressure 5~50Kg/cm ² .

Regarding the dielectric properties, ie, the dielectric constant, dielectric loss tangent, and heat resistance, of the high-frequency circuit substrate manufactured above, the following examples further give a detailed description.

Example 1

Preparation of resin glue:

Take a container, add 100 parts by weight of brominated bisphenol A epoxy resin DER530A80 (DOW company, EEW is 435g/eq), and then add 2.0 parts by weight of dicyandiamide curing agent (Ningxia Darong, amino equivalent 21g/eq) eq) solvent and DMF solvent, add to the above resin and stir evenly, then add 0.075 parts by weight of curing accelerator 2-ethyl-4-methylimidazole, and finally add an appropriate amount of solvent DMF, continue to stir evenly to form a glue .

Production of prepreg and board:

Treat the polyetherimide fiber cloth (manufactured by Japan KURARAY Company) at 80~150°C for 30~90 minutes, then impregnate the polyetherimide fiber cloth with the above-mentioned prepared glue, and control the temperature of the fiber cloth. The volume content is 50%, and then baked at 155°C for 5-10 minutes to remove the solvent to obtain a prepreg. Use several prepared prepregs to stack each other, press a piece of copper foil on each side of it, and cure it in a hot press to obtain a high-frequency circuit substrate. The curing temperature is 180°C and the curing pressure is 25Kg/ cm ² , the curing time is 45min.

Example 2

Preparation of resin glue:

Take a container, add 100 parts by weight of brominated bisphenol A epoxy resin DER530A80 (DOW company, EEW is 435g/eq), and then add 24.1 parts by weight of phenolic curing agent TD-2090 (Ningxia Darong, hydroxyl equivalent 105g /eq) dissolved in methyl ethyl ketone solvent, add to the above resin and stir evenly, then add 0.075 parts by weight of curing accelerator 2-ethyl-4-methylimidazole, finally add an appropriate amount of solvent PM, continue to stir evenly and serve Glue.

Production of prepreg and board:

Treat the polyetherimide fiber cloth (manufactured by KURARAY, Japan) at 80-150°C for 30-90 minutes, then impregnate the polyetherimide fiber cloth with the above-mentioned prepared glue, and control the temperature of the fiber cloth. The volume content is 50%, and then baked at 155°C for 5-10 minutes to remove the solvent to obtain a prepreg. Use several prepared prepregs to stack each other, press a piece of copper foil on each side of the prepreg, and cure it in a hot press to obtain a high-frequency circuit substrate. The curing temperature is 190 ° C and the curing pressure is 30Kg/ cm ² , the curing time is 90min.

Example 3

Preparation of resin glue:

Get a container, add 70 parts by weight of dicyclopentadiene type novolak epoxy resin HP-7200-H (Japan DIC company, EEW is 288g/eq), and then add 30 parts by weight of cyanate ester (manufactured by Shanghai Huifeng Company) ) was dissolved in butanone solvent, added to the above resin and stirred evenly, then 0.075 parts by weight of curing accelerator zinc caprylate was added, and finally an appropriate amount of butanone solvent was added, and the glue was formed by continuing to stir evenly.

Production of prepreg and board:

Treat the polyetherimide fiber cloth (manufactured by KURARAY, Japan) at 80-150°C for 30-90 minutes, then impregnate the polyetherimide fiber cloth with the above-mentioned prepared glue, and control the temperature of the fiber cloth. The volume content is 50%, and then baked at 155°C for 5-10 minutes to remove the solvent to obtain a prepreg. Use several prepared prepregs to stack each other, press a piece of copper foil on each side of it, and cure it in a hot press to obtain a high-frequency circuit substrate. The curing temperature is 200 ° C and the curing pressure is 35Kg/ cm ² , the curing time is 100mi.

Example 4

Preparation of resin glue:

Take a container, add 100 parts by weight of polybutadiene B3000 (Nippon Soda Company, 1,2-ethylene content 90%), and then add 3.0 parts by weight of cumene peroxide curing agent (manufactured by Shanghai Takahashi Company) solvent and toluene solvent, add to the above resin and stir evenly, continue to stir evenly to form a glue.

Production of prepreg and board:

Treat the polyetherimide fiber cloth (manufactured by KURARAY, Japan) at 80-150°C for 30-90 minutes, then impregnate the polyetherimide fiber cloth with the above-mentioned prepared glue, and control the temperature of the fiber cloth. The volume content is 50%, and then baked at 155°C for 5-10 minutes to remove the solvent to obtain a prepreg. Use several prepared prepregs to stack each other, press a piece of copper foil on each side of it, and cure it in a hot press to obtain a high-frequency circuit substrate. The curing temperature is 220°C and the curing pressure is 25Kg/ cm ² , the curing time is 120min.

Example 5

Preparation of resin glue:

Get a container, add 70 parts by weight of dicyclopentadiene type novolak epoxy resin HP-7200-H (Japan DIC company, EEW is 288g/eq), and then add 30 parts by weight of cyanate ester (manufactured by Shanghai Huifeng Company) ) was dissolved in butanone solvent, added to the above resin and stirred evenly, then 0.075 parts by weight of curing accelerator zinc caprylate was added, and finally an appropriate amount of butanone solvent was added, and the glue was formed by continuing to stir evenly.

Production of prepreg and board:

Treat the polyetherimide fiber cloth (manufactured by KURARAY, Japan) at 80-150°C for 30-90 minutes, then impregnate the polyetherimide fiber cloth with the above-mentioned prepared glue, and control the temperature of the fiber cloth. The volume content is 30%, and then baked at 155°C for 5-10 minutes to remove the solvent to obtain a prepreg. Use several prepared prepregs to stack each other, press a piece of copper foil on each side of the prepreg, and cure it in a hot press to obtain a high-frequency circuit substrate. The curing temperature is 220 ° C and the curing pressure is 25Kg/ cm ² , the curing time is 120min.

Example 6

Preparation of resin glue:

Get a container, add 70 parts by weight of dicyclopentadiene type novolak epoxy resin HP-7200-H (Japan DIC company, EEW is 288g/eq), and then add 30 parts by weight of cyanate ester (manufactured by Shanghai Huifeng Company) ) was dissolved in butanone solvent, added to the above resin and stirred evenly, then 0.075 parts by weight of curing accelerator zinc caprylate was added, and finally an appropriate amount of butanone solvent was added, and the glue was formed by continuing to stir evenly.

Production of prepreg and board:

Treat the polyetherimide fiber cloth (manufactured by Japan KURARAY Company) at 80~150°C for 30~90 minutes, then impregnate the polyetherimide fiber cloth with the above-mentioned prepared glue, and control the temperature of the fiber cloth. The volume content is 75%, and then baked at 155°C for 5-10 minutes to remove the solvent to obtain a prepreg. Use several prepared prepregs to stack each other, press a piece of copper foil on each side of the prepreg, and cure it in a hot press to obtain a high-frequency circuit substrate. The curing temperature is 220 ° C and the curing pressure is 25Kg/ cm ² , the curing time is 120min.

Example 7

Preparation of resin glue:

Take a container, add 100 parts by weight of polybutadiene B3000 (Nippon Soda Company, 1,2-ethylene content 90%), and then add 3.0 parts by weight of cumene peroxide curing agent (manufactured by Shanghai Takahashi Company) solvent and toluene solvent, add to the above resin and stir evenly, continue to stir evenly to form a glue.

Production of prepreg and board:

Treat the polyetherimide non-woven fabric (manufactured by KURARAY, Japan) at 80-150°C for 30-90 minutes, then impregnate the polyetherimide fiber cloth with the above-mentioned prepared glue, and control the fiber cloth The volume content is 50%, and then baked at 155 ° C for 5 to 10 minutes to remove the solvent to obtain a prepreg. Use several prepared prepregs to stack each other, press a piece of copper foil on each side of it, and cure it in a hot press to obtain a high-frequency circuit substrate. The curing temperature is 220°C and the curing pressure is 25Kg/ cm ² , the curing time is 120min.

Comparative example 1

Preparation of resin glue:

Take a container, add 100 parts by weight of brominated bisphenol A epoxy resin DER530A80 (DOW company, EEW is 435g/eq), and then add 2.0 parts by weight of dicyandiamide curing agent (Ningxia Darong, amino equivalent 21g/eq) eq) solvent and DMF solvent, add to the above resin and stir evenly, then add 0.075 parts by weight of curing accelerator 2-ethyl-4-methylimidazole, and finally add an appropriate amount of solvent DMF, continue to stir evenly to form a glue .

Production of prepreg and board:

Then impregnate the electronic grade E glass fiber cloth 2116 (Nittobo Co., thickness 0.09mm) with the above prepared glue and control the volume content of the fiber cloth to 50%, and then bake it at 155°C for 5-10 minutes. The solvent was removed to obtain a prepreg. Use several prepared prepregs to stack each other, press a piece of copper foil on each side of it, and cure it in a hot press to obtain a circuit board. The curing temperature is 180°C and the curing pressure is 25Kg/cm ² , The curing time is 45min.

Comparative example 2

Preparation of resin glue:

Take a container, add 100 parts by weight of brominated bisphenol A epoxy resin DER530A80 (DOW company, EEW is 435g/eq), and then add 2.0 parts by weight of dicyandiamide curing agent (Ningxia Darong, amino equivalent 21g/eq) eq) solvent and DMF solvent, add to the above resin and stir evenly, then add 0.075 parts by weight of curing accelerator 2-ethyl-4-methylimidazole, and finally add an appropriate amount of solvent DMF, continue to stir evenly to form a glue .

Production of prepreg and board:

Then use the above-mentioned prepared glue to stain low-dielectric constant electronic grade NE glass fiber cloth 2116 (Nittobo Co., thickness 0.09mm) and control the volume content of the fiber cloth to 50%, then bake at 155 ° C for 5 ~10 minutes, the solvent was removed to make a prepreg. Use several prepared prepregs to stack each other, press a piece of copper foil on each side of it, and cure it in a hot press to obtain a circuit board. The curing temperature is 180°C and the curing pressure is 25Kg/cm ² , The curing time is 45min.

Comparative example 3

Preparation of resin glue:

Take a container, add 100 parts by weight of brominated bisphenol A epoxy resin DER530A80 (DOW company, EEW is 435g/eq), and then add 2.0 parts by weight of dicyandiamide curing agent (Ningxia Darong, amino equivalent 21g/eq) eq) solvent and DMF solvent, add to the above resin and stir evenly, then add 0.075 parts by weight of curing accelerator 2-ethyl-4-methylimidazole, and finally add an appropriate amount of solvent DMF, continue to stir evenly to form a glue .

Production of prepreg and board:

Then soak the polyethylene fiber cloth UHMWPE (Shanghai Ruisi Company) with the above-mentioned prepared glue and control the volume content of the fiber cloth to 50%, and then bake it at 155°C for 5-10 minutes to remove the solvent to make a prepreg. Use several prepared prepregs to stack each other, press a piece of copper foil on each side of it, and cure it in a hot press to obtain a circuit board. The curing temperature is 180°C and the curing pressure is 25Kg/cm ² , The curing time is 45min.

Table 1. The physical data of each embodiment

performance Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Dk(10G) 3.7 3.6 3.4 2.7 3.6 3.2 2.68 Df(10G) 0.012 0.0012 0.008 0.0038 0.0085 0.007 0.035 flame retardant V-0 V-0 V-0 V-0 V-0 V-0 V-0

Table 2. Physical property data of each comparative example

performance Comparative example 1 Comparative example 2 Comparative example 3 Dk(10G) 4.4 4.2 2.6 Df(10G) 0.018 0.016 0.003 flame retardant V-0 V-0 V-2

Physical property analysis

As can be seen from the physical property data results in Table 1 and Table 2, the high-frequency circuit substrate materials made in Examples 1-4 have lower dielectric constant and dielectric loss tangent, and good high-frequency characteristics, while Comparative Examples 1-4 In 2, electronic grade E glass fiber cloth and NE glass fiber cloth are used as reinforcing materials, and the dielectric constant and dielectric loss tangent are relatively high. Comparative example 3 uses polyethylene fiber cloth as reinforcing material, although it has low dielectric constant and dielectric Loss, but because polyethylene itself does not have flame retardancy, it cannot meet the requirements of UL 94V-0 for electronic products.

The above examples do not limit the content of the composition of the present invention in any way. Any minor modifications, equivalent changes and modifications made to the above examples according to the technical essence of the present invention or composition components or content still belong to the technology of the present invention. within the scope of the program.

Claims (10)

1. a matrix material is characterized in that, it comprises that component and volume percent thereof are as follows: polyetherimide strongthener 10 ~ 90% and compositions of thermosetting resin 10 ~ 90%;

The structural formula of the polyetherimide of described polyetherimide strongthener is shown below:

Wherein R1, R2 are

Or-(CH ₂) _m-, m is 2 ~ 10 integer.

2. matrix material as claimed in claim 1 is characterized in that, the volume percent of described polyimide strongthener is 25 ~ 80%.

3. matrix material as claimed in claim 2 is characterized in that, the volume percent of described polyimide strongthener is 30 ~ 60%.

4. matrix material as claimed in claim 1 is characterized in that, described polyetherimide strongthener is polyether-imide fiber woven cloth, polyetherimide non-woven fabrics or polyetherimide glass fiber paper.

5. matrix material as claimed in claim 1, it is characterized in that, described compositions of thermosetting resin includes thermosetting resin, this thermosetting resin be Resins, epoxy, resol, benzoxazine resin, polyphenylene oxide resin, cyanate ester resin, polyimide resin, bimaleimide resin, hydrocarbon resin, polyorganosiloxane resin, teflon resin, polyethersulfone resin, polyether ketone resin, and the modified resin of aforementioned each thermosetting resin in one or more compositions.

6. matrix material as claimed in claim 5, it is characterized in that, described compositions of thermosetting resin also includes solidifying agent and curing catalyst, solidifying agent is one or more mixtures in Dyhard RU 100, aromatic amine, resol and the anhydride compound, and curing catalyst is one or more mixtures in glyoxaline compound and derivative compound, piperidines, Lewis acid, triphenylphosphine and the organometallic complex.

7. matrix material as claimed in claim 5, it is characterized in that, described compositions of thermosetting resin also includes fire retardant and filler, fire retardant adopts brominated or halogen-free flame retardants, and described brominated flame-retardant is the two tetrabromo phthalimides of decabromodiphynly oxide, TDE, brominated styrene or ethylene; Described halogen-free flame retardants is three (2, the 6-3,5-dimethylphenyl) phosphine, 10-(2, the 5-dihydroxy phenyl)-9, the 10-dihydro-9-oxy is mixed-10-phosphine phenanthrene-10-oxide compound, 2,6-two (2, the 6-3,5-dimethylphenyl) phosphino-benzene or 10-phenyl-9, the 10-dihydro-9-oxy is mixed-10-phosphine phenanthrene-10-oxide compound, phenoxy group phosphine cyanogen compound, phosphoric acid ester, phosphate ester salt compound or hydrated metal compound, described filler is for having mineral filler or organic filler, and mineral filler is selected from powdered quartz, fused silica, preparing spherical SiO 2, hollow silicon dioxide, glass powder, aluminium nitride, boron nitride, silicon carbide, aluminium hydroxide, magnesium hydroxide, titanium dioxide, strontium titanate, barium titanate, aluminum oxide, barium sulfate, talcum powder, Calucium Silicate powder, calcium carbonate, boehmite, in zinc borate and the mica one or more; Organic filler is selected from one or more in polytetrafluorethylepowder powder, polyphenylene sulfide and the polyethersulfone powder.

8. high-frequency circuit board that uses matrix material as claimed in claim 1 to make, it is characterized in that, it comprises: several layers of mutual superimposed prepreg and be overlaid on Copper Foil on these superimposed prepreg one or both sides, at least one prepreg made by described matrix material in these several layers of prepregs.

9. the making method of a high-frequency circuit board as claimed in claim 8 is characterized in that, comprises the steps:

Step 1, by volume per-cent provides matrix material each component: polyetherimide strongthener 10 ~ 90% and compositions of thermosetting resin 10 ~ 90%;

Step 2, compositions of thermosetting resin is mixed with glue;

Step 3, the glue dipping polyetherimide strongthener made from above-mentioned, baking obtains prepreg;

Step 4, getting above-mentioned prepreg, to count Zhang Jinhang superimposed, is covered with Copper Foil in the one or both sides of superimposed prepreg, is cured in press and makes described high-frequency circuit board, and solidification value is 150 ~ 300 ℃, solidifying pressure 5 ~ 50Kg/cm ²

10. the making method of high-frequency circuit board as claimed in claim 9 is characterized in that, described polyetherimide strongthener is polyether-imide fiber woven cloth, polyetherimide non-woven fabrics or polyetherimide glass fiber paper.