Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
  • C08F232/08—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable

Definitions

• Embodiments disclosed hereinbelow relate generally to polymers for forming layers/films useful in the manufacture of a variety of types of displays and more specifically norbornene-type polymers and compositions thereof for forming such layers/films having high transparency over the visible light spectrum.
• LCDs typically encompass color filter layers, polarizing layers, leveling layers, scratch preventative layers and the like.
• materials that are used for such layers often must also evolve or change to meet more demanding requirements resulting from the aforementioned evolution. Therefore a need exists for transparent layers which can meet such evolved requirements.
• molecular weight values of polymers such as weight average molecular weights (Mw) and number average molecular weights (Mn), are determined by gel permeation chromatography using polystyrene standards.
• Tg polymer glass transition temperature
• Td polymer decomposition temperatures
• transparent polymer As used herein, the phrases "transparent polymer”, “transparent layer” or “transparent film” will be understood to mean a polymer, layer or film that is essentially transparent to radiation in the range of 400nm to 750nm (the visible light range). That is to say that such a transparent polymer or transparent layer will allow at least 95% transmission of visible light in the aforementioned range to pass therethrough. While transmission over the entire visible spectrum is mentioned herein, the actual measurement of % transmission is performed at 400nm as transmission of light at the low end of the visible spectrum is generally more problematic than higher wavelengths.
• hydrocarbyl refers to a hydrocarbon a group that contains only carbon and hydrogen, non-limiting examples being alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, aryl, aralkyl and alkaryl.
• alkyl and cycloalkyl refer, respectively, to acyclic or cyclic saturated hydrocarbyls having an appropriate carbon chain length from Ci to C25.
• suitable alkyl groups include, but are not limited to, -CH 3 , -(CH 2 ) 3 CH 3 , -(CH 2 ) 4 CH 3 , -(CH 2 )5CH 3 , -(CH 2 ) 9 CH 3 , -(CH 2 ) 23 CH 3j cyclopentyl, methylcyclopentyl, cyclohexyl and methylcyclohexyl.
• alkenyl and cycloalkenyl refer, respectively, to acyclic or cyclic saturated hydrocarbon groups having at least one carbon to carbon double bond and an appropriate carbon chain length of from C 2 to C 2 s.
• Non-limiting examples include, among others, vinyl groups and groups derived from propylene, butene, cyclopentene, cyclohexane and isopropylprenyl.
• aryl refers to aromatic hydrocarbyls that include, without limitation, groups such as phenyl, biphenyl, benzyl and xylyl.
• alkaryl or “aralkyl” are used herein interchangeably and refer to an aromatic hydrocarbyl substituted with at least one alkyl, cycloalkyl, alkenyl or cycloalkenyl group, for example, groups derived from toluene, butylbenzene, cyclohexylbenzene and l,2-dihydro-l, l '-biphenyl.
• halohydrocarbyl refers to any of the previously described hydrocarbyl groups where at least one hydrogen has been replaced by a halogen and "perhalocarbyl” refers to such a hydrocarbyl group where all hydrogens have been replaced by a halogen, e.g. pentafluorobenzene, respectively.
• heterohydrocarbyl refers to any of the previously described hydrocarbyl groups where at least one of the carbon atoms is replaced with N, O, S, Si or P.
• Non-limiting examples include heterocyclic aromatic groups such as pyrrolyl, furanyl, and pyridenyl as well as non-aromatic groups such as epoxies, alcohols, ethers, thioethers and silyl ethers. .
• hydrocarbyl is a generic term inclusive of the more specific terms halohydrocarbyl, perhalohydrocarbyl and heterohydrocarbyl. Further, it will be understood that any of such moieties can be further substituted and where appropriate, in terms of the number of carbon atoms, linear, branched or cyclic. Non-limiting examples of suitable substituent groups include, among others, hydroxyl groups, epoxy groups, benzyl groups, carboxylic acid and carboxylic acid ester groups, amides and imides. Still further, it will be understood that the term “hydrocarbylene” refers to a divalent radical formed by removing a hydrogen atom from any of the aforementioned hydrocarbyls.
• norbornene-type is used herein to mean a monomer in accordance with Structure 1 shown below, or a polymeric material that was formed from at least one such norbornene-type monomer and therefore has at least one repeat unit in accordance with Structure 2, also shown below:
• norbornene-type monomer is used herein to mean, in
• Embodiments in accordance with the present disclosure are directed to
• norbornene-type polymers compositions that encompass such polymers and methods that utilize such polymer compositions to form a transparent polymer layer or film having a pencil hardness of 4H or higher, that retains at least 95% of its initial transparency at 400nm after exposure in air to a temperature of 280°C for 30 min; that exhibits a high degree of thermal stability in that the percent weight loss of such film does not exceed 1 % during exposure, in air, to a temperature of 280°C for 30min and that exhibits no more than a 2% change in film thickness (for a 3 um film) after soaking in N-Methyl-2-pyrrolidone (NMP) at 40°C for l Omin.
• NMP N-Methyl-2-pyrrolidone
• R a , R b , R c , and R d is a hydrocarbyl group in accordance with one of Formulae B, C or D:
• n is an integer from 1 to 4;
• A if present, is a hydrocarbyl linking group selected from methylene, or a C2 to Ce alkylene and
• R 1 and R 2 are each independently selected from hydrogen, fluorine, methyl, perfluromethyl, ethyl or perfluoroethyl.
• suitable hydrocarbyl linking groups A include methylene, ethylene, propylene,
• Non-limiting examples of useful glycidyl alkyl ether pendent groups in accordance with Formula B include, but are not limited, to glycidyl methyl ether, glycidyl ethyl ether, glycidyl propyl ether, glycidyl isopropyl ether, glycidyl butyl ether, glycidyl isobutyl ether, glycidyl hexyl ether.
• Non-limiting examples of useful alkyl epoxy pendent groups in accordance with Formula C include, but are not limited, butyl epoxy, pentyl epoxy, hexyl epoxy and octyl epoxy.
• a ⁇ is a linking group selected from methylene, or a C2 to C6 alkylene or ether
• R 3 represents hydrogen, methyl, a C2-C4 hydrocarbyl, a nitrile (CN), a C1-C3 perfluorohydrocarbyl or a halogen (F, CI, Br).
• Representative perfluorohydrocarbyls include but are not limited to perfluoromethyl and perfluoroethyl.
• At least one of R a , R b , R c , and R d is
• hydrocarbyl group in accordance with one of Formulae E, F, G, or H:
• a T if present, is as defined above; n is an integer from 1 to 6, n* is an integer from 0 to 3, each R* independently represents hydrogen or fluorine, R 1 and R are each independently selected from hydrogen, fluorine, methyl,
• Non-limiting examples of suitable pendent groups in accordance with Formula E include, but are not limited to, C3 to Cm alkyl and perfluroalkyl hydrocarbyl groups such as -A ⁇ -C4Fg or -A ⁇ -C 6 Fi3-
• suitable pendent groups in accordance with Formulae F and G include, but are not limited to, Ci to Ce acetates and carboxylates, respectively, where Q, if present, is selected from a C 2 to C9 alkylene and Z is selected from one of
• exemplary acetates and carboxylates include, among others, -A ⁇ -CH 2 -C(0)OC 2 H 5 , -A ⁇ -C(CF 3 ) 2 -C(0)OC H9, -A ⁇ -CH 2 - OC(0)CH 3 or -A ⁇ -C(CF 3 ) 2 -OC(0)C 4 H9.
• Non-limiting examples of suitable pendent groups in accordance with Formula H include, but are not limited to, C3 to Cio alcohols, acetals and ether-alcohols such as -CH 2 -0-CH 2 -C(CF 3 )2-OH (where n* is 0, A ⁇ is -CH 2 -0-CH 2 - and each of R 1 and R 2 is perfluoromethyl) or -CH 2 - C(CF 3 ) 2 -OH (where n* is 0, A ⁇ is -CH 2 - and each of R 1 and R 2 is perfluoromethyl).
• Exemplary First type monomer embodiments in accordance with the present disclosure include, but are not limited to:
• Exemplary second type monomer embodiments in accordance with the present disclosure include, but are not limited to:
• norbornene-type layer forming polymers compositions that encompass such polymers and methods that utilize such polymer compositions to form a transparent polymer layer. It will therefore be understood that such norbornene-type layer forming polymer embodiments are formed via 2, 3 enchainment of at least one of said first type of monomer and at least one of said second type of monomer as are exemplified by Examples 1 through 6, presented below as non-limiting representations of some polymer embodiments in accordance with the present disclosure.
• layer forming polymer embodiments encompass one of more layer forming polymer embodiments, a casting solvent and one or more additives.
• layer forming composition embodiments are exemplified by Examples 7 through 12, presented below as non-limiting representations of some polymer composition embodiments in accordance with the present disclosure.
• such casting solvents include, but are not limited, to N- methylpyrrolidone (NMP), Gamma-Butyrolactone (GBL), N,N-dimethylacetamide (DMA), dimethyl sulfoxide (DMSO), diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), methyl lactate, ethyl lactate, butyl lactate, methyl ethyl ketone (MEK), methyl amyl ketone (MAK), cyclohexanone and mixtures thereof.
• NMP N- methylpyrrolidone
• GBL Gamma-Butyrolactone
• DMA N,N-dimethylacetamide
• DMSO dimethyl sulfoxide
• PGME propylene glycol monomethyl ether
• PMEA propylene glycol monomethyl ether acetate
• such additives include, but are not limited to, thermal acid generators (TAGs), antioxidants and synergists where exemplary TAGs include, among others, SI-45L, S1-60L, SI-80L, SI-IOOL, SI-1 10L, SI-150L, S1-145L, 150 and 160 manufactured by SAN SHIN CHEMICAL INDUSTRY CO., LTD.; and
• SI-150L is (dimethyl-p-acetoxysulfoniumhexafluoro antimonate)
• SI-100L is (dibenzylmethyl-p-hydroxyphenylsulfoniumhexafluoro antimonate)
• SI-60L is (1 - naphtylmethylmethyl-p-hydroxyphenylsulfonium hexafluoroantimonate.
• ADEKA STAB AO-20 ADEKA STAB AO-30
• ADEKA STAB AO-40 ADEKA STAB AO-50
• ADEKA STAB AO-60 ADEKA STAB AO-80
• ADEKA STAB AO-330 Sumilizer GM, Sumilizer GS, Sumilizer GA-80, Sumilizer MDP-S, Sumilizer BBM-S, Sumilizer WX-R, IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1098, IRGANOX 1 135, IRGANOX 1330, 1RGANOX 1726, IGRANOX 1425, IRGANOX 1520,
• Examples 1 through 12 are non- limiting examples. That is to say that such are provided only to demonstrate that some embodiments in accordance with the present invention have been actually reduced to practice.
• norbornene-type monomers provided hereinabove, one of ordinary skill will know that the aforementioned examples are not the only possible polymer and/or composition embodiments that can be in accordance with this disclosure.
• such method embodiments encompass the forming of a desired/appropriate polymer composition and applying or casting such composition over/onto a substrate.
• Such casting encompasses any appropriate method for applying a polymer composition onto a substrate, for example by a spin coating, a spray coating or a doctor blade method.
• film forming embodiments in accordance with the present disclosure encompass a post application bake (PAB) and a curing bake, where the latter is performed at a temperature sufficient to activate the thermal acid generator (TAG) that is present in the polymer composition where such TAG activation initiates crosslinking of the polymer which serves to, among other things, harden the layer/film.
• PAB post application bake
• TAG thermal acid generator
• MeOAcNB bis(bicyclo[2.2.1]hept-5-en-2-ylmethyl acetate, 7.87 g, 47.4 mmol
• MGENB 2.13 g, 1 1.8 mmol
• the solution was sparged with nitrogen for 30 min to remove oxygen and then heated to 60 °C.
• ( ⁇ 6 - toluene)Ni(C6F5)2 (0.164 g, 0.34 mmol) in 7.00 g of toluene (prepared in a glove box) was added via syringe to the reaction vessel.
• the mixture was allowed to stir at 60 °C for 4.0 hr, after which the solution was cooled to room temperature.
• the reaction mixture diluted 50g of toluene was then treated with an acetic acid (2.65 g, 44.0 mmol) and 30% cone, of H 2 0 2 aq (5.02g 44.0 mmol) to remove Ni residues and then washed with water.
• the solvents were removed by rotovaporation to give a light yellow solid.
• the yellow solid was redissolved in THF (50 wt%) and was added to hexane (20 fold excess) to give a light yellow powder that was filtered and dried by the vacuum at 40 °C for 16 hr.
• HFANB (3.13 g, 1 1.4 mmol), C 4 F 9 NB (1.19 g, 3.8 mmol) and MGENB (0.68 g, 3.8 mmol) was dissolved in toluene (8.85 g) and MEK (0.75 g) and charged to a reaction vessel. The solution was sparged with nitrogen for 30 min to remove oxygen and then heated to 60 °C. Once at temperature, ⁇ 6 -toluene)Ni(C6Fs)2 (0.184 g, 0.38 mmol) in 5.40 g of toluene (prepared in a glove box) was added via syringe to the reaction vessel.
• HFANB/C 4 F9NB/ GENB polymer was isolated.
• HFANB (2.08 g, 7.6 mmol
• C4F 9 NB (2.38 g, 7.6 mmol)
• MGENB (0.68 g, 3.8 mmol) was dissolved in toluene (8.85 g) and MEK (0.75 g) and charged to a reaction vessel. The solution was sparged with nitrogen for 30 min to remove oxygen and then heated to 60 °C. Once at temperature, (T) 6 -toluene)Ni(C6F 5 ) 2 (0.184 g, 0.38 mmol) in 5.40 g of toluene (prepared in a glove box) was added via syringe to the reaction vessel.
• HFANB (4.30 g, 15.7 mmol) and MGENB (0.70 g, 3.9 mmol) was dissolved in toluene (9.25 g) and MEK (0.75 g) and charged to a reaction vessel. The solution was sparged with nitrogen for 30 min to remove oxygen and then heated to 60 °C. Once at temperature, ⁇ 6 -toluene)Ni(C 6 F 5 )2 0.190 g, 0.39 mmol) in 5.00 g of •toluene (prepared in a glove box) was added via syringe to the reaction vessel. The mixture was allowed to stir at 60 °C for 7.0 hr, after which the solution was cooled to room temperature.
• the reaction mixture TFTF (20 g) was then treated with an acetic acid (3.72 g, 62.0 mmol) and 30% H202aq (7.03 g 60.0 mmol) to remove Ni residues and then washed with water. The solvents were removed by rotovaporation to give a light yellow solid. The yellow solid was redissolved in THF (50 wt%) and was added to hexane (20 fold excess) to give a light yellow powder that was filtered and dried by the vacuum at 40 °C for 16 hr. Approximately, 3.25 g (65 %) of the HFANB/MGENB polymer was isolated.
• MeOAcNB (7.51 g, 45.2 mmol) and EONB (2.49 g, 11.3 mmol) was dissolved in toluene (16.00 g) and MEK (2.33 g) and charged to a reaction vessel. The solution was sparged with nitrogen for 30 min to remove oxygen and then heated to 60 °C. Once at temperature, ⁇ 6 -toluene)Ni(C 6 F 5 ) 2 0.156 g, 0.32 mmol) in 5.00 g of toluene (prepared in a glove box) was added via syringe to the reaction vessel. The mixture was allowed to stir at 60 °C for 4.0 hr, after which the solution was cooled to room temperature. The reaction mixture diluted in toluene (30 g) and THF (20 g) was then treated with an acetic acid (3.06 g, 51.0 mmol) and 30%
• EPENB (4.66 g, 24.0 mmol) and MGENB (1.32 g, 6.0 mmol) was dissolved in toluene (12.00 g) and MEK (0.9 g) and charged to a reaction vessel. The solution was sparged with nitrogen for 30 min to remove oxygen and then heated to 60 °C. Once at temperature, ⁇ 6 -toluene)Ni(C 6 F 5 ) 2 (0..073 g, 0.15 mmol) in 5.00 g of toluene (prepared in a glove box) was added via syringe to the reaction vessel. The mixture was allowed to stir at 60 °C for 5.0 hr, after which the solution was cooled to room temperature.
• reaction mixture diluted in toluene (10 g) and THF (6 g) was then treated with an acetic acid (1.4 g, 23.3 mmol) and 30% F ⁇ Oaaq (2.7 g 23.8 mmol) to remove Ni residues and then washed with water. The solvents were removed by rotovaporation to give a light yellow solid. The yellow solid was redissolved in THF (50 wt%) and was added to hexanes (20 fold excess) to give a white powder that was filtered and dried by the vacuum at 40 °C for 16 hr.
• Mn and Mw are determined by a standard GPC technique using a polystyrene standard.
• antioxidant/synergist materials are used. The manufacturer of each material as well as the material's chemical name is provided the first time each is used in the examples below, thereafter only the manufacturer's trade designation was provided.
• each polymer composition, of Examples 7-12 encompasses the same three antioxidant/synergist components it should be understood that as such examples are non-limiting, the use of these specific components is illustrative only and should be understood only to indicated that for the type of thermal and optical stability exhibited by film embodiments of the present disclosure, the use of more than one type of antioxidant/synergist is advantageous, where such types of antioxidants/synergists encompass phenolics, phosphites, thioethers and mixtures thereof.
• the base polymer was a MeOAcNB homopolymer cast onto a glass wafer to form a 3 ⁇ film as measured after a post application bake (PAB) at 1 10°C for lOOsec.
• PAB post application bake
• Examples 1 through 6 were used to prepare a 17 weight percent (wt%) polymer solution in PGMEA.
• the formulation additives listed below, each in the amount indicated, were then added to and dissolved in the polymer solution, however, for Example 12, after which and the solution was filtered through a 1 micron syringe filter.
• SI-150L was added as 0.08g of a 50 wt % GBL solution, where SI-150L is the trade name of Sanshin Chemical Industry CO., LTD. for (dimethyl-p-acetoxysulfoniumhexafluoro antimonate).
• SI-150L is the trade name of Sanshin Chemical Industry CO., LTD. for (dimethyl-p-acetoxysulfoniumhexafluoro antimonate).
• antioxidant/synergist additives the amount, in grams, added for each additive is indicated in Table 3, below.
• the additives used were ADK STAB AO-60, the trade name of ADEKA CORPORATION for (pentaerythritol tetrakis ⁇ 3-(3,5-di-tert- butyl-4-hydroxyphenyl)propionate ⁇ ); ADK STAB PEP-36 the trade name of ADEKA CORPORATION for (3,9-Bis(2,6-di-tert-butyl-4-methyl phenoxy)- 2,4,8,10-tetraoxa-3,9-diphosphaspiro(5.5)undecane; and ADEKA SATB AO-412S the trade name of ADEKA CORPORATION for (2,2-bis[[3-(dodecylthio)-l - oxopropoxy]methyl]propane-l ,3-diylbis[3-(dodecylthio)
• Each formulated solution was spun-cast onto a glass wafer to form a 3um film.
• the film After casting, the film received a post application bake (PAB) at 1 10°C for lOOsec. Transparency at 400nm was measured before and after thermal treatment in air at 280°C for 30min.
• PAB post application bake
• Each formulated solution was spun-cast onto a 4 inch silicon wafer to form a 3 ⁇ film.
• the film received a post application bake (PAB) at 1 10°C for l OOsec and a subsequent cure bake, performed in air for 30 min at 250°C.
• PAB post application bake
• a portion of the cured film was scratched off the silicon wafer and a TG/DTA analysis performed thereon.
• the measurement condition was 10°C per minute temperature ramp under N 2 flow and the result is provided as the temperature where 1 % weight loss was observed.
• Each formulated solution was spun-cast onto a 4 inch silicon wafer to form a 3 ⁇ film.
• the film received a post application bake (PAB) at 1 10°C for l OOsec and a subsequent cure bake, performed in air for 30 min at 250°C.
• PAB post application bake
• a pencil hardness test was performed using the procedure of ASTM D3363 except for the absence of specific temperature and humidity control, ambient (at the time of testing) temperature and humidity control was employed.
• Each formulated solution was spun-cast onto a 4 inch silicon wafer to form a 3 ⁇ film.
• the film received a post application bake (PAB) at 1 10°C for l OOsec and a subsequent cure bake, performed in air for 30 min at 250°C.
• PAB post application bake
• the film thickness was measured, the film' soaked in NMP at 40°C for lOmin and the film thickness remeasured. The difference in film thick was recorded as percent film thickness loss.

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