Indan bis-o-aminophenols and polymers prepared therefrom

Abstract

The present disclosure provides indane bis-o-aminophenol compounds capable of producing soluble polyimides, functional polyimides, and poly-o-hydroxyamides.

Description

Cross-references to related applications

[0001] This application claims priority to U.S. Provisional Application Serial No. 63 / 608,468, filed December 11, 2023, the contents of which are incorporated herein by reference in their entirety. Technical Field

[0002] This application relates to compounds suitable for the preparation of polyimides and polybenzoxazoles commonly used in the microelectronics industry. Background Technology

[0003] In semiconductor packaging applications, the requirements for dielectric materials are constantly evolving. Electronic packaging trends are moving towards faster processing speeds, greater complexity, and higher packaging density, while maintaining high levels of reliability. With the development of electronic packaging technology and the continuous shrinking of chip sizes, the demand for innovative and high-performance resin compositions is constantly increasing. There is a need to develop new monomers of polyimides and polybenzoxazoles suitable for preparing materials that meet the challenging requirements of the microelectronics industry. Summary of the Invention

[0004] This disclosure provides an indane bis-o-aminophenol compound having formula Ia; (Ia) Where R 1 R 2 R 3 R 4 and R 5 Each is an independent hydrogen atom, substituted or unsubstituted C1-C 12 Alkyl groups, partially halogenated or completely halogenated C1-C 12 Alkyl, substituted or unsubstituted C4-C 18 cycloalkyl, substituted or unsubstituted C6-C 22 Aryl or substituted or unsubstituted C5-C 22 heteroaryl; R 11 and R 12 Each is independently a hydrogen atom, a straight-chain or branched C1-C4 alkyl group, a C1-C4 alkyl group partially or completely halogenated, or a C5-C alkyl group. 12 cycloalkyl, C6-C 18 Aryl, C5-C 18 Heteroaryl, C1-C4 alkoxy or halogen atom.

[0005] In some embodiments, this disclosure provides a composition comprising a dielectric film forming composition comprising (a) at least one polymer comprising at least one indane bis-o-aminophenol compound of formula (1a) as a diamine comonomer; and (b) a comonomer derived from dianhydride, a comonomer derived from dianhydride chloride, or a combination thereof, wherein the polymer provides a dielectric layer that, when present in a microelectronic device, imparts good reliability to the device through the modified dielectric layer. Detailed Implementation

[0006] This disclosure provides indane bis-o-aminophenol compounds suitable as comonomers for preparing polymers that meet the challenging requirements of the microelectronics industry. Specifically, the comonomers enable the preparation of fully cyclized polyimides and fully cyclized polyimides containing functional groups selected from: substituted or unsubstituted linear alkenyl groups, substituted or unsubstituted linear alkynyl groups, (meth)acrylic groups, or hydroxyl groups, wherein the polyimides are soluble in commonly used formulation solvents.

[0007] In other embodiments, the comonomers of this disclosure enable the preparation of polybenzoxazole precursors, which, upon cyclization on a matrix, produce polybenzoxazoles with high-temperature stability, wherein these polybenzoxazole precursors are soluble in commonly used formulation solvents.

[0008] Some embodiments of this disclosure provide indane bis-o-aminophenol compounds with structure Ia: (Ia) Where R 1 R 2 R 3 R 4 and R 5 Each is an independent hydrogen atom, substituted or unsubstituted C1-C 12 Alkyl groups, partially halogenated or completely halogenated C1-C 12 Alkyl, substituted or unsubstituted C4-C 18 cycloalkyl, substituted or unsubstituted C6-C 22 Aryl or substituted or unsubstituted C5-C 22 heteroaryl; R 11 and R 12 Each is independently a hydrogen atom, a straight-chain or branched C1-C4 alkyl group, a C1-C4 alkyl group partially or completely halogenated, or a C5-C alkyl group. 12 cycloalkyl, C6-C 18 Aryl, C5-C 18 Heteroaryl, C1-C4 alkoxy or halogen atom.

[0009] In some embodiments, an indane bis-o-aminophenol compound having formula Ib is provided: (Ib) Where R 1 R 2 R 3 R 4 and R 5 Each is an independent hydrogen atom, substituted or unsubstituted C1-C 12 Alkyl or substituted or unsubstituted C4-C 18 cycloalkyl; R 11 and R 12 Each is independently a hydrogen atom, a straight-chain or branched C1-C4 alkyl group, or a C5-C alkyl group. 12 Cycloalkyl or C1-C4 alkoxy.

[0010] In some embodiments, indane bis-o-aminophenol compounds having the following formula are provided: (Ic) Where R 1 or R 4 Each is independently either substituted or unsubstituted C1-C 12 Alkyl; R 2 R 3 and R 5 Independently a hydrogen atom, substituted or unsubstituted C1-C 12 Alkyl or substituted or unsubstituted C4-C 18 cycloalkyl; and R 11 and R 12 Each is independently a hydrogen atom, a straight-chain or branched C1-C4 alkyl group, or a C5-C alkyl group. 12 Cycloalkyl or C1-C4 alkoxy.

[0011] In some embodiments, an indane bis-o-aminophenol compound having formula Id is provided: (Id) Where R 1 or R 4 Independently substituted or unsubstituted C1-C 12 Alkyl; R 2 and R 3 For hydrogen atoms; R 5 Hydrogen atom, substituted or unsubstituted C1-C 12 Alkyl or substituted or unsubstituted C4-C 18 cycloalkyl; R 11 and R 12Each is independently a hydrogen atom, a straight-chain or branched C1-C4 alkyl group, or a C5-C alkyl group. 12 Cycloalkyl or C1-C4 alkoxy.

[0012] R 1 R 2 R 3 R 4 R 5 R 11 and R 12 Substituted or unsubstituted C1-C 12 Examples of alkyl groups include (but are not limited to) methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, and 2-methylhexyl. 1 R 2 R 3 R 4 R 5 R 11 and R 12 Substituted or unsubstituted C4-C 18 Examples of cycloalkyl groups include (but are not limited to) cyclopentyl, cyclohexyl, and cycloheptyl. Partially or completely halogenated C1-C... 12 Examples of alkyl groups include trifluoromethyl, pentafluoroethyl, etc. R 1 R 2 R 3 R 4 R 5 R 11 and R 12 Substituted or unsubstituted C6-C 22 Examples of aryl groups include phenyl, 4-methyl-phenyl, and 2,4,6-trimethyl-naphthyl groups. Substituted or unsubstituted C4-C 22 heteroaryl; R 1 R 2 R 3 R 4 R 5 R 11 and R 12 Examples include furanyl, pyrazinyl, pyrroleyl, and other groups. 11 and R 12 Examples of C1-C4 alkoxy groups include methoxy, ethoxy, isopropoxy, butoxy, etc.

[0013] Examples of indane bis-o-aminophenol compounds (Ia) include (but are not limited to): .

[0014] The synthesis of bisphenol compounds containing the indane moiety can be achieved via a simple route: the bisphenol compound is directly condensed with sulfuric acid, followed by conversion of the dimer to indane bisphenol using an organic sulfonic acid or organic acid (such as methanesulfonic acid, trifluoromethanesulfonic acid, formic acid, acetic acid, etc.) (Method 1). An example of this method via a stable 4-[2-isopropylidene]phenol carbocation from bisphenol A is disclosed in Wei-Fu Chen; Organic Letters, 2004, Vol. 6, Vol. 14, pp. 2341-2343. The indane bisphenol compounds used to practice this disclosure are commercially available and prepared using conventional methods. Examples of such methods are disclosed, for example, in U.S. Patent No. 4,988,785, the entire contents of which are incorporated herein by reference.

[0015] Method 1 In Method 1, the condensation of bisphenol A enables the production of substituted indane bisphenol compounds in a single-step or two-step process, wherein R 1 R 2 R 3 R 4 R 5 R 11 and R 12 It has the same meaning as previously stated, and R 8 Hydrogen atom, substituted or unsubstituted C1-C 12 Alkyl groups, partially halogenated or completely halogenated C1-C 12 Alkyl, substituted or unsubstituted C4-C 18 cycloalkyl, substituted or unsubstituted C6-C 22 Aryl or substituted or unsubstituted C6-C 22 Mixed aromatic compounds.

[0016] Alternatively, bisphenol compounds containing the indane moiety can be obtained by converting the amino group of diaminophenyl indane to a hydroxyl group via a diazo reaction to form indane bisphenol (method 2), wherein R 1 R 2 R 3 R 4 R 5 R 11 and R 12 It has the same meaning as previously stated. An example of such a method for the preparation of stable 4-[2-isopropylidene]-phenol from α-methylstyrene is disclosed in Masanori Terasaki Chemistry Letters 2005, Vol. 34, Vol. 2, 188-189.

[0017] Method 2 Indane bisphenol is nitrated with dilute nitric acid (6% to 40% by weight) and then the nitro compound is reduced to form an indane bis-o-aminophenol compound (method 3).

[0018] Examples of such methods for nitration and reduction of nitrobisphenol compounds are disclosed, for example, in U.S. Patent No. 6,861,560, the entire contents of which are incorporated herein by reference.

[0019] Method 3 Alternatively, the hydroxyl groups of indane bis-o-aminophenol compounds can be protected before nitration and deprotected after nitration (Method 4).

[0020] Method 4 Log P Log P is an important molecular physical property that affects a wide range of parameters in formulations. It is a measure of the bias of a compound's solubility in water or organic solvents (such as octanol) when uncharged. More technically, it is the logarithm of the partition coefficient (P) between the aqueous and lipophilic phases. Log P is a partition coefficient predicted by structure, a measure of hydrophobicity. Although log P It is a constant, but its value depends on the choice of organic partition solvent and, to a lesser extent, on the measurement conditions. (ACD / Labs log...) P The algorithm specifically calculates the partition between oct-1-ol and water (the most commonly used system). Examples of Log P values ​​for bis-o-aminophenols are: 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (log P 0.74), 2,2-bis(3-amino-4-hydroxyphenyl)propane (log P 1.35), 9,9-bis(3-amino-4-hydroxyphenyl)fluorene (log P 2.71), bis(3-amino-4-hydroxyphenyl)sulfone (1.03), and 6-amino-3-(3'-amino-4'-hydroxyphenyl)-1,1,3-trimethyl-2,3-dihydro-1 H -Indene-5-ol (indenebis-o-aminophenol) (Log P 2.61).

[0021] (5) or (6)-Amino-1-(4-aminophenyl)-1,3,3-trimethylindene (DAPI) is a diamine monomer. Due to its inherent asymmetry and non-planarity, it can form solvent-soluble polyimides even when reacting with rigid dianhydrides. Furthermore, DAPI-based polyimide polymers are quite rigid, as evidenced by the high glass transition temperature observed in these systems and their thermal oxidative stability due to the absence of readily oxidizable benzyl hydrogen. The combination of log P, inherent asymmetry, and non-planarity of indene bis-o-aminophenol compounds endows polyimides and polybenzoxazole polymers with favorable physicochemical properties.

[0022] In other embodiments of this disclosure, polymers are provided that are produced by using at least one of the indane bis-o-aminophenol compounds of this disclosure as comonomers.

[0023] In some embodiments, the polymer may comprise at least one indane bis-o-aminophenol comonomer, and comonomers derived from dianhydrides, comonomers derived from diacid chlorides, or combinations thereof.

[0024] The indaminozide bis-o-aminophenol compounds described in this disclosure can provide fully imidized polyimides. Such polyimides can be used in photosensitive compositions suitable for producing dielectric layers that impart good reliability in microelectronic devices.

[0025] In some embodiments of this disclosure, poly-o-hydroxyamides of structure XI are provided. These polymers are produced by using at least one indane bis-o-aminophenol compound as a first comonomer, another diamine or a mixture of diamines as a second comonomer, and a diacid chloride or a mixture of diacid chlorides as a third comonomer. (II) Where R 1 R 2 R 3 R 4 and R 5 Each is an independent hydrogen atom, substituted or unsubstituted C1-C 12 Alkyl groups, partially halogenated or completely halogenated C1-C 12 Alkyl, substituted or unsubstituted C4-C 18 cycloalkyl, substituted or unsubstituted C6-C 22 Aryl or substituted or unsubstituted C5-C 22 heteroaryl; R 11 and R 12Each is independently a hydrogen atom, a straight-chain or branched C1-C4 alkyl group, a C1-C4 alkyl group partially or completely halogenated, or a C5-C alkyl group. 12 cycloalkyl, C6-C 18 Aryl, C5-C 18 Heteroaryl, C1-C4 alkoxy, or halogen atom; Ar1 ​​and Ar2 are each independently a divalent aromatic group, aliphatic group, or heterocyclic group, or a mixture thereof; Ar 11 It is a divalent aromatic group, aliphatic group, heterocyclic group, or siloxane group; E is a capping group; n1 is an integer from 5 to 200; m1 is an integer from 5 to 200; m2 is an integer from 0 to 200; and n2 is an integer from 0 to 200.

[0026] As used herein, "terminated group" refers to the reaction product of the amino terminal group of a poly-o-hydroxyamide with a monohydric anhydride compound. When added to the polymerization system, the monohydric anhydride compound promotes chain termination in poly-o-hydroxyamides, thereby limiting polymer chain growth.

[0027] In some embodiments, Ar1 and Ar2 include the following portions: .

[0028] Where X1 is -C(O)-C(O)-, -C(O)O-, or -(CH2). p -Si(Z)2-O-Si(Z)2-(CH2) p - Z is H or C1-C6 alkyl, and p is an integer from 1 to 6. In some embodiments, the poly-o-hydroxyamide may contain one or more different Ar1 and Ar2 groups.

[0029] In some embodiments, Ar 11 Includes the following parts: .

[0030] Where X2 is -O-, -S-, -C(CF3)2-, -C(CH3)2-, -CH2-, -SO2-, -NHCO-, -C(O)-, -C(O)-C(O)-, -C(O)O-, or -(CH2). m -Si(Z)2-O-Si(Z)2-(CH2) m -, Z is H or C1-C6 alkyl, and m is an integer from 1 to 6.

[0031] In some embodiments, this disclosure provides a poly-o-hydroxyamide polymer that can be used in positive or negative photosensitive compositions, wherein the positive and negative photosensitive resin compositions are soluble in alkaline aqueous solutions and are capable of forming fine patterns with high resolution. The compositions exhibit good mechanical properties even when cured at low temperatures.

[0032] In some embodiments, this disclosure provides compositions comprising the dielectric film forming compositions described herein, the dielectric film forming compositions comprising (a) at least one polymer containing at least one indane bis-o-aminophenol compound as a diamine comonomer; a comonomer derived from dianhydride or a comonomer derived from dianhydride chloride or a combination thereof, thereby providing a dielectric layer, wherein, when the dielectric layer is present in a microelectronic device, the modified dielectric layer imparts good reliability to the device.

[0033] This disclosure will be illustrated in more detail with reference to the following examples, which are for illustrative purposes and should not be construed as limiting the scope of this disclosure.

[0034] Example Synthesis of 4-isopropenylphenol (IPP) oligomers Bisphenol-A (50 g) was dissolved in concentrated sulfuric acid (300 g) at 25 °C with stirring. After complete dissolution of bisphenol-A (approximately 30 minutes), the solution was slowly poured into 3 L of ice water while stirring vigorously. A viscous solid with a light orange color immediately formed. After the addition was complete, the solution was allowed to rise to room temperature and stirred for 60 minutes. The viscous solid precipitate was filtered, and after crystallization from toluene, the product, 35 g of IPP-oligomery (70% yield), was obtained.

[0035] Preparation of 3-(4'-hydroxyphenyl)-1,1,3-trimethyl-5-indanol Dissolve 25 g of IPP oligomer (prepared from BPA) in 100 ml of formic acid and stir the solution for one hour until a solid precipitate forms. After filtration and drying in an oven, collect 17.5 g of product (75% yield based on BPA, 99% recovery based on IPP dimer).

[0036] 6-Nitro-3-(3'-Nitro-4'-hydroxyphenyl)-1,1,3-trimethyl-2,3-dihydro-1 H Preparation of 5-indenyl alcohol Add 200 mL of acetic acid containing 26.8 g of 3-(4'-hydroxyphenyl)-1,1,3-trimethyl-5-indanol to a three-necked round-bottom flask equipped with a mechanical stirrer and a reflux condenser. Heat the mixture to 50°C, and then add 175 mL (2.3 mol equivalents) of nitric acid (specific gravity: 1.38) dropwise to the solution at 50°C for approximately 1 hour. Afterward, allow the solution to stand at 50°C for 1 hour. Then, add 150 mL of water to the solution while adjusting the slurry concentration to allow sufficient crystallization. Filter the solid and wash with a 50% methanol aqueous solution, then air-dry. Finally, crystallize the crude mixture from 95% ethanol. The product obtained is 34 g of the dinitro compound, 6-nitro-3-(3'-nitro-4'-hydroxyphenyl)-1,1,3-trimethyl-2,3-dihydro-1 H -Indene-5-ol (94% yield).

[0037] 6-Amino-3-(3'-Amino-4'-hydroxyphenyl)-1,1,3-trimethyl-2,3-dihydro-1 H Preparation of 5-indene alcohol (indenebis-o-aminophenol) 30 g of 6-nitro-3-(3'-nitro-4'-hydroxyphenyl)-1,1,3-trimethyl-2,3-dihydro-1 H Indene-5-ol, 0.44 g 5% Pt / C, 0.044 g H3PO2, 0.07 g [VO(acac)2], and 200 g toluene were reacted at 5 bar H2 pressure and 100°C. After the reaction was complete, the solution was concentrated to dryness. The crude solid was purified by recrystallization from an aqueous ethanol solution. The product was 20 g 6-amino-3-(3'-amino-4'-hydroxyphenyl)-1,1,3-trimethyl-2,3-dihydro-1 H -Indene-5-ol (80% yield).

[0038] Melting point of indaminozide bis-o-aminophenol The melting point of indimmon bis-o-aminophenol was determined to be 228°C by differential scanning calorimetry (DSC).

[0039] NMR analysis of indane bis-o-aminophenol 1H NMR (400 MHz): DMSO d6, δ 0.97 (s, 3H), 1.20 (s, 3H), 1.44 (s, 3H), 1.94 (d, 1H), 2.18 (d, 1H), 4.34 (s, 4H, NH2), 6.19 (q, 1H), 6.30 (s, 1H), 6.39 (s, 1H), 6.45 (q, 1H), 8.66 (d, 2H, OH).

[0040] 13 C NMR: 101 MHz, DMSO d6, δ 31.1 (s), 31.5 (s), 31.7 (s), 42.3 (s), 49.6 (s), 60.1 (s), 108.2 (s), 110.3 (s), 113.7 (d), 114.9 (s), 135.9 (d), 137.7 (s), 1420 (d), 143.1 (s), 143.7 (s).

[0041] Although this disclosure has been described in detail with reference to certain embodiments thereof, it should be understood that modifications and variations are within the spirit and scope of the invention described and claimed.

Claims

1. An indane bis-o-aminophenol compound having formula Ia: (Ia) Where R 1 R 2 R 3 R 4 and R 5 Each is an independent hydrogen atom, substituted or unsubstituted C1-C 12 Alkyl groups, partially halogenated or completely halogenated C1-C 12 Alkyl, substituted or unsubstituted C4-C 18 cycloalkyl, substituted or unsubstituted C6-C 22 Aryl or substituted or unsubstituted C5-C 22 heteroaryl; R 11 and R 12 Each is independently a hydrogen atom, a straight-chain or branched C1-C4 alkyl group, a C1-C4 alkyl group partially or completely halogenated, or a C4-C... 12 cycloalkyl, C6-C 18 Aryl, C5-C 18 Heteroaryl, C1-C4 alkoxy or halogen atom.

2. The indane bis-o-aminophenol compound of claim 1, wherein R 1 R 2 R 3 R 4 and R 5 Each is an independent hydrogen atom, substituted or unsubstituted C1-C 12 Alkyl or substituted or unsubstituted C4-C 18 cycloalkyl; R 11 and R 12 Each is independently a hydrogen atom, a hydrogen atom, a straight-chain or branched C1-C4 alkyl group, or a substituted or unsubstituted C4-C group. 12 Cycloalkyl or C1-C4 alkoxy.

3. The indane bis-o-aminophenol compound of claim 1, wherein R 1 or R 4 Each is independently either substituted or unsubstituted C1-C 12 Alkyl; R 2 R 3 and R 5 Independently a hydrogen atom, substituted or unsubstituted C1-C 12 Alkyl or substituted or unsubstituted C4-C 18 cycloalkyl; and R 11 and R 12 Each is independently a hydrogen atom, a straight-chain or branched C1-C4 alkyl group, or a substituted or unsubstituted C4-C group. 12 Cycloalkyl or substituted or unsubstituted C1-C4 alkoxy groups.

4. The indane bis-o-aminophenol compound of claim 1, wherein R 1 or R 4 Each is independently either substituted or unsubstituted C1-C 12 Alkyl; R 2 and R 3 Independently a hydrogen atom; R 5 Hydrogen atom, substituted or unsubstituted C1-C 12 Alkyl or substituted or unsubstituted C4-C 18 cycloalkyl; R 11 and R 12 Each is independently a hydrogen atom, a straight-chain or branched C1-C4 alkyl group, or a C4-C4 alkyl group. 12 Cycloalkyl or C1-C4 alkoxy.

5. The indaminozide bis-o-aminophenol compound of claim 1, wherein the indaminozide bis-o-aminophenol compound is selected from the group consisting of: 。 6. A polyimide polymer comprising a reaction product of components (a), (b) and (c), wherein components (a), (b) and (c) are: (a) At least one indaminozide bis-o-aminophenol compound selected from the group consisting of indaminozide bis-o-aminophenol compounds as described in claim 1. (b) at least one other diamine; and (c) At least one tetracarboxylic acid dianhydride.

7. A polymer comprising a poly-o-hydroxyamide represented by the following general formula (II): (II) Where R 1 R 2 R 3 R 4 and R 5 Each is an independent hydrogen atom, substituted or unsubstituted C1-C 12 Alkyl groups, partially halogenated or completely halogenated C1-C 12 Alkyl, substituted or unsubstituted C4-C 18 cycloalkyl, substituted or unsubstituted C6-C 22 Aryl or substituted or unsubstituted C5-C 22 heteroaryl; R 11 and R 12 Each is independently a hydrogen atom, a straight-chain or branched C1-C4 alkyl group, a C1-C4 alkyl group partially or completely halogenated, or a C4-C... 12 cycloalkyl, C6-C 18 Aryl, C5-C 18 Heteroaryl, C1-C4 alkoxy or halogen atom; Ar1 ​​and Ar2 are divalent aromatic groups, aliphatic groups or heterocyclic groups or mixtures thereof; Ar 11 It is a divalent aromatic group, aliphatic group, heterocyclic group, or siloxane group; E is a capping group; m1 is an integer from 5 to 200; n1 is an integer from 5 to 200; m2 is an integer from 0 to 200; and n2 is an integer from 0 to 200.

Images