Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M149/00—Lubricating compositions characterised by the additive being a macromolecular compound containing nitrogen
  • C10M149/12—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M149/14—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds a condensation reaction being involved
  • C10M149/18—Polyamides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
  • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
  • C09D133/24—Homopolymers or copolymers of amides or imides
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
  • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/20—Diluents or solvents
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/60—Additives non-macromolecular
  • C09D7/61—Additives non-macromolecular inorganic
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/65—Additives macromolecular
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
  • C10M125/02—Carbon; Graphite
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
  • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
  • C10M133/38—Heterocyclic nitrogen compounds
  • C10M133/44—Five-membered ring containing nitrogen and carbon only
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
  • C08K5/37—Thiols

Definitions

• the present invention relates to a coating composition containing a polyamide-imide resin.
• Polyamide-imide resins are resin materials exhibiting excellent heat resistance and mechanical strength. Polyamide-imide resins are therefore used as binder components for coating compositions having lubricating properties.
• polyamide-imide resins have been synthesized using amide-based solvents such as N-methylpyrrolidone (NMP), N-ethylpyrrolidone (NEP), N,N-dimethylacetamide, and N,N-dimethylformamide.
• NMP N-methylpyrrolidone
• NEP N-ethylpyrrolidone
• N,N-dimethylacetamide N,N-dimethylacetamide
• N,N-dimethylformamide N,N-dimethylformamide
• a polyamide-imide resin formed by polymerization in a polymerization solvent consisting of only ⁇ -butyrolactone (GBL) instead of an amide-based solvent and a polyamide-imide resin composition containing the polyamide-imide resin are proposed.
• GBL ⁇ -butyrolactone
• a polyamide-imide resin composition dissolved in a solvent containing ⁇ -butyrolactone and cyclopentanone is proposed, and a coating composition containing a solid lubricant is further proposed.
• the present invention was conceived in order to solve the problem described above, and the object of the present invention is to provide a coating composition containing a polyamide-imide resin which does not raise any concern about reproductive toxicity and which has excellent lubrication durability.
• the present inventors arrived at the present invention as a result of conducting dedicated research in order to achieve the objective described above. That is, the object of the present invention is achieved by a coating composition comprising:
• the solvent having a urea bond preferably has a structure represented by the following chemical formula (A):
• R 1 represents a saturated hydrocarbon group having from 1 to 9 carbons and “n” represents an integer from 1 to 10
• R 1 represents a saturated hydrocarbon group having from 1 to 9 carbons and “n” represents an integer from 1 to 10
• R 1 is particularly preferable for R 1 to be a saturated hydrocarbon group having from 1 to 3 carbons and for “n” to be an integer from 2 to 5.
• the content of the polyamide-imide resin in the resin solution is for example from 10 to 60% by mass and alternatively from 10 to 50% by mass.
• the polyamide-imide resin is preferably prepared by polymerizing a diisocyanate compound and a trivalent carboxylic acid derivative having an acid anhydride group in a solvent having a urea bond.
• the solid lubricant is preferably at least one type selected from the group consisting of fluorine resins, molybdenum disulfide, and graphite.
• the average primary particle size of the solid lubricant is for example from 0.1 to 20 ⁇ m and alternatively from 0.1 to 10 ⁇ m.
• the content of the solid lubricant in the total solid is for example from 5 to 90% by mass and alternatively from 10 to 70% by mass.
• the coating composition of the present invention is a coating composition comprising:
• the solvent having a urea bond in the present invention is not particularly limited as long as it is a solvent which dissolves the polyamide-imide resin, but the solvent preferably has a structure represented by the following chemical formula (A):
• R 1 represents a saturated hydrocarbon group having from 1 to 9 carbons and “n” represents an integer from 1 to 10).
• saturated hydrocarbon group of R 1 examples include straight-chain or branched alkyl groups such as methyl groups, ethyl groups, n-propyl groups, isopropyl groups, n-butyl groups, isobutyl groups, sec-butyl groups, tert-butyl groups, pentyl groups, hexyl groups, and heptyl groups.
• a saturated hydrocarbon group having from 1 to 3 carbons is particularly preferable.
• n represents an integer from 1 to 10, but alternatively an integer from 2 to 5.
• Examples of the solvent having a urea bond used in the present invention include the following compounds:
• solvents may be used alone or as a mixture if necessary.
• the polyamide-imide resin of the present invention is not particularly limited as long as it is a polymer having an amide bond and an imide bond in the molecule, but the polyamide-imide resin can be prepared, for example, by polymerizing a diisocyanate compound and a trivalent carboxylic acid derivative having an acid anhydride group in a solvent having a urea bond.
• diisocyanate compound used in the preparation of the polyamide-imide resin examples include compounds represented by the following chemical formulas:
• diisocyanate compounds include 4,4′-diphenylmethane diisocyanate, 4,4′-diphenylether diisocyanate, xylylene diisocyanate, 3,3′-dimethylbiphenyl-4,4′-diisocyanate, 3,3′-diphenylmethane diisocyanate, 3,3′-dimethoxybiphenyl-4,4′-diisocyanate, paraphenylene diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, naphthalene diisocyanate, and tolylene diisocyarate.
• aromatic compound from the perspective of the mechanical properties, and 4,4′-diphenylmethane diisocyanate and tolylene diisocyanate are particularly preferable.
• diisocyanate compounds may be used alone or as a mixture if necessary.
• the trivalent carboxylic acid derivative having an acid anhydride group used in the preparation of the polyamide-imide resin is not particularly limited as long as it is a derivative of a trivalent carboxylic acid having an acid anhydride group which reacts with isocyanate groups or amino groups, and examples include compounds represented by the following chemical formulas:
• trimellitic acid anhydride is preferable. These trivalent carboxylic acid derivatives having acid anhydride groups may be used alone or as a mixture if necessary.
• the polyamide-imide resin may also be prepared by further adding and polymerizing at least one type of a dicarboxylic acid compound or diol compound and/or a tetravalent carboxylic acid derivative having two acid anhydride groups as polymerization components.
• dicarboxylic acid compound used in the preparation of the polyamide-imide resin examples include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, naphthalene dicarboxylic acid, and oyxdibenzoic acid and aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, azelaic acid, suberic acid, sebacic acid, decanedioic acid, dodecanedioc acid, and cyclohexane dicarboxylic acid.
• An adipic acid is preferable from the perspective of the balance of the mechanical properties.
• diol compound used in the preparation of the polyamide-imide resin examples include aromatic diol compounds such as resorcinol, hydroquinones, biphenyl diols, bisphenol A, naphthalene diols, aromatic polycarbonate diols, and derivatives of aromatic polycarbonate diols such as aromatic polycarbonate diol-chloroformic acid diesters and aliphatic diol compounds such as ethylene glycol, 1,4-butane diol, 1,6-hexane diol, aliphatic polycarbonate diols, and derivatives of aliphatic polycarbonate diols such as aliphatic polycarbonate diol-chloroformic acid diesters. It is preferable to copolymerize at least one type of monomer selected from the group consisting of aliphatic polycarbonate diols or derivatives thereof. These diol compounds may be used alone or as a mixture if necessary.
• An aliphatic polycarbonate diol or a derivative thereof has the function of improving the workability and adhesiveness of the coating, and the content in the polyamide-imide resin is preferably from 1 to 50 mol % and particularly preferably from 5 to 30 mol %.
• the content of the aliphatic polycarbonate diol or a derivative thereof in the polyamide-imide is within the range described above, it is possible to impart sufficient workability and adhesiveness to the coating.
• the content of the aliphatic polycarbonate diol or a derivative thereof exceeds 50 mol %, the solvent resistance tends to be diminished.
• Examples of commercially available aliphatic polycarbonate diols or derivatives thereof include trade names PLACCEL CD-205, 205PL, 205HL, 210, 210PL, 210HL, 220, 220PL, and 220HL produced by Daicel Chemical Industries, Ltd., and these may be used alone or as a mixture if necessary.
• Examples of the tetravalent carboxylic acid derivative having two acid anhydride groups used in the preparation of the polyamide resin include biphenyl tetracarboxylic acid dianhydride, pyromellitic anhydride, oxydiphthalic acid dianhydride, benzophenone tetracarboxlic acid dianhydride, diphenyl sulfone tetracarboxylic acid dianhydride, (hexafluoroisopropylidene)diphthalic acid dianhydride, and terphenyl tetracarboxylic acid dianhydride.
• These tetravalent carboxylic acid derivatives having two acid anhydride groups may be used alone or as a mixture if necessary.
• hydroxynaphthoic acid, oxynaphthoic acid, hydroxybiphenyl carboxylic acid, 1,2-aminododecanoic acid, trimethylolethane, trimethylolpropane, gluconic acid, lactic acid, fumaric acid, DL-malic acid, xylitol, D-sorbitol, and DL-alanine may be further added and polymerized as necessary.
• the compounded amount of the diisocyanate compound, the trivalent carboxylic acid derivative having an acid anhydride group, the dicarboxylic acid compound or diol compound, and the tetravalent carboxylic acid derivative having two acid anhydride groups is preferably such that the amount of the diisocyanate compound is from 0.8 to 1 mole, alternatively from 0.95 to 1.08 moles, and further alternatively from 1.0 to 1.08 moles with respect to a total of 1.0 mole of the trivalent carboxylic acid derivative having an acid anhydride group and, if present, the tetracarboxylic acid derivative having two acid anhydride groups.
• the compounding ratio of the trivalent carboxylic acid derivative having an acid anhydride group and the dicarboxylic acid is preferably from 0.95:0.05 to 0.50:0.50, alternatively from 0.85:0.15 to 0.60:0.40, and alternatively from 0.75:0.25 to 0.65:0.35 as an equivalence ratio.
• the compounding ratio is less than 0.95:0.05, the flexibility of the coating film tends to be diminished, whereas when the compounding ratio exceeds 0.50:0.50, the heat resistance tends to be diminished.
• the polyamide-imide resin of the present invention can be prepared by, but is not limited to, the following methods, for example.
• Method of obtaining a polyamide-imide resin by reacting the diisocyanate compound, the trivalent carboxylic acid derivative having an acid anhydride group, and, if present, the dicarboxylic acid compound or diol compound and the tetracarboxylic acid derivative having two acid anhydride groups all at once; (2) Method of obtaining a polyamide-imide resin by first reacting the dicarboxylic acid compound or diol compound and an excessive amount of the isocyanate compound to synthesize an oligomer having isocyanate groups at the ends and then adding and reacting the trivalent carboxylic acid derivative having an acid anhydride group and, if necessary, the tetracarboxylic acid derivative having two acid anhydride groups; and (3) Method of obtaining a polyamide-imide resin by reacting the isocyanate compound and an excessive amount of the trivalent carboxylic acid derivative having an acid anhydride group and, if necessary, the tetracarboxylic acid derivative having two acid anhydride groups to
• the number-average molecular weight of the polyamide-imide resin of the present invention is for example from 10,000 to 75,000, alternatively from 15,000 to 50,000, and further alternatively from 20,000 to 35,000.
• the number-average molecular weight of the polyamide-imide resin is sampled at the time of the synthesis of the resin and measured with a gel permeation chromatograph (GPC) using the calibration curve of standard polystyrene.
• the resin solution of the present invention is a solution in which a polyamide-imide resin is dissolved in a solvent having a urea bond, and the content of the polyamide-imide resin in the resin solution is preferably from 10 to 60% by mass and particularly preferably from 10 to 50% by mass.
• the content of the polyamide-imide resin in the resin solution is within the range described above, it is possible to impart sufficient lubricating properties and abrasion resistance to the coating.
• the powdered solid lubricant of the present invention has the function of improving the slidability of the coating.
• solid lubricants include organic microparticles such as fluorine resins, polyolefins, and polyamides and inorganic microparticles such as sulfides, graphite, boron nitride, and metal oxides.
• polytetrafluoroethylene examples include polytetrafluoroethylene, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymers, tetrafluoroethylene-hexafluoropropylene copolymers, tetrafluoroethylene-ethylene copolymers, polyvinylidene fluoride, polychlorotrifluoroethylene, polyethylene, polyamide, molybdenum disulfide, tungsten disulfide, graphite, hexagonal boron nitride, aluminum oxide, and zinc oxide. It is preferable to use at least one type selected from the group consisting of fluorine resins, molybdenum disulfide, and graphite.
• the average primary particle diameter of the solid lubricant of the present invention can be measured by observations using an electron microscope or with a laser diffraction and scattering method.
• the average primary particle diameter of the solid lubricant is preferably from 0.1 to 20 ⁇ m and particularly preferably from 0.1 to 10 ⁇ m.
• the content of the solid lubricant of the present invention in the total solid is preferably from 5 to 90% by mass and particularly preferably from 10 to 70% by mass.
• the content of the solid lubricant is within the range described above, it is possible to sufficiently improve the lubricating properties and the lubrication durability of the coating.
• the coating composition of the present invention may also contain one or more types of additives such as a UV absorber, a photostabilizer, an antioxidant, a thermal polymerization inhibitor, a leveling agent, an anti-foaming agent a thickening agent, an anti-settling agent, a pigment (an organic coloration pigment or an inorganic pigment), a coloration dye, an infrared radiation absorber, an optical brightener, a dispersing agent, conductive microparticles, an antistatic agent, an antifogging agent, a coupling agent, and the like, if necessary, as long as the object of the present invention is not inhibited.
• additives such as a UV absorber, a photostabilizer, an antioxidant, a thermal polymerization inhibitor, a leveling agent, an anti-foaming agent a thickening agent, an anti-settling agent, a pigment (an organic coloration pigment or an inorganic pigment), a coloration dye, an infrared radiation absorber, an optical brightener
• the coating composition of the present invention may be applied with any method.
• coating methods that can be used include dipping methods, spincoat methods, flowcoat methods, spraying methods, bar-coating methods, gravure coating methods, roll coating methods, blade coating methods, air knife coating methods, and the like.
• a thickness of the coating film is not particularly limited, but the thickness is preferably from 1 to 50 ⁇ m and more preferably from 5 to 30 ⁇ m. After application, the coating film may be dried to remove the solvent and, if necessary, baked.
• Powdered graphite was added to a polyamide-imide resin solution (produced by Hitachi Chemical Co., Ltd., solid content: approximately 30% by mass) containing a polyamide-imide resin dissolved in 1,3-dimethyl-2-imidazolidinone (DMI) prepared in DMI, so that the content of the powdered graphite was 50 parts by mass per 100 parts by mass of the polyamide-imide resin, and mixed at room temperature.
• DMI 1,3-dimethyl-2-imidazolidinone
• a polyamide-imide resin solution (produced by Hitachi Chemical Co., Ltd., HPC-3010) in which a polyamide-imide resin was dissolved in ⁇ -butyrolactone (GBL) was used, and powdered graphite was added, so that the content of the powdered graphite was 50 parts by mass per 100 parts by mass of the polyamide-imide resin, and mixed at room temperature. This mixture was diluted using GBL so that the solid content concentration was 15% by mass to form a coating composition to be used in evaluation tests.
• GBL ⁇ -butyrolactone
• a coating composition to be used in evaluation tests was formed in the same manner as in Practical Example 1 with the exception that the powdered graphite was replaced with silica (organo silica sol: DMI solution: solid content of approximately 20% by mass).
• a polyamide-imide resin solution (produced by Hitachi Chemical Co., Ltd., HPC-5000) in which a polyamide-imide resin was dissolved in N-methylpyrrolidone (NMP) was used, and powdered graphite was added, so that the content of the powdered graphite was 50 parts by mass per 100 parts by mass of the polyamide-imide resin, and mixed at room temperature. This mixture was diluted using NMP so that the solid content concentration was 15% by mass to form a coating composition to be used in evaluation tests.
• NMP N-methylpyrrolidone
• the resulting coating composition was spray-coated onto a test piece (ring) subjected to sandblasting treatment in advance. After the test piece was dried for 10 minutes at 80° C., the test piece was baked for 30 minutes at 240° C. to obtain a test piece for testing.
• the coating composition of the present invention can be suitably used in the sliding members of various devices which require excellent slidability and lubrication durability.
• the coating composition can be used for the surface treatment of crank shafts, slide bearings, pistons, gaskets, gears, door panels, instrument panels, door looks, timing belts, and body seals, glass runs, and weather stripping for sunroofs.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
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• Wood Science & Technology (AREA)
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• Inorganic Chemistry (AREA)
• Paints Or Removers (AREA)
• Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
• Lubricants (AREA)
• Compositions Of Macromolecular Compounds (AREA)

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• 2013
  • 2013-08-02 US US14/418,462 patent/US20150166924A1/en not_active Abandoned
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