Polyimides and methods of making, compositions thereof

Abstract

The present application relates to the technical field of organic synthesis, and particularly provides a polyimide and a preparation method and a composition thereof.The polyimide of the present application is shown as formula 1, wherein n is an integer of 10-100; A is selected from one or more of substituted or unsubstituted aromatic hydrocarbon groups, saturated or unsaturated aliphatic groups; R1 is selected from one or more of hydrogen, alkyl, cycloalkyl, aryl; and R is selected from one or more of substituted or unsubstituted aromatic hydrocarbon groups, saturated or unsaturated aliphatic groups.The present application adopts an anhydride containing a terminal carboxyl structure, and terminates the polyimide to form an oligomer prepolymer containing a carboxyl group, and then introduces a polyphenyl ether containing a terminal hydroxyl group to form an ester group structure, so as to obtain a polyester imide.The material has a lower dielectric constant and higher adhesion, and the polyimide is applied to a thermoplastic polyimide (TPI), so that the pressure bonding temperature is lower.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of organic synthesis, and more particularly to a polyimide and a preparation method, composition thereof. BACKGROUND

[0002] The advent of the 5G high-frequency communication era provides a rare opportunity for the development of polymer dielectric materials. Low dielectricity has become one of the most active research directions in the field of basic and applied research of polymer materials. Low dielectric polymer materials themselves contain high technical content and added value. Foreign countries attach great importance to the basic and applied research of such materials, and have realized the commercialization of various materials. In particular, Japanese enterprises currently occupy the commanding point of the high-frequency, low-dielectric FCCL related industry chain from raw materials to products, and have formed a relatively strict intellectual property protection network.

[0003] The conventional PI film is mainly used as a coverlay and a flexible substrate in the existing three-layer FCCL, and the conventional epoxy resin and acrylic resin are used as adhesives. The conventional PI and thermoplastic PI are mainly used to prepare a two-layer FCCL. The above-mentioned conventional materials often produce high signal loss in 5G high-frequency signal transmission, and therefore are difficult to meet the application requirements. SUMMARY

[0004] Therefore, the purpose of the present application is to provide a polyimide and a preparation method and composition thereof. The present application uses an anhydride containing a terminal carboxyl group to cap the polyimide to form an oligomer prepolymer containing a carboxyl group, and then introduces a polyphenyl ether containing a terminal hydroxyl group to form an ester group, thereby obtaining a polyester imide. The material has a lower dielectric constant and higher adhesion. The polyimide is applied to thermoplastic polyimide (TPI), and the pressure bonding temperature is lower.

[0005] In order to achieve the above-mentioned purpose, the present application adopts the following technical solutions:

[0006] a polyimide as shown in Formula 1,

[0007]

[0008] In Formula 1, n is an integer of 10-100; n 11 is an integer of 1-40; m is an integer of 0-4;

[0009] A is selected from one or more of a substituted or unsubstituted aromatic hydrocarbon group, a saturated or unsaturated aliphatic group;

[0010] R1 is selected from one or more of hydrogen, an alkyl group, a cycloalkyl group, and an aryl group;

[0011] R is selected from one or more of substituted or unsubstituted aromatic hydrocarbon groups, saturated or unsaturated aliphatic groups;

[0012] Z1, Z2 are independently selected from one or more of hydrogen, substituted or unsubstituted alkyl groups, substituted or unsubstituted cycloalkyl groups, substituted or unsubstituted aryl groups.

[0013] In the formula 1 of the present application, n 11 is an integer of 1 to 20; m is 2 or 3;

[0014] A is selected from substituted or unsubstituted C6 to C40 aryl groups, substituted or unsubstituted C3 to C20 aliphatic rings;

[0015] R1 is selected from hydrogen, C1 to C10 saturated aliphatic hydrocarbon groups, preferably hydrogen;

[0016] R is selected from substituted or unsubstituted C6 to C40 aryl groups, substituted or unsubstituted C3 to C20 aliphatic rings;

[0017] Z1, Z2 are independently selected from one or more of hydrogen, C1 to C6 alkyl groups, C1 to C6 cycloalkyl groups, C6 to C10 aryl groups; Z1, Z2 are preferably hydrogen.

[0018] In some embodiments of the present application, the polyimide is specifically

[0019]

[0020] The above polyimide, n 11 is an integer of 1 to 20, the sum of n1 and n2 is 10 to 100; the glass transition temperature is about 40°C to 140°C, and the weight average molecular weight (by gel permeation chromatography) is 100 or more and less than 1000.

[0021] The present application also provides a method for preparing the above polyimide, comprising:

[0022] (1) mixing a diamine represented by formula 2 and a diacid anhydride represented by formula 3 to perform an amidation reaction, and then mixing with an acid anhydride represented by formula 4 to form a compound represented by formula 5;

[0023] NH2-R-NH2

[0024] Formula 2;

[0025] In formula 2, R is selected from one or more of substituted or unsubstituted aromatic hydrocarbon groups, saturated or unsaturated aliphatic groups;

[0026]

[0027] In formula 3, A is selected from one or more of substituted or unsubstituted aromatic hydrocarbon groups, saturated or unsaturated aliphatic groups.

[0028]

[0029] In formula 4, Z is selected from one or more of hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl;

[0030]

[0031] In formula 5, n is an integer of 10 to 100;

[0032] A is selected from one or more of substituted or unsubstituted aromatic hydrocarbon group, saturated or unsaturated aliphatic group;

[0033] R is selected from one or more of substituted or unsubstituted aromatic hydrocarbon group, saturated or unsaturated aliphatic group;

[0034] Z1, Z2 are independently selected from one or more of hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl;

[0035] (2) mixing and reacting the compound shown in formula 5 with the compound shown in formula 6 to obtain a polyimide;

[0036]

[0037] In formula 6, n 11 is an integer of 1 to 40; m is an integer of 0 to 4; R1 is selected from one or more of hydrogen, alkyl, cycloalkyl, aryl.

[0038] In formula 5 of the present application, A is selected from substituted or unsubstituted C6 to C40 aryl, substituted or unsubstituted C3 to C20 aliphatic ring.

[0039] R is selected from substituted or unsubstituted C6 to C40 aryl, substituted or unsubstituted C3 to C20 aliphatic ring.

[0040] Z1, Z2 are independently selected from one or more of hydrogen, C1 to C6 alkyl, C1 to C6 cycloalkyl, C6 to C10 aryl, and Z1, Z2 are preferably hydrogen.

[0041] In formula 4 of the present application, Z is preferably hydrogen; the acid anhydride shown in formula 4 is preferably trimellitic anhydride.

[0042] In formula 6 of the present application, n 11 is an integer of 1 to 20; m is preferably 2; R1 is selected from C1 to C10 saturated aliphatic group; R1 is preferably hydrogen; the compound shown in formula 6 is preferably n 11is an integer of 1 to 20; preferably, the compound represented by Formula 6 is a polyphenyl ether having a molecular weight of 840 to 10,000 g / mol.

[0043] In the present application, various known dianhydrides can be used as the polymerization monomer dianhydride for preparing the polyimide.

[0044] Specifically, the dianhydride can be exemplified by, for example, pyromellitic dianhydride, 3,4,3',4'-biphenyl tetracarboxylic dianhydride, 2,3,3',4'-biphenyl tetracarboxylic dianhydride, 2,3,2',3'-biphenyl tetracarboxylic dianhydride, 3,4,3',4'-benzophenone tetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 3,4,3',4'-diphenyl ether tetracarboxylic dianhydride, 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, 3,4,3',4'-diphenyl sulfone tetracarboxylic dianhydride, 2,3,3',4'-diphenyl sulfone tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)phenyl dianhydride, 1,3-bis(3,4-dicarboxyphenoxy)phenyl dianhydride, 3,4-dicarboxybenzoic acid-(3,4-dicarboxyphenol) ester dianhydride, and 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, etc. aromatic dianhydrides; fluorine-containing aromatic dianhydrides such as 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride; alicyclic structure-containing dianhydrides such as cyclohexane tetracarboxylic dianhydride, cyclobutane tetracarboxylic dianhydride; and combinations of two or more of the above.

[0045] In the present application, various known dianhydrides can be used as the polymerization monomer dianhydride for preparing the polyimide.

[0046] In the present application, various known dianhydrides can be used as the polymerization monomer dianhydride for preparing the polyimide.

[0047] In the present application, various known dianhydrides can be used as the polymerization monomer dianhydride for preparing the polyimide.

[0048] For example, aliphatic diamines such as diaminocyclohexane, isophorone diamine, diaminodicyclohexylmethane, diaminodicyclohexylether, 1,3- adamantanediamine, 1,3-bisaminomethylcyclohexane, dimethyldiaminodicyclohexylmethane, tetramethyldiaminodicyclohexylmethane, diaminodicyclohexylpropane, diaminodicyclo[2.2.1]heptane, diaminodicyclo[2.2.2]octane, bis(aminomethyl)-dicyclo[2.2.1]heptane, and the like, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylbenzophenone, 3,4'-diaminodiphenylbenzophenone, 3,3'-diaminodiphenylbenzophenone, 2,2-bis(4-aminophenyl)propane, 2,2-bis(3-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[(4-aminophenoxy)phenyl]hexafluoropropane, 1,4-bis(3-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,2-di(4-aminophenyl)ethane, 1,2-di(4-aminophenyl)ethene, 1,4-bis(3-aminobenzoyl)benzene, 1,3-bis(3-aminobenzoyl)benzene, 4,4'-diamino-3,3'-dimethylbiphenyl, 4,4'-diamino-2,2'-dimethylbiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 4,4'-bis(3-aminophenoxy)biphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(3-aminophenoxy)phenyl]ether, bis[4-(4-aminophenoxy)phenyl]ether, and the like, aromatic diamines or fluorine-containing aromatic diamines. Aliphatic chain diamines such as ethylenediamine, propylenediamine, butylenediamine, pentanediamine, hexanediamine, octanediamine, polyether amine, and the like.

[0049] In the embodiments of the present application, the diamine is preferably one or more of diaminocyclohexane, isophorone diamine, diaminodicyclohexylmethane, 1,3-bisaminomethylcyclohexane, dimethyldiaminodicyclohexylmethane, diaminodicyclohexylpropane.

[0050] In the present application, the molar ratio of the diamine and the acid anhydride represented by Formula 4 is (0.1-55): 1, preferably (0.9-1.2): 1, more preferably 1.05: 1, 1.03: 1, 0.9: 1, 1.04: 1, 1: 1, 1.15: 1, 1.1: 1, or 1.17: 1.

[0051] The molar ratio of the diamine to the diacid anhydride is (100-115):100, preferably (101-115):100, and more preferably (103-108):100;

[0052] The molar ratio of the diamine to the compound shown in Formula 6 is (0.1–55):1, preferably (3–50):1, more preferably (3–17):1; and even more preferably 10.5:1, 3.8:1, 5.5:1, 5.6:1, 13:1, 17:1, 50:1 or 3.4:1.

[0053] In this invention, the amidation reaction is carried out at a temperature of 50°C to 250°C for a time of 5 to 25 hours.

[0054] In this invention, a polycondensation reaction is preferably carried out in a solvent at a temperature of 50°C to 120°C (preferably 80°C to 100°C) for about 0.1 hours to 12 hours (preferably 0.1 hours to 5 hours). Then, an imidization reaction is carried out at a temperature of about 120°C to 250°C (preferably 150°C to 200°C) for 0.5 hours to 20 hours (preferably 1 hour to 10 hours).

[0055] In this invention, the amidation reaction is carried out in a solvent; the solvent is preferably an organic solvent. The organic solvent is any organic solvent that can dissolve the product and can be heated to the desired temperature. Examples of such solvents include aprotic polar solvents such as dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, sulfolane, and triethylene glycol dimethyl ether; ketone solvents such as cyclohexanone and butanone; phenolic solvents such as m-cresol, phenol, and chlorophenol; and aromatic solvents such as toluene and xylene. The organic solvent can be one or more of the above solvents combined.

[0056] In the imidization reaction, known dehydrating agents and catalysts can also be used. Examples of reaction catalysts include triethylamine, dimethylaniline, pyridine, methylpyridine, isoquinoline, etc., and combinations of two or more can also be used. Examples of dehydrating agents include acetic anhydride, benzoic anhydride, etc., and combinations of two or more can also be used.

[0057] The present invention also provides a composition comprising: a polyimide of Formula 1, a crosslinking agent, a hydrocarbon resin, and a solvent;

[0058]

[0059] In Equation 1, n is an integer from 10 to 100; n 11 is an integer from 1 to 40; m is an integer from 0 to 4;

[0060] A is selected from one or more of substituted or unsubstituted aromatic hydrocarbon groups, saturated or unsaturated aliphatic groups;

[0061] R1is selected from one or more of hydrogen, alkyl, cycloalkyl, aryl;

[0062] R is selected from one or more of substituted or unsubstituted aromatic hydrocarbon group, saturated or unsaturated aliphatic group;

[0063] Z1, Z2are independently selected from one or more of hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl.

[0064] In the formula 1 of the present application, n 11 is an integer of 1 to 20; m is 2 or 3;

[0065] A is selected from substituted or unsubstituted C6-C40 aryl, substituted or unsubstituted C3-C20 aliphatic ring;

[0066] R1is selected from hydrogen, C1-C10 saturated aliphatic hydrocarbon group, preferably hydrogen;

[0067] R is selected from substituted or unsubstituted C6-C40 aryl, substituted or unsubstituted C3-C20 aliphatic ring;

[0068] Z1, Z2are independently selected from one or more of hydrogen, C1-C6 alkyl, C1-C6 cycloalkyl, C6-C10 aryl, preferably hydrogen.

[0069] In some embodiments of the present application, the polyimide is specifically

[0070]

[0071] The above polyimide, n 11 is an integer of 1 to 20, the sum of n1 and n2 is 10 to 100; the glass transition temperature is about 40°C to 140°C, and the weight average molecular weight (by gel permeation chromatography) is 100 or more and less than 1000.

[0072] In the present application, the mass ratio of the polyimide, the crosslinking agent, the hydrocarbon resin, and the solvent is 100: (1-15): (5-25): (150-400).

[0073] In the present application, the hydrocarbon resin includes one or more of styrene-butadiene copolymer, styrene-isoprene-styrene block copolymer, styrene-butadiene-divinylbenzene copolymer, polystyrene, polybutadiene; C5 / C9 hydrogenated petroleum resin.

[0074] In the present application, the crosslinking agent includes an epoxy compound and a silane coupling agent.

[0075] In the present application, the silane coupling agent includes one or more of N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane.

[0076] In the present application, the epoxy compound includes one or more of phenol type epoxy compound, bisphenol A type epoxy compound, hydrogenated bisphenol A type epoxy compound, bisphenol F type epoxy compound, hydrogenated bisphenol F type epoxy compound, phenol novolac type epoxy compound, stilbene type epoxy compound, epoxy compound containing triazine skeleton, siloxane type epoxy resin, chain aliphatic epoxy compound, alicyclic epoxy compound, glycidyl amine type epoxy compound, glycidyl ester type epoxy compound, dicyclopentadiene type epoxy compound, arylalkylene type epoxy compound.

[0077] In the present application, the composition further includes one or more of flame retardant, leveling agent, inorganic filler.

[0078] In the present application, the flame retardant includes one or more of ammonium polyphosphate, aluminum diethylphosphinate, triphenyl phosphate, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, or hexaphenoxy cyclotriphosphazene, and the use amount of the phosphorus-containing flame retardant is not particularly limited; the content of the flame retardant is 1 mass part to 30 mass parts with respect to 100 mass parts of the composition.

[0079] In the present application, the inorganic filler includes one or more of magnesium hydroxide, aluminum hydroxide, silicon dioxide, silicon powder, graphite powder, magnesium carbonate, calcium carbonate, magnesium silicate, calcium silicate, magnesium oxide, calcium oxide, aluminum oxide, aluminum nitride, boron nitride; and the use amount of the inorganic filler is 1 mass part to 30 mass parts with respect to 100 mass parts of the composition.

[0080] In the present application, the leveling agent is a silicone oil and / or organosiloxane.

[0081] The polyimide composition of the present application can be used as a composite film of a copper-clad plate by being coated on a PI base film. The coating method is not particularly limited, and the thickness of the formed film is not particularly limited, as long as the film thickness after drying is 0.5 to 100 μm. These film-shaped adhesive materials can also be surface-protected with various protective films.

[0082] The present application also provides a polyimide film obtained by curing the above composition at 180 to 300°C.

[0083] In the present application, the method for preparing the polyimide film preferably comprises: curing the above composition at 180-300℃ under a pressure of 5-10 MPa for 60-100 min to obtain the polyimide film.

[0084] The present application adopts anhydride containing terminal carboxyl structure to cap polyimide to form oligomer pre-polymer containing carboxyl, then introduces polyphenyl ether containing terminal hydroxyl to form ester structure, to obtain polyester imide, which has lower dielectric constant and higher adhesion, and the application of polyimide in thermoplastic polyimide (TPI) has lower pressure bonding temperature. DETAILED DESCRIPTION

[0085] The technical solutions of the present application will be described clearly and completely below in combination with the embodiments of the present application. Obviously, the described embodiments are only some of the embodiments of the present application, but not all the embodiments. Based on the embodiments in the present application, all the other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0086] In order to further illustrate the present application, the following examples are used for detailed description. The raw materials used in the following examples of the present application are all commercially available.

[0087] The test methods used in the examples and comparative examples of the present application are as follows:

[0088] 1) Determination of weight average molecular weight: gel permeation chromatograph (PL-GPC120, Polymer Laboratories, UK) is used for testing.

[0089] 2) Determination of glass transition temperature: static thermal mechanical analyzer (TMA Q400), test atmosphere is nitrogen, heating rate is 5℃ / min, temperature range is 20-200℃.

[0090] Example 1

[0091] 1. Into a reaction vessel, 4,4'-diaminodicyclohexylmethane (0.105 mol, 22.089 g), dimethylacetamide (8.712 g), and toluene (109.03 g) were added and dissolved with stirring. Cyclohexanetetracarboxylic dianhydride (0.1 mol, 22.42 g) was added, and then the reaction was carried out at 80°C for 5 hours. Trimellitic anhydride (0.01 mol, 79.82 g) was added, and then the reaction was carried out at 160°C for 8 hours. Next, polyphenylene ether (0.01 mol, 8.4 g, polyphenylene ether molecular weight: 840 g / mol) and a catalyst, tetrabutyl titanate (1% of trimellitic anhydride), were added to the reaction vessel, and then the reaction was carried out at 175°C for 6 hours, thereby obtaining a polyimide solution. In this example, the molar ratio of the diacid anhydride / diamine was 100:105. The weight average molecular weight of the polyimide was 710, and the glass transition temperature was 100°C. The structure is shown below.

[0092]

[0093] 2. The polyimide (100 g), cyclohexanone (400 g), were dissolved with stirring. Then, p- benzenediol diglycidyl ether (1 g), N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane (3 g), polystyrene (15 g), hexaphenoxy cyclotriphosphazene (10 g), and silica (5 g) were added to the reaction.

[0094] 3. The composition slurry obtained in the above step 2 was coated on a polyimide support substrate, and then dried at 100°C for 10 hours, thereby obtaining a semi-cured adhesive sheet having a thickness of 20 μm.

[0095] 4. On the semi-cured adhesive sheet containing the polyimide support substrate obtained in the above step 3, a low-roughness electrolytic copper foil (ten-point average roughness (Rz): 1.0 μm) having a thickness of 18 μm was overlapped, and then, under a pressure of 5 MPa at 300°C, the copper foil was laminated for 30 minutes, thereby obtaining a copper-clad laminate.

[0096] Example 2

[0097] 1. Into a reaction vessel, 2,2-bis[4-(4-aminophenoxy)phenyl]propane (0.073 mol, 29.97 g), 4,4'-diaminodiphenyl ketone (0.03 mol, 6.3675 g), cyclohexanone (150 g) were stirred and dissolved. 3,4,3',4'-diphenyl ether tetra carboxylic dianhydride (0.1 mol, 31.02 g) was added, and then the reaction was carried out at 120°C for 0.1 hour. Trimellitic anhydride (0.006 mol, 47.89 g) was added, and then the reaction was carried out by heating to 160°C for 8 hours. Next, polyphenyl ether (0.006 mol, 3.02 g, polyphenyl ether molecular weight: 840 g / mol) and a catalyst, tetrabutyl titanate (1% of trimellitic anhydride) were added to the reaction vessel, and then the reaction was carried out by heating to 175°C for 6 hours, thereby obtaining a polyimide solution. In this example, the molar ratio of the diacid anhydride / diamine was 100:103. The weight average molecular weight of the polyimide was 760, and the glass transition temperature was 40°C. The structure is shown below.

[0098]

[0099] 2. Into a reaction vessel, polyimide (100 g), cyclohexanone (400 g) were stirred and dissolved. Then, diglycidyl aniline (10 g), N-2-(aminoethyl)-3-aminopropyl trimethoxy silane (0.1 g), styrene-butadiene copolymer (25 g), ammonium polyphosphate (8 g), magnesium hydroxide (1 g) were added to the reaction.

[0100] 3. The composition slurry obtained in the above step 2 was coated on a polyimide support substrate, and then dried at 80°C for 16 hours, thereby obtaining a semi-cured adhesive sheet having a thickness of 18 μm.

[0101] 4. On the semi-cured adhesive sheet containing the polyimide support substrate obtained in the above step 3, a low-roughness electrolytic copper foil (ten-point average roughness (Rz): 1.0 μm) having a thickness of 18 μm was overlapped, and then, by pressing at a pressure of 5 MPa at 300°C for 60 minutes, a copper-clad laminate was obtained.

[0102] Example 3

[0103] 1. Into a reaction vessel, 1,3-bis(4-aminophenoxy)benzene (0.088 mol, 25.725 g), m-phenylenediamine (0.02 mol, 2.1628 g), sulfolane (100 g) were added and dissolved with stirring. 3,4,3',4'-benzophenonetetracarboxylic dianhydride (0.1 mol, 31.02 g) was added, and then the reaction was carried out at 50°C for 12 hours. Trimellitic anhydride (0.016 mol, 127.7 g) was added, and then the reaction was carried out by heating to 160°C for 8 hours. Next, polyphenylene ether (0.016 mol, 12.90 g) and a catalyst, tetrabutyl titanate (1% of trimellitic anhydride) were added to the reaction vessel, and then the reaction was carried out by heating to 175°C for 6 hours, thereby obtaining a solution of polyimide. In this example, the molar ratio of the diacid anhydride / diamine was 100:108. The weight average molecular weight of the polyimide was 630, and the glass transition temperature was 90°C. The structure is shown below.

[0104]

[0105] 2. Into a reaction vessel, polyimide (100 g), cyclohexanone (400 g) were added and dissolved with stirring. Then, dicyclopentadiene phenol epoxy resin (5 g), 3-aminopropyltrimethoxysilane (1 g), styrene-isoprene-styrene block copolymer (5 g), aluminum diethylphosphinate (13 g), and aluminum hydroxide (5 g) were added to the reaction.

[0106] 3. The composition slurry obtained in the above step 2 was coated on a polyimide support film using a coating apparatus, and then dried at 70°C for 12 hours, thereby obtaining a prepreg having a thickness of 22 μm.

[0107] 4. On the prepreg containing the polyimide support substrate obtained in the above step 3, a low-roughness electrolytic copper foil (ten-point average roughness (Rz): 1.0 μm) having a thickness of 18 μm was overlapped, and then, by pressing at a pressure of 5 MPa at 300°C for 40 minutes, a copper-clad laminate was obtained.

[0108] Example 4

[0109] 1. Into a reaction vessel, 1,3-adamantanediamine (0.025 mol, 4.1565 g), 1,4-diaminocyclohexane (0.079 mol, 9.02 g), dimethylformamide (57 g), toluene (50 g) were added and dissolved with stirring. Cyclohexanetetracarboxylic dianhydride (0.1 mol, 20.49 g) was added, and then the reaction was carried out at 85°C for 0.1 hour. Trimellitic anhydride (0.008 mol, 63.85 g) was added, and then the reaction was carried out by heating to 160°C for 8 hours. Next, polyphenylene ether (0.008 mol, 6.45 g, polyphenylene ether molecular weight: 840 g / mol) and a catalyst, tetrabutyl titanate (1% of trimellitic anhydride) were added to the reaction vessel, and then the reaction was carried out by heating to 175°C for 6 hours, thereby obtaining a polyimide solution. In this example, the molar ratio of the diacid anhydride / diamine was 100:104. The weight average molecular weight of the polyimide was 820, and the glass transition temperature was 55°C.

[0110] 2. The polyimide (100 g), cyclohexanone (165 g) were dissolved with stirring. Then, cyclohexanedicarboxylic acid diglycidyl ester (3 g), 3-aminopropyl triethoxysilane (2.5 g), styrene-butadiene-divinylbenzene copolymer (21 g), triphenyl phosphate (2 g), and silica (18 g) were added to the reaction.

[0111] 3. The composition slurry obtained in the above step 2 was coated on a polyimide support film using a coating apparatus, and then dried at 90°C for 16 hours, thereby obtaining a prepreg having a thickness of 21 μm.

[0112] 4. On the prepreg containing the polyimide support film obtained in the above step 3, a low-roughness electrolytic copper foil (ten-point average roughness (Rz): 1.0 μm) having a thickness of 18 μm was overlaid, and then, the laminate was pressed at a pressure of 5 MPa at 300°C for 50 minutes, thereby obtaining a copper-clad laminate.

[0113] Example 5

[0114] 1. Into a reaction vessel, 1,3-bisaminomethylcyclohexane (0.09991 mol, 14.21 g), bis(4-aminophenyl)tetramethyldisiloxane (0.0001 mol, 0.0249 g), N-methyl-2-pyrrolidone (52 g), triethyleneglycol dimethyl ether (50 g) were added and dissolved with stirring. 3,4,3',4'-biphenyltetracarboxylic dianhydride (0.1 mol, 29.422 g) was added, and then the reaction was carried out at 120°C for 7 hours. Trimellitic anhydride (0.002 mol, 31.92 g) was added, and then the reaction was carried out at 160°C for 8 hours. Next, polyphenylene ether (0.002 mol, 1.6128 g, polyphenylene ether molecular weight: 840 g / mol) and a catalyst, tetrabutyl titanate (1% of trimellitic anhydride) were added to the reaction vessel, and then the reaction was carried out at 175°C for 6 hours, thereby obtaining a polyimide solution. In this example, the molar ratio of the diacid anhydride / diamine was 100:101. The weight average molecular weight of the polyimide was 950, and the glass transition temperature was 60°C. The structure is shown below.

[0115]

[0116] 2. The polyimide (100 g), cyclohexanone (250 g) were dissolved with stirring. Then, to the reaction were added diglycidyl phthalate (7 g), 3-glycidoxypropyltrimethoxysilane (2 g), polybutadiene (10 g), 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (15 g), and silicon fine powder (13 g).

[0117] 3. The composition slurry obtained in the above step 2 was coated on a polyimide support film using a coating apparatus, and then dried at 95°C for 13 hours, thereby obtaining a prepreg having a thickness of 20 μm.

[0118] 4. On the prepreg containing the polyimide support film obtained in the above step 3, a low-roughness electrolytic copper foil (ten-point average roughness (Rz): 1.0 μm) having a thickness of 18 μm was overlapped, and then, under a pressure of 5 MPa at 300°C, the laminate was pressed for 50 minutes, thereby obtaining a copper-clad laminate.

[0119] Example 6

[0120] 1. To a reaction vessel, diamino-dicyclohexylpropane (0.1 mol, 23.842 g), 1,3- bisaminomethylcyclohexane (0.015 mol, 2.133 g), phenol (140 g) were added and dissolved with stirring. 3,4,3',4'-biphenyltetracarboxylic dianhydride (0.05 mol, 14.711 g), 3,4,3',4'-diphenyl ether tetracarboxylic dianhydride (0.05 mol, 15.51 g) were added portionwise, and then the reaction was carried out at 110°C for 10 hours. Trimellitic anhydride (0.03 mol, 478.8 g) was added, and then the reaction was carried out by heating to 160°C for 8 hours. Next, polyphenyl ether (0.03 mol, 24.192 g, polyphenyl ether molecular weight: 840 g / mol) and a catalyst, tetrabutyl titanate (1% of trimellitic anhydride) were added to the reaction vessel, and then the reaction was carried out by heating to 175°C for 6 hours, thereby obtaining a polyimide solution. In this example, the molar ratio of the diacid anhydride / diamine was 100:115. The weight average molecular weight of the polyimide was 340, and the glass transition temperature was 62°C.

[0121] 2. The polyimide (100 g), cyclohexanone (200 g) were dissolved with stirring. Then, dimer acid diglycidyl ester (2 g), 3-glycidoxypropylmethyldimethoxysilane (2.3 g), C5 / C9 hydrogenated petroleum resin (17 g), ammonium polyphosphate (18 g), and graphite powder (22 g) were added to the reaction.

[0122] 3. The composition slurry obtained in the above Step 2 was coated on a polyimide support film using a coating apparatus, and then dried at 90°C for 8 hours, thereby obtaining a prepreg having a thickness of 21 μm.

[0123] 4. On the prepreg containing the polyimide support film obtained in the above Step 3, a low-roughness electrolytic copper foil (ten-point average roughness (Rz): 1.0 μm) having a thickness of 18 μm was overlaid, and then, under a pressure of 5 MPa at 290°C, the laminate was pressed for 30 minutes, thereby obtaining a copper-clad laminate.

[0124] Example 7

[0125] 1. Into a reaction vessel, 1,4-diaminobicyclo[2.2.2]octane (0.090 mol, 12.4389 g), 1,3-bis(3-aminophenoxy)benzene (0.02 mol, 58.468 g), triethylamine (133 g), chlorophenol (100 g) were added, and dissolved with stirring. 3,4,3',4'-biphenyltetracarboxylic dianhydride (0.1 mol, 29.422 g) was added, and then the reaction was carried out at 90°C for 4 hours. Trimellitic anhydride (0.02 mol, 319.2 g) was added, and then, heating was carried out to 160°C for 8 hours. Next, polyphenyl ether (0.02 mol, 16.128 g, polyphenyl ether molecular weight: 840 g / mol) and a catalyst, tetrabutyl titanate (1% of trimellitic anhydride) were added to the reaction vessel, and then, heating was carried out to 175°C for 6 hours, thereby obtaining a polyimide solution. In this example, the molar ratio of the diacid anhydride / diamine was 100:110. The weight average molecular weight of the polyimide was 310, and the glass transition temperature was 90°C.

[0126] 2. Into a reaction vessel, the polyimide (100 g) was dissolved with stirring in cyclohexanone (230 g). Then, butanediol diglycidyl ether (6 g), 3-mercaptopropylmethyldimethoxysilane (1.9 g), styrene-butadiene-divinylbenzene copolymer (18 g), aluminum diethylphosphinate (13 g), and calcium carbonate (17 g) were added to the reaction.

[0127] 3. The composition slurry obtained in the above-described step 2 was coated on a polyimide support film using a coating apparatus, and then, drying was carried out at 90°C for 16 hours, thereby obtaining a prepreg having a thickness of 20 μm.

[0128] 4. On the prepreg containing the polyimide support film obtained in the above-described step 3, a low-roughness electrolytic copper foil (ten-point average roughness (Rz): 1.0 μm) having a thickness of 18 μm was overlapped, and then, pressing was carried out at a pressure of 5 MPa and at 285°C for 60 minutes, thereby obtaining a copper-clad laminate.

[0129] Example 8

[0130] 1. Into a reaction vessel, 4,4'-diaminodicyclohexylmethane (0.090 mol, 18.9333 g), p-phenylenediamine (0.027 mol, 2.9198 g), sulfolane (150 g) were added and dissolved with stirring. 3,4,3',4'-diphenyl ether tetra carboxylic dianhydride (0.1 mol, 23.7620 g) was added, and then the reaction was carried out at 85°C for 1 hour. Trimellitic anhydride (0.034 mol, 542.64 g) was added, and then the reaction was carried out by heating to 160°C for 8 hours. Next, polyphenyl ether (0.034 mol, 27.42 g, polyphenyl ether molecular weight: 840 g / mol) and a catalyst, tetrabutyl titanate (1% of trimellitic anhydride) were added to the reaction vessel, and then the reaction was carried out by heating to 175°C for 6 hours, thereby obtaining a polyimide solution. In this example, the molar ratio of the diacid anhydride / diamine was 100:117. The weight average molecular weight of the polyimide was 590, and the glass transition temperature was 42°C, and the structure is shown below.

[0131]

[0132] 2. The polyimide (100 g), cyclohexanone (300 g) were dissolved with stirring. Then, diglycidyl aniline (8 g), 3-acryloyloxypropyltrimethoxysilane (2.8 g), styrene-isoprene-styrene block copolymer (20 g), triphenyl phosphate (8 g), magnesium silicate (12 g) were added to the reaction.

[0133] 3. The composition slurry obtained in the above step 2 was coated on a polyimide support film using a coating apparatus, and then dried at 85°C for 16 hours, thereby obtaining a prepreg having a thickness of 19 μm.

[0134] 4. On the prepreg containing the polyimide support film obtained in the above step 3, a low-roughness electrolytic copper foil (ten-point average roughness (Rz): 1.0 μm) having a thickness of 18 μm was overlapped, and then, pressure-bonded at a pressure of 5 MPa at 300°C for 60 minutes, thereby obtaining a copper-clad laminate.

[0135] Experimental Example

[0136] 1) Measurement of dielectric constant and dielectric loss of adhesive material

[0137] The prepreg obtained in the example was cured at 150°C for 2 hours and at 200°C for 2 hours, thereby obtaining a cured product sheet having a film thickness of 50 μm. This was fixed in a split post die resonator (SPDR), and the dielectric constant and dielectric loss tangent at 10 GHz were measured using a vector network analyzer (N5244A, Agilent Technologies, Inc.).

[0138] 2) Adhesion and peel strength test experiment

[0139] For the copper-clad laminate obtained in the example, the peel strength (N / cm) at 90° tensile was tested using a tensile tester.

[0140] 3) Solder resistance experiment

[0141] For the copper-clad laminate obtained in the example, after curing, it was floated in a solder bath at 288°C for 30 seconds with the copper foil side facing down, and it was confirmed whether there was any change in appearance. No change was recorded as passing, and foaming, swelling was recorded as failing. The test results are shown in Tables 1 and 2.

[0142] Table 1

[0143]

[0144] Table 2

[0145]

[0146] Comparative Example 1

[0147] This comparative example, compared with Example 1, omits the endcapping step with trimellitic anhydride, and specifically includes:

[0148] 1. Into a reaction vessel, diamino dicyclohexyl methane (0.1 mol, 21.037 g), dimethylacetamide (8.712 g), toluene (109.03 g) were added and dissolved with stirring. Cyclohexane tetracarboxylic dianhydride (0.1 mol, 22.42 g) was then added, and a reaction was carried out at 80°C for 5 hours. An imidization reaction was then carried out continuously at a temperature of 160°C for 8 hours, thereby obtaining a polyimide; the molar ratio of the diacid anhydride to the diamine was 100:100. The glass transition temperature of the polyimide was 40°C.

[0149] 2. Into cyclohexanone (400 g), the polyimide (100 g) was added and dissolved with stirring, followed by the addition of p-phenylenediamine diglycidyl ether (1 g), N-2-(aminoethyl)-3- aminopropylmethyldimethoxysilane (3 g), polystyrene (15 g), hexaphenoxy cyclotriphosphazene (10 g), and silica (5 g), and a composition slurry was obtained after the reaction.

[0150] 3. The composition slurry obtained in Step 2 above was coated on a polyimide support substrate, and then dried at 100°C for 10 hours, thereby obtaining a semi-cured adhesive sheet having a thickness of 20 μm.

[0151] 4. A copper-clad laminate was obtained by laminating an 18-μm-thick electrolytic copper foil (ten-point average roughness (Rz): 1.0 μm) having a low roughness onto the prepreg containing the polyimide support substrate obtained in the above step 3, and pressing at 5 MPa and 285°C for 30 minutes.

[0152] Comparative Example 2

[0153] This comparative example, compared to Example 1, omits the epoxy compound (crosslinking agent), and specifically includes:

[0154] 1. Into a reaction vessel, diamino-dicyclohexylmethane (0.105 mol, 22.089 g), dimethylacetamide (8.712 g), and toluene (109.03 g) were added and dissolved with stirring. Cyclohexanetetracarboxylic dianhydride (0.1 mol, 22.42 g) was then added, and the reaction was carried out at 80°C for 5 hours. Trimellitic anhydride (0.01 mol, 79.82 g) was then added, and the reaction was carried out by heating to 160°C for 8 hours. Next, polyphenylene ether (0.01 mol, 8.4 g) and a catalyst, tetrabutyl titanate (1% of the trimellitic anhydride), were added to the reaction vessel, and the reaction was carried out by heating to 175°C for 6 hours, thereby obtaining a polyimide solution; the molar ratio of the diacid anhydride / diamine was 100:105. The weight average molecular weight of the polyimide was 20,000, and the glass transition temperature was 100°C.

[0155] 2. The polyimide (100 g) was dissolved with stirring in cyclohexanone (400 g). Then, 3-aminopropyltrimethoxysilane (1 g), styrene-isoprene-styrene block copolymer (5 g), and aluminum diethylphosphinate (13 g) were added to the reaction, and a composition slurry was obtained after the reaction.

[0156] 3. The composition slurry obtained in the above step 2 was coated on a polyimide support substrate, and then dried at 100°C for 10 hours, thereby obtaining a prepreg having a thickness of 20 μm.

[0157] 4. A copper-clad laminate was obtained by laminating an 18-μm-thick electrolytic copper foil (ten-point average roughness (Rz): 1.0 μm) having a low roughness onto the prepreg containing the polyimide support substrate obtained in the above step 3, and pressing at 5 MPa and 285°C for 30 minutes.

[0158] Referring to Table 3, Table 3 is a comparison of the properties of the films (prepregs) prepared in Comparative Examples 1 and 2 and the copper-clad laminates obtained.

[0159] Table 3

[0160]

[0161] In summary, the composition slurry provided by the present application does not have the insulating properties of low dielectric constant and low dielectric loss at a frequency of 10 GHz; has no good bonding properties for low profile copper foil and other insulating substrates; in addition, has poor low moisture absorption, solder resistance and heat resistance.

[0162] The foregoing description of the disclosed embodiments enables one of ordinary skill in the art to make or utilize the application. Numerous modifications of the embodiments can be made without departing from the spirit or scope of the application. Any reference to claimed subject matter can include any combination of features described herein. The disclosure is not to be limited to the exact details shown and described, for purposes of exemplification and description herein, but rather covers any modifications and equivalents within the scope of the claimed subject matter.

Claims

1. Polyimide as shown in Formula 1, In Equation 1, n is an integer from 10 to 100; n 11 is an integer from 1 to 40; m is an integer from 0 to 4; A is selected from one or more of substituted or unsubstituted aromatic hydrocarbon groups, saturated or unsaturated aliphatic groups; R1 is selected from one or more of hydrogen, alkyl, cycloalkyl, and aryl; R is selected from one or more of substituted or unsubstituted aromatic hydrocarbon groups, saturated or unsaturated aliphatic groups; Z1 and Z2 are independently selected from one or more of hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, and substituted or unsubstituted aryl.

2. The polyimide according to claim 1, characterized in that, In Formula 1, A is selected from substituted or unsubstituted C6-C40 aryl groups and substituted or unsubstituted C3-C20 aliphatic rings. R1 is selected from hydrogen and saturated aliphatic hydrocarbon groups from C1 to C10; R is selected from substituted or unsubstituted C6-C40 aryl groups and substituted or unsubstituted C3-C20 aliphatic rings; Z1 and Z2 are independently selected from one or more of hydrogen, C1-C6 alkyl, C1-C6 cycloalkyl, and C6-C10 aryl.

3. The polyimide according to claim 1, characterized in that, It is The sum of n1 and n2 is 10 to 100.

4. The method for preparing polyimide according to any one of claims 1-3, characterized in that, include: (1) Mix the diamine shown in Formula 2 and the diacid anhydride shown in Formula 3, carry out an amidation reaction, and then mix and react with the acid anhydride shown in Formula 4 to form the compound shown in Formula 5. NH2-R-NH2 formula 2; In Formula 2, R is selected from one or more of substituted or unsubstituted aromatic hydrocarbon groups, saturated or unsaturated aliphatic groups; In Formula 3, A is selected from one or more of substituted or unsubstituted aromatic hydrocarbon groups, saturated or unsaturated aliphatic groups; In Formula 4, Z is selected from one or more of hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, and substituted or unsubstituted aryl. In Equation 5, n is an integer from 10 to 100; A is selected from one or more of substituted or unsubstituted aromatic hydrocarbon groups, saturated or unsaturated aliphatic groups; R is selected from one or more of substituted or unsubstituted aromatic hydrocarbon groups, saturated or unsaturated aliphatic groups; Z1 and Z2 are independently selected from one or more of hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, and substituted or unsubstituted aryl. (2) The compound shown in Formula 5 is mixed and reacted with the compound shown in Formula 6 to obtain polyimide; In Equation 6, n 11 R1 is an integer from 1 to 40; m is an integer from 0 to 4; R1 is selected from one or more of hydrogen, alkyl, cycloalkyl, and aryl.

5. The method for preparing polyimide according to claim 4, characterized in that, The molar ratio of the diamine and the anhydride shown in Formula 4 is (0.1–55):1; The molar ratio of the diamine to the diacid anhydride is (100-115):100; The molar ratio of the diamine to the compound shown in Formula 6 is (0.1–55):

1.

6. The method for preparing polyimide according to claim 4, characterized in that, The temperature of the amidation reaction is 50℃~250℃.

7. The composition, characterized in that, include: The polyimide, crosslinking agent, hydrocarbon resin, and solvent shown in Formula 1; In Equation 1, n is an integer from 10 to 100; n 11 is an integer from 1 to 40; m is an integer from 0 to 4; A is selected from one or more of substituted or unsubstituted aromatic hydrocarbon groups, saturated or unsaturated aliphatic groups; R1 is selected from one or more of hydrogen, alkyl, cycloalkyl, and aryl; R is selected from one or more of substituted or unsubstituted aromatic hydrocarbon groups, saturated or unsaturated aliphatic groups; Z1 and Z2 are independently selected from one or more of hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, and substituted or unsubstituted aryl.

8. The composition according to claim 7, characterized in that, The mass ratio of the polyimide, crosslinking agent, hydrocarbon resin and solvent is 100:(1-15):(5-25):(150-400).

9. The composition according to claim 7 or 8, characterized in that, The crosslinking agent includes epoxy compounds and silane coupling agents.

10. A polyimide film, characterized in that, The composition according to any one of claims 7-9 is cured at 180-300°C.

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