Polyimides, methods of making the same, compositions, polyimide films

Abstract

The present application relates to the technical field of 5G high-frequency copper-clad plate, and particularly relates to polyimide, a preparation method thereof, a composition and a polyimide film. The polyimide 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 substituted or unsubstituted saturated aliphatic hydrocarbon groups; 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, seals the polyimide to form an oligomer prepolymer containing a carboxyl group, and then introduces a fatty alcohol containing a terminal hydroxyl group to form an ester group structure, so as to obtain a polyester polyimide. 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.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of 5G high-frequency copper-clad plate, in particular to a polyimide, a preparation method thereof, a composition, and a polyimide film. BACKGROUND

[0002] The implementation of 5G communication technology relies on new materials to a greater extent than any previous generation. This is mainly determined by the characteristics of 5G communication technology. 5G communication has the characteristics of super-high-speed signal transmission (up to about 10 Gbps), ultra-low delay (<1 ms), and multi-user access. This puts stringent requirements on the comprehensive performance of existing materials. Given that dielectric materials with low dielectric constant (low-Dk) and low dielectric loss (low-Df) have important application prospects in the fields of high-frequency signal transmission, mobile phone antennas, and millimeter wave radar antennas, such materials are widely used in the design and manufacturing process of components for 5G communication application requirements. Currently, materials with good application prospects in 5G communication technology mainly include polytetrafluoroethylene (PTFE), LCP, modified polyphenyl ether (MPPE), and modified polyimide (MPI). PI film has been used in the integrated circuit industry for many years, is easy to design, and has a large room for performance improvement, so it has good application prospects in the field of 5G communication.

[0003] However, there is currently no polyimide material that has both adhesive properties and a low dielectric constant. SUMMARY

[0004] Therefore, the purpose of the present application is to provide a polyimide, a preparation method thereof, a composition, and a polyimide film. The present application uses an anhydride containing a terminal carboxyl group to cap the polyimide to form an oligomer pre-polymer containing a carboxyl group, and then introduces a fatty alcohol containing a terminal hydroxyl group to form an ester group structure to obtain a polyester polyimide. This material has a lower dielectric constant and higher adhesion. The polyimide is applied to thermoplastic polyimide (TPI), which has a lower pressure bonding temperature.

[0005] To achieve the above 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 from 10 to 100;

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

[0010] R1 is selected from substituted or unsubstituted saturated aliphatic hydrocarbon group;

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

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

[0013] In the formula 1 of the present application, A is selected from substituted or unsubstituted C6-C40 aryl group, substituted or unsubstituted C3-C20 aliphatic ring;

[0014] R1 is selected from substituted or unsubstituted C1-C10 saturated aliphatic hydrocarbon group, preferably C1-C5 saturated aliphatic hydrocarbon group or hydroxyl-substituted C1-C5 saturated aliphatic hydrocarbon group, more preferably

[0015] R is selected from substituted or unsubstituted C6-C40 aryl group, substituted or unsubstituted C3-C20 aliphatic ring;

[0016] Z1, Z2 are independently selected from one or more of hydrogen, C1-C6 alkyl group, C1-C6 cycloalkyl group, C6-C10 aryl group.

[0017] In the present application, the polyimide is an ester group-containing polyimide oligomer, specifically

[0018]

[0019]

[0020] In the above polyimide, the sum of n1 and n2 is 10-100; the glass transition temperature is about 40°C-140°C, and the weight average molecular weight (referring to the use of gel permeation chromatography) is 100 or more and less than 1000.

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

[0022] (1) mixing the diamine shown in formula 2 and the diacid anhydride shown in formula 3 to perform amide reaction, and then mixing with the acid anhydride shown in formula 4 to form the compound shown in formula 5;

[0023] NH2-R-NH2 Formula 2;

[0024] In formula 2, R is selected from one or more of substituted or unsubstituted aromatic hydrocarbon group, saturated or unsaturated aliphatic group;

[0025]

[0026] In formula 3, A is selected from one or more of substituted or unsubstituted aromatic hydrocarbon group, saturated or unsaturated aliphatic group;

[0027]

[0028] In formula 4, Z is selected from one or more of hydrogen, substituted or unsubstituted alkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted aryl group;

[0029]

[0030] In formula 5, n is an integer of 10 to 100;

[0031] A is selected from one or more of substituted or unsubstituted aromatic hydrocarbon group, saturated or unsaturated aliphatic group;

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

[0033] Z1, Z2 are independently selected from one or more of hydrogen, substituted or unsubstituted alkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted aryl group;

[0034] (2) mixing and reacting the compound shown in formula 5 with R1-OH to obtain polyimide; R1 is selected from substituted or unsubstituted saturated aliphatic group.

[0035] In formula 4 of the present application, Z is preferably hydrogen; the acid anhydride shown in formula 4 is preferably trimellitic anhydride.

[0036] In formula 5 of the present application, A is selected from substituted or unsubstituted C6-C40 aryl group, substituted or unsubstituted C3-C20 aliphatic ring;

[0037] R is selected from substituted or unsubstituted C6-C40 aryl group, substituted or unsubstituted C3-C20 aliphatic ring;

[0038] Z1, Z2 are independently selected from one or more of hydrogen, C1-C6 alkyl group, C1-C6 cycloalkyl group, C6-C10 aryl group, preferably hydrogen.

[0039] In the present application, R1 is selected from substituted or unsubstituted C1-C10 saturated aliphatic group; preferably C1-C5 saturated aliphatic group or hydroxyl-substituted C1-C5 saturated aliphatic group, more preferably R1-OH is preferably ethylene glycol or glycerol.

[0040] The polymeric monomer dianhydride for preparing polyimide in the present application can use various known dianhydrides.

[0041] Specifically, the binary acid anhydride can be exemplified by, for example, pyromellitic dianhydride, 3,4,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,2',3'-biphenyltetracarboxylic dianhydride, 3,4,3',4'-benzophenonetetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic 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-naphthalenetetracarboxylic 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, and the like aromatic dianhydride; 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride and the like fluorine-containing aromatic dianhydride; cyclohexanetetracarboxylic dianhydride, cyclobutanetetracarboxylic dianhydride and the like alicyclic structure-containing dianhydride; and also a combination of two or more of the above.

[0042] In the embodiment of the present application, the binary acid anhydride is preferably one or more of 3,4,3',4'-biphenyltetracarboxylic dianhydride, 3,4,3',4'-diphenyl ether tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)phenyl dianhydride, 1,3-bis(3,4-dicarboxyphenoxy)phenyl dianhydride, and 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride.

[0043] The polymeric monomer diamine for preparing the polyimide of the present application can use various known diamines.

[0044] 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.

[0045] In the embodiments of the present application, the diamine is preferably one or more of diaminocyclohexane, isophorone diamine, diaminodicyclohexylmethane, 1,3-bisaminomethylcyclohexane, dimethyldiaminodicyclohexylmethane, diaminodicyclohexylpropane.

[0046] 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.

[0047] The molar ratio of the diamine and the dianhydride is (100-115): 100, preferably (101-115): 100, more preferably (103-108): 100.

[0048] The molar ratio of the diamine and R1-OH is (0.1-55): 1, preferably (3-50): 1, more preferably (3-17): 1; still more preferably 10.5: 1, 3.8: 1, 5.5: 1, 5.6: 1, 13: 1, 17: 1, 50: 1, or 3.4: 1.

[0049] In the present application, the temperature of the amidation reaction is 50°C to 250°C, and the time is 5 to 25 hours.

[0050] The present application preferably performs the polycondensation reaction of the dianhydride and the diamine in a solvent at a temperature of 50°C to 120°C (preferably 80°C to 100°C) for about 0.1 hour to 12 hours (preferably 0.1 hour to 5 hours). Subsequently, the imidization reaction is performed at a temperature of about 120°C to 250°C (preferably 150°C to 200°C) for 0.5 hour to 20 hours (preferably 1 hour to 10 hours).

[0051] In the present application, the amidation reaction is performed in a solvent; the solvent is preferably an organic solvent. The organic solvent is one that can dissolve the product and can accommodate the desired temperature to which the heating is performed, and such solvents include, for example, non-protic polar solvents such as dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, sulfolane, triethylene glycol dimethyl ether, ketone solvents such as cyclohexanone and butanone, phenol solvents such as m-cresol, phenol, and chlorophenol, and aromatic hydrocarbon solvents such as toluene and xylene. The organic solvent can be a combination of one or more of the above solvents.

[0052] In the imidization reaction, known reaction dehydrating agents and catalysts can also be used. As the reaction catalyst, for example, triethylamine, dimethylaniline, pyridine, methylpyridine, isoquinoline, and the like can be used, and two or more thereof can be combined. As the dehydrating agent, for example, acetic anhydride, benzoic anhydride, and the like can be used, and two or more thereof can be combined.

[0053] The present application also provides a composition comprising: a polyimide represented by Formula 1, a crosslinking agent, a hydrocarbon resin, and a solvent;

[0054]

[0055] In Formula 1, n is an integer of 10 to 100;

[0056] A is selected from one or more of substituted or unsubstituted aromatic hydrocarbon groups, saturated or unsaturated aliphatic groups;

[0057] R1is selected from substituted or unsubstituted saturated aliphatic hydrocarbon groups;

[0058] R is selected from one or more of substituted or unsubstituted aromatic hydrocarbon groups, saturated or unsaturated aliphatic groups;

[0059] Z1, Z2are independently selected from one or more of hydrogen, substituted or unsubstituted alkyl groups, substituted or unsubstituted cycloalkyl groups, substituted or unsubstituted aryl groups.

[0060] In the present invention, the mass ratio of the polyimide, the crosslinking agent, the hydrocarbon resin and the solvent is 100: (1-15): (5-25): (150-400).

[0061] In the present invention, the hydrocarbon resin includes polymers obtained by polymerization of olefins in the field of petrochemicals such as ethylene, propylene, styrene, butadiene, isoprene and hydrogenated products thereof; the hydrocarbon resin also includes resins obtained from natural sources such as rosin, terpene resin, natural rubber, C5 / C9 petroleum resin and hydrogenated products thereof. Preferably, the hydrocarbon resin includes one or more of homopolymers of butadiene, styrene, isoprene and copolymers thereof, and C5 / C9 petroleum resin and hydrogenated products thereof. Specifically, 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.

[0062] In the present invention, the crosslinking agent includes an epoxy compound and a silane coupling agent.

[0063] In the present invention, the silane coupling agent refers to a reactive alkoxysilane compound, with the structure formula: D-Si(R1)m(OR2)3-m m (3-m) wherein D represents a hydrocarbon group substituent containing amino, epoxy, acryloyloxy, mercapto group, R1represents hydrogen or a hydrocarbon group with carbon atom number 1-10, R2represents a hydrocarbon group with carbon atom number 1-10, and m represents 0, 1 or 2. Specifically, examples include N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3- mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane or 3- acryloyloxypropyltrimethoxysilane.

[0064] ​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, silicone type epoxy resin, chain aliphatic epoxy compound, alicyclic epoxy compound, glycidyl amine type epoxy compound, glycidyl ester type epoxy compound, dicyclopentadiene type epoxy compound, aryl alkylene type epoxy compound.

[0065] In the present application, the composition further includes one or more of flame retardant, leveling agent, inorganic filler.

[0066] In the present application, the flame retardant includes one or more of polyphosphoric acid, hypophosphite, phosphate ester, phosphazene type flame retardant; specifically includes one or more of ammonium polyphosphate, aluminum diethyl hypophosphite, 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.

[0067] 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; the use amount of the inorganic filler is not particularly limited in the present application, 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.

[0068] In the present application, the leveling agent is a silicone oil and / or organosiloxane.

[0069] The polyimide composition of the present application can be used as a composite film of 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 by various protective films.

[0070] The present application also provides a polyimide film, which is obtained by curing the above-mentioned composition at 180 to 200°C.

[0071] The polyimide film of the present application is preferably obtained by the following method: curing the above-mentioned composition at 180 to 200°C under a pressure of 5 to 10 MPa for 60 to 100 minutes to obtain a polyimide film.

[0072] In the prior art, in order to reduce the dielectric constant and dielectric loss of the polymer insulating adhesive material, a large amount of low-polar groups need to be used. However, the low-polar substances often cause the reduction of the adhesion of the insulating material to copper circuits and other insulating substrates, and it is difficult to achieve both. The acid anhydride containing a terminal carboxyl group is used to cap the polyimide to form an oligomer prepolymer containing a carboxyl group, and then a fatty alcohol containing a terminal hydroxyl group is introduced to form an ester group structure to obtain 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. DETAILED DESCRIPTION

[0073] The technical solutions of the present application will be described clearly and completely in combination with the embodiments of the present application. Obviously, the described embodiments are only a part 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 are within the protection scope of the present application.

[0074] In order to further illustrate the present application, the following embodiments are described in detail. The raw materials used in the following embodiments of the present application are all commercially available goods.

[0075] The test methods used in the embodiments and comparative examples of the present application are as follows:

[0076] 1) Determination of weight average molecular weight: a gel permeation chromatograph (PL-GPC120, Polymer Laboratories Company, UK) is used for testing.

[0077] 2) Determination of glass transition temperature: a static thermal mechanical analyzer (TMA Q400), the test atmosphere is nitrogen, the heating rate is 5℃ / min, and the temperature range is 20-200℃.

[0078] Example 1

[0079] 1. Into a reaction vessel, 4,4'-diaminodicyclohexylmethane (0.105 mol, 22.089 g), dimethylacetamide (8.712 g), and toluene (109.03 g) were stirred and dissolved. 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 by heating to 160°C for 8 hours. Next, ethylene glycol (0.01 mol, 0.6207 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 resin. In this example, the molar ratio of the diacid anhydride / diamine was 100:105. The weight average molecular weight of the polyimide resin was 800, and the glass transition temperature was 100°C. The structure is shown below.

[0080]

[0081] 2. The polyimide resin (100 g) obtained in Step 1 and cyclohexanone (400 g) were stirred and dissolved, and then p-phenylenediamine 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 system.

[0082] 3. The composition slurry obtained in 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.

[0083] 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 180°C, the copper foil was laminated for 30 minutes, thereby obtaining a copper-clad laminate.

[0084] Example 2

[0085] 1. Into a reaction vessel was added 2,2-bis[4-(4-aminophenoxy)phenyl]propane (0.073 mol, 29.97 g), 4,4'-diaminobenzophenone (0.03 mol, 6.3675 g), cyclohexanone (150 g), and stirred to dissolve. 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, ethylene glycol (0.006 mol, 0.3724 g) and a catalyst, tetrabutyl titanate (1% of the 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 resin. In this example, the molar ratio of the diacid anhydride / diamine was 100:103. The weight average molecular weight of the polyimide resin was 850, and the glass transition temperature was 40°C.

[0086]

[0087] 2. The polyimide resin (100 g) obtained in Step 1, cyclohexanone (400 g), were stirred to dissolve. Then, diglycidyl aniline (10 g), N-2-(aminoethyl)-3-aminopropyl trimethoxysilane (0.1 g), styrene-butadiene copolymer (25 g), ammonium polyphosphate (8 g), and magnesium hydroxide (1 g) were added to the reaction system.

[0088] 3. The composition slurry obtained in Step 2 above 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.

[0089] 4. On the semi-cured adhesive sheet containing the polyimide support substrate obtained in Step 3 above, 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 180°C, the copper foil was laminated for 60 minutes, thereby obtaining a copper-clad laminate.

[0090] Example 3

[0091] 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 stirred to dissolve. 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, ethylene glycol (0.016 mol, 0.993 g) and a catalyst, tetrabutyl titanate (1% of the 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 resin. In this example, the molar ratio of the diacid anhydride / diamine was 100:108. The weight average molecular weight of the polyimide resin was 680, and the glass transition temperature was 90°C.

[0092]

[0093] 2. The polyimide resin (100 g) obtained in Step 1, cyclohexanone (400 g) were stirred to dissolve. 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 system.

[0094] 3. The composition slurry obtained in Step 2 above 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.

[0095] 4. On the prepreg containing the polyimide support substrate obtained in Step 3 above, 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 180°C, the copper foil was laminated for 40 minutes, thereby obtaining a copper-clad laminate.

[0096] Example 4

[0097] 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 with heating to 160°C for 8 hours. Next, ethylene glycol (0.008 mol, 0.4966 g) and a catalyst, tetrabutyl titanate (1% of trimellitic anhydride) were added to the reaction vessel, and then the reaction was carried out with heating to 175°C for 6 hours, thereby obtaining a solution of polyimide resin. In this example, the molar ratio of dianhydride / diamine was 100:104. The weight average molecular weight of the polyimide resin was 830, and the glass transition temperature was 55°C.

[0098] 2. The polyimide resin obtained in Step 1 (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 system.

[0099] 3. The composition slurry obtained in Step 2 above 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.

[0100] 4. A low-roughness electrolytic copper foil (ten-point average roughness (Rz): 1.0 μm) having a thickness of 18 μm was overlaid on the prepreg having a polyimide support film obtained in Step 3 above, and then laminated at a pressure of 5 MPa and at 180°C for 50 minutes, thereby obtaining a copper-clad laminate.

[0101] Example 5

[0102] 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), triethylene glycol 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, glycerol (0.002 mol, 0.18418 g) 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 solution of polyimide resin. In this example, the molar ratio of the diacid anhydride / diamine was 100:101. The weight average molecular weight of the polyimide resin was 970, and the glass transition temperature was 60°C. The structure is shown below.

[0103]

[0104] 2. The polyimide resin obtained in Step 1 (100 g), cyclohexanone (250 g) were dissolved with stirring. Then, to the reaction system, 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) were added.

[0105] 3. The composition slurry obtained in Step 2 above 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.

[0106] 4. On the prepreg containing the polyimide support film obtained in Step 3 above, 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 180°C, the laminate was pressed for 50 minutes, thereby obtaining a copper-clad laminate.

[0107] Example 6

[0108] 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, to the reaction vessel, glycerol (0.03 mol, 2.7627 g) and a catalyst, tetrabutyl titanate (1% of trimellitic anhydride) were added, and then the reaction was carried out by heating to 175°C for 6 hours, thereby obtaining a solution of polyimide resin. In this example, the molar ratio of the diacid anhydride / diamine was 100:115. The weight average molecular weight of the polyimide resin was 380, and the glass transition temperature was 62°C.

[0109] 2. The polyimide resin (100 g) obtained in Step 1 was dissolved with stirring in cyclohexanone (200 g). Then, to the reaction system, 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.

[0110] 3. The composition slurry obtained in Step 2 above 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.

[0111] 4. On the prepreg containing the polyimide support film obtained in Step 3 above, 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 170°C, the laminate was pressed for 30 minutes, thereby obtaining a copper-clad laminate.

[0112] Example 7

[0113] 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 the reaction was carried out by heating to 160°C for 8 hours. Next, glycerol (0.02 mol, 1.8418 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 resin. In this example, the molar ratio of the diacid anhydride / diamine was 100:110. The weight average molecular weight of the polyimide resin was 340, and the glass transition temperature was 90°C.

[0114] 2. The polyimide resin obtained in Step 1 (100 g), cyclohexanone (230 g) were dissolved with stirring. Then, butanediol diglycidyl ether (6 g), 3-mercaptopropylmethyldimethoxysilane (1.9 g), styrene-butadiene-divinylbenzene copolymer (18 g), aluminum diethylphosphinate (13 g), calcium carbonate (17 g) were added to the reaction system.

[0115] 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 20 μm.

[0116] 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 165°C, the copper foil was laminated for 60 minutes, thereby obtaining a copper-clad laminate.

[0117] Example 8

[0118] 1. Add 4,4'-diaminodicyclohexylmethane (0.090 mol, 18.9333 g), p-phenylenediamine (0.027 mol, 2.9198 g), and sulfolane (150 g) to a reaction vessel and stir to dissolve. Add 3,4,3',4'-diphenyl ether tetracarboxylic dianhydride (0.1 mol, 23.7620 g) and react at 85°C for 1 hour. Add trimellitic anhydride (0.034 mol, 542.64 g) and heat to 160°C for 8 hours. Next, add glycerol (0.034 mol, 3.131 g) and tetrabutyl titanate (1% of trimellitic anhydride) to the reaction vessel and heat to 175°C for 6 hours to obtain a polyimide resin solution. In this example, the molar ratio of diacid anhydride / diamine is 100:117. The polyimide resin has a weight-average molecular weight of 650 and a glass transition temperature of 42℃, and its structure is shown below.

[0119]

[0120] 2. Dissolve the polyimide resin (100g) and cyclohexanone (300g) obtained in step 1 by stirring. Then add diglycidyl aniline (8g), 3-acryloyloxypropyltrimethoxysilane (2.8g), styrene-isoprene-styrene block copolymer (20g), triphenyl phosphate (8g), and magnesium silicate (12g) to the reaction system.

[0121] 3. The slurry composition obtained in step 2 is coated onto a polyimide support film using a coating equipment, and then dried at 85°C for 16 hours to obtain a semi-cured adhesive sheet with a thickness of 19 μm.

[0122] 4. Overlay an 18μm thick low-roughness electrolytic copper foil (ten-point average roughness (Rz): 1.0μm) onto the semi-cured adhesive sheet containing the polyimide support film obtained in step 3 above, and press it at a pressure of 5MPa and 180℃ for 60 minutes to obtain a copper-clad laminate.

[0123] Experimental Example

[0124] 1) Determination of dielectric constant and dielectric loss of adhesive materials

[0125] The semi-cured adhesive sheet obtained in the example was cured at 150°C for 2 hours and then at 200°C for 2 hours to obtain a cured sheet with a film thickness of 50 μm. This was then fixed in a split dielectric resonator (SPDR), and the dielectric constant and dielectric loss tangent at 10 GHz were measured using a vector network analyzer (N5244A, Agilent Technologies).

[0126] 2) Adhesion and peel strength test experiment

[0127] For the copper-clad laminate obtained in the example, the peel strength (N / cm) at 90° tensile was tested using a tensile tester.

[0128] 3) Solder resistance experiment

[0129] 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, 2.

[0130] Table 1

[0131]

[0132] Table 2

[0133]

[0134]

[0135] Comparative Example 1

[0136] This comparative example, compared with Example 1, omits the endcapping step with trimellitic anhydride, and specifically includes:

[0137] 1. Into a reaction vessel, add diaminodicyclohexylmethane (0.1 mol, 21.037 g), dimethylacetamide (8.712 g), toluene (109.03 g), and stir to dissolve. Add cyclohexane tetracarboxylic dianhydride (0.1 mol, 22.42 g), and then carry out the reaction at 80°C for 5 hours. Then continue heating to a temperature of 160°C and carry out the imidization reaction for 8h, thereby obtaining a polyimide; the molar ratio of the diacid anhydride to the diamine is 100:100. The glass transition temperature of the polyimide is 40°C.

[0138] 2. Add the polyimide resin obtained in step 1 (100 g) to cyclohexanone (400 g), stir to dissolve, then add 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 after the reaction, obtain a composition slurry.

[0139] 3. Apply the composition slurry obtained in the above step 2 to a polyimide support substrate, then dry at 100°C for 10 hours, thereby obtaining a semi-cured adhesive sheet with a thickness of 20 μm.

[0140] 4. On the polyimide support substrate-containing prepreg sheet obtained in the above step 3, a 18-μm-thick electrolytic copper foil (ten-point average roughness (Rz): 1.0 μm) of low roughness was overlaid, and pressure-bonding was performed at 5 MPa and 180°C for 30 minutes, thereby obtaining a copper-clad laminate.

[0141] Comparative Example 2

[0142] This comparative example, compared with Example 1, omits the epoxy compound (crosslinking agent), and specifically includes:

[0143] 1. Into a reaction vessel, diamino-dicyclohexyl methane (0.105 mol, 22.089 g), dimethylacetamide (8.712 g), and toluene (109.03 g) were added and dissolved with stirring. Then, cyclohexane tetracarboxylic dianhydride (0.1 mol, 22.42 g) was added, and the reaction was performed at 80°C for 5 hours. Then, trimellitic anhydride (0.01 mol, 79.82 g) was added, and the reaction was performed at 160°C for 8 hours. Next, ethylene glycol (0.01 mol, 0.6207 g) and a catalyst, tetrabutyl titanate (1% of the trimellitic anhydride), were added to the reaction vessel, and the reaction was performed at 175°C for 6 hours, thereby obtaining a solution of a polyimide resin; the molar ratio of the diacid anhydride / diamine was 100:105. The weight average molecular weight of the polyimide resin was 800, and the glass transition temperature was 100°C.

Claims

1. A polyimide represented by Formula 1, ###0001### Formula 1 wherein n is an integer of 10 to 100; A is selected from one or more of substituted or unsubstituted aromatic hydrocarbon groups, saturated or unsaturated aliphatic groups; R1 is selected from hydroxyl-substituted C1 to C5 saturated aliphatic groups; R is selected from one or more of substituted or unsubstituted aromatic hydrocarbon groups, saturated or unsaturated aliphatic groups; 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. A is selected from substituted or unsubstituted C6 to C40 aryl groups, substituted or unsubstituted C3 to C20 aliphatic rings; 2. The polyimide according to claim 1, characterized by R is selected from substituted or unsubstituted C6 to C40 aryl groups, substituted or unsubstituted C3 to C20 aliphatic rings; 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. which is 3. The polyimide of claim 1, wherein The sum of n1 and n2 is 10 to 100. Comprising:

4. The method for producing a polyimide according to any one of claims 1 to 3, characterized by, (1) mixing a diamine represented by Formula 2 and a diacid anhydride represented by Formula 3, performing an amidation reaction, and then mixing with an acid anhydride represented by Formula 4 to form a compound represented by Formula 5; NH2— R— NH2 Formula 2; R is selected from one or more of substituted or unsubstituted aromatic hydrocarbon groups, saturated or unsaturated aliphatic groups; A is selected from one or more of substituted or unsubstituted aromatic hydrocarbon groups, saturated or unsaturated aliphatic groups; Z is selected from one or more of hydrogen, substituted or unsubstituted alkyl groups, substituted or unsubstituted cycloalkyl groups, substituted or unsubstituted aryl groups; n is an integer of 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, 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. (2) mixing the compound represented by Formula 5 with R1-OH to obtain a polyimide; R1 is selected from hydroxyl-substituted C1 to C5 saturated aliphatic groups. The molar ratio of the diamine to the acid anhydride represented by Formula 4 is (0.1 to 55): 1; 5. The method of producing a polyimide according to claim 4, characterized by, The molar ratio of the diamine to the diacid anhydride is (100 to 115): 100; The molar ratio of the diamine to R1-OH is (0.1 to 55):

1. The temperature of the amidation reaction is 50°C to 250°C.

6. The method of producing a polyimide according to claim 4, characterized by, Comprising:

7. Composition characterized in that, A polyimide represented by Formula 1, a crosslinking agent, a hydrocarbon resin, and a solvent; n is an integer of 10 to 100; A is selected from one or more of substituted or unsubstituted aromatic hydrocarbon groups, saturated or unsaturated aliphatic groups; R1 is selected from hydroxyl-substituted C1 to C5 saturated aliphatic groups; R is selected from one or more of substituted or unsubstituted aromatic hydrocarbon groups, saturated or unsaturated aliphatic groups; 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. ​ 8. The composition of claim 7, wherein, The mass ratio of the polyimide, the crosslinking agent, the hydrocarbon resin and the solvent is 100:(1-15):(5-25):(150-400).

9. The composition according to claim 7 or 8, characterized in that, The crosslinking agent comprises an epoxy compound and a silane coupling agent.

10. A polyimide film characterized by, The composition of any one of claims 7-9 is cured at 180-200°C.

Images