WO2005097867A1 - Process for making polyesters - Google Patents
Process for making polyesters Download PDFInfo
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- WO2005097867A1 WO2005097867A1 PCT/IB2005/000879 IB2005000879W WO2005097867A1 WO 2005097867 A1 WO2005097867 A1 WO 2005097867A1 IB 2005000879 W IB2005000879 W IB 2005000879W WO 2005097867 A1 WO2005097867 A1 WO 2005097867A1
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- WIPO (PCT)
- Prior art keywords
- dianhydride
- polyester
- diol
- carboxyl groups
- hydroxyl
- Prior art date
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- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/81—Preparation processes using solvents
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/46—Polyesters chemically modified by esterification
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/916—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31786—Of polyester [e.g., alkyd, etc.]
Definitions
- the present invention relates to novel process for preparing polyesters.
- Such polymers are useful in compositions in the coatings, adhesives, sealants, elastomers, and photolithography fields.
- Polyesters with terminal reactive groups are widely used in thermosetting coatings and articles.
- low molecular weights are preferred for such polyesters because high molecular weights lead to insufficient reactive groups.
- Low molecular polyesters are usually oily oligomers which might not possess desirable properties, e.g., glass transition temperatures, thermal stability, easiness of purification, etc. These types of polyesters are not suitable for applications where both reasonably high molecular weights and high crosslinking density are required.
- polyesters are required to have relatively high molecular weights for high thermal stability.
- high contents of reactive groups in the polyesters are needed to achieve a high crosslinking density to prevent intermixing with photoresists.
- polyesters preferably have pendant reactive groups.
- the number of pendant reactive groups in such a polyester can be easily adjusted to obtain desired crosslinking properties.
- the number of pendant reactive groups is independent of the molecular weight of the polyester.
- Reactive groups in polyesters suitable for crosslinking chemistry are usually hydroxyl, carboxylic acid, etc.
- polyesters are normally prepared by condensation polymerization using monomers bearing the same reactive groups. This usually makes it very difficult to prepare high molecular weight polyesters with high contents of reactive groups.
- both high molecular and high contents of reactive groups can be achieved by preparing branched polyesters which are partially crosslinked. Those partially crosslinked polyesters usually have very limited solubility in organic solvents. For applications where polyesters need to be dissolved in solvents, highly branched polyesters are usually not very useful.
- the present invention relates to a novel polyester preparation method that can lead to high molecular weight polyesters with high contents of reactive groups.
- Polyesters prepared by this method can be linear and/or branched and/or partially crosslinked and have good solubility in common organic solvents used in the end product in which the polyester is used.
- the present invention relates to a process for making a polyester.
- the process comprises reacting a dianhydride with a diol, optionally in the presence of a catalyst, in a media which includes a solvent in which the polyester is insoluble, the dianhydride and the diol being present in substantially stoichiometric amounts.
- the polyester formed can be further processed by either (A) partially or fully esterifying carboxyl groups on the polyester with a capping compound selected from monohydric alcohols and mixtures thereof optionally in the presence of a catalyst or (B) converting some or all carboxyl groups on the polyester to hydroxyl groups by reacting the carboxyl groups with a hydroxyl-forming compound selected from aromatic oxide, aliphatic oxide, alkylene carbonate and mixtures thereof optionally in the presence of a catalyst.
- the present invention also relates to a process for making a polyester which comprises: (i) reacting a dianhydride with a diol, optionally in the presence of a catalyst, in a media which includes a solvent in which the polyester is insoluble, the dianhydride and the diol being present in substantially stoichiometric amounts; (ii) separating the polyester from the media of step (i); and (iii) partially or fully esterifying carboxyl groups on the polyester of step (ii) with a capping compound selected from monohydric alcohols and mixtures thereof optionally in the presence of a catalyst.
- the present invention also relates to a process for making a polyester which comprises: (i) reacting a dianhydride with a diol, optionally in the presence of a catalyst, in a media which includes a solvent in which the polyester is insoluble, the dianhydride and the diol being present in substantially stoichiometric amounts; (ii) separating the polyester from the media of step (i); and (iii) converting some or all carboxyl groups on the polyester of step (ii) to hydroxyl groups by reacting the carboxyl groups with a hydroxyl-forming compound selected from aromatic oxide, aliphatic oxide, alkylene carbonate and mixtures thereof optionally in the presence of a catalyst.
- a hydroxyl-forming compound selected from aromatic oxide, aliphatic oxide, alkylene carbonate and mixtures thereof optionally in the presence of a catalyst.
- the present invention also relates to a process for making a polyester which comprises: (i) reacting a dianhydride with a diol, optionally in the presence of a catalyst, in a media which includes a solvent in which the polyester is insoluble, the dianhydride and the diol being present in substantially stoichiometric amounts; and (ii) partially or fully esterifying carboxyl groups on the polyester of step (i) with a capping compound selected from monohydric alcohols and mixtures thereof optionally in the presence of a catalyst.
- the present invention also relates to a process for making a polyester which comprises: (i) reacting a dianhydride with a diol, optionally in the presence of a catalyst, in a media which includes a solvent in which the polyester is insoluble, the dianhydride and the diol being present in substantially stoichiometric amounts; and (ii) converting some or all carboxyl groups on the polyester of step (i) to hydroxyl groups by reacting the carboxyl groups with a hydroxyl-forming compound selected from aromatic oxide, aliphatic oxide, alkylene carbonate and mixtures thereof optionally in the presence of a catalyst.
- the present invention also relates to a process for making a polyester comprising the steps of: (i) mixing together a dianhydride, a diol, and a hydroxyl- forming compound selected from aromatic oxide, aliphatic oxide, alkylene carbonate, and mixtures thereof under reaction conditions to react the dianhydride with the diol, the dianhydride and the diol being present in substantially stoichiometric amounts; (ii) reacting the mixture of (i) under conditions to react carboxyl groups on the polyester with the hydroxyl-forming compound to convert carboxyl groups to hydroxyl groups; and (iii) separating the polyester from step (ii).
- a catalyst can be added to the mixture prior to step (ii).
- the formed polyester can be then separated from the reaction media and further used in formulating various products.
- the capping compound include methanol, ethanol, propanol, isopropanol, 1-butanol, isobutanol, 2-methyl-2-butanol, 2-methyl-1-butanol, 3- methyl-1-butanol, tertiary butanol, cyclopentanol, cyclohexanol, 1-hexanol, 1- heptanol, 2-heptanol, 3-heptanol, 1-n-octanol, 2-n-octanol and the like.
- the hydroxyl-forming compound include styrene oxide, propylene oxide, ethylene carbonate and the like.
- the dianhydride can have the formula where A is a tetravalent radical selected from the group consisting of unsubstituted or substituted aliphatic, unsubstituted or substituted aromatic, unsubstituted or substituted cycloaliphatic, unsubstituted or substituted heterocyclic groups and combinations thereof.
- Tetravalent radicals A can be selected from
- n1 1 to 6
- n2 1 to 8
- n3 1 to 4
- R 2 o is selected from a direct bond, O, CO,
- dianhydride examples include pyromellitic dianhydride, 3,6- diphenylpyromellitic dianhydride, 3,6-bis(trifluoromethyl)pyromellitic dianhydride, 3,6- bis(methyl)pyromellitic dianhydride, 3,6-diiodopyromellitic dianhydride, 3,6- dibromopyromellitic dianhydride, 3,6-dichloropyromellitic dianhydride, 3,3',4,4'- benzophenonetetracarboxylic acid dianhydride, 2,3,3',4'- benzophenonetetracarboxylic acid dianhydride, 2,2',3,3'-benzophenone tetracarboxylic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 2,3,3'4'-biphenyltetracarboxylic acid dianhydride, 2,3,
- the diol can have the formula
- B is an unsubstituted or substituted hydrocarbylene group.
- B include unsubstituted or substituted linear or branched alkylene optionally containing one or more oxygen or sulfur atoms, unsubstituted or substituted arylene, and unsubstituted or substituted aralkylene. Additional examples include methylene, ethylene, propylene, butylene, 1-phenyl-1 ,2-ethylene, 2-bromo-2-nitro-1 ,3-propylene, 2-bromo-2-methyl-1 ,3-propylene, -CH2OCH2-, -CH 2 CH 2 OCH 2 CH2-,
- the dianhydride can be a mixture of one or more dianhydrides.
- the diol can be a mixture of one or more diols.
- the present invention provides a novel process for making polyesters using a dianhydride and a diol as major reactants. While polyfunctional anhydrides have been used to chain-extend hydroxyl-terminated prepolymers to increase molecular weights, reacting a dianhydride and a diol to prepare polyesters is considered impractical. It has surprisingly been found by the inventors that polyesters with relatively high molecular weights can readily be prepared using the present invention.
- the polyester made by reacting a dianhydride with a diol, can be further processed either by (A) partially or fully esterifiying carboxyl groups on the polyester with a capping compound in the presence of a catalyst or (B) converting some or all carboxyl groups on the polyester to hydroxyl groups by reacting the carboxyl groups with a hydroxyl-forming compound.
- Processing under (A) above generally results in a linear polyester.
- Processing under (B) above can result in either generally linear polyesters or partially crosslinked polyesters, depending upon the temperature at which the hydroxyl-forming compound is reacted with the polyester. Generally, if the reaction temperature is about less than or equal to 80°C, the resulting polyester is generally linear.
- reaction temperature is about greater than or equal to 80°C
- the resulting polyester generally has some partial crosslinking occurring.
- Catalysts can be used to enhance the reaction.
- Processing under (B) is normally carried out at atmospheric pressure under inert gas atmosphere. However, if the hydroxyl-forming compound has a boiling point lower than the reaction temperature and no additional solvent is used, increased pressure can be used.
- the present invention relates to a process for making a polyester and a polyester, preparable by that process as disclosed above and below.
- the present invention also relates to the use of these polyesters in coating, adhesive, sealant, elastomer and photolithography compositions.
- the process comprises reacting a dianhydride with a diol, optionally in the presence of a catalyst, in a media which includes a solvent in which the polyester is insoluble, the dianhydride and the diol being present in substantially stoichiometric amounts.
- the polyester formed can be further processed by either (A) partially or fully esterifying carboxyl groups on the polyester with a capping compound selected from monohydric alcohols and mixtures thereof optionally in the presence of a catalyst or (B) converting some or all carboxyl groups on the polyester to hydroxyl groups by reacting the carboxyl groups with a hydroxyl-forming compound selected from aromatic oxide, aliphatic oxide, alkylene carbonate and mixtures thereof optionally in the presence of a catalyst.
- the present invention also relates to a process for making a polyester which comprises: (i) reacting a dianhydride with a diol, optionally in the presence of a catalyst, in a media which includes a solvent in which the polyester is insoluble, the dianhydride and the diol being present in substantially stoichiometric amounts; (ii) separating the polyester from the media of step (i); and (iii) partially or fully esterifying carboxyl groups on the polyester of step (ii) with a capping compound selected from monohydric alcohols and mixtures thereof optionally in the presence of a catalyst.
- the present invention also relates to a process for making a polyester which comprises: (i) reacting a dianhydride with a diol, optionally in the presence of a catalyst, in a media which includes a solvent in which the polyester is insoluble, the dianhydride and the diol being present in substantially stoichiometric amounts; (ii) separating the polyester from the media of step (i); and (iii) converting some or all carboxyl groups on the polyester of step (ii) to hydroxyl groups by reacting the carboxyl groups with a hydroxyl-forming compound selected from aromatic oxide, aliphatic oxide, alkylene carbonate and mixtures thereof optionally in the presence of a catalyst.
- a hydroxyl-forming compound selected from aromatic oxide, aliphatic oxide, alkylene carbonate and mixtures thereof optionally in the presence of a catalyst.
- the present invention also relates to a process for making a polyester which comprises: (i) reacting a dianhydride with a diol, optionally in the presence of a catalyst, in a media which includes a solvent in which the polyester is insoluble, the dianhydride and the diol being present in substantially stoichiometric amounts; and (ii) partially or fully esterifying carboxyl groups on the polyester of step (i) with a capping compound selected from monohydric alcohols and mixtures thereof optionally in the presence of a catalyst.
- the present invention also relates to a process for making a polyester which comprises: (i) reacting a dianhydride with a diol, optionally in the presence of a catalyst, in a media which includes a solvent in which the polyester is insoluble, the dianhydride and the diol being present in substantially stoichiometric amounts; and (ii) converting some or all carboxyl groups on the polyester of step (i) to hydroxyl groups by reacting the carboxyl groups with a hydroxyl-forming compound selected from aromatic oxide, aliphatic oxide, alkylene carbonate and mixtures thereof optionally in the presence of a catalyst.
- the present invention also relates to a process for making a polyester comprising the steps of: (i) mixing together a dianhydride, a diol, and a hydroxyl- forming compound selected from aromatic oxide, aliphatic oxide, alkylene carbonate, and mixtures thereof under reaction conditions to react the dianhydride with the diol, the dianhydride and the diol being present in substantially stoichiometric amounts; (ii) reacting the mixture of (i) under conditions to react carboxyl groups on the polyester with the hydroxyl-forming compound to convert carboxyl groups to hydroxyl groups; and (iii) separating the polyester from step (ii).
- a catalyst can be added to the mixture prior to step (ii).
- the formed polyester can be then separated from the reaction media and further used in formulating various products.
- the capping compound include methanol, ethanol, propanol, isopropanol, 1-butanol, isobutanol, 2-methyl-2-butanol, 2-methyl-1-butanol, 3- methyl-1-butanol, tertiary butanol, cyclopentanol, cyclohexanol, 1-hexanol, 1- heptanol, 2-heptanol, 3-heptanol, 1-n-octanol, 2-n-octanol and the like.
- the hydroxyl-forming compound include styrene oxide, propylene oxide, ethylene carbonate and the like.
- the dianhydride can have the formula where A is a tetravalent radical selected from the group consisting of unsubstituted or substituted aliphatic, unsubstituted or substituted aromatic, unsubstituted or substituted cycloaliphatic, unsubstituted or substituted heterocyclic groups and combinations thereof.
- Tetravalent radical A can be selected from
- Some examples of the compound of formula include
- dianhydride examples include pyromellitic dianhydride, 3,6- diphenylpyromellitic dianhydride, 3,6-bis(trifluoromethyl)pyromellitic dianhydride, 3,6- bis(methyl)pyromellitic dianhydride, 3,6-diiodopyromellitic dianhydride, 3,6- dibromopyromellitic dianhydride, 3,6-dichloropyromellitic dianhydride, 3,3',4,4'- benzophenonetetracarboxylic acid dianhydride, 2,3,3',4'- benzophenonetetracarboxylic acid dianhydride, 2,2',3,3'-benzophenone tetracarboxylic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 2,3,3'4'-biphenyltetracarboxylic acid dianhydride, 2,3,
- the diol can have the formula
- B is an unsubstituted or substituted hydrocarbylene group.
- B include unsubstituted or substituted linear or branched alkylene optionally containing one or more oxygen or sulfur atoms, unsubstituted or substituted arylene, and unsubstituted or substituted aralkylene. Additional examples include methylene, ethylene, propylene, butylene, 1-phenyl-1,2-ethylene, 2-bromo-2-nitro-1 ,3-propylene, 2-bromo-2-methyl-1 ,3-propylene, -CH2OCH2-, -CH2CH2OCH2CH2-,
- the dianhydride can be a mixture of one or more dianhydrides.
- the diol can be a mixture of one or more diols.
- the present invention provides a novel process for making polyesters using a dianhydride and a diol as major reactants. While polyfunctional anhydrides have been used to chain-extend hydroxyl-terminated prepolymers to increase molecular weights, reacting a dianhydride and a diol to prepare polyesters is considered impractical. It has surprisingly been found by the inventors that polyesters with relatively high molecular weights can readily be prepared using the present invention.
- the polyester made by reacting a dianhydride with a diol, can be further processed either by (A) partially or fully esterifiying carboxyl groups on the polyester with a capping compound in the presence of a catalyst or (B) converting some or all carboxyl groups on the polyester to hydroxyl groups by reacting the carboxyl groups with a hydroxyl-forming compound.
- Processing under (A) above generally results in a linear polyester.
- Processing under (B) above can result in either generally linear polyesters or partially crosslinked polyesters, depending upon the temperature at which the hydroxyl-forming compound is reacted with the polyester. Generally, if the reaction temperature is about less than or equal to 80°C, the resulting polyester is generally linear.
- the resulting polyester generally has some partial crosslinking occurring. Catalysts can be used to enhance the reaction. Processing under (B) is normally carried out at atmospheric pressure under inert gas atmosphere. However, if the hydroxyl-forming compound has a boiling point lower than the reaction temperature and no additional solvent is used, increased pressure can be used.
- the dianhydride can have the formula
- Tetravalent radical A is a tetravalent radical selected from the group consisting of unsubstituted or substituted aliphatic, unsubstituted or substituted aromatic, unsubstituted or substituted cycloaliphatic, unsubstituted or substituted heterocyclic groups and combinations thereof.
- Tetravalent radical A can be selected from
- n1 1 to 6
- n2 1 to 8
- n3 1 to 4
- R 2 o is selected from a direct bond, O, CO,
- dianhydride examples include pyromellitic dianhydride, 3,6- diphenylpyromellitic dianhydride, 3,6-bis(trifluoromethyl)pyromellitic dianhydride, 3,6- bis(methyl)pyromellitic dianhydride, 3,6-diiodopyromellitic dianhydride, 3,6- dibromopyromellitic dianhydride, 3,6-dichloropyromellitic dianhydride, 3,3',4, ⁇ '- benzophenonetetracarboxylic acid dianhydride, 2,3,3 , ,4'- benzophenonetetracarboxylic acid dianhydride, 2,2',3,3'-benzophenone tetracarboxylic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 2,3,3'4'-biphenyltetracarboxylic acid dianhydride,
- B is an unsubstituted or substituted hydrocarbylene group.
- B include unsubstituted or substituted linear or branched alkylene optionally containing one or more oxygen or sulfur atoms, unsubstituted or substituted arylene, and unsubstituted or substituted aralkylene.
- Additional examples include methylene, ethylene, propylene, butylene, 1-phenyl-1 ,2-ethylene, 2-bromo-2-nitro-1 ,3-propylene, 2-bromo-2-methyl-1 ,3-propylene, -CHjOCHjr-, -CH 2 CH 2 OCH 2 CH2-, — CH2CH2SCH2CH2 — , or — CH CH 2 SCH 2 CH2SCH2CH2 — .
- the dianhydride can be a mixture of one or more dianhydrides.
- the diol can be a mixture of one or more diols.
- substantially stoichiometric amount refers to molar ratios of dianhydride/diol of about 1 , and generally between about 0.90 to about 1.20. Typically, a slight excess of either dianhydride or diol can be used in order to control molecular weight.
- the term "hydrocarbyl group” is used in its ordinary sense, which is well-known to those skilled in the art, as a univalent group formed by removing one hydrogen atom from a moiety having a predominantly hydrocarbon character. Examples of hydrocarbyl groups, which can be unsubstituted or substituted, include:
- hydrocarbon groups that are, aliphatic (e.g., alkyl, alkylenyl or alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl), aromatic, aliphatic-, and alicyclic-substituted aromatic substituents, as well as cyclic substituents wherein the ring is completed through another portion of the molecule (e.g., two substituents together form an alicyclic radical); monocyclic or polycyclic alkylene, arylene, aralkylene.
- Examples of the monocyclic cycloalkylene group can have from 4 to 50 carbon atoms, and include such as, for example, cyclopentylene and cyclohexylene groups, and the polycyclic cycloalkylene group can have from 5 to 50 carbon atoms and include such as, for example, 7-oxabicyclo[2,2,1]heptylene, norbornylene, adamantylene, diamantylene, and triamantylene.
- arylene group examples include monocyclic and polycyclic groups such as, for example, phenylene, naphthylene, biphenyl-4,4'-diyl, biphenyl-3,3'-diyl, and biphenyl-3,4'-diyl groups.
- Aryl refers to an unsaturated aromatic carbocyclic group of from 6 to 50 carbon atoms having a single ring or multiple condensed (fused) rings and include, but are not limited to, for example, phenyl, tolyl, dimethylphenyl, 2,4,6- trimethylphenyl, naphthyl, anthryl and 9,10-dimethoxyanthryl groups.
- Aralkyl refers to an alkyl group containing an aryl group. It is a hydrocarbon group having both aromatic and aliphatic structures, that is, a hydrocarbon group in which an alkyl hydrogen atom is substituted by an aryl group, for example, tolyl, benzyl, phenethyl and naphthylmethyl groups.
- Heteroatoms include sulfur, oxygen, nitrogen, and encompass substituents as pyridyl, furyl, thienyl and imidazolyl.
- substituents as pyridyl, furyl, thienyl and imidazolyl.
- no more than two, preferably no more than one, non- hydrocarbon substituent will be present for every ten carbon atoms in the hydrocarbyl group; typically, there will be no non-hydrocarbon substituents in the hydrocarbyl group.
- hydrocarbyl groups are substituted or unsubstituted linear or branched aliphatic (C ⁇ - 50 ) alkyl group, substituted or unsubstituted linear or branched aliphatic (C ⁇ - 50 ) alkylene group, substituted or unsubstituted linear or branched thio- alkylene aliphatic (C1- 50 ) group, substituted or unsubstituted cycloalkylene, substituted or unsubstituted benzyl, alkoxy alkylene, alkoxyaryl, substituted aryl, hetero cycloalkylene, heteroaryl, oxocyclohexyl, cyclic lactone, benzyl, substituted benzyl, hydroxy alkyl, hydroxyalkoxyl, alkoxy alkyl, alkoxyaryl, alkylaryl, alkenyl, substituted aryl, hetero cycloalkyl, heteroaryl, nitroalkyl, halo
- Z is hydrocarbyl group
- hydrocarbylene group is a divalent group formed by removing two hydrogen atoms from a moiety having a predominantly hydrocarbon character, the free valences of which are not engaged in a double bond.
- hydrocarbylene groups include, but are not limited to, alkylene, thio-alkylene, cycloalkylene, arylene, examples of W set forth below and the like.
- W are, without limitations, substituted or unsubstituted aliphatic
- C50 cycloalkylene, substituted (C1-C 50 ) cycloalkylene, hydroxy alkylene, alkoxy alkylene, alkoxyarylene, alkylarylene, (C1-C 50 ) alkenylene, biphenylene, phenylene, unsubstituted or substituted arylene, hetero cycloalkylene, heteroarylene, halo alkylene, or mixtures thereof.
- L are, without limitations, (C 1 -C 50 ) alkyl, substituted (CrC 50 ) alkyl, cycloalkyl, substituted cycloalkyl, oxocyclohexyl, cyclic lactone, benzyl, substituted benzyl, hydroxy alkyl, hydroxyalkoxyl, alkoxy alkyl, alkoxyaryl, alkylaryl, alkenyl, substituted aryl, hetero cycloalkyl, heteroaryl, or mixtures thereof.
- aliphatic refers to a predominantly hydrocarbon chain which is nonaromatic.
- Substituted or unsubstituted alkylene or thioalkylene (C1-C50) group means an alkylene or an thioalkylene group which is predominantly a hydrocarbon chain that may be linear or branched containing up to 50 carbon atoms, and where the substituents are those which do not typically change the hydrocarbon nature of the chain and may be all organic compounds known to those of ordinary skill in the art, such as ether, ester, hydroxyl, alkynol, cyano, nitro, acyl, halogen, phenyl and substituted phenyl.
- Alkyl refers to a hydrocarbon chain containing up to 50 carbon atoms, and may be methyl, ethyl, propyl, isopropyl, butyl, etc.
- a thioalkylene group contains one or more sulfur atoms in the chain.
- An oxoalkylene group contains one or more oxygen atoms in the chain.
- Examples of aliphatic substituted or unsubstituted alkylene (C1-C 50 ) group which may be linear or branched, are without limitation, methylene, ethylene, propylene, isopropylene, butylenes, isobutylene, pentylene, hexylene, heptylene, octylene, methylhexylene, ethyloctylene, phenylalkylene, nitroalkylene, bromonitroalkylene and substituted phenylalkylene.
- aliphatic substituted or unsubstituted thio-alkylene (C1-C 50 ) group is without limitation, 3,6- dithio-1 ,8-octylene (also known as 1 ,2-bis(ethylthio)ethylene having the formula -CH 2 CH 2 SCH 2 CH 2 SCH 2 CH 2 - from 3,6-dithiaoctane-1 ,8-diol, also known at 2,2'- (ethylenethio)diethanol).
- the cycloalkyl groups may be mono or polycyclic, examples of which are cyclopentyl, cyclohexyl, cycloheptyl, adamantly, as well as those described above, and may be unsubstituted or substituted as described above.
- Aryl refers to substituted or unsubstituted aromatic groups such as phenyl or naphthyl or anthracyl.
- the aryl group may be part of the polymer backbone or linked to the backbone.
- Halogen refers to fluorine, chlorine and bromine.
- Examples of B include hydrocarbylene groups as described above, for example, alkylene, thio-alkylene, oxoalkylene, aromatic or mixtures thereof, phenyl and naphthyl and substituted variations thereof.
- Examples include methylene, ethylene, propylene, butylene, -CH 2 OCH2-, -CH 2 CH 2 OCH 2 CH2-, -CHsCHsSCHsCHs-, -CH 2 CH 2 SCH 2 CH 2 SCH 2 CH2-, phenylethylene, alkylnitroalkylene, bromonitroalkylene, and the like.
- R 2 o is CO or SO2
- B is alkylene, for example, methylene, ethylene, propylene, — CH 2 OCH 2 — , — CH 2 CH 2 OCH2CH2— , -CH 2 CH 2 SCH 2 CH 2 -, -CH 2 CH2SCH2CH 2 SCH2CH2-, .
- Examples of the diols used to synthesize the polymer of the present invention which are represented by the compound of formula (2) are, for example and include, ethylene glycol, diethylene glycol, propylene glycol, 1-phenyl-1 ,2-ethanediol, 2- bromo-2-nitro-1 ,3-propanediol, 2-methyl-2-nitro-1 ,3-propanediol, diethylbis(hydroxymethyl)malonate, 1 ,6-hexanediol, and 3,6-dithio-1 ,8-octanediol.
- aromatic diols examples include 2,6-bis(hydroxymethyl)-p-cresol and 2,2 -(1 ,2- phenylenedioxy)-diethanol, 1 ,4-benzenedimethanol.
- the diols are condensed with dianhydride compounds of formula (1) of the present invention, examples of which include aromatic dianhydrides, examples of which include pyromellitic dianhydride, 3,6-diphenylpyromellitic dianhydride, 3,6- bis(trifluoromethyl)pyromellitic dianhydride, 3,6-bis(methyl)pyromellitic dianhydride, 3,6-diiodopyromellitic dianhydride, 3,6-dibromopyromellitic dianhydride, 3,6- dichloropyromellitic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride, 2,3,3',4'-benzophenonetetracarboxylic acid dianhydride, 2,2',3,3'- benzophenone tetracarboxylic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid
- a polyester is first prepared by the reaction of a dianhydride and a diol in a media which includes a solvent in which the polyester is insoluble.
- the polyester may be further modified by (A) partially or fully esterifying carboxyl groups on the polyester with a capping compound selected from monohydric alcohols and mixtures thereof in the presence of a catalyst or (B) converting some or all carboxyl groups on the polyester to hydroxyl groups by reacting the carboxyl groups with a hydroxyl-forming compound selected from aromatic oxide, aliphatic oxide, alkylene carbonate and mixtures thereof optionally in the presence of a catalyst.
- monohydric alcohols include linear or branched C 1 -C 10 alkanols such as methanol, ethanol, propanol, pentanol, isopropanol, 1-butanol, isobutanol,
- the hydroxyl-forming compound is selected from aromatic oxide, aliphatic oxide, alkylene carbonate and mixtures thereof.
- aromatic oxides include: styrene oxide, 1 ,2-epoxy- phenoxypropane, glycidyl-2-methylphenyl ether, (2,3-epoxypropyl)benzene, 1- phenylpropylene oxide, stilbene oxide, 2- (or 3- or 4-)halo(chloro, fluoro, bromo, iodo) stilbene oxide, benzyl glycidyl ether, C MO straight or branched chain alkyl(e.g., methyl, ethyl, propyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, and the like etc)phenyl glycidyl ether, 4- halo(chloro, fluoro, bromo, iodo)phenyl glycidyl ether, glycidyl 4-C ⁇ - ⁇ o straight or branched chain al
- aliphatic oxides include ethylene oxide, propylene oxide, butylene oxides, including isobutylene oxide, 1 ,2-butylene oxide and 2,3-butylene oxide, pentylene oxide, cyclohexene oxide, decyl glycidyl ether, and dodecyl glycidyl ether.
- alkylene carbonates examples include those compounds having the formula
- R ⁇ is C 2 -C alkyl where the aliphatic ring carbons are unsubstituted or substituted with a group selected from C1-C10 alkyl, C ⁇ -Cio aryl, or C 6 -C15 aralkyl group.
- alkylene carbonates are ethylene carbonate, propylene carbonate, and butylene carbonates.
- the reaction of the diol and dianhydride can take place in a media which includes a solvent, or mixture of solvents, in which the polyester with the desired molecular weight is insoluble or, in some instances, in the absence of solvent, for example, in the process where the dianhydride, diol, and hydroxyl-forming compound are mixed together, the hydroxyl-forming compound can function as a solvent, whether as in liquid form or, for example, when solid, for example, ethylene carbonate, by heating to its melting temperature, the reactants are in a liquid.
- solvents that are useful include dioxane, acetonitrile, mixture of tetrahydrofuran (THF)/acetonitrile, and mixture of THF/dioxane. It is useful to use a media where the dianhydride and diol are soluble and the polyester is not so that as the reaction progresses, the formed polyester will precipitate out of solution.
- the temperature at which the reactions occur generally ranges from about room temperature to about 170°C.
- the reaction time can vary from about 4 to about 48 hours.
- the dianhydride, diol, and hydroxyl-forming compound selected from aromatic oxide, aliphatic oxide, alkylene carbonate, and mixtures thereof are mixed together under reaction conditions to react the dianhydride with the diol, the dianhydride and the diol being present in substantially stoichiometric amounts, the mixing optionally occurring in a media in which the polyester is insoluble, the reaction conditions are typically a reaction time of from about 3 to about 24 hours at a temperature ranging from about 50 to about 140°C.
- a catalyst can be added to the mixture.
- the temperature of the mixture can be the same as that used to react the dianhydride with the diol or a different range of, for example, from about 60 to about 170°C.
- the reaction time can range from 4 to 24 hours.
- Processing the polyester with a hydroxyl-forming compound can result in either generally linear polyesters or partially crosslinked polyesters, depending upon the temperature at which the hydroxyl-forming compound is reacted with the polyester. Generally, if the reaction temperature is about less than or equal to 80°C, the resulting polyester is generally linear. Generally, if the reaction temperature is about greater than or equal to 80°C, the resulting polyester generally has some partial crosslinking occurring.
- the reaction of the hydroxyl-forming compound and polyester is normally carried out at atmospheric pressure under inert gas atmosphere. However, if the hydroxyl-forming compound has a boiling point lower than the reaction temperature and no additional solvent is used, increased pressure can be used.
- Typical weight average molecular weights of the polyesters prepared by the present process range from about 5,000 to about 300,000.
- the reaction mixture containing the polyester as a precipitate can be filtered to remove the solid polymer.
- the solid monomer can then be rinsed with water or ether.
- the polyester also can be isolated by pouring the reaction mixture into a non-solvent for the polyester and collecting the precipitated product. Additionally, the polyester can be isolated by removal of the solvent by vacuum distillation. While the reaction between the dianhydride and diol typically does not need the presence of a catalyst, catalysts which are well known to those skilled in the art can be added to increase the reaction rate.
- a catalyst can optionally be used when reacting the polyester (from the reaction between dianhydride and diol)) with either the capping compound or the hydroxyl-forming compound.
- Suitable catalysts include onium salts, for example, phosphonium, ammonium, or sulfonium salts. Examples include benzyltributylammonium chloride, benzyltriethylammonium chloride, and benzyltrimethylammonium chloride.
- inorganic acids such as sulfuric acid can also be used.
- the polyesters made by the present inventive process are useful in compositions in the coatings, adhesives, sealants, elastomers, and photolithography fields.
- polyesters prepared by this process can also be used in preparing barrier containers and films, and as molding, extrusion and casting resins, in fabricating molded, extruded or foamed articles, containers, films, film laminates, or coatings using conventional fabricating techniques such as extrusion, compression molding, injection molding, blow molding and similar fabrication techniques commonly used to produce such articles.
- Such articles include films, foams, sheets, pipes, rods, bags and boxes.
- the degree of aromaticity in the polymer may be varied.
- the B component in the polyester is preferably nonaromatic. It is generally known to those of ordinary skill in the art that aromatics decrease the etch rate. For low etch rates and/or high absorptivity, highly aromatic polyesters are desirable, where the B component may be highly aromatic.
- optimum performance may be obtained by controlling the etch rate and the absorptivity by using an aliphatic monomer for B or an appropriate mixture of an aliphatic and an aromatic monomer.
- the aromatic functionality may also be incorporated at other functional points within the polyester.
- an antireflective coating composition for use in the photolithography field.
- antireflective coating compositions typically comprise a polyester made by the process of the present invention, together with following materials which are well known to those skilled in the art - a crosslinking agent, an acid or/and an acid generator, and a solvent, plus if needed other additives such as, for example, monomeric dyes, lower alcohols, surface leveling agents, adhesion promoters, antifoaming agents, etc.
- the polyester In order to form a good antireflective coating from the antireflective coating composition, the polyester should be soluble in the solvent of the composition.
- the formed coating should not be soluble in the solvent of the photoresist, which is to be coated in top of the antireflective coating, and further, the antireflective coating should also not be soluble in the aqueous developer solution used to develop the photoresist.
- the optimum structure of the polyester, having all the necessary properties, may be developed using various strategies, for example, using a mixture of dianhydrides and diols.
- the amount of the polyester made by the present invention can be used in, for example, antireflective coating compositions, in amounts that can range from about 95 weight % to about 50 weight %, preferably about 85 weight % to about 70 weight % and more preferably about 80 weight % to about 70 weight %, relative to the solid portion of the composition.
- Example 1 1.0 mole of pyromellitic dianhydride was suspended in 300 g of acetonitrile in a 2L-flask with a condenser and a mechanical stirrer. Then 1.05 moles of ethylene glycol was added. Under nitrogen, the mixture was heated to a gentle reflux. The reaction was continued for 24 hrs. After cooling the reaction mixture to room temperature, stirring was continued for a few additional hours. A white precipitate formed during the reaction and was collected by suction and washed thoroughly with acetonitrile. The solid was dried in a vacuum oven for 1 day. Yield: about 90 %. The polymer had a weight average molecular 41 ,100 g/mol.
- Example 2 1.0 mole of pyromellitic dianhydride was suspended in 300 g of acetonitrile in a 2L-flask with a condenser and a mechanical stirrer. Then 1.05 moles of ethylene glycol was added. Under nitrogen, the mixture
- Example 6 2.0 mole of pyromellitic dianhydride was suspended in 300 g of acetonitrile in a 5L-flask with a condenser and a mechanical stirrer. Then 2.10 moles of ethylene glycol was added. Under nitrogen, the mixture was heated to a gentle reflux. The reaction was continued for 24 hrs. After cooling the reaction mixture to room temperature, stirring was continued for a few additional hours.
- Example 2 250 g of the polyester polymer prepared in Example 2 were dissolved in a mixture of 750 g of methanol and 750 g of ethyl lactate in a flask. 20 g of concentrated sulfuric acid was added as catalyst. The solution was heated to a gentle reflux. The reaction was maintained for 22 ⁇ 24 hours. After cooling to room temperature, the solution was slowly poured into a large amount of water in a high speed blender. A white polymer obtained was collected by filtration and washed thoroughly with water. Finally, the polymer was dried in a vacuum oven for 1 day. The overall yield was about 50%. The polymer obtained had a weight average molecular weight of 16,900 g/mol.
- Example 9 1.0 mole of pyromellitic dianhydride was dissolved in 600 g of ethylene carbonate in a 1 L-flask with a mechanical stirrer. Then 1.0 mole of ethylene glycol was added. Under nitrogen, the reaction mixture was heated to 120°C. The reaction was continued for 8 hrs. Then 10 g of benzyltriethylammonium chloride was added and the reaction was continued for another 22 hrs at the same temperature. The reaction solution was cooled and filtered. The filtrate was slowly poured into a large amount of water while stirring. A white polymer was collected by filtration and washed thoroughly with water, followed by drying in a vacuum oven. The polymer obtained had a weight average molecular weight of 112,300 g/mol.
- An antireflective coating composition was prepared by dissolving 2.4 g of polymer prepared in Example 6, 0.72 g of tetrakis (methoxymethyl)glycoluril, 0.048 g triethylammonium salt of 10-camphorsulfonic acid in 47.6 g ethyl lactate. The solution was filtered through 0.2 ⁇ m filter.
- the performance of the anti-reflective coating formulation was evaluated using AZ ® EXP AX1020P photoresist (available from AZ Electronic Materials, Clariant Corporation, Somerville, NJ).
- a 108 nm antireflective coating film from the above solution was coated on a silicon wafer and baked at 200°C for 60 seconds.
- the antireflective film was found to have (n) value of 1.51 and (k) value of 0.26.
- AZ ® EXP AX1020P photoresist a 330 nm film was coated and baked at 115°C for 60 seconds.
- the wafer was then imagewise exposed using an ISI 193 nm ministepper with 0.6NA, 0.7 sigma, under conventional illumination with binary mask.
- the exposed wafer was baked at 110°C for 60 seconds and developed using a 2.38 weight % aqueous solution of tetramethyl ammonium hydroxide for 60 seconds.
- the line and space patterns at 0.13 micron were observed under scanning electron microscope and showed no standing waves indicating the efficacy of the bottom anti-reflective coating.
- the use of bottom antireflective coating provides the best solution for the elimination of reflectivity.
- the bottom antireflective coating is applied to the substrate prior to coating with the photoresist and prior to exposure.
- the resist is exposed imagewise and developed.
- the antireflective coating in the exposed area is then etched, typically in an oxygen plasma, and the resist pattern is thus transferred to the substrate.
- the etch rate of the antireflective film should be relatively high in comparison to the photoresist so that the antireflective film is etched without excessive loss of the resist film during the etch process. It is preferred to have a bottom antireflective coating that functions well at exposures less than 230 nm. Such antireflective coatings need to have high etch rates and be sufficiently absorbing to act as antireflective coatings. US 5,935,760 describes a bottom antireflective coating based on a very specific crosslinkable polyester polymer.
Abstract
Description
Claims
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DE200560023438 DE602005023438D1 (en) | 2004-04-05 | 2005-03-31 | PROCESS FOR PREPARING POLYESTERS |
JP2007506856A JP5003958B2 (en) | 2004-04-05 | 2005-03-31 | Polyester manufacturing method |
KR1020067023010A KR101178123B1 (en) | 2004-04-05 | 2005-03-31 | Process for making polyesters |
EP20050718352 EP1751210B1 (en) | 2004-04-05 | 2005-03-31 | Process for making polyesters |
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US10/817,987 US7081511B2 (en) | 2004-04-05 | 2004-04-05 | Process for making polyesters |
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EP (1) | EP1751210B1 (en) |
JP (1) | JP5003958B2 (en) |
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CN (2) | CN101824141B (en) |
DE (1) | DE602005023438D1 (en) |
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WO2008017954A2 (en) | 2006-08-10 | 2008-02-14 | Az Electronic Materials Usa Corp. | Antireflective composition for photoresists |
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US11203661B2 (en) | 2016-07-13 | 2021-12-21 | Akzo Nobel Coatings International B.V. | Process for the manufacture of an epoxy-functional polyester, epoxy-functional polyester obtained by such process and coating composition comprising such epoxy-functional polyester |
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US20080286689A1 (en) * | 2007-05-14 | 2008-11-20 | Hong Zhuang | Antireflective Coating Compositions |
US20090035704A1 (en) * | 2007-08-03 | 2009-02-05 | Hong Zhuang | Underlayer Coating Composition Based on a Crosslinkable Polymer |
US8039201B2 (en) * | 2007-11-21 | 2011-10-18 | Az Electronic Materials Usa Corp. | Antireflective coating composition and process thereof |
US8329387B2 (en) | 2008-07-08 | 2012-12-11 | Az Electronic Materials Usa Corp. | Antireflective coating compositions |
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US20100092894A1 (en) * | 2008-10-14 | 2010-04-15 | Weihong Liu | Bottom Antireflective Coating Compositions |
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US11203661B2 (en) | 2016-07-13 | 2021-12-21 | Akzo Nobel Coatings International B.V. | Process for the manufacture of an epoxy-functional polyester, epoxy-functional polyester obtained by such process and coating composition comprising such epoxy-functional polyester |
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KR20070012447A (en) | 2007-01-25 |
US7081511B2 (en) | 2006-07-25 |
JP2007531815A (en) | 2007-11-08 |
KR101178123B1 (en) | 2012-09-07 |
CN101824141B (en) | 2012-07-04 |
DE602005023438D1 (en) | 2010-10-21 |
CN1946759A (en) | 2007-04-11 |
TWI375693B (en) | 2012-11-01 |
TW200604241A (en) | 2006-02-01 |
US20050234201A1 (en) | 2005-10-20 |
CN101824141A (en) | 2010-09-08 |
EP1751210B1 (en) | 2010-09-08 |
EP1751210A1 (en) | 2007-02-14 |
MY134455A (en) | 2007-12-31 |
JP5003958B2 (en) | 2012-08-22 |
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