Polymer, method for producing the same, composition, polyimide film

Abstract

The present application relates to the technical field of polyimide, and specifically provides a polymer, a preparation method thereof, a composition and a polyimide film.The polymer 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 and R2 are independently selected from one or more of hydrogen, alkyl, cycloalkyl and 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, seals the polyimide to form an oligomer prepolymer containing a carboxyl group, and then introduces an aromatic alcohol 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 thermoplastic polyimide (TPI), so that the pressure bonding temperature is lower.

Description

Technical Field

[0001] This invention relates to the field of polyimide technology, and more specifically, to polymers, preparation methods thereof, compositions thereof, and polyimide films. Background Technology

[0002] Traditionally, epoxy resin films are used as insulating adhesive layers for circuit boards. Cured epoxy resin contains a large number of hydroxyl groups, which can provide strong adhesion to copper foil and other insulating substrates. Although these polar groups provide high adhesive strength, they also have high dielectric constants and dielectric losses, making them unsuitable for the performance requirements of high-frequency signal transmission.

[0003] Polyimide (PI) films have been used in the integrated circuit industry for many years, offering ease of structural design and significant potential for performance improvement. In existing technologies, to reduce the dielectric constant and dielectric loss of polymer insulating adhesives, a large number of low-polarity groups are required. However, low-polarity substances often reduce the adhesion performance of the insulating material to copper circuits and other insulating substrates, making it difficult to achieve both simultaneously. Summary of the Invention

[0004] In view of this, the purpose of the present invention is to provide polymers and their preparation methods, compositions, and polyimide films. The present invention uses an anhydride containing a terminal carboxyl group to end-cap polyimide to form an oligomer prepolymer containing a carboxyl group, and then introduces an aromatic alcohol containing a terminal hydroxyl group to form an ester structure to obtain a polyesterimide. This material has a lower dielectric constant and higher adhesiveness. When polyimide is applied to thermoplastic polyimide (TPI), the compressive strength is lower.

[0005] To achieve the above objectives, the present invention adopts the following technical solution:

[0006] The polymer shown in Formula 1,

[0007]

[0008] In Equation 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 and R2 are independently selected from one or more of hydrogen, alkyl, cycloalkyl, and aryl;

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

[0012] 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.

[0013] In Formula 1 of the present invention, A is selected from substituted or unsubstituted C6-C40 aryl groups and substituted or unsubstituted C3-C20 aliphatic rings.

[0014] R1 and R2 are independently selected from hydrogen and C1 to C10 saturated aliphatic hydrocarbon groups; R1 and R2 are preferably hydrogen.

[0015] R is selected from substituted or unsubstituted C6-C40 aryl groups and substituted or unsubstituted C3-C20 aliphatic rings;

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

[0017] In some embodiments of the present invention, the polymer is specifically...

[0018]

[0019] The polymers described above have a sum of n1 and n2 of 10 to 100; a glass transition temperature of approximately 40°C to 140°C; and a weight-average molecular weight (referring to that obtained by gel permeation chromatography) of 100 or more and less than 1000.

[0020] The present invention also provides a method for preparing the above-mentioned polymer, comprising:

[0021] (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 anhydride shown in Formula 4 to form the compound shown in Formula 5.

[0022] NH2-R-NH2 (Formula 2);

[0023] In Formula 2, R is selected from one or more of substituted or unsubstituted aromatic hydrocarbon groups, saturated or unsaturated aliphatic groups;

[0024]

[0025] In Formula 3, A is selected from one or more of substituted or unsubstituted aromatic hydrocarbon groups, saturated or unsaturated aliphatic groups;

[0026]

[0027] 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.

[0028]

[0029] In Equation 5, n is an integer from 10 to 100;

[0030] A is selected from one or more of substituted or unsubstituted aromatic hydrocarbon groups, saturated or unsaturated aliphatic groups;

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

[0032] 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.

[0033] (2) The compound shown in Formula 5 is mixed and reacted with the compound shown in Formula 6 to obtain polyimide;

[0034]

[0035] In Formula 6, R1 and R2 are independently selected from one or more of hydrogen, alkyl, cycloalkyl, and aryl.

[0036] In Formula 5 of the present invention, A is selected from substituted or unsubstituted C6-C40 aryl groups and substituted or unsubstituted C3-C20 aliphatic rings.

[0037] R is selected from substituted or unsubstituted C6-C40 aryl groups and substituted or unsubstituted C3-C20 aliphatic rings;

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

[0039] In Formula 4 of the present invention, Z is preferably hydrogen; the acid anhydride shown in Formula 4 is preferably trimellitic anhydride; in Formula 6 of the present invention, R1 and R2 are selected from hydrogen and saturated aliphatic hydrocarbon groups of C1 to C10; R1 and R2 are preferably hydrogen; the compound shown in Formula 6 is preferably (1,1'-biphenyl)-4,4'-diol.

[0040] The present invention provides a diacid anhydride as a polymer monomer for preparing polyimide, and various known diacid anhydrides can be used.

[0041] Specifically, examples of dicarboxylic anhydrides include: pyromellitic dianhydride, 3,4,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,2',3'-biphenyltetracarboxylic 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 Aromatic dianhydrides such as 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; fluorinated aromatic dianhydrides such as 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride; dianhydrides containing alicyclic structures such as cyclohexanetetracarboxylic dianhydride and cyclobutanetetracarboxylic dianhydride; or combinations of two or more of the above.

[0042] In embodiments of the present invention, the dicarboxylic 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 present invention provides a diamine monomer for preparing polyimide, and various known diamines can be used.

[0044] For example, diaminocyclohexane, isophorone diamine, diaminodicyclohexylmethane, diaminodicyclohexyl ether, 1,3-adamantane diamine, 1,3-diaminomethylcyclohexane, dimethyldiaminodicyclohexylmethane, tetramethyldiaminodicyclohexylmethane, diaminodicyclohexylpropane, diaminobicyclo[2.2.1]heptane, diaminobicyclo[2.2.2]octane, bis(aminomethyl)-bicyclo[2.2.1]heptane and other alicyclic diamines, 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'-diaminodiphenylbenzene, 3,4'-diaminodiphenylbenzene, 3,3'-diaminodiphenylbenzene, 2,2-bis(4-aminophenyl)propane, 2,2-bis(3- 2,2-Bis(4-aminophenyl)propane, 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-bis(4-aminophenyl)ethane, 1,2-bis(4-aminophenyl)ethylene, 1,4-bis(3-aminobenzoyl)benzene, 1 Aromatic diamines or fluorinated aromatic diamines include 3-bis(3-aminobenzoyl)benzene, 4,4'-diamino-3,3'-dimethylbiphenyl, 4,4'-diamino-2,2'-dimethylbiphenyl, 4,4'-diamino-2,2'-di(trifluoromethyl)biphenyl, 4,4'-bis(3-aminophenoxy)biphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(3-aminophenoxy)phenyl]ether, and bis[4-(4-aminophenoxy)phenyl]ether. Aliphatic chain diamines include ethylenediamine, propylenediamine, butanediamine, pentanediamine, hexanediamine, octanediamine, and polyetheramine.

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

[0046] In this invention, the molar ratio of the diamine and the anhydride shown in Formula 4 is (0.1-55):1, preferably (0.9-1.2):1, and 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 to the diacid anhydride is (100-115):100, preferably (101-115):100, and more preferably (103-108):100;

[0048] The molar ratio of the diamine to the compound shown in Formula 6 is (0.1–55):1, preferably (3–50):1, and 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 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.

[0050] 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).

[0051] 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.

[0052] 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.

[0053] The present invention also provides compositions comprising: a polymer of Formula 1, a crosslinking agent, a hydrocarbon resin, and a solvent;

[0054]

[0055] In Equation 1, n is an integer from 10 to 100;

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

[0057] R1 and R2 are independently selected from one or more of hydrogen, alkyl, cycloalkyl, and aryl;

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

[0059] 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.

[0060] In Formula 1 of the present invention, A is selected from substituted or unsubstituted C6-C40 aryl groups and substituted or unsubstituted C3-C20 aliphatic rings.

[0061] R1 and R2 are independently selected from hydrogen and C1 to C10 saturated aliphatic hydrocarbon groups; R1 and R2 are preferably hydrogen.

[0062] R is selected from substituted or unsubstituted C6-C40 aryl groups and substituted or unsubstituted C3-C20 aliphatic rings;

[0063] Z1 and Z2 are independently selected from one or more of hydrogen, C1-C6 alkyl, C1-C6 cycloalkyl, and C6-C10 aryl; Z1 and Z2 are preferably hydrogen.

[0064] In this invention, the mass ratio of the polymer, crosslinking agent, hydrocarbon resin and solvent shown in Formula 1 is 100:(1-15):(5-25):(150-400).

[0065] In this invention, the hydrocarbon resin includes one or more of the following: styrene-butadiene copolymer, styrene-isoprene-styrene block copolymer, styrene-butadiene-divinylbenzene copolymer, polystyrene, polybutadiene, and C5 / C9 hydrogenated petroleum resin.

[0066] In this invention, the crosslinking agent includes epoxy compounds and silane coupling agents.

[0067] In this invention, the silane coupling agent includes one or more of N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-epoxypropoxypropyltrimethoxysilane, 3-epoxypropoxypropylmethyldimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 3-acryloyloxypropyltrimethoxysilane.

[0068] In this invention, the epoxy compound includes one or more of the following: phenolic epoxy compounds, bisphenol A epoxy compounds, hydrogenated bisphenol A epoxy compounds, bisphenol F epoxy compounds, hydrogenated bisphenol F epoxy compounds, phenolic aldehyde epoxy compounds, stilbene epoxy compounds, epoxy compounds containing a triazine skeleton, siloxane epoxy resins, chain aliphatic epoxy compounds, alicyclic epoxy compounds, glycidylamine epoxy compounds, glycidyl ester epoxy compounds, dicyclopentadiene epoxy compounds, and arylalkylene epoxy compounds.

[0069] In this invention, the composition further includes one or more of flame retardants, leveling agents, and inorganic fillers.

[0070] In this invention, the flame retardant includes one or more of ammonium polyphosphate, aluminum diethylphosphite, triphenyl phosphate, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide or hexaphenoxycyclotriphosphazene, and there is no particular limitation on the amount used as a phosphorus-containing flame retardant; the content of the flame retardant is 1 part by weight to 30 parts by weight relative to 100 parts by weight of the composition.

[0071] In this invention, the inorganic filler includes one or more of magnesium hydroxide, aluminum hydroxide, silicon dioxide, silicon micro powder, graphite powder, magnesium carbonate, calcium carbonate, magnesium silicate, calcium silicate, magnesium oxide, calcium oxide, aluminum oxide, aluminum nitride, and boron nitride; the amount of inorganic filler used is 1 part by weight to 30 parts by weight relative to 100 parts by weight of the composition.

[0072] In this invention, the leveling agent comprises silicone oil and / or organosiloxane.

[0073] The polyimide composition of the present invention can be coated onto a PI-based film to form a composite film for copper-clad laminates. The coating method is not particularly limited, nor is the film thickness, as long as the dried film thickness is 0.5–100 μm. These thin-film adhesive materials can also be surface-protected using various protective films.

[0074] The present invention also provides a polyimide film obtained by curing the above composition at 180–200°C.

[0075] In this invention, the preferred method for preparing the polyimide film includes: curing the above composition at 180-200°C and 5-10 MPa for 60-100 min to obtain a polyimide film.

[0076] This invention uses an anhydride containing a carboxyl-terminated structure to cap polyimide, forming an oligomer prepolymer containing a carboxyl group. Then, an aromatic alcohol containing a hydroxyl-terminated structure is introduced to form an ester structure, resulting in a polyesterimide. This material has a lower dielectric constant and higher adhesiveness. When the polyimide obtained by this invention is applied to thermoplastic polyimide (TPI), the compressive strength is lower. Detailed Implementation

[0077] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0078] To further illustrate the present invention, the following embodiments are provided for detailed description. All raw materials used in the following embodiments of the present invention are commercially available products.

[0079] The testing methods used in the embodiments and comparative examples of this invention are as follows:

[0080] 1) Determination of weight-average molecular weight: The weight-average molecular weight was determined using a gel permeation chromatograph (PL-GPC120, Polymer Laboratories, UK).

[0081] 2) Glass transition temperature determination: Static thermomechanical analyzer (TMA Q400), test atmosphere is nitrogen, heating rate is 5℃ / min, temperature range is 20~200℃.

[0082] Example 1

[0083] 1. Add 4,4'-diaminodicyclohexylmethane (0.105 mol, 22.089 g), dimethylacetamide (8.712 g), and toluene (109.03 g) to a reaction vessel and stir to dissolve. Add cyclohexanetetracarboxylic acid dianhydride (0.1 mol, 22.42 g) and react at 80°C for 5 hours. Add trimellitic anhydride (0.01 mol, 79.82 g) and heat to 160°C for 8 hours. Next, add (1,1'-biphenyl)-4,4'-diol (0.01 mol, 1.8621 g) and tetrabutyl titanate catalyst (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 100:105. The weight-average molecular weight of polyimide is 730, and its glass transition temperature is 100℃. Its structure is shown below.

[0084]

[0085] 2. Dissolve the polyimide (100g) and cyclohexanone (400g) obtained in step 1 by stirring. Then add hydroquinone diglycidyl ether (1g), N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane (3g), polystyrene (15g), hexaphenoxycyclotriphosphazene (10g), and silicon dioxide (5g) to the reaction mixture.

[0086] 3. The slurry composition obtained in step 2 above is coated onto a polyimide support substrate and then dried at 100°C for 10 hours to obtain a semi-cured adhesive sheet with a thickness of 20 μm.

[0087] 4. Overlap an 18μm thick low-roughness electrolytic copper foil (ten-point average roughness (Rz): 1.0μm) onto the semi-cured adhesive sheet containing polyimide support substrate obtained in step 3 above, and press it at a pressure of 5MPa and 180℃ for 30 minutes to obtain a copper-clad laminate.

[0088] Example 2

[0089] 1. Add 2,2-bis[4-(4-aminophenoxy)phenyl]propane (0.073 mol, 29.97 g), 4,4'-diaminobenzophenone (0.03 mol, 6.3675 g), and cyclohexanone (150 g) to a reaction vessel and stir to dissolve. Add 3,4,3',4'-diphenyl ether tetracarboxylic dianhydride (0.1 mol, 31.02 g) and react at 120 °C for 0.1 h. Add trimellitic anhydride (0.006 mol, 47.89 g) and heat to 160 °C for 8 h. Next, add (1,1'-biphenyl)-4,4'-diol (0.006 mol, 1.117 g) and tetrabutyl titanate catalyst (1% of trimellitic anhydride) to the reaction vessel and heat to 175 °C for 6 h to obtain a polyimide resin solution. In this embodiment, the molar ratio of diacid anhydride to diamine is 100:103. The polyimide resin has a weight-average molecular weight of 780 and a glass transition temperature of 40°C, and its structure is shown below;

[0090]

[0091] 2. Dissolve polyimide (100g) and cyclohexanone (400g) by stirring. Then add diglycidyl aniline (10g), N-2-(aminoethyl)-3-aminopropyltrimethoxysilane (0.1g), styrene-butadiene copolymer (25g), ammonium polyphosphate (8g), and magnesium hydroxide (1g) to the reaction mixture.

[0092] 3. The slurry composition obtained in step 2 above is coated onto a polyimide support substrate and then dried at 80°C for 16 hours to obtain a semi-cured adhesive sheet with a thickness of 18 μm.

[0093] 4. Overlay an 18μm thick low-roughness electrolytic copper foil (ten-point average roughness (Rz): 1.0μm) onto the semi-cured adhesive sheet containing polyimide support substrate obtained in step 3 above, and press it at a pressure of 5MPa and 180℃ for 60 minutes to obtain a copper-clad laminate.

[0094] Example 3

[0095] 1. Add 1,3-bis(4-aminophenoxy)benzene (0.088 mol, 25.725 g), m-phenylenediamine (0.02 mol, 2.1628 g), and sulfolane (100 g) to a reaction vessel and stir to dissolve. Add 3,4,3',4'-benzophenone tetracarboxylic dianhydride (0.1 mol, 31.02 g) and react at 50 °C for 12 hours. Add trimellitic anhydride (0.016 mol, 127.7 g) and heat to 160 °C for 8 hours. Next, add (1,1'-biphenyl)-4,4'-diol (0.016 mol, 2.979 g) and tetrabutyl titanate catalyst (1% of trimellitic anhydride) to the reaction vessel and heat to 175 °C for 6 hours to obtain a polyimide resin solution. In this embodiment, the molar ratio of diacid anhydride to diamine is 100:108. The polyimide resin has a weight-average molecular weight of 650 and a glass transition temperature of 90°C, and its structure is shown below;

[0096]

[0097] 2. Dissolve the polyimide (100g) and cyclohexanone (400g) obtained in step 1 by stirring. Then add dicyclopentadiene phenol epoxy resin (5g), 3-aminopropyltrimethoxysilane (1g), styrene-isoprene-styrene block copolymer (5g), aluminum diethylphosphite (13g), and aluminum hydroxide (5g) to the reaction mixture.

[0098] 3. The slurry composition obtained in step 2 above is coated onto a polyimide support film using a coating equipment, and then dried at 70°C for 12 hours to obtain a semi-cured adhesive sheet with a thickness of 22μm.

[0099] 4. Overlap an 18μm thick low-roughness electrolytic copper foil (ten-point average roughness (Rz): 1.0μm) onto the semi-cured adhesive sheet containing polyimide support substrate obtained in step 3 above, and press it at a pressure of 5MPa and 180℃ for 40 minutes to obtain a copper-clad laminate.

[0100] Example 4

[0101] 1. Add 1,3-adamantanediamine (0.025 mol, 4.1565 g), 1,4-diaminocyclohexane (0.079 mol, 9.02 g), dimethylformamide (57 g), and toluene (50 g) to a reaction vessel and stir to dissolve. Add cyclohexanetetracarboxylic acid dianhydride (0.1 mol, 20.49 g) and react at 85 °C for 0.1 h. Add trimellitic anhydride (0.008 mol, 63.85 g) and heat to 160 °C for 8 h. Next, add (1,1'-biphenyl)-4,4'-diol (0.008 mol, 1.4897 g) and tetrabutyl titanate catalyst (1% of trimellitic anhydride) to the reaction vessel and heat to 175 °C for 6 h to obtain a polyimide resin solution. In this embodiment, the molar ratio of diacid anhydride to diamine is 100:104. The weight-average molecular weight of the polyimide resin is 810, and the glass transition temperature is 55°C.

[0102] 2. Dissolve the polyimide (100g) and cyclohexanone (165g) obtained in step 1 by stirring. Then add diglycidyl cyclohexanedicarboxylate (3g), 3-aminopropyltriethoxysilane (2.5g), styrene-butadiene-divinylbenzene copolymer (21g), triphenyl phosphate (2g), and silica (18g) to the reaction mixture.

[0103] 3. The slurry composition obtained in step 2 above is coated onto a polyimide support film using a coating equipment, and then dried at 90°C for 16 hours to obtain a semi-cured adhesive sheet with a thickness of 21 μm.

[0104] 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 50 minutes to obtain a copper-clad laminate.

[0105] Example 5

[0106] 1. Add 1,3-diaminomethylcyclohexane (0.09991 mol, 14.21 g), bis(4-aminophenyl)tetramethyldisiloxane (0.0001 mol, 0.0249 g), N-methyl-2-pyrrolidone (52 g), and triethylene glycol dimethyl ether (50 g) to the reaction vessel and stir to dissolve. Add 3,4,3',4'-biphenyltetracarboxylic dianhydride (0.1 mol, 29.422 g) and then react at 120°C for 7 hours. Trimeric trioxide (0.002 mol, 31.92 g) was added, and the mixture was heated to 160 °C for 8 hours. Next, (1,1'-biphenyl)-4,4'-diol (0.002 mol, 0.3724 g) and tetrabutyl titanate (1% of the trimellitic anhydride) were added to the reaction vessel, and the mixture was heated to 175 °C for 6 hours to obtain a polyimide resin solution. In this example, the molar ratio of diacid anhydride to diamine was 100:101. The polyimide resin had a weight-average molecular weight of 940, a glass transition temperature of 60 °C, and its structure is shown below.

[0107]

[0108] 2. Dissolve the polyimide (100g) and cyclohexanone (250g) obtained in step 1 by stirring. Then add diglycidyl phthalate (7g), 3-epoxypropoxypropyltrimethoxysilane (2g), polybutadiene (10g), 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (15g), and silica powder (13g) to the reaction mixture.

[0109] 3. The slurry composition obtained in step 2 is coated onto a polyimide support film using a coating equipment, and then dried at 95°C for 13 hours to obtain a semi-cured adhesive sheet with a thickness of 20 μm.

[0110] 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 50 minutes to obtain a copper-clad laminate.

[0111] Example 6

[0112] 1. Add diaminodicyclohexylpropane (0.1 mol, 23.842 g), 1,3-diaminomethylcyclohexane (0.015 mol, 2.133 g), and phenol (140 g) to the reaction vessel and stir to dissolve. Add 3,4,3',4'-biphenyltetracarboxylic dianhydride (0.05 mol, 14.711 g) and 3,4,3',4'-diphenyl ether tetracarboxylic dianhydride (0.05 mol, 15.51 g) in portions, and then react at 110 °C for 10 hours. Trimeric trioxide (0.03 mol, 478.8 g) was added, and the mixture was heated to 160 °C for 8 hours. Next, (1,1'-biphenyl)-4,4'-diol (0.03 mol, 5.5863 g) and tetrabutyl titanate (1% of the trimellitic anhydride catalyst) were added to the reaction vessel, and the mixture was heated to 175 °C for 6 hours to obtain a polyimide resin solution. The molar ratio of diacid anhydride to diamine was 100:115. The polyimide resin had a weight-average molecular weight of 360 and a glass transition temperature of 62 °C.

[0113] 2. Dissolve the polyimide (100g) and cyclohexanone (200g) obtained in step 1 by stirring. Then add diglycidyl dimerate (2g), 3-epoxypropoxypropylmethyldimethoxysilane (2.3g), C5 / C9 hydrogenated petroleum resin (17g), ammonium polyphosphate (18g), and graphite powder (22g) to the reaction mixture.

[0114] 3. The slurry composition obtained in step 2 is coated onto a polyimide support film using a coating equipment, and then dried at 90°C for 8 hours to obtain a semi-cured adhesive sheet with a thickness of 21 μm.

[0115] 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 170℃ for 30 minutes to obtain a copper-clad laminate.

[0116] Example 7

[0117] 1. Add 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), and chlorophenol (100 g) to the reaction vessel and stir to dissolve. Add 3,4,3',4'-biphenyltetracarboxylic dianhydride (0.1 mol, 29.422 g) and then react at 90 °C for 4 hours. Trimeric trioxide (0.02 mol, 319.2 g) was added, and the mixture was heated to 160 °C for 8 hours. Next, (1,1'-biphenyl)-4,4'-diol (0.02 mol, 3.724 g) and tetrabutyl titanate (1% of the trimellitic anhydride catalyst) were added to the reaction vessel, and the mixture was heated to 175 °C for 6 hours to obtain a polyimide resin solution. In this example, the molar ratio of diacid anhydride to diamine was 100:110. The polyimide resin had a weight-average molecular weight of 320 and a glass transition temperature of 90 °C.

[0118] 2. Dissolve the polyimide (100g) and cyclohexanone (230g) obtained in step 1 by stirring. Then add butanediol diglycidyl ether (6g), 3-mercaptopropylmethyl dimethoxysilane (1.9g), styrene-butadiene-divinylbenzene copolymer (18g), aluminum diethylphosphite (13g), and calcium carbonate (17g) to the reaction mixture.

[0119] 3. The slurry composition obtained in step 2 is coated onto a polyimide support film using a coating equipment, and then dried at 90°C for 16 hours to obtain a semi-cured adhesive sheet with a thickness of 20 μm.

[0120] 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 165℃ for 60 minutes to obtain a copper-clad laminate.

[0121] Example 8

[0122] 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 (1,1'-biphenyl)-4,4'-diol (0.034 mol, 6.331 g) and tetrabutyl titanate catalyst (1% of trimellitic anhydride) to the reaction vessel and heat to 175°C for 6 hours to obtain a polyimide resin solution. In this embodiment, the molar ratio of diacid anhydride to diamine is 100:117. The polyimide resin has a weight-average molecular weight of 610 and a glass transition temperature of 42°C, and its structure is shown below;

[0123]

[0124] 2. Dissolve the polyimide (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 mixture.

[0125] 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.

[0126] 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.

[0127] Experimental Example

[0128] 1) Determination of dielectric constant and dielectric loss of adhesive materials

[0129] 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).

[0130] 2) Adhesive and peel strength test

[0131] For the copper-clad laminate obtained in the embodiments, the peel strength (N / cm) at 90° tension was tested using a tensile testing machine.

[0132] 3) Solderability test

[0133] For the copper-clad laminate obtained in the examples, after curing, it was floated in a solder bath at 288°C with the copper foil side down for 30 seconds to check for any changes in appearance. No change was recorded as acceptable, while foaming or expansion was recorded as unacceptable. The test results are shown in Tables 1 and 2.

[0134] Table 1

[0135]

[0136] Table 2

[0137]

[0138] Comparative Example 1

[0139] Compared to Example 1, this comparative example omits the end-capping step using trimellitic anhydride, specifically including:

[0140] 1. Add diaminodicyclohexylmethane (0.1 mol, 21.037 g), dimethylacetamide (8.712 g), and toluene (109.03 g) to a reaction vessel and stir until dissolved. Add cyclohexanetetracarboxylic acid dianhydride (0.1 mol, 22.42 g) and react at 80 °C for 5 hours. Then, continue heating to 160 °C for 8 hours for imidization to obtain polyimide; the molar ratio of diacid anhydride to diamine is 100:100. The glass transition temperature of polyimide is 40 °C.

[0141] 2. Add polyimide (100g) to cyclohexanone (400g) and stir to dissolve. Then add hydroquinone diglycidyl ether (1g), N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane (3g), polystyrene (15g), hexaphenoxycyclotriphosphazene (10g) and silica (5g). After reaction, a slurry composition is obtained.

[0142] 3. The slurry composition obtained in step 2 above is coated onto a polyimide support substrate and then dried at 100°C for 10 hours to obtain a semi-cured adhesive sheet with a thickness of 20 μm.

[0143] 4. Overlap an 18μm thick low-roughness electrolytic copper foil (ten-point average roughness (Rz): 1.0μm) onto the semi-cured adhesive sheet containing polyimide support substrate obtained in step 3 above, and press it at a pressure of 5MPa and 180℃ for 30 minutes to obtain a copper-clad laminate.

[0144] Comparative Example 2

[0145] Compared to Example 1, this comparative example omits the epoxy compound (crosslinking agent) and specifically includes:

[0146] 1. Add diaminodicyclohexylmethane (0.105 mol, 22.089 g), dimethylacetamide (8.712 g), and toluene (109.03 g) to a reaction vessel and stir to dissolve. Add cyclohexanetetracarboxylic acid dianhydride (0.1 mol, 22.42 g) and react at 80 °C for 5 hours. Add trimellitic anhydride (0.01 mol, 79.82 g) and heat to 160 °C for 8 hours. Next, add (1,1'-biphenyl)-4,4'-diol (0.01 mol, 1.8621 g) and tetrabutyl titanate catalyst (1% of trimellitic anhydride) to the reaction vessel and heat to 175 °C for 6 hours to obtain a polyimide resin solution; the molar ratio of diacid anhydride / diamine is 100:105. The polyimide resin has a weight-average molecular weight of 20,000 and a glass transition temperature of 100℃.

[0147] 2. Dissolve polyimide (100g) and cyclohexanone (400g) by stirring. Then add 3-aminopropyltrimethoxysilane (1g), styrene-isoprene-styrene block copolymer (5g), and aluminum diethylphosphite (13g) to the reaction mixture. After the reaction, a slurry of the composition is obtained.

[0148] 3. The slurry composition obtained in step 2 above is coated onto a polyimide support substrate and then dried at 100°C for 10 hours to obtain a semi-cured adhesive sheet with a thickness of 20 μm.

[0149] 4. Overlap an 18μm thick low-roughness electrolytic copper foil (ten-point average roughness (Rz): 1.0μm) onto the semi-cured adhesive sheet containing polyimide support substrate obtained in step 3 above, and press it at a pressure of 5MPa and 180℃ for 30 minutes to obtain a copper-clad laminate.

[0150] Please refer to Table 3, which compares the performance of the films (semi-cured adhesive sheets) prepared in Comparative Examples 1 and 2 and the obtained copper-clad laminates.

[0151] Table 3

[0152]

[0153] In summary, the film formed by coating the slurry composition provided by the present invention does not have low dielectric constant and low dielectric loss insulation properties at a frequency of 10 GHz; it does not have good adhesion to low profile copper foil and other insulating substrates; in addition, it has poor moisture absorption, solderability, and heat resistance.

[0154] The above description of the disclosed embodiments enables those skilled in the art to make or use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the invention is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. The polymer as shown in Formula 1, In Equation 1, 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; R1 and R2 are independently 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 polymer of claim 1, wherein In Formula 1, A is selected from substituted or unsubstituted C6-C40 aryl groups and substituted or unsubstituted C3-C20 aliphatic rings. R1 and R2 are independently selected from hydrogen and C1 to C10 saturated aliphatic hydrocarbon groups; 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. Polymer, characterized in that, It is The sum of n1 and n2 is 10 to 100.

4. The method of preparing a polymer according to any one of claims 1 to 2, wherein 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 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 Formula 6, R1 and R2 are independently selected from one or more of hydrogen, alkyl, cycloalkyl, and aryl.

5. The method of claim 4, wherein the polymer is prepared by a process comprising: 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 of claim 4, wherein the polymer is prepared by a process comprising: The temperature of the amidation reaction is 50℃~250℃.

7. Composition characterized in that, include: The polymer shown in Formula 1 or the polymer of claim 3, the crosslinking agent, the hydrocarbon resin, and the solvent; In Equation 1, 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; R1 and R2 are independently 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 of claim 7, wherein, The mass ratio of the polymer shown in Formula 1 or the polymer of claim 3, 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 includes epoxy compounds and silane coupling agents.

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

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