Bisimide dicarboxylic acid, curable resin composition, and cured product

Abstract

Provided is a novel bisimide dicarboxylic acid that has excellent solubility in a low-boiling-point solvent and makes it possible to form a cured product with excellent heat resistance and dielectric characteristics.　The bisimide dicarboxylic acid is a compound represented by formula (1). In formula (1), R 1 and R2 each represent a trivalent hydrocarbon group that is preferably a trivalent hydrocarbon group containing an alicyclic hydrocarbon or an aromatic hydrocarbon ring. L1 represents a divalent group containing an indan ring or a spirobisindane ring.

Description

Bisimidodicarboxylic acid, curable resin composition, and cured product

[0001] The present invention relates to bisimidodicarboxylic acid, a curing agent containing the bisimidodicarboxylic acid, a curable resin composition containing the curing agent, a cured product of the curable resin composition, a prepreg containing the curable resin composition or a semi-cured product thereof, a metal-clad laminate containing the cured product, a printed circuit board containing the cured product, and a semiconductor device containing the cured product.

[0002] Curable resins such as epoxy resins have excellent heat resistance, mechanical properties, and electrical properties. For this reason, these curable resins are widely used industrially as sheet-like or film-like electrical and electronic materials, such as insulating materials for printed circuit boards like coverlay films, semiconductor encapsulating materials like encapsulating films, and adhesive sheets.

[0003] In recent years, semiconductor package substrates have become thinner, and a problem has arisen in that they are prone to warping during mounting. Therefore, the electrical and electronic materials mentioned above are required to have high heat resistance sufficient to suppress warping.

[0004] Furthermore, in semiconductor devices, the speed and frequency of signals are increasing. Therefore, the aforementioned electrical and electronic materials are required to possess both low dielectric constant and low dielectric loss tangent in order to prevent signal loss and attenuation and improve performance.

[0005] Furthermore, sheet-like or film-like electrical and electronic materials are manufactured using a method in which the material is first dissolved in a solvent, and then processed into a sheet through coating and drying processes. Therefore, they are required to have low dielectric constant and low dielectric loss tangent, as well as solvent solubility. In particular, solubility in low-boiling point solvents around 100°C is required from the viewpoint of facilitating drying after coating.

[0006] As such a sheet-like or film-like electrical and electronic material, Patent Document 1 discloses that when bisimidodicarboxylic acid as a curing agent and an epoxy resin are dissolved in an amide-based solvent such as N,N-dimethylformamide, a resin solution with good solubility can be obtained, and that a cured product possessing both low dielectric constant and low dielectric loss tangent can be obtained by using the resin solution.

[0007] Japanese Patent Publication No. 2020-204014

[0008] However, the bisimoidodicarboxylic acid described in Patent Document 1 has a very high softening point, and moreover, it does not dissolve in solvents other than the amino-based solvents mentioned above. Furthermore, the amino-based solvents have high boiling points (for example, the boiling point of N,N-dimethylformamide is 153°C), and a large amount of thermal energy is required for dissolution and drying after coating, which presents a problem.

[0009] Therefore, an object of the present invention is to provide a novel bisimidodicarboxylic acid that has excellent solubility in low-boiling point solvents and can form a cured product with excellent heat resistance and dielectric properties. Another object of the present invention is to provide a curing agent that has excellent solubility in low-boiling point solvents and can form a cured product with excellent heat resistance and dielectric properties when reacted with a curable resin. Another object of the present invention is to provide a curable resin composition comprising the curing agent and capable of forming a cured product with excellent heat resistance and dielectric properties. Another object of the present invention is to provide a cured product of the curable resin composition that has excellent heat resistance and dielectric properties. Another object of the present invention is to provide a prepreg comprising the curable resin composition or a semi-cured product of the curable resin composition and capable of forming a cured product with excellent heat resistance and dielectric properties. Another object of the present invention is to provide a film comprising the curable resin composition or a semi-cured product of the curable resin composition and capable of forming a cured product with excellent heat resistance and dielectric properties. Another object of the present invention is to provide a metal-clad laminate, a printed circuit board, and a semiconductor device comprising the cured product with excellent heat resistance and dielectric properties.

[0010] As a result of intensive studies to solve the above problems, the present inventors have found that the bisimide dicarboxylic acid represented by the following formula (1) has a low softening point and is well soluble in a low-boiling solvent, and that when a curable resin composition containing the bisimide dicarboxylic acid represented by the following formula (1) and a curable resin is subjected to heat treatment, a cured product excellent in heat resistance and dielectric properties can be obtained. The present invention has been completed based on these findings.

[0011] That is, the present invention provides a bisimide dicarboxylic acid represented by the following formula (1). [In formula (1), R １ , R ２ each independently represents a trivalent hydrocarbon group. L １ represents a divalent group represented by the following formula (L1-1), (L1-2), (L1-3), or (L1-4)] (In formulas (L1-1) to (L1-4), R ３ , R ４ each independently represents a single bond or a linking group. Substituents may be bonded to the indane ring and spirobisindane ring shown in the formula. In addition, the wavy bond shown in formulas (L1-1) to (L1-4) is bonded to the nitrogen atom in formula (1))

[0012] The present invention also provides the bisimide dicarboxylic acid, wherein at least one of the above R ３ and R ４ is a divalent group containing an aromatic hydrocarbon ring.

[0013] The present invention also provides the bisimide dicarboxylic acid, wherein the above L １ is a divalent group represented by the following formula (L1-1-1). (In formula (L1-1-1), n1 and n2 each independently represent an integer of 0 or more. Substituents may be bonded to the indane ring and benzene ring shown in the formula. In addition, the wavy bond shown in formula (L1-1-1) is bonded to the nitrogen atom in formula (1))

[0014] The present invention also provides the above R １ and R ２Provided is the bisimide dicarboxylic acid, wherein is a trivalent hydrocarbon group containing an alicyclic hydrocarbon or an aromatic hydrocarbon ring.

[0015] The present invention also provides a curing agent containing the bisimide dicarboxylic acid.

[0016] The present invention also provides a curable resin composition containing the curing agent and a curable resin.

[0017] The present invention further provides the curable resin composition containing at least one curing agent selected from a phenolic curing agent, an imide curing agent (excluding the bisimide dicarboxylic acid represented by the formula (1)), and an acid anhydride curing agent.

[0018] The present invention also provides the curable resin composition, wherein the curable resin is an epoxy resin.

[0019] The present invention further provides the curable resin composition containing a curing accelerator.

[0020] The present invention also provides a cured product of the curable resin composition.

[0021] The present invention also provides a prepreg containing the curable resin composition or a semi-cured product of the curable resin composition and a sheet-like fiber base material.

[0022] The present invention also provides a film containing the curable resin composition or a semi-cured product of the curable resin composition.

[0023] The present invention also provides a metal-clad laminate having a structure in which a metal foil is laminated on a base material, wherein the base material is a base material containing a cured product of the curable resin composition.

[0024] The present invention also provides a printed wiring board including a cured product of the curable resin composition.

[0025] The present invention also provides the printed wiring board, wherein the cured product is a cured product of a prepreg, and the prepreg is a prepreg containing the curable resin composition or a semi-cured product of the curable resin composition and a sheet-like fiber base material.

[0026] The present invention also provides a printed circuit board comprising the cured product, wherein the printed circuit board comprises at least one selected from a surface protective film made of the cured film and an interlayer insulating film made of the cured film, and the film is a film containing the curable resin composition or a semi-cured product of the curable resin composition.

[0027] The present invention also provides a semiconductor device comprising a printed circuit board and a semiconductor element, wherein the printed circuit board is a printed circuit board comprising a cured product of the curable resin composition, and / or the semiconductor element is a semiconductor element sealed with a cured product of the curable resin composition.

[0028] The bisimoidicarboxylic acid of the present invention has a low softening point and excellent solubility in low-boiling point solvents. Furthermore, the bisimoidicarboxylic acid can react with a curable resin to form a cured product with excellent heat resistance and dielectric properties (for example, a cured product possessing both low dielectric constant and low dielectric loss tangent). The curable resin composition containing the bisimoidicarboxylic acid, its semi-cured product, and its cured product are suitably used as insulating materials and encapsulating materials in semiconductor devices.

[0029] <Bisimidodicarboxylic acid> The bisimidodicarboxylic acid of the present invention is a compound represented by the following formula (1).

[0030] In formula (1), R １ , R ２ Each of these independently represents a trivalent hydrocarbon group. １ This represents a divalent group represented by the following formulas (L1-1), (L1-2), (L1-3), or (L1-4). (In formulas (L1-1) to (L1-4), R ３ , R ４ Each of these independently represents a single bond or a linking group. Substituents may be attached to the indan ring or spirobisindan ring shown in the formula. Note that the wavy lines in formulas (L1-1) to (L1-4) each represent a bond to the nitrogen atom in formula (1).

[0031] R１ , R ２ In this context, a trivalent hydrocarbon group is a group obtained by removing three hydrogen atoms from the structural formula of a hydrocarbon.

[0032] Hydrocarbons include aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbon rings, and hydrocarbons in which two or more of these are linked by a single bond.

[0033] Aliphatic hydrocarbons include linear or branched saturated aliphatic hydrocarbons and linear or branched unsaturated aliphatic hydrocarbons. The number of carbon atoms in the saturated aliphatic hydrocarbons is, for example, 1 to 10, and the number of carbon atoms in the unsaturated aliphatic hydrocarbons is, for example, 2 to 10.

[0034] Examples of alicyclic hydrocarbons include 3-6 member saturated alicyclic hydrocarbons such as cyclopropane, cyclopentane, and cyclohexane; 3-6 member unsaturated alicyclic hydrocarbons such as cyclopropene, cyclopentene, and cyclohexene; and perhydronaphthalene, norbornane, norbornene, adamantane, and tricyclo[5.2.1.0 ２，６ Decane, tetracyclo[4.4.0.1 ２，５ 1. ７，１０ This includes cross-linked cyclic hydrocarbons such as dodecane.

[0035] Examples of aromatic hydrocarbon rings include benzene, biphenyl, naphthalene, anthracene, phenanthrene, fluorene, indane, spirobisindane, etc. ６－２０ Aromatic hydrocarbon rings are one example.

[0036] R １ , R ２ Among these, trivalent hydrocarbon groups containing alicyclic hydrocarbons and / or aromatic hydrocarbon rings are preferred, trivalent hydrocarbon groups containing cyclohexane rings and / or benzene rings are more preferred, and trivalent hydrocarbon groups containing benzene rings are particularly preferred, due to their excellent solubility in low-boiling point solvents and the ability to obtain cured products with excellent heat resistance.

[0037] The above formula (1) is preferably the following formula (1-1) or the following formula (1-2), and the following formula (1-1) is particularly preferred. In the following formula, L １ The same applies as above.

[0038] R ３ , R ４ The linking group in is a divalent group having one or more atoms, such as a divalent hydrocarbon group, a carbonyl group (-CO-), a (poly)siloxane group, a sulfonyl group, a hydrocarbon oxy group (-RO-), a hydrocarbon thio group (-RS-), etc. R represents a divalent hydrocarbon group. The divalent hydrocarbon group may have substituents.

[0039] The aforementioned divalent hydrocarbon group is a group obtained by removing two hydrogen atoms from the structural formula of a hydrocarbon, and examples of hydrocarbons are the same as those described above.

[0040] Specific examples of the divalent hydrocarbon group include linear or branched alkylene groups having 1 to 18 carbon atoms, such as methylene, methylmethylene, isopropylidene, ethylene, propylene, and trimethylene; cycloalkylene groups having 3 to 18 carbon atoms (including cycloalkylidene groups), such as 1,2-cyclopentylene, 1,3-cyclopentylene, cyclopentylidene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene, and cyclohexylidene; and arylene groups having 6 to 20 carbon atoms, such as phenylene, indanylene, phenylenebis(methylene), biphenylene, and naphthylene.

[0041] Substituents that a divalent hydrocarbon group may have include, for example, halogeno groups (e.g., fluoro groups, chloro groups, bromo groups, iodo groups), halogen atom-containing groups (e.g., perfluoroalkyl groups such as trifluoromethyl groups), oxo groups, hydroxyl groups, and substituted oxy groups (e.g., C １－４ Alkoxy group, C ６－１０ Aryloxy group, C ７－１６ Aralkyloxy group, C １－４ Acyloxy groups, thiol groups, substituted thio groups (e.g., C １－６ Alkylthio group, C ６－１０ Arylthio group, C ３－１０ Cycloalkylthio group, C １－７ Acylthio group), substituted oxycarbonyl group (for example, C １－４Alkoxycarbonyl group, C ６－１０ Aryloxycarbonyl group, C ７－１６ C(C) groups such as aralkyloxycarbonyl group, substituted or unsubstituted carbamoyl group (e.g., carbamoyl, methylcarbamoyl, etc.) １－４ C such as alkyl-substituted carbamoyl and phenylcarbamoyl groups ６－１０ (aryl-substituted carbamoyl group), cyano group, nitro group, substituted or unsubstituted amino group (e.g., mono or diC such as methylamino group, dimethylamino group, ethylamino group, diethylamino group, etc.) １－４ Alkylamino groups; 5- to 8-membered cyclic amino groups such as 1-pyrrolidinyl groups, piperidino groups, and morpholino groups; C groups such as acetylamino groups, propionylamino groups, and benzoylamino groups. １－１０ Examples include acylamino groups (such as benzenesulfonylamino groups and p-toluenesulfonylamino groups), sulfonic acid groups, and heterocyclic groups.

[0042] The indan rings and spirobisindan rings shown in formulas (L1-1) to (L1-4) above may have substituents attached. There is no particular limit to the number of substituents, for example, 1 to 3. When two or more substituents are attached to the indan ring or spirobisindan ring, these substituents are linked to each other and together with the carbon atoms constituting the indan ring or spirobisindan ring, form a ring (for example, a 3-6 member saturated alicyclic hydrocarbon, C ６－１４ It may also form an aromatic hydrocarbon ring.

[0043] Examples of substituents that may be attached to the indan ring or spirobisindan ring are the same as those that may be present on a divalent hydrocarbon group. Further examples of such substituents include alkyl groups (e.g., methyl group, ethyl group, etc.). １－４ C(alkyl groups, etc.), alkenyl groups (for example, vinyl groups, allyl groups, 1-butenyl groups, etc.) ２－４ Alkenyl group), alkynyl group (e.g., ethynyl group, propynyl group, etc.) ２－４ (Alkynyl group, etc.), C ３－８ Cycloalkyl groups, aryl groups (e.g., phenyl group, naphthyl group, etc.) ６－１０ Examples include aryl groups.

[0044] L １ The group is selected from the divalent groups represented by the above formulas (L1-1), (L1-2), and (L1-3), and among these, the divalent group represented by the above formula (L1-1) is preferred.

[0045] R ３ , R ４ Preferably, at least one of them is a divalent group containing an aromatic hydrocarbon ring.

[0046] R ３ , R ４ Furthermore, in terms of excellent solubility in low-boiling point solvents, it is preferable that the compound contains divalent hydrocarbon groups (e.g., methylene groups, isopropylidene groups, fluorenylene groups), hydrocarbon oxy groups, hydrocarbon thio groups, sulfonyl groups, (poly)siloxane groups, etc. In addition, it is preferable that the divalent hydrocarbon groups have a sulfonic acid group, a halogen group, or a halogen atom-containing group as a substituent.

[0047] L １ As such, a divalent group represented by the following formula (L1-1-1) is particularly preferred. (In formula (L1-1-1), n1 and n2 each independently represent an integer of 0 or greater. Substituents may be attached to the indan ring and benzene ring shown in the formula. Note that the bonds indicated by the wavy lines in formula (L1-1-1) are attached to the nitrogen atom in formula (1).)

[0048] n1 and n2 each independently represent non-negative integers, such as integers between 0 and 3. 0 or 1 are preferred.

[0049] Examples of substituents that may be bonded to the indan ring or benzene ring in formula (L1-1-1), and the number of substituents, are the same as the examples of substituents that may be bonded to the indan ring or spirobisindan ring in formulas (L1-1) to (L1-4) above, and the number of substituents.

[0050] L １ It may also be a divalent group represented by the following formula (L1-1-2). (In formula (L1-1-2), n3 represents an integer of 1 or more. Substituents may be attached to the indan ring and benzene ring shown in the formula. Note that the bonds indicated by the wavy lines in formula (L1-1-2) are attached to the nitrogen atom in formula (1).)

[0051] n3 represents an integer greater than or equal to 1, preferably an integer between 1 and 10.

[0052] Examples of substituents that may be bonded to the indan ring or benzene ring in formula (L1-1-2), and the number of substituents, are the same as the examples of substituents that may be bonded to the indan ring or spirobisindan ring in formulas (L1-1) to (L1-4) above, and the number of substituents.

[0053] The bisimoidicarboxylic acid can react with a curable resin to form a cured product with excellent heat resistance and dielectric properties. Therefore, the bisimoidicarboxylic acid can be suitably used as a curing agent for curable resins.

[0054] Furthermore, the softening point of the bisimidodicarboxylic acid is, for example, 300°C or lower, preferably 200°C or lower, more preferably 180°C or lower, and even more preferably 160°C or lower. The lower limit of the softening point is, for example, 100°C, preferably 120°C, and more preferably 130°C.

[0055] Furthermore, the bisimoidodicarboxylic acid exhibits excellent solubility in low-boiling point solvents. The concentration of the bisimoidodicarboxylic acid in the solution obtained by completely dissolving the bisimoidodicarboxylic acid in a low-boiling point solvent such as methyl ethyl ketone (MEK), a MEK / toluene (mass ratio 2 / 8) mixed solvent, or cyclohexanone at room temperature and atmospheric pressure is, for example, 30% by mass or more, preferably 50% by mass or more, and more preferably 70% by mass or more.

[0056] As described above, the bisimoidicarboxylic acid has a low softening point and excellent solubility in low-boiling point solvents. Therefore, by using the bisimoidicarboxylic acid, a curable resin composition with excellent uniformity can be prepared under mild conditions. Furthermore, since the solvent in a curable resin composition containing a low-boiling point solvent easily volatilizes upon heating, a large amount of thermal energy is not required for drying. In other words, by using the bisimoidicarboxylic acid, it is possible to form a cured product with excellent heat resistance and dielectric properties while reducing costs and environmental impact.

[0057] <Method for Producing Bisimidodicarboxylic Acid> The bisimidodicarboxylic acid represented by formula (1) can be produced, for example, by using a tricarboxylic acid anhydride represented by the following formulas (2) and (2') and a diamine represented by the following formula (3) as raw materials, reacting their functional groups with each other, and then dehydrating and cyclizing them. R in the following formula １ , R ２ , L １ The same applies as above.

[0058]

[0059] Tricarboxylic acid anhydrides include aromatic tricarboxylic acid anhydrides, alicyclic tricarboxylic acid anhydrides, and aliphatic tricarboxylic acid anhydrides. These can be used individually or in combination of two or more.

[0060] Examples of aromatic tricarboxylic acid anhydrides include trimellitic anhydride and 1,2,4-naphthalentricarboxylic acid anhydride.

[0061] Examples of alicyclic tricarboxylic acid components include 1,2,3-cyclohexanetricarboxylic acid anhydride and 1,2,4-cyclohexanetricarboxylic acid anhydride.

[0062] Examples of aliphatic tricarboxylic acid components include 3-carboxymethylglutaric anhydride, 1,2,4-butanetricarboxylic acid-1,2-anhydride, and cis-propene-1,2,3-tricarboxylic acid-1,2-anhydride.

[0063] Examples of diamines include 1-(4-aminophenyl)-1,3,3-trimethylindan-5-amine, 1-(4-aminophenyl)-1,3,3-trimethylindan-6-amine, 6-(4'-aminophenoxy)-1-[4'''-(4''-aminophenoxy)phenyl]-1,1,3-trimethylindan, 6,6'-bis(4-aminophenoxy)-3,3,3',3'-tetramethyl-1,1'-spirobindan, and 2-(aminomethyl)-2,3-dihydro-1H-indene-2 Examples include amines, 1-(aminomethyl)-2,3-dihydro-1H-indene-2-amine, 1,2,3,5,6,7-hexahydro-s-indacene-1,4-diamine, 5,5'-diamino-3,3,3',3'-tetramethyl-2,2',3,3'-tetrahydro-1,1'-spirobi[indene]-6,6'-diol, 1,1,4,6-tetramethylindan-5,7-diamine, compounds represented by the following formula (d1), and analogues thereof (e.g., compounds with substituents). (In the formula, n3' represents an integer between 1 and 10.)

[0064] The compound represented by formula (d1) can be produced, for example, by reacting 2,6-dimethylaniline and α,α'-dihydroxy-1,3-diisopropylbenzene in an organic solvent such as xylene, using activated clay as a catalyst.

[0065] The amount of diamine used is, for example, 0.1 to 0.7 times the molar amount of the tricarboxylic acid anhydride, preferably 0.3 to 0.7 times the molar amount, more preferably 0.4 to 0.6 times the molar amount, and even more preferably 0.45 to 0.55 times the molar amount.

[0066] The reaction between tricarboxylic acid anhydride and diamine may be carried out under solvent conditions or without solvent conditions.

[0067] When reacting tricarboxylic acid anhydride with a diamine in a solvent, suitable solvents include nitrogen-containing solvents such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylpropionamide, 1-ethyl-2-pyrrolidone, and N,N-diethylformamide. Bisimidedicarboxylic acid can be produced by adding a predetermined amount of tricarboxylic acid anhydride and diamine to the solvent, stirring at a temperature of 50 to 80°C, and then imidizing the mixture.

[0068] The method of the imidation reaction is not particularly limited, and examples include a method of heating at a temperature of 250 to 350°C (preferably 280 to 320°C) for 1 to 10 hours (preferably 1 to 3 hours) under a nitrogen atmosphere (heat imidation method), or a method of mixing with a high-boiling point solvent (e.g., toluene, xylene), heating at a temperature of 100 to 250°C (preferably 130 to 170°C) for 1 to 24 hours (preferably 2 to 5 hours), and removing water using a Dean-Stark apparatus or the like (dehydration cyclization method).

[0069] In imidation reactions, chemical imidants may be used to lower the reaction temperature or to improve the reaction rate. Examples of chemical imidants include carboxylic acid anhydrides such as acetic anhydride and propionic anhydride; inorganic dehydrating agents such as phosphorus pentoxide and phosphorus trichloride; carbodiimide compounds such as dicyclohexylcarbodiimide and 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide; acid catalysts such as p-toluenesulfonic acid and sulfuric acid; and base catalysts such as pyridine and imidazole.

[0070] One method for reacting tricarboxylic acid anhydrides with diamines in a solvent-free environment is to utilize the mechanochemical effect. The mechanochemical effect method is a method that uses the mechanical energy generated when the raw materials used in the reaction are crushed to promote the chemical reaction of the solids. After the chemical reaction between the solids using the mechanochemical effect method, the mixture may be heated in a nitrogen atmosphere at a temperature of 250 to 350°C (preferably 280 to 320°C) for 1 to 10 hours (preferably 1 to 3 hours) (heating imidation method).

[0071] When using the aforementioned bisimoidicarboxylic acid to produce a curable resin composition containing bisimoidicarboxylic acid and a curable resin, the bisimoidicarboxylic acid may be reacted with a portion of the curable resin beforehand. By reacting the bisimoidicarboxylic acid with a portion of the curable resin beforehand, the reactivity and solubility can be further improved.

[0072] The method for pre-reacting the bisimidodicarboxylic acid with a portion of the curable resin is not particularly limited. For example, the bisimidodicarboxylic acid and a portion of the curable resin can be mixed while heating under a nitrogen atmosphere (for example, heating at 100 to 250°C for 0.1 to 10 hours). In addition, a curing accelerator may be used in combination to lower the heating temperature during mixing and / or to promote the curing reaction. Examples of curing accelerators include organic phosphines such as triphenylphosphine and tributylphosphine. When a curing accelerator is used, the amount added is preferably 0.01 to 3.0% by mass relative to the curable resin.

[0073] <Curable Resin Composition> The curable resin composition of the present invention comprises the above-mentioned bisimidodicarboxylic acid and a curable resin.

[0074] (Curable resin) The curable resin is a resin having functional groups that are reactive with the bisimidodicarboxylic acid. Examples of the functional groups include epoxy groups, cyanate groups, phenolic hydroxyl groups, C-C double bonds, etc. The number of functional groups in the curable resin is preferably two or more.

[0075] Examples of the curable resins include epoxy resins, cyanate resins, phenolic resins, imide resins, maleimide resins, benzoxazine resins, silicone resins, and acrylic resins. These can be included individually or in combination of two or more.

[0076] The functional group equivalent of the curable resin is not particularly limited, and is, for example, 100 to 3000 g / eq. The upper limit of the functional group equivalent is preferably 2000 g / eq, more preferably 1000 g / eq, even more preferably 500 g / eq, even more preferably 300 g / eq, particularly preferably 250 g / eq, and most preferably 200 g / eq. The lower limit of the functional group equivalent is preferably 150 g / eq.

[0077] Among the curable resins mentioned above, those containing epoxy resin are preferable in that they yield a cured product with excellent heat resistance.

[0078] As the epoxy resin, compounds having two or more epoxy groups in one molecule are preferred. Examples of epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, isocyanurate type epoxy resin, alicyclic epoxy resin, acrylic acid modified epoxy resin, brominated epoxy resin, and phosphorus modified epoxy resin.

[0079] As for the epoxy resin, in particular, at least one selected from bisphenol A type epoxy resin, naphthalene type epoxy resin, bisphenyl type epoxy resin, and anthracene type epoxy resin is preferred, at least one selected from bisphenol A type epoxy resin, naphthalene type epoxy resin, and bisphenyl type epoxy resin is more preferred, naphthalene type epoxy resin and / or bisphenyl type epoxy resin is even more preferred, and naphthalene type epoxy resin is particularly preferred, in that when bisimidodicarboxylic acid and a portion of the epoxy resin are reacted in advance, the reaction product with bisimidodicarboxylic acid (imide group-containing epoxy resin) obtained has excellent fluidity, and the uniformity and heat resistance of the resulting cured product are improved.

[0080] The epoxy resin may be manufactured by a known method or a commercially available product may be used.

[0081] The epoxy equivalent of the epoxy resin is not particularly limited, and is, for example, 100 to 3000 g / eq. The upper limit of the epoxy equivalent is preferably 2000 g / eq, more preferably 1000 g / eq, even more preferably 500 g / eq, even more preferably 300 g / eq, particularly preferably 250 g / eq, and most preferably 200 g / eq. The lower limit of the epoxy equivalent is preferably 150 g / eq.

[0082] The content of the curable resin in the curable resin composition of the present invention is, for example, 30 to 100 parts by mass per 100 parts by mass of the bisimoidodicarboxylic acid. The lower limit of the content of the curable resin is preferably 40 parts by mass, more preferably 50 parts by mass. The upper limit of the content of the curable resin is preferably 80 parts by mass, more preferably 70 parts by mass, even more preferably 65 parts by mass, and particularly preferably 60 parts by mass.

[0083] (Other curing agents) The curable resin composition of the present invention may contain one or more other curing agents other than the above-mentioned bisimoidodicarboxylic acid in order to improve heat resistance.

[0084] Other curing agents are compounds having two or more functional groups that are reactive with the above-mentioned curable resin. The functional group equivalent of the other curing agent is, for example, 80 to 2000 g / eq. The upper limit of the functional group equivalent is preferably 1800 g / eq, more preferably 1600 g / eq. The lower limit of the functional group equivalent is preferably 100 g / eq, more preferably 150 g / eq, even more preferably 300 g / eq, even more preferably 500 g / eq, particularly preferably 1000 g / eq, and most preferably 1200 g / eq.

[0085] Other curing agents include compounds other than the bisimidodicarboxylic acid represented by formula (1), such as imidazoles, dicyandiamides, phenolic curing agents, thiol curing agents, amine curing agents, acid anhydride curing agents, cyanate curing agents, active ester curing agents, and imide curing agents.

[0086] Examples of imidazoles include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-heptadecylimidazole, 2-undecylimidazole, 1,2-dimethylimidazole, 4-methyl-2-phenylimidazole, N-benzyl-2-methylimidazole, 2-phenyl-1-benzyl-1H-imidazole, 1-(2-cyanoethyl)-2-undecylimidazole, Examples include 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, 1-(2-cyanoethyl)-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 2,4-diamino-6-[2-methylimidazolyl-(1)]ethyl-s-triazine, 4,5-di(hydroxymethyl)-2-phenyl-1H-imidazole, and 4-methyl-2-phenyl-5-hydroxymethyl-1H-imidazole.

[0087] Examples of phenolic curing agents include phenol novolac resins, phenol aralkyl resins, biphenyl aralkyl resins, triphenylalkane-type phenolic resins, and dicyclopentadiene-modified phenolic resins.

[0088] Examples of amine-based curing agents include aliphatic polyamines (e.g., diethylenetriamine, triethylenetetramine, tetraethylenepentamine, m-xylenediamine, trimethylhexamethylenediamine, 2-methylpentamethylenediamine, diethylaminopropylamine), alicyclic polyamines (e.g., isophoronediamine, 1,3-bisaminomethylcyclohexane, bis(4-aminocyclohexyl)methane, norbornenediamine, 1,2-diaminocyclohexane), and aromatic polyamines (e.g., 4,4-diaminodiphenylmethane, metaphenylenediamine, diaminodiphenylsulfone).

[0089] Examples of acid anhydride-based curing agents include 4-methylcyclohexane-1,2-dicarboxylic acid anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, methylcyclohexenetetracarboxylic dianhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, ethylene glycol bis-anhydrotrimellitate, glycerin bis(anhydrotrimellitate) monoacetate, and dodecenyl succinic anhydride.

[0090] The imide-based curing agent is a compound different from the bisimidodicarboxylic acid represented by formula (1) above. The imide-based curing agent is a bisimidodicarboxylic acid that does not contain an indan ring or a spirobisindan ring, and is, for example, a compound represented by the following formula (3). (In formula (3), L ２ (This indicates a divalent hydrocarbon group.)

[0091] L ２ It is a divalent hydrocarbon group and does not contain an indan ring or a spirobisindan ring. ２ Examples of divalent hydrocarbon groups in this invention are the same as those described above. In this invention, divalent aliphatic hydrocarbon groups or divalent aromatic hydrocarbon groups are preferred, and linear or branched alkylene groups having 5 or more carbon atoms (for example, 5 to 20) are preferred because they have excellent solubility in low-boiling point solvents and yield cured products with excellent dielectric properties.

[0092] The amount of other hardening agents varies depending on the type of hardening agent.

[0093] If the other curing agent is an imidazole or a dicyandiamide, its content (total content if two or more are included) is, for example, 1 to 10 parts by mass, preferably 1 to 3 parts by mass, per 100 parts by mass of the above-mentioned bisimoidodicarboxylic acid.

[0094] If the other curing agent is a phenolic curing agent, its content (total content if two or more are included) is, for example, 5 to 50 parts by mass per 100 parts by mass of the above-mentioned bisimoidodicarboxylic acid. The lower limit of the content is preferably 6 parts by mass, more preferably 8 parts by mass, and even more preferably 10 parts by mass. The upper limit of the content is preferably 30 parts by mass, more preferably 25 parts by mass, and even more preferably 20 parts by mass.

[0095] If the other curing agent is an imide-based curing agent, its content (total content if two or more types are included) is, for example, 5 to 100 parts by mass per 100 parts by mass of the above-mentioned bisimoidodicarboxylic acid. The lower limit of the content is preferably 10 parts by mass, more preferably 20 parts by mass, even more preferably 30 parts by mass, and particularly preferably 35 parts by mass. The upper limit of the content is preferably 70 parts by mass, more preferably 60 parts by mass, and even more preferably 50 parts by mass.

[0096] If the other curing agent is a curing agent other than dicyandiamides, imidazoles, phenolic curing agents, and imide curing agents among the curing agents listed above, its content (total content if two or more are included) is, for example, 5 to 50 parts by mass, preferably 6 to 35 parts by mass, more preferably 10 to 35 parts by mass, and even more preferably 20 to 35 parts by mass, per 100 parts by mass of the above-mentioned bisimoidodicarboxylic acid.

[0097] Other curing agents include, among them, at least one curing agent selected from phenolic curing agents, imide curing agents, and acid anhydride curing agents (excluding bisimidodicarboxylic acid represented by formula (1) above).

[0098] (Additives) The curable resin composition of the present invention may contain one or more additives such as curing accelerators, inorganic fillers, antioxidants, flame retardants, and solvents, to the extent that they do not impair the effects of the present invention.

[0099] Examples of curing accelerators include tertiary amines such as 4-dimethylaminopyridine, benzyldimethylamine, 2-(dimethylaminomethyl)phenol, and 2,4,6-tris(dimethylaminomethyl)phenol; and organic phosphines such as triphenylphosphine and tributylphosphine.

[0100] The curing accelerator content is, for example, 0.01 to 2.0 parts by mass per 100 parts by mass of curable resin. From the viewpoint of improving the heat resistance and dielectric properties of the resulting cured product, 0.01 to 1 part by mass is preferred, 0.05 to 0.8 parts by mass is more preferred, and 0.1 to 0.7 parts by mass is even more preferred.

[0101] Examples of inorganic fillers include silica, barium sulfate, alumina, aluminum nitride, boron nitride, silicon nitride, glass powder, glass frit, glass fiber, carbon fiber, and inorganic ion exchangers.

[0102] The average particle size of the inorganic filler is preferably 50 nm to 4 μm, and more preferably 100 nm to 3 μm in terms of excellent coatability and processability. The average particle size is determined by laser diffraction particle size distribution measurement.

[0103] Examples of antioxidants include hindered phenol antioxidants, phosphorus-based antioxidants, and thioether-based antioxidants.

[0104] Examples of flame retardants include non-halogenated flame retardants, phosphorus-based flame retardants, nitrogen-based flame retardants, and silicone-based flame retardants. Among these, non-halogenated flame retardants are preferred from the standpoint of environmental impact.

[0105] The curable resin composition may be a solvent-free resin composition or may contain a solvent. By including a solvent in the curable resin composition, the viscosity can be adjusted and the coating properties can be improved.

[0106] The solvent is preferably one that can dissolve the bisimidodicarboxylic acid and the curable resin. Examples of such solvents include alcohol-based solvents such as ethanol, propanol, butanol, methyl cellosolve, ethylene glycol monobutyl ether, and propylene glycol monomethyl ether; ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ether-based solvents such as tetrahydrofuran; aromatic hydrocarbon-based solvents such as toluene, xylene, and mesitylene; nitrogen atom-containing solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone; sulfur atom-containing solvents such as dimethyl sulfoxide; and ester-based solvents such as γ-butyrolactone.

[0107] Among the aforementioned solvents, it is preferable to use low-boiling-point solvents such as methyl ethyl ketone (MEK), MEK / toluene (mass ratio 2 / 8) mixed solvent, and cyclohexanone (solvents with a boiling point of, for example, 160°C or lower under normal pressure (preferably 150°C or lower, more preferably 130°C or lower, even more preferably 120°C or lower, even more preferably 100°C or lower, and particularly preferably 90°C or lower)) from the viewpoint of reducing the heat energy required for the preparation of the curable resin composition and the formation of the cured product, thereby reducing the environmental burden.

[0108] The curable resin composition of the present invention can be prepared, for example, by mixing the above-mentioned bisimoid dicarboxylic acid, the curable resin, and other components to be added as needed, using a mixer such as a homodisperser, a universal mixer, a Banbury mixer, or a kneader.

[0109] When the curable resin composition is subjected to heat treatment, the contained bisimoidodicarboxylic acid and curable resin react to form a crosslinked structure, causing it to harden. If the curable resin composition contains a solvent, the solvent is removed by distillation upon heating.

[0110] The heating temperature (curing temperature) is preferably 80 to 350°C, and more preferably 130 to 300°C. The heating time (curing time) is preferably 1 minute to 24 hours, and more preferably 5 minutes to 10 hours.

[0111] The curable resin composition can be suitably used as an electrical insulating material, a encapsulant, and an adhesive. Specifically, it can be suitably used as a raw material for prepregs, circuit boards, semiconductor encapsulants, build-up films, build-up substrates, adhesives, resists, and the like. Furthermore, since the bisimoidodicarboxylic acid has excellent solubility in various solvents, the curable resin composition can be made into a paint.

[0112] The aforementioned curable resin composition is particularly suitable as a matrix resin for fiber-reinforced plastics and as a raw material for high heat-resistant prepregs.

[0113] <Cured product> The cured product of the present invention is a cured product of the above-mentioned curable resin composition, and is formed by curing the above-mentioned curable resin composition. The cured product includes laminates, cast molded products, adhesive layers, coatings, films, etc.

[0114] The cured product of the present invention has excellent heat resistance, and its glass transition temperature (Tg) is, for example, 150°C or higher, preferably 180°C or higher, more preferably 190°C or higher, and even more preferably 200°C or higher. The upper limit of the glass transition temperature (Tg) is, for example, 300°C, but may also be 250°C.

[0115] The cured product of the present invention exhibits excellent dielectric properties, and the relative permittivity Dk of the cured product is, for example, 3.3 or less, preferably 3.2 or less, more preferably 3.0 or less, even more preferably 2.9 or less, and particularly preferably 2.85 or less at 23°C and a frequency of 5.8 GHz. Furthermore, the dielectric loss tangent Df of the cured product is, for example, 0.030 or less, preferably 0.020 or less, more preferably 0.013 or less, and even more preferably 0.010 or less at 23°C and a frequency of 5.8 GHz.

[0116] The cured product of the present invention can be used, for example, as a forming material for industrial machine parts, general machine parts, automobile, railway, and vehicle parts, aerospace-related parts, electronic and electrical components, building materials, containers and packaging materials, household goods, sports and leisure goods, wind turbine housing components, etc., but is not limited to these.

[0117] As described above, the cured product of the present invention has excellent heat resistance and dielectric properties, and therefore can be suitably used as a forming material for electronic and electrical components (for example, insulating substrates, surface protective films, interlayer insulating films, encapsulants, adhesives, etc.).

[0118] <Prepreg> The prepreg of the present invention comprises the above-mentioned curable resin composition, or a semi-cured product of the above-mentioned curable resin composition, and a sheet-like fibrous substrate.

[0119] The prepreg can be manufactured, for example, by impregnating or coating a sheet-like fibrous substrate with the curable resin composition, drying it, and then, if necessary, partially curing the impregnated or coated curable resin composition.

[0120] The aforementioned sheet-like fibrous substrate is, for example, a woven fabric, nonwoven fabric, robbing, chopped strand mat, surfacing mat, etc., formed from at least one fiber selected from glass fibers such as E glass, A glass, D glass, and S glass; organic fibers such as polyimide, polyester, and tetrafluoroethylene; and mixed fibers thereof.

[0121] The prepreg can be used, for example, to form an insulating substrate in a printed circuit board or a substrate for a metal-clad laminate.

[0122] <Film> The film of the present invention comprises the above-mentioned curable resin composition, or a semi-cured product of the above-mentioned curable resin composition.

[0123] The film of the present invention can be manufactured, for example, by coating the above-mentioned curable resin composition onto a support, drying it, and then, if necessary, partially curing the coated curable resin composition.

[0124] The aforementioned film can be used, for example, to form a surface protective film or an interlayer insulating film on a printed circuit board.

[0125] <Metal-clad laminate> The metal-clad laminate of the present invention has a structure in which metal foil is laminated on a substrate containing a cured product of the above-mentioned curable resin composition.

[0126] The metal-clad laminate preferably has a structure in which metal foil is laminated on a base material made of the cured prepreg.

[0127] Examples of metals that make up metal foil include copper, copper alloys, aluminum, aluminum alloys, silver, gold, zinc, nickel, tin, iron, tungsten, molybdenum, and alloys thereof.

[0128] The aforementioned metal-clad laminate can be manufactured, for example, by subjecting a laminate obtained by layering metal foil on at least one surface of a prepreg to heat treatment or heat and pressure treatment.

[0129] The metal-clad laminate can be used, for example, to form a printed circuit board.

[0130] <Printed Wiring Board> The printed wiring board of the present invention comprises a cured product of the above-mentioned curable resin composition.

[0131] A printed circuit board is an insulating substrate on which wiring is formed using a conductive material such as copper foil. Furthermore, a surface protective film may be provided on the surface of the wiring, and an interlayer insulating film may be provided in the gaps between the wiring.

[0132] In printed circuit boards, the cured product of the above-mentioned curable resin composition constitutes, for example, an insulating substrate, a surface protective film, an interlayer insulating film, and the like.

[0133] When the cured product of the above-mentioned curable resin composition constitutes an insulating substrate, it is preferable that the cured product is a cured product of the above-mentioned prepreg.

[0134] When the cured product of the above-mentioned curable resin composition constitutes a surface protective film or an interlayer insulating film, it is preferable that the cured product is a cured product of the above-mentioned film.

[0135] The cured material exhibits excellent heat resistance and dielectric properties. Therefore, printed circuit boards equipped with the cured material have excellent insulation reliability and heat resistance, and can significantly reduce signal transmission loss.

[0136] <Semiconductor Device> The semiconductor device of the present invention comprises a printed circuit board and a semiconductor element. The printed circuit board is a printed circuit board comprising a cured product of the curable resin composition, and / or the semiconductor element is sealed with the cured product of the curable resin composition. That is, the semiconductor device comprises a printed circuit board comprising a cured product of the curable resin composition and / or a semiconductor element sealed with the cured product of the curable resin composition.

[0137] The semiconductor elements may be arranged on a lead frame or substrate in a stacked vertically or horizontally, wired together, and sealed with a encapsulant containing the curable resin composition to form a semiconductor package.

[0138] The semiconductor device has a long lifespan and excellent reliability because the semiconductor elements are sealed with the cured material which has excellent heat resistance and dielectric properties, and the device includes a surface protective film and / or interlayer insulating film which has the cured material which has excellent heat resistance and dielectric properties.

[0139] The configurations and combinations thereof described above are merely examples, and additions, omissions, substitutions, and modifications to the configurations are permitted as appropriate, without departing from the spirit of the present invention. Furthermore, the present invention is not limited by its embodiments.

[0140] The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto.

[0141] Example 1: Preparation of Bisimidodicarboxylic Acid A) 69.5 parts by mass of ATMIA and 100 parts by mass of trimellitic anhydride were mixed and ground three times at a rotational speed of 9000 rpm for 1 minute using an Osaka Chemical Co., Ltd. Wonder Crusher WC-3C to obtain bisimidodicarboxylic acid A. The treated sample was transferred to a glass container and subjected to an imidation reaction at 300°C for 2 hours under a nitrogen atmosphere in an Inert Oven DN411I manufactured by Yamato Scientific Co., Ltd. to obtain bisimidodicarboxylic acid A. １¹H-NMR confirmed that it was a trimer composed of trimellitic acid residue-ATMIA residue-trimellitic acid residue. Furthermore, mass spectrometry revealed that the number-average molecular weight of bisimidodicarboxylic acid A was 615, and it was a solid at room temperature.

[0142] Example 2 (Preparation of Bisimidodicarboxylic Acid B) Bisimidodicarboxylic acid B was obtained in the same manner as in Example 1, except that 117.6 parts by mass of TMHI-AN was used instead of 69.5 parts by mass of ATMIA. The obtained bisimidodicarboxylic acid B １ ¹H-NMR confirmed that it was a trimer composed of a trimellitic acid residue, a TMHI-AN residue, and another trimellitic acid residue. Mass spectrometry revealed that the number-average molecular weight of bisimidodicarboxylic acid B was 799, and it was solid at room temperature.

[0143] Comparative Example 1 (Preparation of Bisimidodicarboxylic Acid C) Bisimidodicarboxylic acid B was obtained in the same manner as in Example 1, except that 52.3 parts by mass of 4,4'-diaminodiphenyl ether was used instead of 69.5 parts by mass of ATMIA. The obtained bisimidodicarboxylic acid B １ ¹H-NMR confirmed that it was a trimer composed of a trimellitic acid residue, a 4,4'-diaminodiphenyl ether residue, and a trimellitic acid residue. Mass spectrometry revealed that the number-average molecular weight of bisimidodicarboxylic acid C was 549, and it was solid at room temperature.

[0144] The softening point of the bisimidodicarboxylic acids obtained in the examples and comparative examples was measured using the method described below, and their solvent solubility was evaluated. The evaluation results are shown in Table 1.

[0145] - The softening point of bisimidodicarboxylic acid was measured in accordance with JIS K7234 (ring-sphere method).

[0146] - Methyl ethyl ketone (MEK), MEK / toluene mixed solvent (mass ratio 2 / 8), and cyclohexanone (CHN) were used as solvents for dissolving bisimidodicarboxylic acid. Under normal pressure, bisimidodicarboxylic acid was added to the solvent and heated to 60°C to dissolve it. The resulting solution was then visually inspected for the presence of insoluble components under normal temperature and pressure, and its solubility was evaluated according to the following criteria. <Evaluation Criteria> Excellent (◎): Dissolves at a bisimidodicarboxylic acid concentration of 70% by mass or higher. No insoluble components. Good (○): Dissolves at a bisimidodicarboxylic acid concentration of 30% by mass or higher and less than 70% by mass. No insoluble components. Acceptable (△): Dissolves at a bisimidodicarboxylic acid concentration of less than 30% by mass. No insoluble components. Unacceptable (×): Insoluble components present.

[0147]

[0148] The raw materials for bisimidodicarboxylic acid are described below. <Acid component> Trimellitus anhydride: Manufactured by Tokyo Chemical Industry Co., Ltd. <Diamine component> ATMIA: A mixture of 1-(4-aminophenyl)-1,3,3-trimethylindan-5-amine and 1-(4-aminophenyl)-1,3,3-trimethylindan-6-amine, manufactured by CHINATECH, "ATMIA" TMHI-AN: 6-(4'-aminophenoxy)-1-[4'''-(4''-aminophenoxy)phenyl]-1,1,3-trimethylindan: Manufactured by JFE, "TMHI-AN" 4,4'-diaminodiphenyl ether: Manufactured by Tokyo Chemical Industry Co., Ltd.

[0149] The bisimoiddicarboxylic acids of Examples 1 and 2 have an indan ring in their structure, resulting in a low softening point, which is below the typical molding temperature of 180°C. Furthermore, these bisimoiddicarboxylic acids exhibit excellent solubility in low-boiling point solvents. On the other hand, the bisimoiddicarboxylic acid of Comparative Example 1 lacks an indan ring, resulting in a very high softening point, significantly exceeding the typical molding temperature. It also exhibited inferior solubility in low-boiling point solvents.

[0150] Example 3 (Preparation of Curable Resin Composition) The curing agent, curable resin, and solvent (MEK) were mixed according to the formulations described in Table 2 and heated at 50°C for 1 hour to dissolve. After cooling, a curing accelerator was added and stirred. This obtained a curable resin composition.

[0151] (Cured product) The obtained curable resin composition was coated onto an aluminum substrate to a thickness of 300 μm, and the oven was heated in an inert oven under a nitrogen atmosphere at 120°C for 1 hour, followed by raising the temperature to 300°C over 8 hours, and then heating at 300°C for 1 hour to carry out the solvent removal and curing reaction. This obtained a laminate having a resin layer on an aluminum substrate. Subsequently, the aluminum substrate was removed from the obtained laminate to obtain a cured product.

[0152] Examples 4-7 and Comparative Example 3: Curable resin compositions were obtained and cured products were obtained in the same manner as in Example 3, except that the formulation was changed as shown in Table 2.

[0153] Comparative Example 2: A curable resin composition and cured product were obtained in the same manner as in Example 3, except that DMF was used as the solvent and reflux heating at 130°C for 0.5 hours was performed instead of heating at 50°C for 1 hour. The reason for changing the solvent to DMF was that MEK did not dissolve the resin.

[0154] The curable resin compositions and their cured products obtained in the examples and comparative examples were evaluated as follows. The results are shown in the table below.

[0155] - Glass transition temperature Tg of the cured material The Tg of the cured material was measured using a differential scanning calorimetry (DSC) under the following conditions. <Measurement conditions> Apparatus: Perkin Elmer DSC 6000 Heating rate: 10°C / min The temperature was raised from 25°C to 300°C, and the starting temperature of the discontinuous change derived from the transition temperature in the obtained heating curve was defined as the glass transition temperature.

[0156] Dielectric properties of the cured material The relative permittivity Dk and dielectric loss tangent Df of the cured material were measured under the following conditions. <Measurement conditions> Equipment: Keysight Technologies PNA network analyzer N5222B, cavity resonator (Kanto Electronics Applied Development Co., Ltd. CP-521 for 5.8 GHz) Sample dimensions: Length 80 mm x Width 2 mm x Thickness 100 μm Frequency: 5.8 GHz Measurement temperature: 23°C Test environment: 23°C ± 1°C, 50% RH ± 5% RH

[0157]

[0158] The raw materials for the curable resin composition are described below. <Curable Resins> Epoxy resin 1: Bisphenol A type epoxy resin, epoxy equivalent 170 g / eq, manufactured by Tokyo Chemical Industry Co., Ltd. Epoxy resin 2: Cresol novolac type epoxy resin, epoxy equivalent 209 g / eq, manufactured by DIC Corporation as "NEPICLON N-660" Epoxy resin 3: Bisphenol A type epoxy resin, epoxy equivalent 1847 g / eq, manufactured by Nippon Steel Chemical & Material Co., Ltd. as "Epotote YD-017"

[0159] <Curing agent> Bisimidodicarboxylic acid A-C: Bisimidodicarboxylic acid obtained in Examples 1, 2 and Comparative Example 1 TD2131: Phenol novolac resin, functional group equivalent 104 g / eq, "PHENOLITE TD-2131" manufactured by DIC Corporation BI-F5: Imide-based curing agent represented by formula (3) above (L in the formula) ２ (Alkylene group with 5 or more carbon atoms), functional group equivalent 1510 g / eq, manufactured by Unitika Ltd. "BI-F5"

[0160] <Curing accelerator> 2E4Mz: 2-ethyl-4-methylimidazole, manufactured by Tokyo Chemical Industry Co., Ltd.

[0161] <Solvents> MEK: Methyl ethyl ketone, manufactured by Tokyo Chemical Industry Co., Ltd. DMF: N,N-dimethylformamide, manufactured by Tokyo Chemical Industry Co., Ltd.

[0162] The curable resin compositions of Examples 3 to 7, containing the bisimidodicarboxylic acid of the present invention as a curing agent, exhibited excellent solubility in low-boiling point solvents. Furthermore, they were found to have a high glass transition temperature, excellent heat resistance, and superior dielectric properties. A comparison of Examples 3 to 5 with Examples 6 to 7 shows that using only the bisimidodicarboxylic acid of the present invention (i.e., bisimidodicarboxylic acid containing an indane ring) as a curing agent improves heat resistance compared to the use of other curing agents in combination. It is also evident that even when other curing agents are used in combination, high dielectric properties can be maintained by including the bisimidodicarboxylic acid of the present invention in a specific proportion.

[0163] On the other hand, the curable resin composition of Comparative Example 2 used bisimidodicarboxylic acid that does not contain an indan ring as a curing agent, resulting in low solubility in low-boiling point solvents. Although the resulting cured product had a high glass transition temperature, its dielectric properties were significantly inferior to those of the cured products of Examples 3 to 7. Furthermore, the curable resin composition of Comparative Example 3 used phenol novolac as a curing agent, resulting in high solubility in low-boiling point solvents. However, the resulting cured product had a low glass transition temperature, poor heat resistance, and inferior dielectric properties.

[0164] From these results, it can be seen that introducing an indan ring into bisimidodicarboxylic acid not only significantly improves the softening point and solvent solubility, but also enhances the heat resistance and dielectric properties of the resulting cured product.

[0165] The bisimoiddicarboxylic acid of the present invention has a low softening point and excellent solubility in low-boiling point solvents. Furthermore, the bisimoiddicarboxylic acid can react with a curable resin to form a cured product with excellent heat resistance and dielectric properties. The curable resin composition containing the bisimoiddicarboxylic acid, its semi-cured product, and its cured product are suitably used in semiconductor devices as insulating materials, encapsulants, adhesives, and the like.

Claims

1. Bisimidedicarboxylic acid represented by the following formula (1). [In formula (1), R １ , R ２ Each of these independently represents a trivalent hydrocarbon group. １ This refers to a divalent group represented by the following formulas (L1-1), (L1-2), (L1-3), or (L1-4). (In formulas (L1-1) to (L1-4), R ３ , R ４ Each of these independently represents a single bond or a linking group. Substituents may be attached to the indan ring or spirobisindan ring shown in the formula. Note that the bonds indicated by the wavy lines in formulas (L1-1) to (L1-4) are attached to the nitrogen atom in formula (1).

2. The aforementioned R ３ and R ４ The bisimidodicarboxylic acid according to claim 1, wherein at least one of the groups is a divalent group containing an aromatic hydrocarbon ring.

3. Said L １ The bisimide dicarboxylic acid according to claim 1, wherein is a divalent group represented by the following formula (L1-1-1). (In formula (L1-1-1), n1 and n2 each independently represent an integer of 0 or greater. Substituents may be attached to the indan ring and benzene ring shown in the formula. Note that the bonds indicated by the wavy lines in formula (L1-1-1) are attached to the nitrogen atom in formula (1).) 4. The R １ and R ２ are trivalent hydrocarbon groups containing an alicyclic hydrocarbon or an aromatic hydrocarbon ring, and the bisimide dicarboxylic acid according to claim 1.

5. A curing agent comprising bisimoidodicarboxylic acid as described in any one of claims 1 to 4.

6. A curable resin composition comprising the curing agent and curable resin described in claim 5.

7. The curable resin composition according to claim 6, further comprising at least one curing agent selected from phenolic curing agents, imide curing agents, and acid anhydride curing agents (excluding bisimidodicarboxylic acid represented by formula (1) above).

8. The curable resin composition according to claim 6, wherein the curable resin is an epoxy resin.

9. The curable resin composition according to claim 6, further comprising a curing accelerator.

10. A cured product of the curable resin composition according to claim 6.

11. A prepreg comprising the curable resin composition according to claim 6, or a semi-cured product of the curable resin composition, and a sheet-like fibrous substrate.

12. A film comprising the curable resin composition described in claim 6, or a semi-cured product of the curable resin composition.

13. A metal-clad laminate having a structure in which metal foil is laminated on a substrate, wherein the substrate is a substrate containing a cured product of the curable resin composition described in claim 6.

14. A printed circuit board comprising a cured product of the curable resin composition according to claim 6.

15. The printed circuit board according to claim 14, wherein the cured product is a cured product of a prepreg, and the prepreg is a prepreg comprising the curable resin composition according to claim 6, or a semi-cured product of the curable resin composition, and a sheet-like fibrous substrate.

16. The printed circuit board according to claim 14, wherein the printed circuit board comprising the cured product comprises at least one selected from a surface protective film made of the cured film and an interlayer insulating film made of the cured film, and the film is a film comprising the curable resin composition according to claim 6 or a semi-cured product of the curable resin composition.

17. A semiconductor device comprising a printed circuit board and a semiconductor element, wherein the printed circuit board is a printed circuit board comprising a cured product of the curable resin composition described in claim 6, and / or the semiconductor element is a semiconductor element sealed with a cured product of the curable resin composition described in claim 6.

Images