Amane Mochizuki

Synthesis of aliphatic polyimides containing adamantyl units

Aliphatic polyimides containing adamantyl units (APIs) were prepared by the poly(addition/condensation) of a dianhydride bicyclo[2.2.2]octane-2,3,5,6-tetracarboxylic 2,3 : 5,6-dianhydride with a rigid diamine, 1,3-diaminoadamantane or 3,3′-diamino-1,1′-biadamantyl, and a flexible diamine, 4,4′-methylenebis(cyclohexylamine) or 1,4-cyclohexanediamine. One-step polymerizations were conducted at 80–200°C in m-cresol, producing APIs with inherent viscosities up to 0.53 dL g−1. These APIs are soluble in haloalkanes, m-cresol, and sulfuric acid and show high thermal stability and excellent transparency.

Photosensitive polyimide-precursor based on polyisoimide: dimensionally stable polyimide with a low dielectric constant

Abstract A positive-working photosensitive polyimide (PI) precursor based on fluorinated polyisoimide (FPII) and 2,3,4-tris(1-oxo-2-diazonaphthoquinone-5-sulfonyloxy) benzophenone (D5SB) as a photosensitive compound has been developed. FPII was prepared by ring-opening polyaddition of dianhydrides, pyromellitic dianhydride and biphenyltetracarboxylic dianhydride, with diamine, 2,2′-bis(trifluoromethyl benzidine and followed by treatment with trifluoroacetic anhydride-triethylamine in N-methyl-2-pytrolidinone. The FPII film showed a good solubility in a wide range of organic solvents. The dissolution behaviour of FPII containing 30 wt% of D5SB after exposure was studied and it was found that the difference of dissolution rate between the exposed and the unexposed parts was enough to get a positive pattern due to photochemical reaction of D5SB in the polymer film. The photosensitive fluorinated polyimide (FPI) precursor containing 30 wt% of D5SB showed a sensitivity of 250 mJ cm−2 and a contrast of 1.5 with 436 nm light, when it was developed with a mixture of 2.38% aqueous tetramethylammonium hydroxide solution and 2-propanol at room temperature. The FPI film cured up to 360°C had a low coefficient of thermal expansion of 10.8 ppm °C−1 and a low dielectric constant of 2.89.

Synthesis of Fully Aliphatic Polyimides

Fully aliphatic polyimides (APIs) have been synthesized. APIs were prepared by poly(addition-condensation) of the alicyclic dianhydride bicyclo[2.2.2]octane-2, 3, 5, 6-tetra-carboxylic 2, 3:5, 6-dianhydride with the aliphatic diamine 5-amino-1, 3, 3-trimethylcyclo-hexanemethylamine, the mixture of 2, 5- and 2, 6-bis(aminomethyl)bicyclo[2.2.1]heptane or 1, 4-cyclohexanebis(methylamine) in m-cresol at high temperature. The polymerization proceeded smoothly at 200 °C and produced APIs with inherent viscosities up to 0.48 dl g−1. The APIs were soluble in a wide range of polar solvents and showed high thermal stability and excellent transparency.

New positive-type photosensitive polyimide: poly(hydroxyimide) with diazonaphthoquinone

Abstract A positive working photosensitive polyimide based on polyhydroxyimide (PHI) and 2,3,4-tris[1-oxo-2-diazonaphthoquinone-4-sulfonyloxy] benzophenone (D4SB) as a photoreactive compound has been developed. The PHI was prepared by the ring-opening polyaddition of 4,4′-hexafluoroisopropylidenebis(phthalic anhydride) (6FDA), 4,4′-diamino-4″-hydroxytriphenylmethane (DHTM), and 4,4′-oxydianiline (ODA), followed by thermal cyclization in refluxing xylene. The PHI film showed excellent transparency to UV light. The photosensitive polyimide containing 30 wt% of D4SB showed a sensitivity of 250 mJ/cm 2 and a contrast of 5.2 when it was exposed to 436 nm light followed by developing with a 1% aqueous tetramethylammonium hydroxide (TMAH) solution at 35°C.

Synthesis of head-to-tail polyurethanes from nonsymmetric diisocyanate and ethylene glycol with organotin catalysts

An ordered head-to-tail (HT) polyurethane was successfully prepared by the polyaddition reaction of p-isocyanatobenzyl isocyanate with ethylene glycol with dibutyltin dilaurate as a catalyst. Furthermore, the HT regularity of polyurethane was improved to 83% with 1,1,3,3-tetraphenyl-1,3-dichlorodistannoxane. The polymerization was conducted in N,N-dimethylformamide at 30 °C with both monomers mixed at once. The microstructure of the polymer was investigated by 1H and 13C NMR spectroscopy, and the polymer obtained by the polyaddition reaction had the expected HT linkages. The constitutional regularity of the polymers influenced the thermal properties and crystallinity.

Preparation and Properties of Polyisoimides as a Highly Dimensionally Stable Polyimide Precursor with Low Dielectric Constant

Fluorinated polyimides (PIs) with low dielectric constant and high dimensional stability have been developed using polyisoimides (PIIs) as a polyimide precursor. The PIIs were prepared by the ring-opening polyaddition of the dianhydrides pyromellitic dianhydride, biphenyltetracarboxylic dianhydride and 4, 4′-hexafluoropropylidenedi(phthalic anhydride) with the diamines 2, 2′-dimethylbenzidine and 2, 2′-bis(trifluoromethyl)benzidine, followed by treatment with trifluoroacetic anhydride/triethylamine or dicyclohexylcarbodiimide in N;N-dimethylacetamide. The PIIs were soluble in a wide range of solvents including dipolar aprotic solvents, cyclohexanone and tetrahydrofuran at room temperature, and easy to convert to corresponding PIs by high thermal treatment. The resulting PIs showed low dielectric constants of less than 3 at 1 MHz as well as low CTEs. Furthermore, during the isomerization reaction, migration of copper in the PI film was hardly observed.

Synthesis and characterization of ordered polyurethanes from nonsymmetric diisocyanate and ethylene glycol

An ordered polyurethane with a head-to-head (H-H) or tail-to-tail (T-T) content over 95% was prepared by polyaddition reaction of a nonsymmetric monomer, p-isocyanatobenzyl isocyanate (1) with a symmetric monomer, ethylene glycol (2). The model reactions were studied in detail to demonstrate the feasibility of polymer formation. The polymerization was conducted in THF in the presence of triethylamine (TEA) at 0 °C by slow addition of a half amount of 2 to 1, followed by removing THF and then adding the rest of 2 in DMF at once at 30 °C in the presence of dibutyltin dilaurate (DBTL). The microstructure of the polymer obtained was investigated by 13C NMR spectroscopy, and it was found that the polymer had the expected structural regularity. The constitutional regularity of polymers influenced their thermal properties.

Positive-working alkaline-developable photosensitive polyimide precursor based on polyisoimide using diazonaphthoquinone as a dissolution inhibitor

Abstract A positive-working photosensitive polyimide precursor based on polyisoimide (PII) and 2,3,4-tris(1-oxo-2-diazonaphthoquinone-4-sulfonyloxy) benzophenone (D4SB) as a photoreactive compound has been developed. The polyisoimide was prepared by the ring-opening polyaddition reaction of 4,4′-hexafluoroisopropylidenebis(phthalic anhydride) (6FDA) and 3,3′-diaminodiphenylsulfone (3,3′-DDS), followed by treatment with trifluoroacetic anhydride-triethylamine in N -methyl-2-pyrrolidone (NMP). The polyisoimide film showed excellent transparency to u.v. light, and good solubility in a wide range of organic solvents. The dissolution behaviour of the polyisoimide film containing 20 wt% of D4SB after exposure and post-exposure bake (PEB) has been studied and it has been found that the dissolution rate of an exposed area was ∼80 times faster than of an unexposed area, due to the photochemical reaction of D4SB in the polymer film. The photosensitive polyimide precursor containing 20 wt% of D4SB showed a sensitivity of 250 mJ cm −2 and a contrast of 2.4 with 435 nm light, when it was post-baked at 150°C for 10 min, followed by developing with 5% tetramethylammonium hydroxide solution at 45°C.

Novel photosensitive polymer based on polycarbodiimide and photoamine generator

A novel photosensitive polymer based on end-capped polycarbodiimide (E-PCD) and the photoamine generator N-{((4,5-dimethoxy-2-nitrobenzyl)oxy)car- bonyl}-2,6-dimethylpiperidine (1) was developed. The E-PCD was prepared by polycon- densation of tolylene-2,4-diisocyanate in the presence of 3-methy-1-phenyl-2-phos- pholene-1-oxide as a catalyst. The reaction of carbodiimide and secondary amine was studied. The nucleophilic addition of amine to the carbodiimide moiety proceeded smoothly and provided a guanidine base that acted as a crosslinking agent. A litho- graphic evaluation of the system of E-PCD and 1 revealed that the dissolution rate of the exposed area after the postexposure bake decreased drastically, although no obvi- ous change of the dissolution rate in the unexposed area was observed. The E-PCD containing 10 wt % 1 functioned as a negative working photosensitive polymer when it was exposed to 365-nm UV light, postbaked at 120 °C for 5 min, and developed with toluene at 25 °C.

Synthesis and Characterization of Ordered Polyurethanes from Tolylene 2,4-Diisocyanate and Ethylene Glycol

An ordered polyurethane with a head-to-head or tail-to-tail (H–H or T–T) content of 90% was prepared by polyaddition reaction of a nonsymmetric monomer, tolylene 2,4-diisocyanate (1) with a symmetric monomer, ethylene glycol (2). The polymerization was conducted in toluene in the presence of dibutyltin dilaurate (DBTL) at 0°C by slow addition of a half amount of 2 to 1, followed by removing toluene and then adding the rest of 2 in DMF at once at room temperature in the presence of DBTL. Furthermore, the authentic ordered and random polymers were prepared to verify the structure of the ordered polymer and it was found that the polymer had the expected structural regularity. The constitutional regularity of polymers influenced on their thermal properties.