Polyimide, adhesive, cured product, adhesive sheet, resin-coated copper foil, copper-clad laminate, printed wiring board

Abstract

To provide a polyimide, an adhesive, a cured product, an adhesive sheet, a copper foil with resin, a copper-clad laminate, and a printed wiring board.SOLUTION: A polyimide is disclosed, the polyimide being a reaction product of a monomer group including aromatic tetracarboxylic acid anhydrides and diamines including dimer diamines and aromatic diamines, with a linear expansion coefficient of 2,500 ppm / K or less.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to polyimides, adhesives, cured products, adhesive sheets, resin-coated copper foils, copper-clad laminates, and printed wiring boards. [Background technology]

[0002] Various known adhesives are used to manufacture mobile communication devices such as mobile phones and smartphones, their base station equipment, network-related electronic devices such as servers and routers, and printed wiring boards included in large computers.

[0003] The present applicant has proposed a "polyimide-based adhesive composition containing a polyimide resin obtained by reacting aromatic tetracarboxylic acids with diamines containing 30 mol% or more of a specific dimer diamine, a thermosetting resin, a flame retardant, and an organic solvent" (see Patent Document 1). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent No. 5534378 Summary of the Invention [Problem to be solved by the invention]

[0005] The problem to be solved by the present invention is to provide a polyimide having a low dielectric loss tangent after curing and good compatibility with a crosslinking agent. [Means for solving the problem]

[0006] The present inventors have found that the above problems can be solved by using a specific component.

[0007] The present disclosure provides the following: (Item 1) A polyimide, The polyimide is a compound obtained by mixing an aromatic tetracarboxylic acid anhydride and Diamines including dimer diamines and aromatic diamines is a reactant of a group of monomers comprising Polyimide having a linear expansion coefficient of 2500 ppm / K or less. (Item 2) An adhesive comprising the polyimide described in the above item. (Item 3) A cured product of the adhesive described above. (Item 4) An adhesive sheet having the cured product described in the above item on at least one side of a support film. (Item 5) A resin-coated copper foil comprising the cured product described in the above item and a copper foil. (Item 6) Resin-coated copper foils and Copper clad laminates, including copper foil or insulating sheets. (Item 7) A printed wiring board having a circuit pattern on the copper foil surface of the copper-clad laminate described in the above item.

[0008] In the present disclosure, one or more of the above-described features may be provided in further combinations in addition to the combinations explicitly stated. [Effects of the Invention]

[0009] The polyimide of the present disclosure has a low dielectric loss tangent when cured and has good compatibility with crosslinking agents. DETAILED DESCRIPTION OF THE INVENTION

[0010] Throughout this disclosure, the range of the values ​​of the physical properties, contents, etc. may be set as appropriate (for example, by selecting from the upper and lower limit values ​​described in each item below). Specifically, when the upper and lower limits of the value α include A3, A2, and A1 (where A3 > A2 > A1), the range of the value α may be, for example, A3 or less, A2 or less, less than A3, less than A2, A1 or more, A2 or more, greater than A1, greater than A2, A1 to A2 (A1 or more and less than A2), A1 to A3, A2 to A3, A1 or more and less than A3, A1 or more and less than A2, A2 or more and less than A3, greater than A1 and less than A3, greater than A1 and less than A2, greater than A2 and less than A3, greater than A1 ...

[0011] In the present disclosure, the components, conditions, numerical values, etc. are not limited to those specifically described in the specification. As long as the problem to be solved by the present invention is solved, the components, conditions, numerical values, etc. are not particularly limited.

[0012] In the present disclosure, the "non-volatile content" refers to the total mass of components other than the organic solvent and water. In one embodiment, the non-volatile content of the target A is the total mass of components remaining when 1 g of the target A is heated at 180°C and reaches a constant weight.

[0013] [Polyimide] The present disclosure provides a polyimide comprising: The polyimide is a compound obtained by mixing an aromatic tetracarboxylic acid anhydride and Diamines including dimer diamines and aromatic diamines is a reactant of a group of monomers comprising Provided is a polyimide having a linear expansion coefficient of 2500 ppm / K or less.

[0014] <Aromatic tetracarboxylic acid anhydride> The aromatic tetracarboxylic acid anhydrides may be used alone or in combination of two or more.

[0015] Examples of aromatic tetracarboxylic acid anhydrides include 2,2',3,3'-biphenyltetracarboxylic acid dianhydride, 2,3',3,4'-biphenyltetracarboxylic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, pyromellitic dianhydride, 1,2,3,4-benzenetetracarboxylic acid anhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic acid dianhydride, 4,4'-oxydiphthalic anhydride, and 4,4'-[propane-2,2-diylbis(1,4-phenyleneoxy)]diphthalic acid dianhydride. Anhydrides, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,3',3,4'-diphenyl ether tetracarboxylic dianhydride, bis(2,3-dicarboxyphenyl)ether dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane Dianhydrides, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, bis(2,3-dicarboxyphenoxyphenyl)sulfone dianhydride, bis(3,4-dicarboxyphenoxyphenyl)sulfone dianhydride, 1,4,5,8-naphthalenetetracarboxylic anhydride, 2,3,6,7-naphthalenetetracarboxylic anhydride, 2,3,6,7-anthracenetetracarboxylic anhydride Examples of suitable dianhydrides include carboxylic acid dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic acid dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, and 2,2-bis(3,3',4,4'-tetracarboxyphenyl)tetrafluoropropane dianhydride.

[0016] In one embodiment, the aromatic tetracarboxylic acid anhydride is preferably a compound represented by formula (1), more preferably a compound having a biphenyl structure, and even more preferably 3,3',4,4'-biphenyltetracarboxylic acid dianhydride.

[0017] <Formula (1)> [ka] (In formula (1), p represents —OCO— or —COO—H2C—HC(—OC(═O)—CH3)—CH2—OCO—, and p represents an integer of 1 to 20.

[0018] The upper and lower limits of the content of the aromatic tetracarboxylic acid anhydride relative to 100 mol% of the monomer group are, for example, 75 mol%, 70 mol%, 65 mol%, 60 mol%, 55 mol%, 50 mol%, etc. In one embodiment, the content is preferably 50 mol% to 75 mol%.

[0019] The upper and lower limits of the content of the aromatic tetracarboxylic acid anhydride relative to 100% by mass of the monomer group are, for example, 75% by mass, 70% by mass, 65% by mass, 60% by mass, 55% by mass, 50% by mass, etc. In one embodiment, the content is preferably 50% by mass to 75% by mass.

[0020] <Diamine> The diamines may be used alone or in combination of two or more.

[0021] Examples of the diamine include dimer diamine, aromatic diamine, and diaminopolysiloxane.

[0022] (Dimer diamine) In the present disclosure, dimer diamine is a compound in which all carboxyl groups of a dimer acid, which is a dimer of an unsaturated fatty acid such as oleic acid, have been substituted with primary amino groups (see, for example, JP-A-9-12712). Non-limiting general formulas of dimer diamines are shown below (in each formula, m+n is preferably 6 to 17, p+q is preferably 8 to 19, and the dashed lines represent carbon-carbon single bonds or carbon-carbon double bonds). [ka]

[0023] Commercially available dimer diamine products include, for example, Versamine 551 (manufactured by Cognix Japan KK), Versamine 552 (manufactured by Cognix Japan KK; hydrogenated Versamine 551), PRIAMINE 1075, and PRIAMINE 1074 (all manufactured by Croda Japan KK).

[0024] The upper and lower limits of the content of the dimer diamine component relative to 100 mol% of diamine are, for example, 60 mol%, 55 mol%, 50 mol%, 45 mol%, 40 mol%, 35 mol%, 30 mol%, 25 mol%, 20 mol%, etc. In one embodiment, the content is preferably 20 mol% to 60 mol%.

[0025] The upper and lower limits of the content of the dimer diamine component relative to 100% by mass of diamine are, for example, 60% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, 20% by mass, etc. In one embodiment, the content is preferably 20% by mass to 60% by mass.

[0026] The upper and lower limits of the content of dimer diamine relative to 100 mol% of the monomer group are, for example, 30 mol%, 25 mol%, 20 mol%, 15 mol%, 10 mol%, 5 mol%, etc. In one embodiment, the content is preferably 5 mol% to 30 mol%.

[0027] The upper and lower limits of the content of dimer diamine relative to 100% by mass of the monomer group are, for example, 30% by mass, 25% by mass, 20% by mass, 15% by mass, 10% by mass, 5% by mass, etc. In one embodiment, the content is preferably 5% by mass to 30% by mass.

[0028] (aromatic diamine) In this disclosure, "aromatic diamine" refers to a compound having two amino groups (-NH2) directly bonded to an aromatic group.

[0029] Examples of aromatic diamines include 4,4'-diaminobiphenyl, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenyl ether, 4,4'-(4,4'-isopropylidenediphenyl-1,1'-diyldioxy)dianiline, 9,9'-bis(aminophenyl)fluorene, 9,9'-bis(4-amino-3-methylphenyl)fluorene, 9,9'-bis(4-amino-3-fluorophenyl)fluorene, 9,9'-bis(4-amino-3-hydroxyphenyl)fluorene, 9,9'-bis(4-methyl-3-aminophenyl)fluorene, 9,9'-bis(4-fluoro-3-aminophenyl)fluorene, 9,9'-bis(4-hydroxy-3-aminophenyl)fluorene, and 9,9'-bis[4-(4-aminophenoxy)phenyl]fluorene.

[0030] In one embodiment, the aromatic diamine is preferably a compound represented by formula (2), and more preferably a fluorene skeleton-containing diamine. <Formula (2)> [ka] (Wherein, Y represents a single bond, -SO2-, -CO-, -O-, -O-C6H4-O-, -O-C6H4-C(CH3)2-C6H4-O-, -COO-(CH2) q -OCO-, -COO-H2C-HC(-OC(=O)-CH3)-CH2-OCO- or [ka] and q represents an integer of 1 to 20. It is expressed by:

[0031] The upper and lower limits of the content of aromatic diamine in 100 mol% of diamine are, for example, 80 mol%, 75 mol%, 70 mol%, 65 mol%, 60 mol%, 55 mol%, 50 mol%, 45 mol%, 40 mol%, 35 mol%, 30 mol%, 25 mol%, 20 mol%, etc. In one embodiment, the content is preferably 20 mol% to 80 mol%, more preferably 30 mol% to 70 mol%.

[0032] The upper and lower limits of the aromatic diamine content in 100% by mass of diamine are, for example, 72% by mass, 70% by mass, 65% by mass, 60% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, 20% by mass, 15% by mass, 14% by mass, etc. In one embodiment, the content is preferably 14% by mass to 72% by mass, and more preferably 22% by mass to 60% by mass.

[0033] The upper and lower limits of the content of the aromatic diamine in 100 mol% of the monomer group are, for example, 40 mol%, 35 mol%, 30 mol%, 25 mol%, 20 mol%, 15 mol%, 10 mol%, etc. In one embodiment, the content is preferably 10 mol% to 40 mol%, more preferably 15 mol% to 35 mol%.

[0034] The upper and lower limits of the content of the aromatic diamine in 100% by mass of the monomer group are, for example, 42% by mass, 40% by mass, 36% by mass, 35% by mass, 30% by mass, 25% by mass, 20% by mass, 15% by mass, 10% by mass, 9% by mass, etc. In one embodiment, the content is preferably 9% by mass to 42% by mass, and more preferably 14% by mass to 36% by mass.

[0035] (diaminopolysiloxane) Examples of diaminopolysiloxanes include α,ω-bis(2-aminoethyl)polydimethylsiloxane, α,ω-bis(3-aminopropyl)polydimethylsiloxane, α,ω-bis(4-aminobutyl)polydimethylsiloxane, α,ω-bis(5-aminopentyl)polydimethylsiloxane, α,ω-bis[3-(2-aminophenyl)propyl]polydimethylsiloxane, α,ω-bis[3-(4-aminophenyl)propyl]polydimethylsiloxane, 1,3-bis(3-aminopropyl)tetramethyldisiloxane, and 1,3-bis(4-aminobutyl)tetramethyldisiloxane.

[0036] The upper and lower limits of the content of diaminopolysiloxane relative to 100 mol% of diamine are, for example, 5, 4, 3, 2, 1, 0 mol%, etc. In one embodiment, the content is preferably 0 to 5 mol%.

[0037] The upper and lower limits of the content of diaminopolysiloxane relative to 100% by mass of diamine are, for example, 5% by mass, 4% by mass, 3% by mass, 2% by mass, 1% by mass, 0% by mass, etc. In one embodiment, the content is preferably 0% by mass to 5% by mass.

[0038] The upper and lower limits of the content of diaminopolysiloxane relative to 100 mol% of the monomer group are, for example, 5 mol%, 4 mol%, 3 mol%, 2 mol%, 1 mol%, 0 mol%, etc. In one embodiment, the content is preferably 0 mol% to 5 mol%.

[0039] The upper and lower limits of the content of diaminopolysiloxane relative to 100% by mass of the monomer group are, for example, 5% by mass, 4% by mass, 3% by mass, 2% by mass, 1% by mass, 0% by mass, etc. In one embodiment, the content is preferably 0% by mass to 5% by mass.

[0040] The upper and lower limits of the molar ratio of aromatic tetracarboxylic anhydride to diamine [aromatic tetracarboxylic anhydride / diamine] are, for example, 1.5, 1.4, 1.3, 1.2, 1.1, 1.0, etc. In one embodiment, the molar ratio is preferably 1.0 to 1.5 from the viewpoints of solvent solubility and solution stability.

[0041] The upper and lower limits of the mass ratio of aromatic tetracarboxylic anhydride to diamine [aromatic tetracarboxylic anhydride / diamine] are, for example, 1.5, 1.4, 1.2, 1.0, 0.9, 0.7, 0.6, 0.5, etc. In one embodiment, the mass ratio is preferably 0.5 to 1.5.

[0042] <Other Monomers> In one embodiment, the monomer group may include monomers other than those mentioned above (also referred to as "other monomers"), such as aliphatic tetracarboxylic acid anhydrides.

[0043] In one embodiment, the content of other monomers in the monomer group is, for example, less than 5 mol%, less than 4 mol%, less than 1 mol%, less than 0.9 mol%, less than 0.5 mol%, less than 0.1 mol%, or 0 mol%.

[0044] In one embodiment, the content of other monomers in the monomer group is, for example, less than 5% by mass, less than 4% by mass, less than 1% by mass, less than 0.9% by mass, less than 0.5% by mass, less than 0.1% by mass, or 0% by mass.

[0045] <Physical properties of polyimide> Examples of upper and lower limits of the linear expansion coefficient of the polyimide include 2500 ppm / K, 2400 ppm / K, 2300 ppm / K, 2200 ppm / K, 2100 ppm / K, 2000 ppm / K, 1900 ppm / K, 1800 ppm / K, 1700 ppm / K, 1600 ppm / K, 1500 ppm / K, 1000 ppm / K, 900 ppm / K, 800 ppm / K, 700 ppm / K, 600 ppm / K, 500 ppm / K, 400 ppm / K, 300 ppm / K, 200 ppm / K, and 100 ppm / K. In one embodiment, the linear expansion coefficient is preferably 2500 ppm / K or less, and more preferably 100 ppm / K to 2500 ppm / K.

[0046] The upper and lower limits of the glass transition temperature of the polyimide are, for example, 230°C, 220°C, 210°C, 200°C, 190°C, 180°C, 170°C, 160°C, 150°C, 140°C, and 130°C. In one embodiment, the glass transition temperature is preferably 130°C to 230°C.

[0047] The measurement conditions for the linear expansion coefficient and the glass transition temperature are, for example, as follows: Thermomechanical analyzer: Product name "TMA7100" manufactured by Shimadzu Corporation Load: 12mN Sample width: 4mm Chuck distance: 10mm Heating from 40℃ to 200℃ at 10℃ / min The glass transition temperature is the temperature at the intersection of the tangent lines before and after the change in slope. The evaluation sample can be produced, for example, by the following method. (1) Polyimide is coated onto release paper (manufactured by San-A Chemical Co., Ltd.), and dried at 150°C for 5 minutes and then at 170°C for 30 minutes to obtain a laminated film with a polyimide layer formed. (2) The release paper is peeled off from the laminated film to obtain three 15 μm thick polyimide films, which are then laminated together and melted in a heat press at 170° C. to obtain a 45 μm thick polyimide film (evaluation sample).

[0048] Examples of upper and lower limits of the weight-average molecular weight of the polyimide include 50,000, 45,000, 40,000, 35,000, 30,000, 25,000, 20,000, 15,000, 10,000, 7,500, 5,500, and 5,000. In one embodiment, the weight-average molecular weight is preferably 5,000 to 50,000 from the viewpoints of dielectric properties, solvent solubility, and flexibility.

[0049] The upper and lower limits of the number average molecular weight of the polyimide are, for example, 40,000, 30,000, 20,000, 10,000, 7,500, 5,000, 3,000, and 2,000. In one embodiment, the number average molecular weight of the polyimide is preferably 2,000 to 40,000 from the viewpoints of dielectric properties, solvent solubility, and flexibility.

[0050] The conditions for measuring the weight average molecular weight and the number average molecular weight include, for example, the following conditions. Model: Product name "HLC-8320GPC" (manufactured by Tosoh Corporation) Column: Product name "TSKgel SuperHZM-M" (manufactured by Tosoh Corporation) Developing solvent: THF Flow rate: 0.35mL / min Measurement temperature: 40℃ Detector: RI Standard: Polystyrene Polymer concentration: 0.4 wt%

[0051] <Polyimide manufacturing method, etc.> The polyimide can be produced by various known methods, including a step of polyaddition reaction of a group of monomers including an aromatic tetracarboxylic anhydride and a diamine such as dimer diamine to obtain a polyaddition product (polyaddition step), followed by an imidization reaction (dehydration ring-closing reaction) to obtain a polyimide (imidization step).

[0052] In one embodiment, the reaction temperature in the polyaddition step is preferably about 60 to 120°C, and more preferably about 80 to 100°C.

[0053] In one embodiment, the reaction time for the polyaddition step is preferably about 0.1 to 2 hours, and more preferably about 0.1 to 0.5 hours.

[0054] In one embodiment, the reaction temperature in the imidization step is preferably about 80 to 250°C, and more preferably about 100 to 200°C.

[0055] In one embodiment, the reaction time for the imidization step is preferably about 0.5 to 50 hours, and more preferably about 1 to 20 hours.

[0056] In the imidization reaction step, various known reaction catalysts, dehydrating agents, and organic solvents described below can be used. The various known reaction catalysts, dehydrating agents, and organic solvents described below can be used alone or in combination of two or more.

[0057] Examples of the reaction catalyst include aliphatic tertiary amines such as triethylamine, aromatic tertiary amines such as dimethylaniline, and heterocyclic tertiary amines such as pyridine, picoline, and isoquinoline.

[0058] Examples of the dehydrating agent include aliphatic acid anhydrides such as acetic anhydride, and aromatic acid anhydrides such as benzoic anhydride.

[0059] The imide ring closure rate of the polyimide is not particularly limited. Here, the "imide ring closure rate" refers to the content of cyclic imide bonds in the polyimide, and can be determined by various spectroscopic means such as NMR or IR analysis. From the viewpoint of obtaining good room temperature adhesion and heat-resistant adhesion, the imide ring closure rate of the polyimide is preferably about 70% or more, more preferably about 85 to 100%.

[0060] [glue] The present disclosure provides an adhesive comprising the above polyimide.

[0061] The upper and lower limits of the content of the polyimide relative to 100% by mass of the adhesive are, for example, 90% by mass, 85% by mass, 80% by mass, 75% by mass, 70% by mass, 65% by mass, 60% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, 20% by mass, 15% by mass, 10% by mass, 5% by mass, etc. In one embodiment, the content is preferably about 5% by mass to 90% by mass.

[0062] <Crosslinking agent> In one embodiment, the adhesive contains a crosslinking agent. The crosslinking agents may be used alone or in combination of two or more.

[0063] Examples of the crosslinking agent include epoxides, benzoxazines, bismaleimides, cyanate esters, polyisocyanates, and trimer triamines.

[0064] (epoxide) Examples of epoxides include phenol novolac type epoxides, cresol novolac type epoxides, bisphenol A type epoxides, bisphenol F type epoxides, bisphenol S type epoxides, hydrogenated bisphenol A type epoxides, hydrogenated bisphenol F type epoxides, stilbene type epoxides, triazine skeleton-containing epoxides, fluorene skeleton-containing epoxides, linear aliphatic epoxides, alicyclic epoxides, glycidylamine type epoxides, triphenolmethane type epoxides, alkyl-modified triphenolmethane type epoxides, biphenyl type epoxides, dicyclopentadiene skeleton-containing epoxides, naphthalene skeleton-containing epoxides, aryl alkylene type epoxides, tetraglycidylxylylenediamine, dimer acid-modified epoxides which are dimer acid-modified products of the above epoxides, and dimer acid diglycidyl esters. In one embodiment, from the viewpoint of a balance of heat-resistant adhesion, moisture absorption solder heat resistance, and low dielectric properties, the epoxide is preferably bisphenol A epoxide, bisphenol F epoxide, hydrogenated bisphenol A epoxide, or alicyclic epoxide.

[0065] Commercially available epoxides include, for example, "jER828," "jER834," and "jER807" manufactured by Mitsubishi Chemical Corporation, "ST-3000" manufactured by Nippon Steel Chemical Co., Ltd., "Celloxide 2021P" manufactured by Daicel Chemical Industries, Ltd., "YD-172-X75" manufactured by Nippon Steel Chemical Co., Ltd., and "TETRAD-X" manufactured by Mitsubishi Gas Chemical Co., Inc.

[0066] In particular, tetraglycidyl diamine of the following structure has good compatibility with the above polyimides. Furthermore, its use facilitates achieving a low loss modulus of the adhesive layer, and also improves its heat-resistant adhesiveness and low dielectric properties. [ka] (wherein Y represents a phenylene group or a cyclohexylene group).

[0067] When an epoxide is used as the crosslinking agent, a curing agent for the epoxide and an active ester curing agent can be used in combination. The curing agents can be used alone or in combination of two or more.

[0068] Curing agents for epoxides include, for example, succinic anhydride, phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, 3-methyl-hexahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, or a mixture of 4-methyl-hexahydrophthalic anhydride and hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl-tetrahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, norbornane-2,3-dicarboxylic anhydride, methylnorbornane-2,3-dicarboxylic anhydride, methylcyclohexene dicarboxylic anhydride, 3-dodecenyl succinic anhydride, octadec ... Examples of suitable curing agents include acid anhydride curing agents such as nicotinic anhydride; amine curing agents such as dicyandiamide (DICY), aromatic diamines (trade names "Lonzacure M-DEA" and "Lonzacure M-DETDA," both manufactured by Lonza Japan Co., Ltd.), and aliphatic amines; phenolic curing agents such as phenol novolac resin, cresol novolac resin, bisphenol A novolac resin, triazine-modified phenol novolac resin, and phenolic hydroxyl group-containing phosphazene (trade name "SPH-100" manufactured by Otsuka Chemical Co., Ltd.); cyclic phosphazene compounds; and rosin-based crosslinking agents such as maleic acid-modified rosin and its hydride. The epoxide curing agent is preferably a phenolic curing agent, and more preferably a phenolic hydroxyl group-containing phosphazene curing agent.

[0069] Examples of active ester-based curing agents include those containing a dicyclopentadienyldiphenol structure described in JP-A-2019-183071, those containing a naphthalene structure, acetylated phenol novolac, and benzoylated phenol novolac.

[0070] Commercially available active ester curing agents include, for example: Those containing a dicyclopentadienyldiphenol structure include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000", "HPC-8000H", "HPC-8000-65T", "HPC-8000H-65MT", "HPC-8000L-65MT", "HPC-8150-62T", "EXB-8000L", "EXB-8000L-65TM", and "EXB-8150-65T" (all manufactured by DIC Corporation); Examples containing a naphthalene structure include "EXB9416-70BK" (manufactured by DIC Corporation); As an acetylated product of phenol novolac, "DC808" (manufactured by Mitsubishi Chemical Corporation); Examples of benzoylated phenol novolak include "YLH1026," "YLH1030," and "YLH1048" (manufactured by Mitsubishi Chemical Corporation).

[0071] Examples of active ester-based curing agents include those obtained by reacting a polyfunctional phenol compound with an aromatic carboxylic acid, as described in Japanese Patent No. 5152445.

[0072] Among the curing agents, active ester curing agents and phenolic curing agents are preferred, and active ester curing agents are particularly preferred. In one embodiment, when the nonvolatile content of the adhesive is taken as 100% by mass, the amount of the curing agent used is preferably about 0.1% by mass to 120% by mass, and more preferably about 10% by mass to 40% by mass.

[0073] When an epoxide and a curing agent for an epoxide are used in combination as a crosslinking agent, a reaction catalyst can be further used in combination. The reaction catalysts can be used alone or in combination of two or more.

[0074] Examples of reaction catalysts include tertiary amines such as 1,8-diaza-bicyclo[5.4.0]undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol; imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and 2-heptadecylimidazole; organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, and phenylphosphine; and tetraphenylboron salts such as tetraphenylphosphonium tetraphenylborate, 2-ethyl-4-methylimidazole tetraphenylborate, and N-methylmorpholine tetraphenylborate.

[0075] In one embodiment, the amount of the reaction catalyst used is preferably about 0.01% by mass to 5% by mass, where the nonvolatile content of the adhesive is 100% by mass.

[0076] (benzoxazine) Examples of benzoxazine include 6,6-(1-methylethylidene)bis(3,4-dihydro-3-phenyl-2H-1,3-benzoxazine), 6,6-(1-methylethylidene)bis(3,4-dihydro-3-methyl-2H-1,3-benzoxazine), etc. A phenyl group, a methyl group, a cyclohexyl group, etc. may be bonded to the nitrogen of the oxazine ring.

[0077] Commercially available benzoxazine products include, for example, "Benzoxazine Fa type" and "Benzoxazine Pd type" manufactured by Shikoku Chemicals Corporation, and "RLV-100" manufactured by Air Water Corporation.

[0078] (bismaleimide) Examples of bismaleimides include 4,4'-diphenylmethane bismaleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, 4,4'-diphenyl ether bismaleimide, and 4,4'-diphenylsulfone bismaleimide.

[0079] Commercially available bismaleimides include, for example, "BAF-BMI" manufactured by JFE Chemical Corporation.

[0080] (cyanate ester) Examples of cyanate esters include 2-allylphenol cyanate ester, 4-methoxyphenol cyanate ester, 2,2-bis(4-cyanatophenol)-1,1,1,3,3,3-hexafluoropropane, bisphenol A cyanate ester, diallylbisphenol A cyanate ester, 4-phenylphenol cyanate ester, 1,1,1-tris(4-cyanatophenyl)ethane, 4-cumylphenol cyanate ester, 1,1-bis(4-cyanatophenyl)ethane, 4,4'-bisphenol cyanate ester, and 2,2-bis(4-cyanatophenyl)propane.

[0081] An example of a commercially available cyanate ester product is "PRIMASET BTP-6020S (manufactured by Lonza Japan Co., Ltd.)".

[0082] (Polyisocyanate) In this disclosure, a "polyisocyanate" is a compound having two or more isocyanate groups (-N=C=O).

[0083] Examples of polyisocyanates include linear aliphatic polyisocyanates, branched aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and their biurets, isocyanurates, allophanates, adducts, etc. Polyisocyanates may be used alone or in combination of two or more.

[0084] Examples of the linear aliphatic group include a linear alkylene group. The linear alkylene group is represented by the general formula: -(CH2) n It is expressed as - (n is an integer greater than or equal to 1).

[0085] Examples of the straight-chain alkylene group include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group, an n-heptylene group, an n-octylene group, an n-nonylene group, and an n-decamethylene group.

[0086] Examples of the linear aliphatic polyisocyanate include methylene diisocyanate, dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, and decamethylene diisocyanate.

[0087] Examples of the branched aliphatic group include a branched alkylene group.

[0088] A branched alkylene group is a group in which at least one hydrogen atom of a straight-chain alkylene group is substituted with an alkyl group, and is a group that does not have a cyclic structure.

[0089] Examples of the branched alkylene group include a diethylpentylene group, a trimethylbutylene group, a trimethylpentylene group, and a trimethylhexylene group (trimethylhexamethylene group).

[0090] Examples of branched aliphatic polyisocyanates include diethylpentylene diisocyanate, trimethylbutylene diisocyanate, trimethylpentylene diisocyanate, and trimethylhexamethylene diisocyanate.

[0091] Examples of the alicyclic group include a cycloalkylene group.

[0092] Examples of the cycloalkylene group include a monocyclic cycloalkylene group, a bridged ring cycloalkylene group, and a fused ring cycloalkylene group.

[0093] In the cycloalkylene group, one or more hydrogen atoms may be replaced by a straight-chain or branched alkyl group.

[0094] In this disclosure, a monocyclic ring refers to a ring structure formed by a covalent carbon bond and having no internal bridged structure. A fused ring refers to a ring structure in which two or more monocyclic rings share two atoms (i.e., each ring shares (fused) only one edge with another). A bridged ring refers to a ring structure in which two or more monocyclic rings share three or more atoms.

[0095] Examples of the monocyclic cycloalkylene group include a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclodecylene group, and a 3,5,5-trimethylcyclohexylene group.

[0096] Examples of the bridged ring cycloalkylene group include a tricyclodecylene group, an adamantylene group, and a norbornylene group.

[0097] Examples of the fused ring cycloalkylene group include a bicyclodecylene group.

[0098] Examples of the alicyclic polyisocyanate include monocyclic alicyclic polyisocyanates, crosslinked cyclic alicyclic polyisocyanates, and condensed cyclic alicyclic polyisocyanates.

[0099] Examples of monocyclic alicyclic polyisocyanates include hydrogenated xylene diisocyanate, isophorone diisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, cycloheptylene diisocyanate, cyclodecylene diisocyanate, 3,5,5-trimethylcyclohexylene diisocyanate, and dicyclohexylmethane diisocyanate.

[0100] Examples of the crosslinked alicyclic polyisocyanate include tricyclodecylene diisocyanate, adamantane diisocyanate, and norbornene diisocyanate.

[0101] An example of the condensed ring alicyclic polyisocyanate is bicyclodecylene diisocyanate.

[0102] Examples of the aromatic group include a monocyclic aromatic group, a fused ring aromatic group, etc. In addition, one or more hydrogen atoms of the aromatic group may be substituted with a linear or branched alkyl group.

[0103] Examples of the monocyclic aromatic group include a phenyl group (phenylene group), a tolyl group (tolylene group), and a mesityl group (mesitylene group).

[0104] Examples of the fused ring aromatic group include a naphthyl group (naphthylene group).

[0105] Examples of aromatic polyisocyanates include monocyclic aromatic polyisocyanates and condensed ring aromatic polyisocyanates.

[0106] Examples of the monocyclic aromatic polyisocyanate include dialkyldiphenylmethane diisocyanates such as 4,4'-diphenyldimethylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanates such as 4,4'-diphenyltetramethylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-dibenzyl isocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, and m-tetramethylxylylene diisocyanate.

[0107] An example of the condensed ring aromatic polyisocyanate is 1,5-naphthylene diisocyanate.

[0108] The biuret form of polyisocyanate is, for example, The following structural formula: [ka] [where n b is an integer equal to or greater than 1, and R bA ~R bE are each independently an alkylene group, an arylene group, or a group formed by combining an alkylene group and an arylene group, and R bα ~R bβ are each independently an isocyanate group or [ka] (n b1 is an integer greater than or equal to 0, and R b1 ~R b5 are each independently an alkylene group, an arylene group, or a group formed by combining an alkylene group and an arylene group, and R b '~R b '' each independently represent an isocyanate group or R bα ~R bβ It is a group of its own. R b4 ~R b5 , R b '' may be different groups for each structural unit. bD~R bE , R bβ may have different groups for each structural unit.

[0109] Examples of the group formed by combining an alkylene group and an arylene group include an alkylenearylenealkylene group.

[0110] The alkylene arylene alkylene group is -R alkylene -R arylene -R alkylene - (In the formula, R alkylene represents an alkylene group, and R arylene represents an arylene group) It is a group represented by:

[0111] Examples of biuret polyisocyanates include Duranate 24A-100, Duranate 22A-75P, and Duranate 21S-75E (all manufactured by Asahi Kasei Corporation), and Desmodur N3200A (a biuret of hexamethylene diisocyanate) (all manufactured by Sumitomo Bayer Urethane Co., Ltd.).

[0112] The isocyanurate of polyisocyanate is, for example, The following structural formula: [ka] [where n i is an integer greater than or equal to 0, and R iA ~R iE are each independently an alkylene group, an arylene group, or a group formed by combining an alkylene group and an arylene group, and R iα ~R iβ are each independently an isocyanate group or [ka] (n i1 is an integer greater than or equal to 0, and R i1 ~R i5are each independently an alkylene group, an arylene group, or a group formed by combining an alkylene group and an arylene group, and R i '~R i '' each independently represent an isocyanate group or R iα ~R iβ It is a group of its own. R i5 , R i '' may be different groups for each structural unit. iD ~R iE , R iβ may have different groups for each structural unit.

[0113] Examples of isocyanurate polyisocyanates include Duranate TPA-100, Duranate TKA-100, Duranate MFA-75B, and Duranate MHG-80B (all manufactured by Asahi Kasei Corporation), Coronate HXR (an isocyanurate of hexamethylene diisocyanate) (all manufactured by Tosoh Corporation), Takenate D-131N (an isocyanurate of xylene diisocyanate), Takenate D204EA-1 (an isocyanurate of toluene diisocyanate), and Takenate D-127N (an isocyanurate of hydrogenated xylene diisocyanate) (all manufactured by Mitsui Chemicals, Inc.), and VESTANAT T1890 / 100 (an isocyanurate of isophorone diisocyanate) (all manufactured by Evonik Japan Co., Ltd.).

[0114] The allophanate form of polyisocyanate is, for example, The following structural formula: [ka] [where n a is an integer greater than or equal to 0, and R aA is an alkyl group or an aryl group, and R aB ~R aG are each independently an alkylene group, an arylene group, or a group formed by combining an alkylene group and an arylene group, and R aα ~R aγ are each independently an isocyanate group or [ka] (n a1 is an integer greater than or equal to 0, and R a1 ~R a6 are each independently an alkylene group or an arylene group, and R a '~R a ''' each independently represent an isocyanate group or R aα ~R aγ It is a group of its own. R a1 ~R a4 , R a '~R a ''' may be a different group for each structural unit. aB ~R aE , R aα ~R aγ may have different groups for each structural unit.

[0115] An example of a commercially available allophanate product of polyisocyanate is Takenate D-178N (manufactured by Mitsui Chemicals, Inc.).

[0116] Examples of polyisocyanate adducts include: The following structural formula: [ka] [where n ad is an integer greater than or equal to 0, and R adA ~R adE are each independently an alkylene group, an arylene group, or a group formed by combining an alkylene group and an arylene group, and R ad1 ~R ad2 are each independently [ka] (In the formula, n ad’ is an integer greater than or equal to 0, and R ad’ ~R ad’’ are each independently an alkylene group, an arylene group, or a group formed by combining an alkylene group and an arylene group, and Rad’’’ is R ad1 ~R ad2 Its own base, R ad’ ~R ad’’’ may have different groups for each structural unit. and R adD ~R adE , R ad2 may be different groups for each structural unit.] an adduct of trimethylolpropane and polyisocyanate represented by The following structural formula [ka] [where n ad1 is an integer greater than or equal to 0, and R adα ~R adε are each independently an alkylene group or an arylene group, and R adA ~R adB are each independently [ka] (In the formula, n ad1’ is an integer greater than or equal to 0, and R adδ’ ~R adε’ are each independently an alkylene group, an arylene group, or a group formed by combining an alkylene group and an arylene group, and R adB’ is R adA ~R adB Its own base, R adδ’ ~R adε’ , R adB’ may have different groups for each structural unit. and R adδ ~R adε may be different groups for each structural unit.] Examples of suitable glycerin compounds include an adduct of glycerin and polyisocyanate represented by the following formula:

[0117] Examples of polyisocyanate adducts include Duranate P301-75E (both manufactured by Asahi Kasei Corporation), Takenate D110N, Takenate D160N (both manufactured by Mitsui Chemicals, Inc.), and Coronate L (both manufactured by Tosoh Corporation).

[0118] (trimer triamine) Trimer triamines are obtained by substituting all carboxyl groups of trimer acid, which is a trimer of unsaturated fatty acids such as oleic acid (see, for example, JP 2013-505345 A), with primary amino groups, and various known trimer triamines can be used without particular limitation. A non-limiting structural formula of trimer triamine is shown below (the dashed line represents a carbon-carbon single bond or a carbon-carbon double bond, and R represents an ethylene group (-CHCH-) or an ethenylene group (-CH=CH-)). [ka]

[0119] An example of a commercially available trimer triamine product is PRIAMINE 1071 (manufactured by Croda Japan Co., Ltd.) The content of the trimer triamine component in commercially available products is usually about 15 to 20 mass %, and the remainder may be more than 80 mass % dimer diamine.

[0120] The upper and lower limits of the content of the crosslinking agent relative to 100 parts by mass of the polyimide (based on nonvolatile content) are, for example, 900 parts by mass, 800 parts by mass, 700 parts by mass, 600 parts by mass, 500 parts by mass, 400 parts by mass, 300 parts by mass, 200 parts by mass, 100 parts by mass, 50 parts by mass, 20 parts by mass, 10 parts by mass, 5 parts by mass, etc. In one embodiment, the content is preferably 5 parts by mass to 900 parts by mass.

[0121] The upper and lower limits of the content of the crosslinking agent relative to 100% by mass of the adhesive are, for example, 80% by mass, 70% by mass, 60% by mass, 50% by mass, 40% by mass, 30% by mass, 20% by mass, 10% by mass, 5% by mass, 2% by mass, etc. In one embodiment, the content is preferably 2% by mass to 80% by mass.

[0122] <Flame retardant> In one embodiment, the adhesive contains a flame retardant. The flame retardants may be used alone or in combination of two or more.

[0123] Examples of the flame retardant include phosphorus-based flame retardants and inorganic fillers.

[0124] (Phosphorus-based flame retardants (phosphorus-containing flame retardants)) Examples of the phosphorus-based flame retardant include polyphosphoric acid, phosphoric acid ester, and phosphazene derivatives that do not contain a phenolic hydroxyl group. In one embodiment, from the viewpoints of flame retardancy, heat resistance, bleed-out resistance, etc., the phosphorus-based flame retardant is preferably a cyclic phosphazene derivative.

[0125] Examples of commercially available cyclic phosphazene derivatives include SPB-100 manufactured by Otsuka Chemical Co., Ltd. and Lavitol FP-300B manufactured by Fushimi Pharmaceutical Co., Ltd.

[0126] (inorganic filler) Examples of inorganic fillers include silica fillers, phosphorus-based fillers, fluorine-based fillers, and inorganic ion exchange fillers.

[0127] Examples of commercially available inorganic fillers include "FB-3SDC" and "SFP-20M" manufactured by Denka Co., Ltd., "SC-2500-SPJ", "SC-2500-SXJ", and "SC-2500-SVJ" manufactured by Admatechs Co., Ltd., "Exolit OP935" manufactured by Clariant Chemicals K.K., "KTL-500F" manufactured by Kitamura Co., Ltd., and "IXE" manufactured by Toagosei Co., Ltd.

[0128] The upper and lower limits of the content of the flame retardant relative to 100 parts by mass of the polyimide (converted to nonvolatile content) are, for example, 150 parts by mass, 100 parts by mass, 50 parts by mass, 10 parts by mass, 5 parts by mass, 1 part by mass, etc. In one embodiment, the content is preferably 1 part by mass to 150 parts by mass.

[0129] <Reactive alkoxysilyl compounds> In one embodiment, the adhesive comprises a reactive alkoxysilyl compound of the general formula: General formula: Z-Si(R 1 ) a (OR 2 ) 3-a (wherein Z represents a group containing a functional group reactive with an acid anhydride group, R 1 represents hydrogen or a hydrocarbon group having 1 to 8 carbon atoms, R 2 represents a hydrocarbon group having 1 to 8 carbon atoms, and a represents 0, 1, or 2.

[0130] The reactive alkoxysilyl compound can adjust the melt viscosity of the adhesive layer of the adhesive of the present disclosure while maintaining the low dielectric properties of the adhesive layer, thereby increasing the interfacial adhesion between the adhesive layer and the substrate (the so-called anchor effect) and suppressing the exudation of the cured layer from the edge of the substrate.

[0131] Examples of the reactive functional group contained in Z in the above general formula include an amino group, an epoxy group, a thiol group, etc. In one embodiment, from the viewpoint of achieving good reactivity and flow control effects, the reactive alkoxysilyl compound is preferably a compound in which Z contains an amino group.

[0132] Examples of compounds in which Z contains an amino group include N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and 3-ureidopropyltrialkoxysilane.

[0133] Examples of compounds in which Z contains an epoxy group include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane.

[0134] Examples of compounds in which Z contains a thiol group include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 3-mercaptopropylmethyldiethoxysilane.

[0135] The upper and lower limits of the content of the reactive alkoxysilyl compound relative to 100 parts by mass of the polyimide (based on nonvolatile content) are, for example, 5 parts by mass, 2.5 parts by mass, 1 part by mass, 0.5 parts by mass, 0.1 parts by mass, 0.05 parts by mass, 0.01 parts by mass, etc. In one embodiment, the content is preferably 0.01 parts by mass to 5 parts by mass.

[0136] <Organic solvents> In one embodiment, the adhesive contains an organic solvent. The organic solvents may be used alone or in combination of two or more.

[0137] Examples of organic solvents include aprotic polar solvents such as N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, N-methylcaprolactam, methyl triglyme, and methyl diglyme; alicyclic solvents such as cyclohexanone and methylcyclohexane; alcoholic solvents such as methanol, ethanol, propanol, benzyl alcohol, and cresol; and aromatic solvents such as toluene.

[0138] The upper and lower limits of the content of the organic solvent relative to 100% by mass of the adhesive are, for example, 90% by mass, 95% by mass, 80% by mass, 75% by mass, 70% by mass, 65% by mass, 60% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, etc. In one embodiment, the content is preferably 40% by mass to 90% by mass.

[0139] The upper and lower limits of the content of the organic solvent relative to 100 parts by mass of the polyimide (based on nonvolatile content) are, for example, 900 parts by mass, 800 parts by mass, 700 parts by mass, 600 parts by mass, 500 parts by mass, 400 parts by mass, 300 parts by mass, 200 parts by mass, 150 parts by mass, etc. In one embodiment, the content is preferably 150 parts by mass to 900 parts by mass.

[0140] <Additives> The adhesive may contain an additive other than the polyimide, crosslinking agent, flame retardant, reactive alkoxysilyl compound, or organic solvent.

[0141] Examples of the additives include ring-opening esterification reaction catalysts, dehydrating agents, plasticizers, weathering agents, antioxidants, heat stabilizers, lubricants, antistatic agents, brighteners, colorants, conductive agents, mold release agents, surface treatment agents, viscosity modifiers, silica fillers, and fluorine fillers.

[0142] In one embodiment, the content of the additive may be, for example, less than 1 part by mass, less than 0.1 parts by mass, less than 0.01 parts by mass, or 0 parts by mass relative to 100 parts by mass of the adhesive. Also, for example, the content of the additive may be, for example, less than 1 part by mass, less than 0.1 parts by mass, less than 0.01 parts by mass, or 0 parts by mass relative to 100 parts by mass of any of the polyimide, crosslinking agent, flame retardant, reactive alkoxysilyl compound, and organic solvent.

[0143] The adhesive can be produced by dispersing and mixing polyimide and, if necessary, a crosslinking agent, a flame retardant, a reactive alkoxysilyl compound, an organic solvent, and additives by various known means. The order in which the components are added is not particularly limited. Various known devices (such as an emulsifying disperser or an ultrasonic disperser) can be used as the dispersing and mixing means.

[0144] The adhesive can be used as an interlayer insulating material, an adhesive for copper-clad laminates, an adhesive for printed wiring boards, a binder for electrical storage devices, a binder for lithium ion batteries, etc. Since the linear expansion coefficient is a predetermined value, the adhesive can be preferably used as an interlayer insulating material.

[0145] [Cured product] The present disclosure provides a cured product of the adhesive.

[0146] Examples of methods for producing a cured product include a method including a step of applying the adhesive composition to a suitable support, a step of curing the composition by heating to volatilize the organic solvent, and a step of peeling off the support.

[0147] In one embodiment, the thickness of the cured product is preferably about 3 to 40 μm.

[0148] Examples of the support include release paper, release film, and the support film described below.

[0149] When producing the cured product, the adhesive composition may be used in combination with various known adhesive compositions other than the adhesive.

[0150] [Adhesive sheet] The present disclosure provides an adhesive sheet having the above-described cured product on at least one surface of a support film.

[0151] In one embodiment, the adhesive sheet is obtained by applying the adhesive onto a support film and curing it by heating, or by laminating a cured product according to the present disclosure onto a support film.

[0152] Examples of the support film include polyimide, polyester, polyimide-silica hybrid, polyethylene, polypropylene, polyethylene terephthalate, polyethylene naphthalate, polymethyl methacrylate resin, polystyrene resin, polycarbonate resin, acrylonitrile-butadiene-styrene resin, ethylene terephthalate, aromatic polyester resins obtained from phenol, phthalic acid, hydroxynaphthoic acid, or the like and parahydroxybenzoic acid (so-called liquid crystal polymers; such as "Vextar" manufactured by Kuraray Co., Ltd.), cycloolefin polymers, and fluorine-based resins (such as polytetrafluoroethylene (PTFE), perfluoroalkoxyalkane (PFA), and polyvinylidene fluoride (PVDF)).

[0153] The adhesive may be applied to the support film using, for example, a coater such as a comma, die, knife, or lip coater. The thickness of the coating layer after drying is preferably about 1 μm to 100 μm, more preferably about 3 μm to 50 μm. The adhesive layer of the adhesive sheet may be protected with various protective films.

[0154] [Resin-coated copper foil] The present disclosure provides a resin-coated copper foil comprising the above-mentioned cured product and a copper foil.

[0155] The resin-coated copper foil is prepared by applying the adhesive to a copper foil and then heat-curing the adhesive, or by laminating the cured product to a copper foil. Examples of the copper foil include rolled copper foil and electrolytic copper foil.

[0156] Copper foils that have been subjected to various surface treatments (roughening, rust prevention, etc.) can also be used. Examples of rust prevention treatments include plating treatments using plating solutions containing Ni, Zn, Sn, etc., and mirror-finish treatments such as chromate treatments.

[0157] In one embodiment, the thickness of the copper foil is preferably about 1 μm to 100 μm, and more preferably about 2 to 38 μm.

[0158] Examples of the coating means include methods using a coater such as a comma, die, knife, or lip coater.

[0159] The adhesive layer of the resin-coated copper foil may be uncured or may be partially or completely cured under heat. A partially cured adhesive layer is in a state known as B-stage. The thickness of the adhesive layer is preferably about 0.5 μm to 30 μm. A copper foil may be further laminated to the adhesive surface of the resin-coated copper foil to produce a double-sided resin-coated copper foil.

[0160] [Copper-clad laminate] The present disclosure provides a copper-clad laminate comprising the resin-coated copper foil and a copper foil or insulating sheet.

[0161] Copper-clad laminates are also called CCLs (Copper Clad Laminates). Specifically, copper-clad laminates are produced by pressing the resin-coated copper foil onto at least one or both sides of various known copper foils or insulating sheets under heat. When a resin-coated copper foil is bonded to one side, a different material may be pressed onto the other side. Furthermore, the number of resin-coated copper foils, copper foils, and insulating sheets in the copper-clad laminate is not particularly limited.

[0162] In one embodiment, the insulating sheet is preferably a prepreg or the support film. Prepreg refers to a sheet-like material made by impregnating a reinforcing material such as glass cloth with a resin and curing it to the B stage (JIS C 5603). The resin may be an insulating resin such as the polyimide, phenolic resin, epoxy resin, polyester resin, liquid crystal polymer, or aramid resin.

[0163] In one embodiment, the thickness of the insulating sheet is preferably about 20 μm to 500 μm.

[0164] In one embodiment, the heating conditions are preferably about 150°C to 280°C, and more preferably about 170°C to 240°C.

[0165] In one embodiment, the pressure bonding conditions are preferably about 0.5 MPa to 20 MPa, and more preferably about 1 MPa to 8 MPa.

[0166] [Printed wiring board] The present disclosure provides a printed wiring board having a circuit pattern on the copper foil surface of the above-mentioned copper-clad laminate.

[0167] Examples of patterning methods for forming a circuit pattern on the copper foil surface of a copper-clad laminate include subtractive and semi-additive methods. Examples of semi-additive methods include patterning the copper foil surface of a copper-clad laminate with a resist film, electrolytic copper plating, removing the resist, and etching with an alkaline solution. The thickness of the circuit pattern layer in the printed wiring board is not particularly limited. A multilayer substrate can also be obtained by laminating the same printed wiring board or another known printed wiring board or printed circuit board on the printed wiring board as a core. During lamination, the adhesive composition can be used in combination with other known adhesive compositions. The number of layers in the multilayer substrate is not particularly limited. Via holes may be inserted and the interior may be plated after each lamination. The line / space ratio of the circuit pattern is preferably approximately 1 μm / 1 μm to 100 μm / 100 μm. The height of the circuit pattern is preferably approximately 1 μm to 50 μm. [Example]

[0168] The present invention will be described in detail below through examples and comparative examples. However, the above-mentioned description of the preferred embodiments and the following examples are provided for illustrative purposes only and are not intended to limit the present invention. Therefore, the scope of the present invention is not limited to the embodiments or examples specifically described herein, but is limited only by the claims. Furthermore, in each example and comparative example, numerical values ​​such as parts and % are based on mass unless otherwise specified.

[0169] Example 1 A reaction vessel equipped with a stirrer, a water divider, a thermometer, and a nitrogen gas inlet tube was charged with 210.00 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (trade name "BPDA" manufactured by Mitsubishi Chemical Corporation; hereafter abbreviated as BPDA), 1543.42 g of cyclohexanone, and 111.31 g of methylcyclohexane and heated to 100 °C. Next, 183.55 g of dimer diamine (trade name "PRIAMINE 1075" manufactured by Croda Japan Co., Ltd.) and 118.44 g of 9,9'-bis(aminophenyl)fluorene (trade name "BAF" manufactured by Osaka Gas Chemicals Co., Ltd.) were added dropwise, and the imidization reaction was carried out at 140 °C for 12 hours to obtain a polyimide solution with a nonvolatile content of 22.6%. The molar ratio of dimer diamine to 9,9'-bis(aminophenyl)fluorene was 50 / 50.

[0170] Unless otherwise specified, the examples and comparative examples other than Example 1 were carried out in the same manner as Example 1, except for the changes shown in the table below.

[0171] Comparative Example 2 A reaction vessel equipped with a stirrer, a water divider, a thermometer, and a nitrogen gas inlet tube was charged with 350.00 g of 4,4'-[propane-2,2-diylbis(1,4-phenyleneoxy)]diphthalic dianhydride (trade name "BisDA-1000"), 1382.64 g of cyclohexanone, and 198.66 g of methylcyclohexane, and heated to 40°C. Next, 89.85 g of 4,4'-diaminodiphenyl ether (trade name "ODA", manufactured by JFE Chemical Corporation; hereinafter abbreviated as ODA) was added, and the mixture was heated again to 60°C. Then, 103.85 g of dimer diamine (trade name "PRIAMINE 1075", manufactured by Croda Japan Co., Ltd.) was added dropwise, and the mixture was subjected to an imidization reaction at 140°C for 12 hours, yielding a polyimide solution with a non-volatile content of 24.5%. The molar ratio of dimer diamine to ODA is 30 / 70.

[0172] <Preparation of polyimide film> The polyimides of the examples and comparative examples were coated onto release paper (manufactured by San-A Kaken Co., Ltd.), and dried at 150°C for 5 minutes and then at 170°C for 30 minutes to obtain a laminated film with a polyimide layer. Next, the release paper was peeled off from the film to obtain three 15 μm thick polyimide films, which were then laminated and melted by a heat press at 170°C to obtain a 45 μm thick polyimide film for evaluation.

[0173] <Measurement of linear expansion coefficient and glass transition temperature> The linear expansion coefficient and glass transition temperature were measured under the following conditions using a thermomechanical analyzer (product name "TMA7100", manufactured by Shimadzu Corporation). The glass transition temperature was determined as the temperature at the intersection of the tangent lines before and after the change in slope. Load: 12mN Sample width: 4mm Chuck distance: 10mm Heating from 40℃ to 200℃ at 10℃ / min

[0174] <Measurement of dielectric loss tangent> Using a network analyzer (Keysight Technologies, device name: "P5003A") and a split post dielectric resonator (QWED) with a measurement frequency of 10.124 GHz, the resonant frequency and peak Q value of the resonator alone with nothing inserted were measured. Next, the polyimide film was cut into a piece of 4 cm x 5 cm to prepare a test piece, which was then inserted into a resonator, and the resonance frequency and Q value were measured when the test piece was inserted. The dielectric loss tangent (Df) was calculated from the difference in the Q value between the resonator alone and when the test piece was inserted, and the difference in the resonant frequency.

[0175] <Compatibility with crosslinking components> 91.59 parts by weight of the polyimide solution of Example 1, 0.55 parts by weight of epoxide (trade name: "TETRAD-X", manufactured by Mitsubishi Gas Chemical Company, Inc.) as a crosslinking agent, 1.91 parts by weight of activated ester resin (trade name: "EPICLON HPC-8000-65T", manufactured by DIC Corporation) as an epoxide curing agent, 0.006 parts by weight of imidazole-based epoxy resin (trade name: "2E4MZ-A", manufactured by Shikoku Chemical Industries, Ltd.) as a reaction catalyst, and 5.94 parts by weight of cyclopentanone as a diluent were mixed and stirred thoroughly to obtain an adhesive with a nonvolatile content of 22.5%. The resulting adhesive was applied to glass to a dry film thickness of 15 μm. After application, the coating was dried at 150°C for 5 minutes and then at 170°C for 30 minutes to form a polyimide layer. The compatibility between the polyimide and the crosslinking component was evaluated according to the following criteria. 〇 No unevenness on the coated surface ×: Uneven coating surface

[0176] [Table 1]

[0177] <Explanation of abbreviations> BisDA: 4,4'-[propane-2,2-diylbis(1,4-phenyleneoxy)]diphthalic dianhydride (trade name "BisDA-1000", manufactured by SABIC Innovative Plastics Japan, LLC)

[0178] <Electrolyte resistance> We investigated whether the above polyimide could be used as a binder for lithium-ion batteries. The polyimides of Example 1 and Comparative Example 2 were coated onto release paper (manufactured by San-A Kaken Co., Ltd.) and dried at 150°C for 5 minutes. The peeled polyimide film was dried at 200°C for 2 hours to obtain a polyimide film with a thickness of 20 μm. The mass α of the obtained polyimide film was measured, and the film was immersed in a dimethyl carbonate solvent and stored at room temperature for 72 hours. The immersed solid resin was then removed from the dimethyl carbonate solvent and thoroughly dried at 120°C for 3 hours to remove the dimethyl carbonate adhering to the surface of the solid resin. The mass β was then measured. Using the measured masses α and β, the weight change rate of the polymer was calculated as follows: (α-β) / α×100 (%). A lower weight change rate (closer to 0%) indicates a higher resistance of the polymer to the electrolyte.

[0179] [Table 2]

Claims

1. A polyimide, The polyimide is a compound obtained by mixing an aromatic tetracarboxylic acid anhydride and Diamines including dimer diamines and aromatic diamines is a reactant of a group of monomers comprising the content of the dimer diamine component relative to 100 mol % of the diamine is 20 mol % to 60 mol %; the aromatic tetracarboxylic acid anhydride is 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, the aromatic diamine comprises 9,9'-bis(aminophenyl)fluorene; the content of the 9,9′-bis(aminophenyl)fluorene relative to 100 mol % of the diamine is 40 mol % to 80 mol %; A polyimide having a linear expansion coefficient of 200 ppm / K to 2500 ppm / K.

2. An adhesive comprising the polyimide of claim 1.

3. A cured product of the adhesive according to claim 2.

4. An adhesive sheet having the cured product according to claim 3 on at least one surface of a support film.

5. A resin-coated copper foil comprising the cured product according to claim 3 and a copper foil.

6. The resin-coated copper foil according to claim 5 and Copper clad laminates, including copper foil or insulating sheets.

7. A printed wiring board having a circuit pattern on the copper foil surface of the copper-clad laminate according to claim 6.

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