WO2025139561A1 - Modified maleimide prepolymer, and resin composition and use thereof - Google Patents

Abstract

Disclosed in the present application are a modified maleimide prepolymer, and a resin composition and the use thereof. The modified maleimide prepolymer is prepared by reacting a maleimide resin, a modifier and a sulfhydryl compound, wherein the weight ratio of the maleimide resin to the modifier to the sulfhydryl compound is 100:(1-80):(0.001-5). In the present application, the reaction rate of the maleimide resin and the modifier can be effectively controlled, and a rapid increase in viscosity in the preparation process of a prepreg can be effectively inhibited; therefore, the rheological properties are improved, good heat resistance, a low CTE and a high modulus are maintained, the interlayer peel strength is obviously improved, and the resin composition is suitable for a thin package substrate.

Description

Modified maleimide prepolymer, resin composition and application thereof

This application is based on the Chinese patent application with application number CN202311804108.1 and application date December 26, 2023, and claims the priority of the Chinese patent application. The entire contents of the above patent application are hereby introduced into this application as a reference.

Technical Field

The present application belongs to the technical field of electronic materials, and relates to a modified maleimide prepolymer, a resin composition, and the application of the resin composition in a prepreg, a laminate, an insulating board, an insulating film, a circuit substrate, and an electronic device.

Background Art

With the advancement of science and technology and the development of electronic technology, portability and thinness have become the direction that electronic complete products have always been pursuing. The thinness of complete products requires that the components of electronic products, such as printed circuit boards, be as thin as possible. Therefore, the copper clad laminate substrate needs to have high rigidity and anti-warping ability to meet the structural support and processing requirements of the printed circuit board.

Among the resin materials commonly used to prepare printed circuit boards, bismaleimide is one of the more commonly used resins. It is a thermosetting resin containing a maleimide structure. Its high cross-linking density after curing gives it a high glass transition temperature, excellent thermal stability and high rigidity. It is currently one of the preferred materials for making thin packaging substrates.

However, bismaleimide monomers have defects such as high melting point, poor solubility, high curing reaction temperature, and greater brittleness of the cured resin, which limits their application in thin packaging substrates.

Summary of the invention

The present application provides a modified maleimide prepolymer, a resin composition, and the use of the resin composition in a prepreg, a laminate, an insulating board, an insulating film, a circuit substrate, and an electronic device, so as to solve the problem that the existing resin composition cannot have excellent heat resistance, low CTE, excellent dielectric properties, high peel strength, high modulus, and excellent rheological properties, so as to be suitable for thin packaging substrates.

To achieve the above application purpose, one embodiment of the present application provides a modified maleimide prepolymer obtained by reacting a maleimide resin, a modifier and a thiol compound, wherein the weight ratio of the maleimide resin, the modifier and the thiol compound is 100:(1~80):(0.001~5).

As a further improvement of one embodiment of the present application, the thiol compound is , , , , , At least one of .

As a further improvement of one embodiment of the present application, the modifier is an allyl compound, and the allyl compound is selected from at least one of diallyl bisphenol A, diallyl bisphenol S, allyl phenol oxide resin, allyl phenol formaldehyde resin and diallyl diphenyl ether.

As a further improvement of one embodiment of the present application, the modifier is at least one of an aromatic diamine compound and an aliphatic diamine compound;

The aromatic diamine compound is at least one of unsubstituted phenylenediamine, methylphenylenediamine, dimethylphenylenediamine, trimethylphenylenediamine, tetramethylphenylenediamine, xylene diamine, diaminopyridine, diaminodiphenylmethane, substituted diaminodiphenylmethane, bis[4-(4-aminophenoxy)phenyl]propane, bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, diaminobenzophenone, diaminodiphenyl ether, diaminodiphenyl sulfone, diaminobiphenyl, diaminodiphenyl sulfide, diaminonaphthalene, diaminodiphenylfluorene, and diaminoanthraquinone;

The aliphatic diamine compound is any hydrocarbon long-chain diamine compound containing C2-C36 in the molecular structure.

As a further improvement of one embodiment of the present application, the modifier is an amino silicone resin, and its structure is:

Structural formula (1), wherein R ₁ is any C1-C8 alkylene group, and n is an integer of 1 to 10.

As a further improvement of an embodiment of the present application, the modifier is a cyanate compound, and the cyanate compound is selected from at least one of a cyanate monomer and a cyanate oligomer.

As a further improvement of one embodiment of the present application, the reaction temperature during the preparation of the modified maleimide prepolymer is 60-150° C., the reaction time is 0.5-5 h, and aminophenol is not added during the preparation process.

To achieve the above application purpose, one embodiment of the present application provides a resin composition, including the modified maleimide prepolymer as described above.

As a further improvement of one embodiment of the present application, the resin composition, by weight, comprises:

100 parts by weight of the modified maleimide prepolymer;

1-80 parts by weight of cyanate resin;

Epoxy resin 0~50 parts by weight.

As a further improvement of one embodiment of the present application, the cyanate resin is selected from at least one of bisphenol A type cyanate resin, bisphenol F type cyanate resin, bisphenol S type cyanate resin, bisphenol E type cyanate resin, bisphenol M type cyanate resin, double bond-containing cyanate resin, phosphorus-containing cyanate resin, phenolic cyanate resin, biphenyl type cyanate resin, naphthalene ring type cyanate resin, and dicyclopentadiene type cyanate resin.

As a further improvement of one embodiment of the present application, the epoxy resin is selected from at least one of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol E epoxy resin, phosphorus-containing epoxy resin, o-cresol epoxy resin, bisphenol A novolac epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, triphenylmethane epoxy resin, tetraphenylethane epoxy resin, biphenyl epoxy resin, naphthalene ring epoxy resin, dicyclopentadiene epoxy resin, isocyanate epoxy resin, aralkyl linear phenolic epoxy resin, alicyclic epoxy resin, glycidyl amine epoxy resin, glycidyl ether epoxy resin, and glycidyl ester epoxy resin.

As a further improvement of one embodiment of the present application, the resin composition, by weight, comprises:

100 parts by weight of the modified maleimide prepolymer;

1-70 parts by weight of polyphenylene ether resin;

Cross-linking agent 10~70 parts by weight.

As a further improvement of one embodiment of the present application, the structure of the polyphenylene ether resin is:

Structural formula (19), m and n are integers of 1 to 15 respectively;

wherein R1, R2, R3, R4, R5, R6, R7, and R8 are each independently selected from hydrogen or methyl, X is selected from vinyl, styryl, propenyl, vinylbenzyloxy, methacryloxy, or allyl, and Y is selected from -C(CH ₃ ) ₂ -, -CH(CH ₃ )-, -CH ₂ -, or .

As a further improvement of one embodiment of the present application, the crosslinking agent is selected from at least one of divinylbenzene, bis(vinylbenzyl)ether, triallyl isocyanurate, triallyl cyanurate, di(vinylphenyl)ethane, divinylbiphenyl, and dicyclopentadiene dimethacrylate.

The present application also provides the use of the resin composition in prepregs, laminates, insulating boards, insulating films, circuit substrates and electronic devices.

Due to the application of the above-mentioned technical scheme, the present application has the following beneficial effects compared with the prior art: by adding a small amount of thiol compound in the preparation process of maleimide prepolymer, the reaction rate of maleimide resin and modifier can be well controlled, the rapid increase of viscosity in the preparation process of semi-cured sheet can be suppressed, and the rheological properties can be improved. At the same time, while maintaining excellent heat resistance, low CTE and high modulus, the interlayer peeling strength is significantly improved, the overall performance is improved, and it can be suitable for thin packaging substrates.

As used herein, the term "comprise" and variations of the term, such as "comprises", "comprised", "comprising", "including", and "containing" do not exclude other features, components, elements or steps, unless the context clearly requires otherwise.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG1 is a rheological curve diagram of Example 3 and Comparative Example 2 of the present application.

DETAILED DESCRIPTION

The technical solution of the present application is further introduced below in conjunction with specific implementation methods. The following embodiments are only descriptive and not restrictive, and the protection scope of the present application cannot be limited by them.

One embodiment of the present application provides a modified maleimide prepolymer, a resin composition, and a prepreg, a laminate, an insulating board, an insulating film, a circuit substrate and an electronic device made using the resin composition, that is, the use of the resin composition in a prepreg, a laminate, an insulating board, an insulating film, a circuit substrate and an electronic device.

First, the present application provides a modified maleimide prepolymer, which is prepared by reacting a maleimide resin, a modifier and a thiol compound, wherein the weight ratio of the maleimide resin, the modifier and the thiol compound is 100:(1~80):(0.001~5).

By adding a small amount of mercapto compounds during the preparation of maleimide prepolymers, the reaction rate of maleimide resin and modifier can be well controlled, the rapid increase of viscosity during the preparation of semi-cured sheets can be suppressed, and the rheological properties can be improved. At the same time, while maintaining excellent heat resistance, low CTE and high modulus, the interlayer peel strength is significantly improved, thereby improving the overall performance.

Preferably, the thiol compound is , , , , , At least one of .

More preferably, the thiol compound is or .

Preferably, the weight ratio of the maleimide resin, the modifier and the mercapto compound is 100:(1-80):(0.1-3).

As an optional solution, the modifier is an allyl compound, that is, the modifier contains at least one allyl group. The allyl compound is preferably at least one selected from diallyl bisphenol A, diallyl bisphenol S, allyl phenol oxide resin, allyl phenol formaldehyde resin and diallyl diphenyl ether.

Preferably, the modifier is at least one of an aromatic diamine compound and an aliphatic diamine compound.

The aromatic diamine compound is preferably at least one selected from unsubstituted phenylenediamine, methylphenylenediamine, dimethylphenylenediamine, trimethylphenylenediamine, tetramethylphenylenediamine, xylene diamine, diaminopyridine, diaminodiphenylmethane, substituted diaminodiphenylmethane, bis[4-(4-aminophenoxy)phenyl]propane, bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, diaminobenzophenone, diaminodiphenyl ether, diaminodiphenyl sulfone, diaminobiphenyl, diaminodiphenyl sulfide, diaminonaphthalene, diaminodiphenylfluorene, and diaminoanthraquinone;

The aliphatic diamine compound is preferably selected from any hydrocarbon long-chain diamine compound containing C2-C36 in the molecular structure; more preferably dimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine or decamethylenediamine.

As an optional solution, the modifier is an amino silicone resin, and its structure is:

Structural formula (1), wherein R ₁ is any C1-C8 alkylene group, and n is an integer of 1 to 10.

The amino silicone resin can be selected from X-22-161A, X-22-161B, KF-8010, KF-8012 manufactured by Shin-Etsu Chemical, and DOWSIL™ BY 16-853U and DOWSIL™ BY 16-871 manufactured by Dow Corning.

As an optional solution, the modifier is a cyanate compound, and the cyanate compound is preferably at least one selected from cyanate monomers and cyanate oligomers.

The cyanate ester compound is preferably selected from at least one of bisphenol A type cyanate ester resin, bisphenol F type cyanate ester resin, bisphenol S type cyanate ester resin, bisphenol E type cyanate ester resin, bisphenol M type cyanate ester resin, double bond-containing cyanate ester resin, phosphorus-containing cyanate ester resin, phenolic cyanate ester resin, biphenyl type cyanate ester resin, naphthalene ring type cyanate ester resin, and dicyclopentadiene type cyanate ester resin.

Preferably, the cyanate ester compound is at least one of a naphthalene ring type cyanate ester resin and a phenolic type cyanate ester resin;

The structural formula of the naphthalene ring type cyanate resin is:

Structural formula (2), R ₆ is hydrogen, methyl or ethyl, n ₂ is an integer from 1 to 10;

The structural formula of the phenolic cyanate ester resin is:

Structural formula (3), n is an integer from 1 to 10.

Furthermore, the weight ratio of the maleimide resin, the modifier and the mercapto compound is 100:(1-50):(0.01-3).

Furthermore, the reaction temperature during the preparation of the modified maleimide prepolymer is 60-150° C., the reaction time is 0.5-5 h, and no aminophenol is added during the preparation process.

Specifically, the preparation methods of the modified maleimide prepolymer include the following three methods:

Method 1) 100 parts by weight of maleimide resin, 1 to 80 parts by weight of a modifier and 0.001 to 5 parts by weight of a mercapto compound are reacted at 60 to 150° C. for 0.5 to 5 hours to prepare a modified maleimide prepolymer, and no aminophenol is added during the preparation process.

Method 2) First, 100 parts by weight of maleimide resin and 0.001-5 parts by weight of mercapto compound are reacted at 60-150° C. for 0.5-3 hours, and then 1-80 parts by weight of modifier are added and the reaction is continued at the same temperature for 0.5-2 hours to obtain a modified maleimide prepolymer, and aminophenol is not added during the preparation process.

Method 3) First, 100 parts by weight of maleimide resin and 1-80 parts by weight of modifier are reacted at 60-150° C. for 0.5-3 hours, and then 0.001-5 parts by weight of mercapto compound are added and the reaction is continued for 0.5-2 hours at the same temperature to obtain a modified maleimide prepolymer, and aminophenol is not added during the preparation process.

The maleimide resin is preferably at least one of the following structures:

Structural formula (4);

Structural formula (5);

Structural formula (6);

Structural formula (7), _R1 is methylene, ethylene or , R ₂ is hydrogen, methyl or ethyl, and n is an integer from 1 to 10;

Structural formula (8);

Structural formula (9), n is an integer from 1 to 10;

Structural formula (10), n is an integer from 1 to 10;

Structural formula (11), n is an integer from 1 to 10;

Structural formula (12);

In the structural formula (13), R is hydrogen, methyl or ethyl, and n is an integer of 1 to 10.

The present application also provides a resin composition, comprising the modified maleimide prepolymer as described above.

Furthermore, the present application also provides a resin composition, comprising, by weight:

100 parts by weight of the modified maleimide prepolymer as described above;

1-80 parts by weight of cyanate resin;

Epoxy resin 0~50 parts by weight.

The cyanate resin is preferably selected from at least one of bisphenol A cyanate resin, bisphenol F cyanate resin, bisphenol S cyanate resin, bisphenol E cyanate resin, bisphenol M cyanate resin, double bond-containing cyanate resin, phosphorus-containing cyanate resin, phenolic cyanate resin, biphenyl cyanate resin, naphthalene ring cyanate resin and dicyclopentadiene cyanate resin.

More preferably, the cyanate resin is at least one of a naphthalene ring type cyanate resin and a phenolic type cyanate resin;

The structural formula of the naphthalene ring type cyanate resin is:

Structural formula (2), R ₆ is hydrogen, methyl or ethyl, n ₂ is an integer from 1 to 10;

The structural formula of the phenolic cyanate ester resin is:

Structural formula (3), n is an integer from 1 to 10.

The epoxy resin is preferably selected from at least one of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol E epoxy resin, phosphorus-containing epoxy resin, o-cresol epoxy resin, bisphenol A novolac epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, triphenylmethane epoxy resin, tetraphenylethane epoxy resin, biphenyl epoxy resin, naphthalene ring epoxy resin, dicyclopentadiene epoxy resin, isocyanate epoxy resin, aralkyl linear phenolic epoxy resin, alicyclic epoxy resin, glycidyl amine epoxy resin, glycidyl ether epoxy resin, and glycidyl ester epoxy resin.

More preferably, the epoxy resin is at least one of the following structures:

Structural formula (14), p is an integer from 1 to 10;

Structural formula (15), n is an integer from 1 to 10;

Structural formula (16), m is an integer from 1 to 10;

Structural formula (17), n is an integer from 1 to 10;

Structural formula (18), n is an integer from 1 to 10.

Furthermore, the present application also provides a resin composition, comprising, by weight:

100 parts by weight of the modified maleimide prepolymer as described above;

1-70 parts by weight of polyphenylene ether resin;

Cross-linking agent 10~70 parts by weight.

Preferably, the structure of the polyphenylene ether resin is:

Structural formula (19), m and n are integers of 1 to 15 respectively;

wherein R1, R2, R3, R4, R5, R6, R7, and R8 are each independently selected from hydrogen or methyl, X is selected from vinyl, styryl, propenyl, vinylbenzyloxy, methacryloxy, or allyl, and Y is selected from -C(CH ₃ ) ₂ -, -CH(CH ₃ )-, -CH ₂ -, or .

Preferably, the polyphenylene ether resin can be selected from SA-9000 manufactured by Sabic, which is a modified polyphenylene ether resin terminated with a methacryloyl group, that is, X in the structural formula (19) is a methacryloyloxy group; the polyphenylene ether resin can also be selected from OPE-2ST manufactured by Mitsubishi Chemical, which is a modified polyphenylene ether resin terminated with a styrene group, that is, X in the structural formula (19) is a vinylbenzyloxy group.

The number average molecular weight of the polyphenylene ether resin is preferably 1000-4000 g/mol; more preferably 1500 g/mol, 2000 g/mol, 2500 g/mol, 3000 g/mol or 3500 g/mol.

The crosslinking agent is preferably at least one selected from divinylbenzene, bis(vinylbenzyl)ether, triallyl isocyanurate, triallyl cyanurate, di(vinylphenyl)ethane, divinylbiphenyl, and dicyclopentadiene dimethacrylate.

More preferably, the crosslinking agent is triallyl isocyanurate, dicyclopentadiene dimethacrylate or a combination thereof.

Among them, the structural formula of triallyl isocyanurate (TAIC) is

Structural formula (20).

The structural formula of dicyclopentadiene dimethacrylate (also known as DCP) is

Structural formula (21).

Furthermore, the resin composition further comprises 1 to 50 parts by weight of an elastomer, which is preferably at least one selected from styrene elastomers, methacrylate elastomers, and silicone elastomers.

Specifically, the styrene elastomer can be selected from H1041, H1043, H1051, H1052, H1053, H1221, P1500, P2000, M1911 or M1913 manufactured by Asahi Kasei Corporation; 8004, 8006, 8076, 8104, V9827, 2002, 2005, 2006, 2007, 2104, 7125, 4033, 4044, 4055, 4077 or 4099 manufactured by Kuraray.

The methacrylates may be selected from M51, M52, M22 or D51N manufactured by Arkema; LA-2330 manufactured by Kuraray; and SG-P3 series or SG-80 series manufactured by Nagase.

Silicone elastomers can be selected from X-40-2670, R-170S, X-40-2705, X-40-2701, KMP-600, KMP-605, X-52-7030 manufactured by Shin-Etsu Chemical Co., Ltd.; AY-42-119, EP-2600, EP-2601, EP-2720, TMS-2670, EXL-2315, EXL-2655 manufactured by DOW.

Furthermore, the resin composition further comprises 5 to 50 parts by weight of a flame retardant, wherein the flame retardant is preferably at least one selected from the group consisting of a bromine flame retardant, a phosphorus flame retardant, a nitrogen flame retardant, an organosilicon flame retardant, and an organometallic salt flame retardant.

Preferably, the brominated flame retardant is selected from decabromodiphenyl ether, decabromodiphenyl ethane, brominated styrene or tetrabromophthalamide;

The phosphorus-based flame retardant is selected from inorganic phosphorus, phosphate ester, phosphoric acid, hypophosphorous acid, phosphorus oxide, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, (m is an integer from 1 to 5), , 10-phenyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, tris(2,6-dimethylphenyl)phosphine, phosphazene, modified phosphazene.

Among them, DOPO group is .

Furthermore, the resin composition further comprises 0.01 to 5 parts by weight of a catalyst, wherein the catalyst is at least one of an imidazole catalyst, a pyridine catalyst, and an organic metal salt catalyst.

Preferably, the catalyst is selected from at least one of 4-dimethylaminopyridine, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, modified imidazole and zinc octoate.

Furthermore, the resin composition further comprises 10 to 250 parts by weight of a filler, wherein the filler is selected from at least one of an inorganic filler, an organic filler, and a composite filler.

The inorganic filler is preferably selected from at least one of fused silica, crystalline silica, spherical silica, hollow silica, aluminum hydroxide, aluminum oxide, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate, mica, and glass fiber powder; the organic filler is selected from at least one of polytetrafluoroethylene powder, polyphenylene sulfide, and polyether sulfone powder. The inorganic filler is more preferably selected from spherical silica, aluminum oxide, or aluminum hydroxide.

More preferably, the filler is pre-surface treated with a silane coupling agent, and the silane coupling agent is at least one of an aminosilane coupling agent, a carbon-carbon double bond-containing silane coupling agent, and an epoxy silane coupling agent.

Preferably, the silane coupling agent is selected from the following structures:

Structural formula (20);

Structural formula (21);

Structural formula (22).

The present application also provides the use of the above resin composition in prepregs, laminates, insulating boards, insulating films, circuit substrates and electronic devices, which are specifically described as follows:

The present application also provides a prepreg, comprising a reinforcing material and the aforementioned resin composition, wherein the resin composition is wrapped on the reinforcing material.

The preparation method of the semi-cured sheet is as follows: the resin composition is dissolved in a solvent to prepare a glue solution, and then the reinforcing material is immersed in the glue solution, and the immersed reinforcing material is taken out and baked at a temperature of 100-180° C. for 1-15 minutes; after drying, the semi-cured sheet can be obtained.

The solvent may be selected from at least one of acetone, butanone, methyl isobutyl ketone, N,N-dimethylformamide, N,N-dimethylacetamide, ethylene glycol methyl ether, propylene glycol methyl ether, benzene, toluene, xylene and cyclohexane.

The reinforcing material can be selected from at least one of natural fibers, organic synthetic fibers, organic fabrics, and inorganic fabrics, preferably glass fiber cloth, more preferably E glass fiber cloth, S glass fiber cloth, T glass fiber cloth, or Q glass fiber cloth. The glass fiber cloth is preferably open fiber cloth or flat cloth.

In addition, when the reinforcing material is glass fiber cloth, the glass fiber cloth is chemically treated with a coupling agent in advance to improve the interface bonding between the resin composition and the glass fiber cloth. The coupling agent is preferably an epoxy silane coupling agent or an amino silane coupling agent to make the reinforcing material have good water resistance and heat resistance.

The present application also provides a laminate, comprising a piece of the aforementioned prepreg and a metal foil arranged on at least one side of the surface of the prepreg; or comprising a composite sheet formed by overlapping multiple pieces of the aforementioned prepreg and a metal foil arranged on at least one side of the surface of the composite sheet.

The preparation method of the laminate is: a metal foil is coated on one side or both sides of a prepreg, or at least two prepregs are stacked to form a composite sheet, a metal foil is coated on one side or both sides of the composite sheet, and a metal foil laminate is obtained by hot pressing. The pressing conditions of the hot pressing are: a pressure of 0.2-2MPa, a temperature of 150-250°C, and a pressing time of 2-4h. The metal foil is selected from copper foil or aluminum foil, and the thickness is 5μm, 8μm, 12μm, 18μm, 35μm or 70μm.

The present application also provides an insulating board, comprising at least one of the aforementioned prepreg sheets.

The present application also provides an insulating film, including a carrier film and the aforementioned resin composition coated thereon, and the heat resistance of the insulating film is significantly improved.

The preparation method of the insulating film is as follows: the resin composition is dissolved in a solvent to prepare a glue solution, the glue solution is then coated on a carrier film, and the carrier film coated with the glue solution is heated and dried to obtain the insulating film.

The solvent is selected from at least one of acetone, butanone, methyl isobutyl ketone, N,N-dimethylformamide, N,N-dimethylacetamide, ethylene glycol methyl ether, propylene glycol methyl ether, benzene, toluene, xylene and cyclohexane.

The carrier film is selected from at least one of PET film, PP film, PE film and PVC film.

The present application also provides a circuit substrate, comprising at least one of the aforementioned prepreg and laminate.

The present application also provides an electronic device, comprising the aforementioned circuit substrate.

The technical scheme of the present application is further described below in conjunction with some specific synthesis examples, embodiments and comparative examples. Of course, these embodiments are only a part of the many variations of the embodiments of the present application, but not all.

Synthesis example 1

100 g of maleimide resin, 50 g of modifier, 1.8 g of mercapto compound and an appropriate amount of butanone solvent were added into a beaker, and the mixture was reacted at 110° C. for 90 min to obtain prepolymer A.

The maleimide resin is BMI-2300 manufactured by Yamato Chemical Industry Co., Ltd., the modifier is diallyl bisphenol A compound, and the mercapto compound is p-aminomercaptobenzene.

Synthesis example 2

100 g of maleimide resin, 50 g of modifier, 2.4 g of mercapto compound and an appropriate amount of butanone solvent were added into a beaker, and the mixture was reacted at 125° C. for 110 min to obtain prepolymer B.

The maleimide resin is KI-80 produced by KI Chemical, the modifier is 4,4'-diaminodiphenylmethane compound, and the mercapto compound is p-mercaptophenol.

Synthesis example 3

100 g of maleimide resin, 40 g of modifier, 3 g of mercapto compound and an appropriate amount of butanone solvent were added into a beaker, and reacted at 100° C. for 120 min to obtain prepolymer C.

The maleimide resin is KI-80 manufactured by KI Chemical; the modifier is amino silicone resin, specifically X-22-161B manufactured by Shin-Etsu Chemical; and the mercapto compound is p-aminomercaptobenzene.

Synthesis example 4

100 g of maleimide resin, 1.8 g of mercapto compound and an appropriate amount of butanone solvent were added to a beaker, and the mixture was reacted at 110° C. for 30 min. Then, 50 g of a modifier was added and the mixture was reacted at 110° C. for 60 min to obtain prepolymer D.

The maleimide resin is BMI-2300 manufactured by Yamato Chemical Industry Co., Ltd., the modifier is diallyl bisphenol A compound, and the mercapto compound is p-aminomercaptobenzene.

Synthesis example 5

100 g of maleimide resin, 50 g of modifier, 2.4 g of mercapto compound and an appropriate amount of butanone solvent were added into a beaker, and the mixture was reacted at 125° C. for 110 min to obtain prepolymer E.

The maleimide resin is KI-80 produced by KI Chemical, 50g of the modifier includes 30g of 4,4'-diaminodiphenylmethane compound and 20g of hexamethylenediamine compound, and the mercapto compound is p-mercaptophenol.

Comparative Synthesis Example 1

100 g of maleimide resin, 50 g of 4,4'-diaminodiphenylmethane compound and an appropriate amount of butanone solvent were added into a beaker, and the mixture was reacted at 125° C. for 110 min to obtain prepolymer F.

The maleimide resin used is KI-80 produced by KI Chemical.

Comparative Synthesis Example 2

100 g of maleimide resin, 40 g of amino silicone resin, 3 g of p-aminophenol and an appropriate amount of butanone solvent were added into a beaker and reacted at 100° C. for 120 min to obtain prepolymer G.

The maleimide resin used was KI-80 manufactured by KI Chemical, and the amino silicone resin used was X-22-161B manufactured by Shin-Etsu Chemical.

Comparative Synthesis Example 3

100 g of maleimide resin, 50 g of diallyl bisphenol A compound and an appropriate amount of butanone solvent were added into a beaker, and the mixture was reacted at 110° C. for 90 min to obtain prepolymer H.

The maleimide resin used was BMI-2300 manufactured by Yamato Chemical.

Example

The chemical components and contents of the resin compositions of Examples 1 to 7 and Comparative Examples 1 to 3 are shown in Table 1.

Table 1

Among them, the cyanate resin is DCPD type made by Tianqi, the epoxy resin is HP-4700 made by DIC, the polyphenylene ether resin is SA-9000 made by Sabic, the cross-linking agent is triallyl isocyanurate (also known as TAIC), the filler is spherical silica, and the catalyst is 2-methylimidazole.

The above-mentioned embodiment and comparative example also disclose a prepreg, comprising glass fiber cloth as a reinforcing material and a resin composition coated on the glass fiber cloth by an impregnation method, wherein the glass fiber cloth is a fiber-spreading cloth pre-treated with an epoxy silane coupling agent.

Specifically, the components of the resin compositions of Examples 1 to 7 and Comparative Examples 1 to 3 in Table 1 were dissolved in butanone, stirred and mixed, and then diluted to a glue solution with a solid content of 65 wt %; the T glass fiber cloth used as a reinforcing material was pretreated with an epoxy silane coupling agent, immersed in the above glue solution, taken out after infiltration, placed in a blast drying oven at 160° C., and baked for 3 to 6 minutes to obtain a prepreg.

The above embodiments and comparative examples also disclose a laminate, which is prepared by the following method:

The above-mentioned semi-cured sheet was cut into 300×300 mm and stacked into a certain stacking structure. Then, a low-profile electrolytic copper foil with a thickness of 12 μm was placed on both sides of the combined sheet, placed in a vacuum hot press, and hot pressed for 1.5 h at a pressure of 1.5 MPa and a temperature of 220°C to obtain a copper-clad laminate.

The above-mentioned embodiments and comparative examples also disclose an insulating board, comprising at least one of the above-mentioned prepreg sheets.

The above-mentioned embodiments and comparative examples also disclose an insulating film, comprising a carrier film and the above-mentioned resin composition coated thereon,

The above-mentioned embodiment and comparative example also disclose a circuit substrate, including a prepreg sheet mentioned above, which is prepared by a conventional preparation method in the prior art, and will not be described in detail here.

The copper-clad laminates obtained in Examples 1 to 7 and Comparative Examples 1 to 3 were subjected to performance testing, and the test results are shown in Table 2. The performance testing method includes:

(1) Glass transition temperature (Tg): The DMA (thermomechanical analysis) method was used to test the dynamic mechanical properties of the steel using a dynamic mechanical properties tester (TA DMA Q800, USA) in accordance with the method specified in IPC-TM-650 2.4.25. The heating rate was 10°C/min and the atmosphere was nitrogen.

(2) PCT water absorption: The water absorption rate was determined according to the method of IPC-TM-6502.6.2.1. Specifically, three samples with a length × width of 10 cm × 10 cm and a thickness of 0.8 mm were taken, and the electrolytic copper foil on both sides was removed. The samples were dried at 120°C for 2 h and weighed. The weight was recorded as W ₁ . The samples were then treated in a pressure cooker at 121°C and 2 atmospheres for 7 h. After the free water on the surface was absorbed, the samples were placed in a desiccator for cooling and then weighed. The weight was recorded as W ₂ . The water absorption rate was determined to be (W ₂ -W ₁ )/W ₁ × 100%.

(3) X/Y-axis thermal expansion coefficient (CTE): The TMA method was used to measure the CTE in accordance with IPC-TM-650 method. The heating rate was 10°C/min and the test temperature range was 30-100°C. The rheological curves of Example 3 and Comparative Example 2 are shown in FIG1 .

(4) Dk and Df: The dielectric constant Dk and dielectric loss Df at 10 GHz were measured using the plate method in accordance with IPC-TM-650 2.5.5.9.

(5) Peel strength (PS): The peel strength of the copper foil layer of the laminate was tested according to the "after thermal stress" experimental conditions in IPC-TM-650 2.4.8 method.

(6) Modulus: Measured according to the DMA method specified in IPC-TM-650 2.4.24.4.

Table 2

Referring to Table 2, compared with the comparative example, the copper-clad laminate further prepared from the resin composition of the embodiment of the present application not only has excellent heat resistance, low CTE, and high modulus, but also has better peel strength, lower dielectric constant and dielectric loss value, and can be suitable for thin packaging substrates.

In addition, referring to FIG. 1 , it can be seen that compared with Comparative Example 2, Example 3 has a lower minimum melt viscosity and a wider rheological window, which indicates that Example 3 has a slower reactivity and better wettability during high-temperature lamination.

It should be understood that although this specification is described according to implementation modes, not every implementation mode contains only one independent technical solution. This description of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each implementation mode may also be appropriately combined to form other implementation modes that can be understood by those skilled in the art.

The detailed descriptions listed above are merely specific descriptions of feasible implementation methods of the present application. They are not intended to limit the scope of protection of the present application. Any equivalent implementation methods or changes that do not deviate from the technical spirit of the present application should be included in the scope of protection of the present application.

Claims (15)

A modified maleimide prepolymer is characterized in that it is prepared by reacting a maleimide resin, a modifier and a thiol compound, wherein the weight ratio of the maleimide resin, the modifier and the thiol compound is 100:(1-80):(0.001-5). The modified maleimide prepolymer according to claim 1, characterized in that the thiol compound is , , , , , At least one of . The modified maleimide prepolymer according to claim 1, characterized in that the modifier is an allyl compound, and the allyl compound is selected from at least one of diallyl bisphenol A, diallyl bisphenol S, allyl phenol oxide resin, allyl phenol formaldehyde resin and diallyl diphenyl ether. The modified maleimide prepolymer according to claim 1, characterized in that the modifier is at least one of an aromatic diamine compound and an aliphatic diamine compound; The aromatic diamine compound is at least one of unsubstituted phenylenediamine, methylphenylenediamine, dimethylphenylenediamine, trimethylphenylenediamine, tetramethylphenylenediamine, xylene diamine, diaminopyridine, diaminodiphenylmethane, substituted diaminodiphenylmethane, bis[4-(4-aminophenoxy)phenyl]propane, bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, diaminobenzophenone, diaminodiphenyl ether, diaminodiphenyl sulfone, diaminobiphenyl, diaminodiphenyl sulfide, diaminonaphthalene, diaminodiphenylfluorene, and diaminoanthraquinone; The aliphatic diamine compound is a hydrocarbon long-chain diamine compound containing any one of C2-C36 in its molecular structure. The modified maleimide prepolymer according to claim 1, characterized in that the modifier is an amino silicone resin, and its structure is: Structural formula (1), wherein R ₁ is any one of C1-C8 alkylene groups, and n is an integer of 1 to 10. The modified maleimide prepolymer according to claim 1, characterized in that the modifier is a cyanate compound, and the cyanate compound is selected from at least one of a cyanate monomer and a cyanate oligomer. The modified maleimide prepolymer according to claim 1, characterized in that the reaction temperature during the preparation of the modified maleimide prepolymer is 60-150° C., the reaction time is 0.5-5 h, and aminophenol is not added during the preparation process. A resin composition, characterized in that it comprises the modified maleimide prepolymer according to any one of claims 1 to 7. The resin composition according to claim 8, characterized in that it comprises, by weight: 100 parts by weight of the modified maleimide prepolymer; 1-80 parts by weight of cyanate resin; Epoxy resin 0~50 parts by weight. The resin composition according to claim 9 is characterized in that the cyanate resin is selected from at least one of bisphenol A type cyanate resin, bisphenol F type cyanate resin, bisphenol S type cyanate resin, bisphenol E type cyanate resin, bisphenol M type cyanate resin, double bond-containing cyanate resin, phosphorus-containing cyanate resin, phenolic cyanate resin, biphenyl type cyanate resin, naphthalene ring type cyanate resin, and dicyclopentadiene type cyanate resin. The resin composition according to claim 9 is characterized in that the epoxy resin is selected from at least one of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol E epoxy resin, phosphorus-containing epoxy resin, o-cresol epoxy resin, bisphenol A novolac epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, triphenylmethane epoxy resin, tetraphenylethane epoxy resin, biphenyl epoxy resin, naphthalene ring epoxy resin, dicyclopentadiene epoxy resin, isocyanate epoxy resin, aralkyl linear phenolic epoxy resin, alicyclic epoxy resin, glycidyl amine epoxy resin, glycidyl ether epoxy resin, and glycidyl ester epoxy resin. The resin composition according to claim 8, characterized in that it comprises, by weight: 100 parts by weight of the modified maleimide prepolymer; 1-70 parts by weight of polyphenylene ether resin; Cross-linking agent 10~70 parts by weight. The resin composition according to claim 12, characterized in that the structure of the polyphenylene ether resin is: Structural formula (19), m and n are integers of 1 to 15 respectively; wherein R1, R2, R3, R4, R5, R6, R7, and R8 are each independently selected from hydrogen or methyl, X is selected from vinyl, styryl, propenyl, vinylbenzyloxy, methacryloxy, or allyl, and Y is selected from -C(CH ₃ ) ₂ -, -CH(CH ₃ )-, -CH ₂ -, or . The resin composition according to claim 12, characterized in that the crosslinking agent is selected from at least one of divinylbenzene, bis(vinylbenzyl)ether, triallyl isocyanurate, triallyl cyanurate, di(vinylphenyl)ethane, divinylbiphenyl, and dicyclopentadiene dimethacrylate. A use of the resin composition as claimed in any one of claims 8 to 14 in prepregs, laminates, insulating boards, insulating films, circuit substrates and electronic devices.