Indane bis-o-aminophenols and polymers prepared therefrom

Abstract

There are provided indane bis-o-aminophenol compounds capable of producing soluble polyimides, functional polyimides, and poly-o-hydroxyamides.

Description

[0001] INDANE BIS-O-AMINOPHENOLS AND POLYMERS PREPARED

[0002] THEREFROM

[0003] CROSS-REFERENCE TO RELATED APPLICATION

[0004] The present application claims priority to U.S. Provisional Application Serial No. 63 / 608,468, filed on December 11 , 2023, the contents of which are hereby incorporated by reference in their entirety.

[0005] TECHNICAL FIELD

[0006] This application relates to chemical compounds suitable for the preparation of polyimides and polybenzoxazoles commonly used in the in microelectronics industry.

[0007] BACKGROUND

[0008] Dielectric material requirements for semiconductor packaging applications are continuously evolving. The trend in electronic packaging continues to move towards faster processing speeds, increased complexity and higher packing density while maintaining a high level of reliability. As electronic packaging technology advances and chips continue to shrink in size, the demand for innovative and high-performance resin compositions is growing. There is a demand for development of new monomers which are suitable for the preparation of polyimides and polybenzoxazoles that meet the challenging requirements of the microelectronics industry. SUMMARY

[0009] The present disclosure provides indane bis-o-aminophenol compounds having formula la; wherein each of R1, R2, R3, R4, and R5independently, is a hydrogen atom, a substituted or unsubstituted C1-C12 alkyl, a partially halogen substituted or fully halogen substituted C1-C12 alkyl, a substituted or unsubstituted C4-C18 cycloalkyl, a substituted or unsubstituted C6-C22 aryl, or a substituted or unsubstituted C5-C22 heteroaryl; each of R11and R12independently is a hydrogen atom, a linear or branched C1-C4 alkyl, a partially halogen substituted or fully halogen substituted C1-C4 alkyl, a C5-C12 cycloalkyl, a C6-C18 aryl, a C5-C18 heteroaryl group, a C1-C4 alkoxy group, or a halogen atom.

[0010] In some embodiments, the disclosure provides compositions comprising dielectric film-forming compositions including (a) at least one polymer comprising at least one indane bis-o-aminophenol compound of formula (1 a) as a diamine comonomer; and b) a comonomer derived from a dianhydride, a comonomer derived from a diacid chloride, or a combination thereof, wherein the polymer provides a dielectric layer, and when the dielectric layer is present in a microelectronic device, the modified dielectric layer imparts good reliability to the device.

[0011] DETAILED DESCRIPTION

[0012] The disclosure provides indane bis-o-aminophenol compounds which are suitable as comonomers for the preparation of polymers that meet the challenging requirements of the microelectronics industry. In particular, 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.

[0013] In other embodiments, the comonomers of the disclosure enable the preparation of polybenzoxazole precursors which, after cyclization on a substrate, produce polybenzoxazoles with high temperature stability, wherein these polybenzoxazole precursors are soluble in commonly used formulation solvents.

[0014] Some embodiments of the disclosure provide indane bis-o-aminophenol compounds of structure la: wherein each of R1, R2, R3, R4, and R5independently, is a hydrogen atom, a substituted or unsubstituted C1-C12 alkyl, a partially halogen substituted or fully halogen substituted C1-C12 alkyl, a substituted or unsubstituted C4-C18 cycloalkyl, a substituted or unsubstituted C6-C22 aryl, or a substituted or unsubstituted C5-C22 heteroaryl; each of R11and R12independently, is a hydrogen atom, a linear or branched C1-C4 alkyl, a partially halogen substituted or fully halogen substituted Ci-C4alkyl, a C5-C12 cycloalkyl, a C6-C18 aryl, a C5-C18 heteroaryl group, a C1-C4 alkoxy group or a halogen atom.

[0015] In some embodiments there are provided indane bis-o-aminophenol compounds having formula lb: wherein each of R1, R2, R3, R4, and R5independently, is a hydrogen atom, a substituted or unsubstituted C1-C12 alkyl, or a substituted or unsubstituted C4-C18 cycloalkyl; each of R11and R12independently, is a hydrogen atom, a linear or branched

[0016] C1-C4 alkyl, a C5-C12 cycloalkyl, or a C1-C4 alkoxy group.

[0017] In some embodiments, there are provided indane bis-o-aminophenol compounds having formula : wherein R1or R4each independently is a substituted or unsubstituted Ci -

[0018] C12 alkyl group; R2, R3, and R5, are independently a hydrogen atom, a substituted or unsubstituted Ci-Ci2alkyl, or a substituted or unsubstituted C4-C18 cycloalkyl; and each of R11and R12is independently a hydrogen atom, a linear or branched C1-C4 alkyl, a C5-

[0019] C12 cycloalkyl, or a C1-C4 alkoxy group.

[0020] In some embodiments there are provided indane bis-o-aminophenol compounds having formula Id:

[0021] wherein R1or R4is independently a substituted or unsubstituted C1-C12 alkyl group; R2and R3are a hydrogen atom; R5is a hydrogen atom, a substituted or unsubstituted C1-C12 alkyl, or a substituted or unsubstituted C4-C18 cycloalkyl; each of R11and R12independently, is a hydrogen atom, a linear or branched C1-C4 alkyl, a C5- C12 cycloalkyl, or a C1-C4 alkoxy group.

[0022] Examples of substituted or unsubstituted C1-C12 alkyl groups in R1, R2, R3, R4, R5, R11and R12include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, amyl, hexyl, and 2-methylhexyl. Examples of substituted or unsubstituted C4-C18 cycloalkyl in R1, R2, R3, R4, R5, R11and R12include, but are not limited to, cyclopentyl, cyclohexyl, and cycloheptyl. Examples of a partially halogen substituted or fully halogen substituted C1-C12 alkyl include trifluoromethyl, pentafluoroethyl and the like. Examples of a substituted or unsubstituted C6-C22 aryl in in R1, R2, R3, R4, R5, R11and R12include phenyl, 4-methyl-phenyl, 2,4,6-trimethyl- naphthyl and the like. Examples of a substituted or unsubstituted C4-C22 heteroaryl; R1, R2, R3, R4, R5, R11and R12include furanyl; pyrazinyl, pyrrolyl and the like. Examples of C1-C4 alkoxy groups in R11and R12include methoxy, ethoxy, isopropyloxy, butoxy, and the like.

[0023] Examples of indane bis-o-aminophenol compound (la) include, but are not limited to:

[0024] The synthesis of bisphenol compounds comprising an indane moiety can be accomplished by a facile route through a direct condensation of bisphenol compounds with sulfuric acid and subsequent conversion of the dimers to indane bisphenol using organic sulfonic acid or organic acid such as methane sulfonic acid, trifluoromethane sulfonic acid, formic acid, acetic acid and the like (Process 1 ). Examples of such processes through a stable 4-[2-lsopropylidene]-phenol carbocation from bisphenol A are disclosed in Wei-Fu Chen; Organic Letters, 2004 Vol. 6, No. 14 pp 2341-2343. Indane bisphenol compounds for use in the practice of this disclosure can be obtained from commercial sources and are prepared using conventional processes. Examples of such processes are disclosed in, e.g., U.S. Patent No. 4,988,785, the entire contents of which are hereby incorporated by reference.

[0025] Process 1 In Process 1 , the condensation of bisphenol A enables production of substituted indane bisphenol compounds in a single or in a two-step process wherein R1, R2, R3, R4, R5, R11and R12have the same meaning described earlier and R8is a hydrogen atom, a substituted or unsubstituted C1-C12 alkyl, a partially halogen substituted or fully halogen substituted C1-C12 alkyl, a substituted or unsubstituted C4-C18 cycloalkyl, a substituted or unsubstituted C6-C22 aryl, or a substituted or unsubstituted C6-C22 heteroaryl group.

[0026] Alternatively, the bisphenol compounds comprising an indane moiety can be accomplished by the conversion of the amino groups of diamino phenyl indane to hydroxyl groups by diazonium reaction forming indane bisphenol (Process 2) wherein R1, R2, R3, R4, R5, R11and R12have the same meaning described earlier. Examples of such processes through a stable 4-[2-lsopropylidene]-phenol from a-methylstyrene are disclosed in Masanori Terasaki Chemistry Letters 2005, Vol.34, No.2, 188-189.

[0027] Process 2 Nitration of indane bisphenols using dilute nitric acid (6-40 wt%) and subsequent reduction of nitro compounds form indane bis-o-aminophenol compounds (Process 3). Examples of such process of nitration and reduction of nitro bisphenol compounds are disclosed in, e.g., U.S. Patent No. 6,861 ,560 and the entire contents of which are hereby incorporated by reference.

[0028] Process 3

[0029] Alternatively, hydroxyl groups of indane bis-o-aminophenol compounds can be protected before nitration and hydroxyl group deprotection occurs after nitration (Process 4). Process 4

[0030] Log P is an important molecular physical property that influences a wide range of parameters in formulations. Log P is the measure of the preference of a compound to be dissolved in either water or an organic solvent (such as octanol) when uncharged. More technically, it is the logarithm of the partition coefficient (P) of a molecule between an aqueous and lipophilic phase. Log P predicts the partition coefficient, a measure of hydrophobicity, from structure. Although log P is a constant, its value is dependent on the choice of the organic partitioning solvent and, to a lesser degree, on the conditions of measurement. ACD / Labs’ log P algorithms specifically calculate partitioning between octan-1-ol and water— the most commonly used system. An example of Log P of bis-o- aminophenol are: 2,2-Bis(3-amino-4-hydroxyphenyl)hexafluoropropane (log P 0.74), 2,2-Bis(3-amino-4-hydroxylphenyl)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-1H-inden-5-ol (Indane bis-o-aminophenol) (LogP 2.61 ). (5) or (6)-amino-1-(4-aminophenyl)-1 ,3,3-trimethylindane (DAPI) are diamine monomers which form solvent soluble polyimides with even rigid dianhydrides due to inherent asymmetry and non-planarity. At the same time, the DAPI based polyimide polymers are quite rigid which is evident from the high glass transition temperatures observed for these systems and thermoxidative stability due to absence of oxidatively susceptible benzylic hydrogens. The combination of logP, inherent asymmetry and non- planarity of indane bis-o-aminophenol compounds will provide good physicochemical properties of polyimide and polybenzoxazole polymers.

[0031] In other embodiments of this disclosure there are provided polymers produced by using at least one indane bis-o-aminophenol compound of the invention as a comonomer.

[0032] In some embodiments, the polymer may be comprised of at least one indane bis- o-aminophenol comonomer and a comonomer derived from a dianhydride, a comonomer derived from a diacid chloride, or a combination thereof.

[0033] The indane bis-o-aminophenol compounds described in this disclosure can provide fully imidized polyimides. Such polyimides can be used in photosensitive compositions which can be used in dielectric compositions suitable for producing dielectric layers that impart good reliability in microelectronic devices.

[0034] In some embodiments of this disclosure there are provided poly-o- hydroxyamides of Structure XI. These polymers are produced by utilizing at least one indane bis-o-aminophenol compound as a first comonomer and another diamine or mixture of diamines as a second comonomer, and a diacid chloride or mixture of diacid chlorides as a third comonomer: wherein each of R1, R2, R3, R4, and R5independently, is a hydrogen atom, a substituted or unsubstituted C1-C12 alkyl, a partially halogen substituted or fully halogen substituted C1-C12 alkyl, a substituted or unsubstituted C4-C18 cycloalkyl, a substituted or unsubstituted C6-C22 aryl, or a substituted or unsubstituted C5-C22 heteroaryl; each of R11and R12independently is a hydrogen atom, a linear or branched C1-C4 alkyl, a partially halogen substituted or fully halogen substituted Ci-C4alkyl, a C5-C12 cycloalkyl, a C6-C18 aryl, a C5-C18 heteroaryl group, a C1-C4 alkoxy group or a halogen atom; An and Ar2 are each independently a divalent aromatic, aliphatic, or heterocyclic group, or mixtures thereof; Arn is a divalent aromatic, aliphatic, or heterocyclic group or siloxane group; E is an end-capping group; ni is an integer from 5 to 200; mi is an integer from 5 to 200; m2 is an integer from 0 to 200 and n2 is an integer from 0 to 200.

[0035] As used herein, “end-capping group” refers to the reaction products of amino end groups of poly-o-hydroxyamides with monoanhydride compounds. Monoanhydride compounds, when added to the polymerization system, facilitate termination of a poly-o- hydroxyamide chain, thereby limiting polymer chain growth.

[0036] In some embodiments, An and Ar2 include the following moieties: in which Xi is -C(O)-C(O)-, -C(O)O- or -(CH2)p-Si(Z)2-O-Si(Z)2-(CH2)p-, Z is H or Ci-C6alkyl and p is an integer from 1 to 6. In some embodiments, the poly-o-hydroxyamide can contain one or more different An and Ar2groups.

[0037] In some embodiments, Arn includes the following moieties:

[0038] in which X2is -0-, -S-, -C(CF3)2-, -C(CH3)2- -CH2- -S02- -NHCO-, -C(0)-, -C(0)- C(0)-, -C(0)0-, or -(CH2)m-Si(Z)2-O-Si(Z)2-(CH2)m-, Z is H or Ci-Ce alkyl and m is an integer from 1 to 6. In certain embodiments, the disclosure provides poly-o-hydroxyamide polymers that can be used in positive tone or negative tone photosensitive compositions, wherein the positive photosensitive resin composition and the negative photosensitive resin composition are soluble in an aqueous alkaline solution and are capable of forming a fine pattern with high resolution. The compositions have good mechanical properties even when cured at low temperature.

[0039] In some embodiments, the disclosure provides compositions comprising the dielectric film-forming compositions described herein including (a) at least one polymer comprising at least one indane bis-o-aminophenol compound as diamine comonomer; a comonomer derived from a dianhydride, or a comonomer derived from a diacid dichloride, 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. The present disclosure is 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 the present disclosure. EXAMPLES

[0040] Synthesis of 4-lsopropenyl phenol (IPP) Oligomers

[0041] Bisphenol-A (50 g) is dissolved and stirred in concentrated sulfuric acid (300g) at 25°C. After, bisphenol-A is completely dissolved (about 30 minutes), the solution is poured slowly into 3L of ice-water while vigorously stirring. A sticky solid with slight orange color is formed instantaneously. After complete addition, the temperature of the solution is allowed to rise to room temperature and the solution is stirred for 60 minutes. The sticky solid precipitates are filtered, and after crystallization from toluene, the product, 35 g of IPP-oligomers (70% yield) is obtained. Preparation of 3-(4'Hydroxyphenyl)-1,1,3-trimethyl-5-indanol

[0042] IPP-oligomers, (25 g, prepared from BPA) are dissolved in 100ml formic acid and the solution is stirred for a period of one hour until solid precipitates are formed. After filtration and drying in the oven, 17.5g (75% yield based on BPA, 99% recovery by IPP-dimers) product is collected.

[0043] Preparation of 6-nitro-3-(3'-nitro-4'hydroxyphenyl)-1,1,3-trimethyl-2,3-dihydro-1H- inden-5-ol

[0044] To a 3-neck round bottom flask equipped with a mechanical stirrer and a reflux condenser is added 26.8 grams of 3-(4’-Hydroxyphenyl)-1 ,1 ,3-trimethyl-5-indanolin 200 ml of acetic acid. The mixture is warmed to 50 degrees centigrade and then 175 mL (2.3 molar equivalent) of nitric acid (specific gravity: 1 .38) is added dropwise to the solution for about 1 hour at 50 degrees centigrade. Thereafter, the solution is left at 50 degrees centigrade for 1 hour. Then, 150 mL of water is added to the solution while adjusting a slurry concentration for sufficiently depositing the crystallized substance. The solid is filtered and washed with 50 percent aqueous methanol and then dried in air. Finally, the crude mixture is crystallized from 95 percent ethanol. The product, 34 g of dinitro compound, 6-n itro-3-(3’-n itro-4’-hydroxyphenyl)-1 , 1 , 3-trimethy I-2, 3-d ihydro-1 / - / -inden-5- ol (94% yield) is obtained.

[0045] Preparation of 6-amino-3-(3'-amino-4'-hydroxyphenyl)-1 ,1 ,3-trimethyl-2,3-dihydro- 1H-inden-5-ol (Indane bis-o-aminophenol)

[0046] To a pressure reactor equipped with a mechanical stirrer is added 30 grams of 6-nitro-3- (3’-nitro-4’-hydroxyphenyl)-1 ,1 ,3-trimethyl-2,3-dihydro-1 H-inden-5-ol,0.44 grams of 5 percent Pt / C, 0.044 grams of H3PO2, 0.07 grams of [V0(acac)2], and 200 grams of toluene. The reaction is performed under 5 bar H2 pressure at 100 degrees centigrade. The solution is concentrated to dryness after completion of reaction. The crude solid is purified by recrystallization from aqueous ethanol. The product, 20 g of 6-amino-3-(3'- amino-4'-hydroxyphenyl)-1 ,1 ,3-trimethyl-2,3-dihydro-1 / 7-inden-5-ol (80% yield) is obtained.

[0047] Melting Point of Indane bis-o-aminophenol

[0048] The melting point of Indane bis-o-aminophenol was 228°C measured by DSC (differential scanning calorimetry). NMR Analysis of Indane bis-o-aminophenol

[0049] 1H NMR (400 MHz): DMSO d6, 5 0.97 (s, 3H), 1.20 (s, 3H), 1.44 (s, 3H), 1.94 (d, 1 H),

[0050] 2.18 (d, 1 H), 4.34 (s, 4H, NH2), 6.19 (q, 1 H), 6.30 (s, 1 H), 6.39 (s, 1 H), 6.45 (q, 1 H), 8.66 (d, 2H, OH).13C NMR: 101 MHz, DMSO d6, 5 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).

[0051] While the invention has been described in detail with reference to certain embodiments thereof, it will be understood that modifications and variations are within the spirit and scope of that which is described and claimed.

Claims

WHAT IS CLAIMED IS:1 . An indane bis-o-aminophenol compound having formula la:wherein each of R1, R2, R3, R4, and R5independently, is a hydrogen atom, a substituted or unsubstituted C1-C12 alkyl, a partially halogen substituted or fully halogen substituted C1-C12 alkyl, a substituted or unsubstituted C4-C18 cycloalkyl, a substituted or unsubstituted C6-C22 aryl, or a substituted or unsubstituted C5-C22 heteroaryl; each of R11and R12is independently a hydrogen atom, a linear or branched C1-C4 alkyl, a partially halogen substituted or fully halogen substituted Ci-C4alkyl, a C4-C12 cycloalkyl, a Ce-Ci8 aryl, a C5-C18 heteroaryl group, a C1-C4 alkoxy group or a halogen atom.

2. The indane bis-o-aminophenol compound of claim 1 , wherein each of R1, R2, R3, R4, and R5each independently, is a hydrogen atom, a substituted or unsubstituted Ci-Ci2alkyl, or a substituted or unsubstituted C4-C18 cycloalkyl; each of R11and R12independently, is a hydrogen atom, a hydrogen atom, a linear or branched C1-C4 alkyl, a substituted or unsubstituted C4-C12 cycloalkyl, or a C1-C4 alkoxy group.

3. The indane bis-o-aminophenol compound of claim 1 , wherein R1or R4each independently is a substituted or unsubstituted C1-C12 alkyl; R2, R3, and R5, are independently a hydrogen atom, a substituted or unsubstituted C1-C12 alkyl, or a substituted or unsubstituted C4-C18 cycloalkyl; and each of R11and R12is independently a hydrogen atom, a linear or branched C1-C4 alkyl, a substituted or unsubstituted C4-C12 cycloalkyl, or a substituted or unsubstituted C1-C4 alkoxy group.

4. The indane bis-o-aminophenol compound of claim 1 , wherein R1or R4each independently is a substituted or unsubstituted C1-C12 alkyl group; R2and R3is independently a hydrogen atom; R5is a hydrogen atom, a substituted or unsubstituted C1-C12 alkyl, or a substituted or unsubstituted C4-C18 cycloalkyl; each of R11and R12independently, is a hydrogen atom, a linear or branched C1-C4 alkyl, a C4-C12 cycloalkyl, or a C1-C4 alkoxy group.

5. The indane bis-o-aminophenol compound of claim 1 , wherein the indane bis-o-aminophenol compound is selected from the following compounds:

6. A polyimide polymer, comprising the reaction product of components (a), (b), and (c), wherein components (a), (b), and (c), are:(a) at least one indane bis-o-aminophenol compound selected from the group consisting of an indane bis-o-aminophenol compound of 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):wherein each of R1, R2, R3, R4, and R5independently, is a hydrogen atom, a substituted or unsubstituted C1-C12 alkyl, a partially halogen substituted or fully halogen substituted C1-C12 alkyl, a substituted or unsubstituted C4-C18 cycloalkyl, a substituted or unsubstituted C6-C22 aryl, or a substituted or unsubstituted C5-C22 heteroaryl; each of R11and R12independently is a hydrogen atom, a linear or branched C1-C4 alkyl, a partially halogen substituted or fully halogen substituted Ci-C4alkyl, a C4-C12 cycloalkyl,a Ce-Ci8 aryl, C5-C18 heteroaryl group, a C1-C4 alkoxy group or a halogen atom; An and Ar2 are a divalent aromatic, aliphatic, or heterocyclic group, or mixtures thereof; Arn is a divalent aromatic, aliphatic, or heterocyclic group or siloxane group; E is an end-capping group; mi is an integer from 5 to 200; ni is an integer from 5 to 200; m2 is an integer from 0 to 200 and n2 is an integer from 0 to 200.