EP3687716A1 - Method of making silver-containing dispersions with nitrogenous bases - Google Patents
Method of making silver-containing dispersions with nitrogenous basesInfo
- Publication number
- EP3687716A1 EP3687716A1 EP18779896.2A EP18779896A EP3687716A1 EP 3687716 A1 EP3687716 A1 EP 3687716A1 EP 18779896 A EP18779896 A EP 18779896A EP 3687716 A1 EP3687716 A1 EP 3687716A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- silver
- cellulose
- containing dispersion
- cellulose acetate
- aqueous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
- B22F1/056—Submicron particles having a size above 100 nm up to 300 nm
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/102—Metallic powder coated with organic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/103—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing an organic binding agent comprising a mixture of, or obtained by reaction of, two or more components other than a solvent or a lubricating agent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/107—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing organic material comprising solvents, e.g. for slip casting
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0393—Flexible materials
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
- H05K1/092—Dispersed materials, e.g. conductive pastes or inks
- H05K1/097—Inks comprising nanoparticles and specially adapted for being sintered at low temperature
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/15—Position of the PCB during processing
- H05K2203/1545—Continuous processing, i.e. involving rolls moving a band-like or solid carrier along a continuous production path
Definitions
- This invention relates to a method for forming a non-aqueous dispersion of a silver nanoparticle composite by mixing a cellulosic polymer, a hydroxylic solvent, and reducible silver ions, to which a nitrogenous base is introduced, to form a silver nanoparticle composite. After cooling and isolation, the silver nanoparticle composite is re-dispersed in one or more organic solvents for future use, for example as an "ink" to form electrically-conductive articles.
- This invention also relates to the non-aqueous silver-containing dispersions obtained using the inventive method.
- silver has desirable electrical and thermal conductivity, catalytic properties, and antimicrobial behavior.
- silver and silver-containing compounds have been widely used in alloys, metal plating processes, electronic devices, imaging sciences, medicine, clothing or other fibrous materials, and other commercial and industrial articles and processes to take advantage of silver's beneficial properties.
- silver compounds or silver metal have been described for use as metallic patterns or electrodes in metal wiring patterns, printed circuit boards (PCB's), flexible printed circuit boards (FPC's), antennas for radio frequency identification (RFID) tags, plasma display panels (PDP's), liquid crystal displays (LCD's), organic light emitting diodes (OLED's), flexible displays, and organic thin film transistors (OTFT's), among other electronic devices known in the art.
- PCB's printed circuit boards
- FPC's flexible printed circuit boards
- antennas for radio frequency identification (RFID) tags radio frequency identification
- PDP's plasma display panels
- LCD's liquid crystal displays
- OLED's organic light emitting diodes
- flexible displays flexible displays
- OFT's organic thin film transistors
- Silver is an ideal conductor having electrical conductivity 50 to 100 times greater than indium tin oxide that is commonly used today in many devices.
- the art has described the preparation of electrically-conductive films by forming and developing (reducing) a silver halide image in "photographic" silver halide emulsions through an appropriate mask to form electrically- conductive grid networks having silver wires having average sizes (width and height) of less than 10 ⁇ and having appropriate lengths.
- Inkjet printing and flexographic printing have also been proposed for providing patterns of silver or silver-containing compounds, requiring the careful fabrication of a silver-containing paste or "ink” with desirable surface tension, viscosity, stability, and other physical properties required for such application processes.
- High silver content has generally been required for high electrical conductivity, and calcination or sintering may be additionally required for increasing electrical conductivity of printed silver inks.
- Some approaches to providing silver metal is to employ a chemical ink formulation where the silver source is a molecular precursor or cation (such as a silver salt) that is then chemically reacted (or reduced) to produce silver metal.
- Electrically-conductive inks that are in the form of a chemical solution rather than as a suspension or dispersion of metal particles, have gained interest in recent years.
- One conductive ink of this type is known as a Metalorganic Decomposition (MOD) variety ink, for example, as described by Jahn et al. [Chem. Mater. 22, 3067-3071 (2010)] who investigated silver printing using an aqueous transition metal complex [Ag02C(CH20CH2)3H]-containing MOD ink. They reported the formation of metallic silver features having electrical conductivities as high as 2.7 x 10 7 S m "1 , which corresponds to an electrical conductivity that is 43% of that of bulk silver, although a sintering temperature of 250°C was required.
- MOD Metalorganic De
- photocurable compositions containing catalytic silver particles can be printed and cured on a suitable transparent substrate, for example, a continuous roll of a transparent polyester film, and then electroless metal plating can be carried out on the catalytic silver particles.
- a suitable transparent substrate for example, a continuous roll of a transparent polyester film
- electroless metal plating can be carried out on the catalytic silver particles.
- these methods require that high quantities of purchased silver particles be uniformly dispersed within the photocurable compositions so that coatings or printed patterns have a sufficiently high concentration of catalytic sites. Without effective dispersing, silver particles readily agglomerate, leading to less ineffective electroless plating and electrical conductivity.
- U.S. Patent Application Publication 2012/0225126 (Geckeler et al.) describes a solid-state method for preparing silver nanoparticles using a mixture of a silver salt and a water-soluble polymer such as a starch or cellulose derivative that acts as a silver ion reducing agent.
- the mixture is milled by a high-speed vibration milling process to form silver nanoparticles within the water-soluble starch or cellulosic polymer so that a solvent is not needed for synthesis or transportation of the silver nanoparticles.
- U.S. Patent 6,572,673 discloses a process for preparing metal nanoparticles, comprising reacting suitable metal salts and anionic surfactant containing an anionic group such as a carboxylic group, sulfate group, or sulfonate group as reducing agent in water under reflux at a temperature of 50-140°C. Such processes are carried out in aqueous solutions.
- U.S. Patent 9,005,663 discloses a method for making silver nanoparticles, comprising reacting a silver salt with a phosphene amino acid.
- the phosphene amino acid reactant is an expensive material.
- U.S. Patent 7,892,317 discloses a process for the synthesis of silver nano particle, consisting of reacting silver salt and an anionic surfactant, or a nonionic surfactant, and a reducing agent in an aqueous solution at room temperature.
- U.S. Patent 9,496,068 discloses a process for the synthesis of amine coated silver nano particles via thermal decomposition of oxalate ion-alkylamine-alkyl diamine-silver complex.
- U.S. Patent Application Publication 2010/0040863 discloses a process for producing carboxyiic acid-stabil ed silver nanopatticles by heating a mixture of a silver salt long alkyl chain earboxyUc acid and a tertiary amine in methanol .
- U. S. Patent Application Publication 2014/0312284 discloses a process for producing an organoamine stabilized silver nanoparticle by reduction of silver salts with hydrazine in methanol.
- hydrazine is a toxic material and it would not be desirable to include it in a manufacturing process.
- Cellulose is a polydisperse linear homopolymer consisting of regioselective and enantioselective P-l,4-glycosidic linked D-glucose units.
- the homopolymer contains three reactive hydroxyl groups at the C-2, C-3 and C-6 atoms that are in general, accessible to the typical chemical conversions of primary and secondary -OH groups.
- Modifying the structure of cellulosic polymers can improve their solubility, leading to the synthesis of various cellulose derivatives (cellulosics) that come in all forms and structures depending on the functional group(s) used in place of the hydroxyl groups on the cellulose chain.
- cellulose derivatization can involve partial or full esterification or etherification of the hydroxyl groups on the cellulose chain by reaction with various reagents to afford cellulose derivatives like cellulose esters and cellulose ethers.
- cellulose acetate is recognized as the most important organic ester of cellulose owing to its extensive industrial and commercial importance.
- Properties of cellulose derivatives (esters and ethers) are determined primarily by the functional group. However, they can be modified significantly by adjusting the degree of functionalization and the degree of polymerization of the polymer backbone to modify solubility in various solvents.
- the present invention provides a method comprising, in sequence:
- reducible silver ions present in an amount of a weight ratio of (b) reducible silver ions to the one or more (a) polymers of at least 5: 1 and up to and including 50: 1;
- the method can further comprise:
- the present invention provides a non-aqueous silver-containing dispersion prepared from the method described herein, which non-aqueous silver- containing dispersion comprises:
- a silver nanoparticle composite comprising silver and one or more (a) polymers selected from one or more of cellulose acetate, cellulose acetate phthalate, cellulose acetate butyrate, cellulose acetate propionate, cellulose acetate trimellitate, hydroxypropylmethyl cellulose phthalate, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropylmethyl cellulose, and
- carboxymethyl cellulose wherein silver is present in the silver nanoparticle composite at a weight ratio to the one or more (a) polymers of at least 5: 1 and up to and including 50: 1;
- a nitrogenous base having a pKa in acetonitrile of at least 15 and up to and including 25 at 25°C, the nitrogenous base being present in an equimolar amount or molar excess in relation to the amount of silver.
- the present invention provides a simple, safe, and inexpensive way to generate a unique non-aqueous dispersion of silver nanoparticles from a nonaqueous silver precursor composition comprising reducible silver ions, a cellulosic polymer, and a nitrogenous base.
- the method according to this invention can be readily and safely carried out for manufacturing high weight fraction, fully dispersed silver nanoparticles that have long term stability as the silver nanoparticles do not readily agglomerate in the relatively benign organic solvents.
- These silver nanoparticle-containing compositions can be easily deposited or formed into patterns for various uses.
- the present invention provides these advantages by means of using a nitrogenous base to facilitate faster silver ion reduction in the presence of the cellulosic polymer.
- the cellulosic polymers and organic solvents used in the nonaqueous silver precursor compositions also facilitate silver ion reduction and provide physical stability of the resulting silver nanoparticles using inexpensive and environmentally safe dispersing agents.
- the inventive compositions and methods can thus be used to provide compositions or dispersions of silver nanoparticles that can be used in various ways, for example, as applied to a substrate in a pattern for further processing.
- FIG. 1 is a graphical representation of particle size distribution as described below in Invention Example 1.
- FIG. 2 is a graphical representation of particle size distribution as described below in Invention Example 2.
- FIG. 3 is a graphical representation of chemical analysis of the silver nanoparticles-cellulose polymer composite prepared in Invention Example 2 below.
- FIG. 4 is a graphical representation of particle size distribution as described below in Invention Example 3. DETAILED DESCRIPTION OF THE INVENTION
- weight % refers to the amount of a component or material based on the total amount of a non-aqueous silver precursor composition or non-aqueous dispersion. In other embodiments, “weight %” can refer to the % solids (or dry weight) of a dry layer, coating, thin film, or silver-containing pattern.
- non-aqueous as applied to the compositions and dispersions according to the present invention means that solvent media used to form such compositions are predominantly organic in nature and water is not purposely added but may be present in an amount of less than 10 weight % by virtue of being part of a chemical component, or particularly less than 5 weight %, or even less than 1 weight %, of the total weight of all solvents in the composition.
- non-aqueous silver precursor composition means that the silver present therein is predominantly (greater than 50 weight % of total silver) in the form of reducible silver ions.
- the average dry thickness of silver nanoparticle-containing lines, grid lines, or other pattern features described herein can be the average of at least 2 separate measurements taken, for example, using electron microscopy, optical microscopy, or profilometry all of which should provide substantially the same results for the same test sample.
- dry in reference to thickness and width of lines, patterns, or layers, refers to embodiments in which at least 80 weight % of originally present organic solvent(s) has been removed.
- mean particle size is measured using dynamic light scattering (DLS), that is sometimes referred to as Quasi-Elastic Light Scattering (QELS), and is a well-established technique for measuring the size and size distribution of molecules and particles typically in the submicron region, and even lower than 1 nm.
- DLS dynamic light scattering
- QELS Quasi-Elastic Light Scattering
- Commercial DLS instruments are available from, for example, Malvern and Horiba who also supply instructions for use of such equipment, and such equipment and accompany instructions can be used to characterize and carry out the present invention.
- the boiling point of organic solvents described herein can be determined from known publications or measured using standard methods.
- viscosity can be determined at 25°C using any standard commercially available viscometer.
- group particularly when used to define a substituent or a moiety, can itself be substituted or unsubstituted (for example an "alkyl group” refers to a substituted or unsubstituted alkyl group) by replacement of one or more hydrogen atoms with suitable substituents (noted below) such as a fluorine atom.
- suitable substituents such as a fluorine atom.
- substituents on any "groups" referenced herein or where something is stated to be possibly substituted include the possibility of any groups, whether substituted or unsubstituted, which do not destroy properties necessary for the utility of the component or non-aqueous silver precursor composition.
- substituents on any of the mentioned groups can include known substituents such as halogen (for example, chloro and fluoro); alkoxy, particularly those with 1 to 5 carbon atoms (for example, methoxy and ethoxy); substituted or unsubstituted alkyl groups, particularly lower alkyl groups (for example, methyl and trifluoromethyl), particularly either of those having 1 to 6 carbon atoms (for example, methyl, ethyl, and t-butyl); and other substituents that would be readily apparent in the art.
- substituents on any of the mentioned groups can include known substituents such as halogen (for example, chloro and fluoro); alkoxy, particularly those with 1 to 5 carbon atoms (for example, methoxy and ethoxy); substituted or unsubstituted alkyl groups, particularly lower alkyl groups (for example, methyl and trifluoromethyl), particularly either of those having 1 to 6 carbon atoms (for example, methyl, ethy
- total Hansen solubility parameter and “total Hansen parameter” refer to the same thing.
- Solubility Parameters also named reverse solvency principle
- Each chemical molecule is given three Hansen parameters, each generally measured in Mpa 0 5 : 6d, the energy from dispersion bonds between molecules, 6 P , the energy from polar bonds between molecules; and 5h, the energy from hydrogen bonds between molecules.
- the "total Hansen solubility parameter" is defined as:
- the total Hansen parameters of organic solvent mixtures can be calculated using the sum of volume fractions of the individual organic solvent components in the premix solution.
- Total Hansen parameters as well as the three-component Hansen parameters for dispersive, polar, and hydrogen-bonding components of the solubility parameter, are readily available in the literature.
- non-aqueous silver-containing dispersions described herein can be used for forming metallic silver patterns and electrodes for example in membrane touch switches (MTS), battery testers, biomedical, electroluminescent lamps, radio frequency identification (RFID) antenna, flat panel displays such as plasma display panel (PDP) and organic light emitting diode (OLED) displays, printed transistors and thin film photovoltaics, and thereby reduce the number of steps for pattern formation in such devices.
- MTS membrane touch switches
- RFID radio frequency identification
- PDP plasma display panel
- OLED organic light emitting diode
- non-aqueous silver precursor compositions described herein have actual and potential uses in various technologies and industries. Most specifically, they can be used to provide silver metal for various purposes, including but not limited to, the formation of electrically-conductive grids or patterns of fine wires or other geometric forms, the formation of silver seed particles for electroless plating with other electrically-conductive metals, and the formation of silver in various materials for antimicrobial activity.
- non-aqueous silver precursor compositions according to the present invention are useful to provide silver metal in nonaqueous dispersions that in turn can be used to provide electrically-conductive metal patterns.
- electrically-conductive metal patterns can be incorporated into various devices including but not limited to, touch screens or other transparent display devices, and in modern electronics such as solar cell electrodes, electrodes in organic thin film transistors (OTFTs), flexible displays, radio frequency identification tags, light antennas, and other devices that would be readily apparent to one skilled in the art.
- the non-aqueous silver precursor compositions according to the present invention contain four essential components for purposes of providing silver metal in the form of silver nanoparticles according to the present invention: one or more (a) polymers (such as one or more cellulosic polymers) as described below; (b) reducible silver ions in the form of one or more silver salts or silver complexes as described below; an organic solvent medium consisting of (c) or more organic solvents, as described below; and (d) one or more nitrogenous bases, as described below.
- No other components are purposely added to the non-aqueous silver precursor compositions according to the present invention to achieve the inventive advantages or purposes, and as noted above, water is not purposely included.
- (e) carbon black can be present as a fifth essential component.
- the non-aqueous silver precursor composition according to this invention can be converted into a corresponding non-aqueous dispersion or non-aqueous silver-containing dispersion comprising a silver nanoparticle composite comprising both silver and one or more polymers as described below. It is desirable that at least 90 mol %, at least 95 mol %, or even at least 98 mol % (which means "substantially all") of the (b) reducible silver ions are converted to silver during this process.
- the one or more (a) polymers, (b) reducible silver ions, (c) organic solvents, and nitrogenous bases can be combined in general by mixing them under suitable ambient conditions so that thermal reduction does not occur prematurely to any appreciable extent.
- the (a), (c), and (d) components can be formulated or mixed to form a premix solution and under appropriate heating, the (b) reducible silver ions can be added the premix solution in a controlled fashion.
- the (a), (b), and (c) components can be formulated or mixed to form a premix solution, and the (d) nitrogenous base can be added to the premix solution in a controlled fashion. Details of these methods are described below.
- the non-aqueous silver precursor composition is formed, and it generally has a % solids of at least 1% and up to and including 50%, or more typically of at least 5% and up to and including 20%.
- the amount of solids, and (c) organic solvents, and viscosity, can thus be adjusted for a particular use or silver ion reduction operation.
- the non-aqueous silver precursor composition is generally in liquid form having a viscosity of at least 1 centipoise (0.001 Pascal sec) and up to and including 5,000 centipoise (5 Pascal sec), or more likely a viscosity of at least 3 centipoise (0.003 Pascal sec) and up to and including 50 centipoise (0.05 Pascal sec), all measured at 25°C.
- the non-aqueous (silver-containing) dispersion described below can have the same or different viscosity as the corresponding non-aqueous silver precursor composition. In most embodiments, the two compositions have essentially the same viscosity, that is, no more than 10% difference.
- the polymers useful in the practice of the present invention are organic in nature and can be used singly or in mixtures of two or more different materials. When used in mixtures, the two or more different materials can be present in the same or different amounts within the total polymer amount. Both cellulose esters and cellulose ethers can be used in the present invention.
- Representative useful polymers for the practice of the present invention are selected from cellulose acetate, cellulose acetate phthalate, cellulose acetate butyrate, cellulose acetate propionate, cellulose acetate trimellitate, hydroxypropylmethyl cellulose phthalate, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropylmethyl cellulose, carboxymethyl cellulose, and mixtures of two or more of such materials.
- Particularly useful polymers according to the present invention include carboxymethyl cellulose, cellulose acetate butyrate, cellulose acetate propionate, ethyl cellulose, and cellulose acetate, individually or in mixtures.
- cellulosic polymers such as cellulose esters that comprise free hydroxy groups directly attached to the polymer backbone to provide a free hydroxyl content in an amount of at least 1%, or at least 2%, and up to and including 5%, based on the total hydroxy groups that could potentially be present in the polymer.
- the remaining hydroxy groups in the molecule would be esterified so that there is relatively low free hydroxyl content.
- the one or more (a) polymers can be present in a total amount of at least 1 weight % and up to and including 25 weight %, or more likely of at least 3 weight % and up to and including 10 weight %, based on the total weight of silver in the non-aqueous silver precursor composition.
- Reducible silver ions can be provided in the non-aqueous silver precursor composition from many sources as long as each silver salt or silver complex in which they are provided is soluble within the one or more (c) hydroxylic organic solvents at an amount of at least 1 g/liter at 20°C.
- silver salts or silver complexes comprised of reducible silver ions and any suitable organic or inorganic anion or complexed moiety (or a combination of anions and complexed moieties) can be used in the practice of the present invention to provide the (b) reducible silver ions for the present invention.
- Such silver complexes can be mononuclear, dinuclear, trinuclear, or higher and each compound generally has a net neutral charge.
- the following classes of useful reducible silver ion-containing salts and reducible silver ion-containing complexes are described as representative materials, but the present invention is not to be interpreted to be limited to them.
- Such reducible silver ion-containing materials can be readily purchased from various commercial sources or prepared using known procedures, starting materials, and reaction conditions unless otherwise indicated.
- a first class of reducible silver ion-containing compounds are silver salts having organic or inorganic anions.
- Some representative silver salts include but not limited to, silver nitrate, silver acetate, silver benzoate, silver nitrite, silver thiocyanate, silver myristate, silver citrate, silver phenyl acetate, silver malonate, silver succinate, silver adipate, silver phosphate, silver perchlorate, silver acetylacetonate, silver lactate, silver salicylate, silver oxalate, silver 2-phenylpyridine, silver trifluoroacetate; silver fluoride and silver fluoride complexes such as silver (I) fluorosulfate, silver (I) trifluoromethane sulfate, silver (I) pentafluoropropionate, and silver (I) heptafluorobutyrate; ⁇ -carbonyl ketone silver (I) complexes; silver proteins; and derivatives of any of these materials
- hindered aromatic N-heterocycle with (b) reducible silver ions can be used in the practice of this invention.
- hindered aromatic N-heterocycle means that the moiety has a "bulky” group located in the a position to the nitrogen atom in the aromatic ring.
- Such bulky groups can be defined using the known "A-value” parameter that is a numerical value used for the determination of the most stable orientation of atoms in a molecule (using conformational analysis) as well as a general representation of steric bulk. A-values are derived from energy measurements of a mono-substituted cyclohexane ring.
- Substituents on a cyclohexane ring prefer to reside in the equatorial position to the axial.
- the useful "bulky” groups in the hindered aromatic N- heterocycle have an A-value of at least 0.05.
- Useful reducible silver ion- containing complexes of this type are described in U.S. Patent 9,377,688 (Shukla), that describes properties, representative compounds, and methods for preparing them.
- reducible silver ions are silver carboxylate-trialkyl, carboxylate-triaryl, and carboxylate-alkylaryl phosphite complexes and mixtures of these compounds.
- reducible silver ions are silver carboxylate-trialkyl, carboxylate-triaryl, and carboxylate-alkylaryl phosphite complexes and mixtures of these compounds.
- carboxylate- trialkyl phosphite and “carboxylate-triaryl phosphite” are to be interpreted herein as indicating that the complex of which it is a part can have three of the same or different alkyl groups, or three of the same or different aryl groups, respectively.
- carboxylate-alkylaryl phosphite refers to a compound having a mixture of a total of three alkyl and aryl groups, in any combination.
- Useful reducible silver ion-containing complexes of this type are described in U.S. Patent 9,375,704 (Shukla) that describes properties, representative compounds, and methods for preparing them.
- Silver-oxime complexes can be used to provide (b) reducible silver ions, and these materials are generally non-polymeric in nature (meaning that the silver complex molecular weight is less than 3,000).
- Useful non-polymeric silver-oxime complexes of this type are described in U.S. Patent 9,387,460 (Shukla) that describes properties, representative compounds, and methods for preparing them.
- Other useful silver complexes comprising (b) reducible silver ions can be represented by the following Structure (V):
- L represents an a-oxy carboxylate
- P represents a 5- or 6-membered N- heteroaromatic compound
- a is 1 or 2
- b is 1 or 2
- c is 1, 2, 3, or 4, provided that when a is 1, b is 1, and when a is 2, b is 2.
- Each of the complexes of Structure (V) comprises one or two reducible silver ions.
- Each reducible silver ion is complexed with one or two a- oxy carboxylate compounds that can be via two oxygen atoms provided from the same molecule of an a-oxy carboxylate compound, or oxygen atoms provided from two molecules of the same or different a-oxy carboxylate compounds.
- the a-oxy carboxylates can be either a-hydroxy carboxylates, a-alkoxy carboxylates, or a-oxy carboxylates. With the a-hydroxy carboxylates and a-alkoxy
- the remainder of the valences of that a-carbon atom can be filled with hydrogen or a branched or linear alkyl group (substituted or unsubstituted) as described below in more detail.
- the a-oxy carboxylate (L) generally has a molecular weight of 250 or less, or 150 or less.
- L of Structure (V) described above can be represented by the following Structure (VI):
- Ri, R2, and R3 are independently hydrogen or branched or linear alkyl groups.
- at least one of Ri through R3 is a branched or linear alkyl group having from 1 to 8 carbon atoms, and any of the hydrogen atoms in such branched or linear alkyl groups can be replaced with a heteroatom such as a fluorine atom substituent.
- Some particularly useful conjugate acids from which a-oxy carboxylates (L) of Structure (VI) can be selected from the group consisting of lactic acid, 2-hydroxybutyric acid, 2-hydroxy-3-methylbutyric acid, 2-hydroxy- 3,3-dimethylbutyric acid, 2-hydroxy-isobutyric acid, 2-hydroxy-2-methylbutyric acid, 2-ethyl-2-hydroxybutyric acid, 2-hydroxy-2,3-dimethylbutyric acid, 2-ethyl- 2-methoxybutyric acid, 2-methoxy-2-methylpropanoic acid, 1- hydroxycyclopentane-l-carboxylic acid, 2,3-dihydroxy-2,3-dimethylsuccinic acid, and 2,4-dihydroxy-2,4-dimethylpentanedioic acid. As noted above, mixtures of these materials can be used in a specific complex if desired.
- L is represented in Structure (V) by the following Structure (VII):
- R 4 is a branched or linear alkyl group having 1 to 8 carbon atoms, including branched iso- and tertiary alkyl groups having 3 to 8 carbon atoms.
- any of the hydrogen atoms in any of the branched or linear alkyl groups optionally can be replaced with a fluorine atom; for example, the terminal carbon atom of a R 4 branched or linear alkyl group can have 1 to 3 fluorine atoms.
- Some useful conjugate acids from which the a-oxy carboxylate (L) represented by Structure (VII) can be selected from the group consisting of pyruvic acid, 3-methylpyruvic acid, 3,3-dimethylpyruvic acid, 3,3-dimethyl-2- oxobutanoic acid, 3,3-dimethyl-2-oxopentanoic acid, and 2,3-dioxosuccinic acid.
- the "P” compound of Structure (V) is a 5- or 6-membered N- heteroaromatic compound such as a 6-membered N-heteroaromatic compound.
- Such 5- or 6-membered N-heteroaromatic compounds can have a pK a of at least 10 and up to and including 22.
- An experimental method for measuring pK a and the pK a values of some N-heteroaromatic bases are known (for example, see Kalijurand et al. J. Org. Chem. 2005, 70, 1019).
- each 5- or 6-membered N-heteroaromatic compound is non-polymeric in nature and has a molecular weight of 200 or less.
- N-heteroaromatic compound has either 5 or 6 atoms in the heterocyclic aromatic ring, at least one of which atoms is a nitrogen atom.
- such heterocyclic aromatic rings generally have at least one carbon atom and at least one nitrogen atom in the ring.
- c is 1, 2, 3, or 4, and in the embodiments where c is 2, 3, or 4, the multiple 5- or 6-membered N- heteroaromatic compound molecules within the single complex molecule can be the same or different.
- the 5- or 6-membered N-heteroaromatic compound can be selected from the group consisting of pyridine, 2- methylpyridine, 4-methylpyridine, 2,6-dimethylpyridine, 2,3 -dimethylpyri dine, 3,4-dimethylpyridine, 4 -pyridyl acetone, 3-chloropyridine, 3-fluoropyridine, oxazole, 4-methyloxazole, isoxazole, 3-methylisoxazole, pyrimidine, pyrazine, pyridazine, and thiazole.
- Representative 5- or 6-membered N-heteroaromatic compounds can be readily obtained from various commercial chemical suppliers located in various countries.
- Still other useful silver complexes are designed with one or two (b) reducible silver ions as described above for the (iv) silver complexes, complexed with both one or two a-oxy carboxylate molecules as described above for the (iv) silver complexes, and one, two, three, or four primary alkylamine molecules.
- such useful silver complexes can be represented by the following Structure (VIII):
- L represents the a-oxy carboxylate
- P represents the primary alkylamine
- a is 1 or 2
- b is 1 or 2
- c is 1, 2, 3, or 4, provided that when a is 1, b is 1, and when a is 2, b is 2.
- P is a primary alkylamine having a boiling point of less than or equal to 175°C, or having a boiling point of less than or equal to 125°C, or even at least 75°C and up to and including 125°C, at atmospheric pressure.
- the useful primary alkyl amines that generally have a molecular weight of less than 500 and are thus considered "non-polymeric" as defined by molecular weight and boiling point.
- primary alkylamine refers herein to compounds that are non-aromatic and are not cyclic in structure. They generally have one or more nitrogen atoms as long as all other features (molecular weight, pKa, boiling point, and oxidation potential) described herein are met. In such compounds, each of the nitrogen atoms has two valences filled by hydrogen atoms and the remaining valence of each nitrogen atom is filled with a substituted or unsubstituted alkyl group (not including alkylaryl groups such as benzyl groups), or with a substituted or unsubstituted alkylene group for compounds defined herein as "primary alkyl diamines" that can be illustrated by the following Structure (IX):
- R5 represents a substituted or unsubstituted, branched or linear, divalent alkylene group having 1 to 5 carbon atoms; and optional substituents include but are not limited to, fluoride atoms for any of the hydrogen atoms in the alkylene group.
- the primary alkyl amines comprise a single nitrogen atom and a single substituted or unsubstituted, branched or linear alkyl group having at least 3 carbon atoms, and generally from 3 to 6 carbon atoms, wherein any of the hydrogen atoms of the alkyl group can be replaced with a fluorine atom.
- Representative useful primary alkylamines can be selected from the group consisting of a propylamine, «-butylamine, t-butylamine, isopropylamine, 2,2,2-trifluoroethylamine, 2,2,3,3,3-pentafluoropropylamine, 3,3,3- trifluoropropylamine, 1,2-dimethylpropylamine, t-amyl amine, and
- isopentylamine isopentylamine.
- Other useful primary alkylamines would be readily apparent to one skilled in the art.
- the primary amine has an
- asymmetric carbon center on an alkyl chain Some examples of such amines include but not limited to, a 2-amino-3-methylbutane, 3,3-dimethyl-2-butylamine, 2-aminohexane, sec-butylamine, and others that would be readily apparent to one skilled in the art from the foregoing description.
- Such primary alkylamines can be substituted with other groups that would be readily apparent to one skilled in the art.
- Useful primary alkyl amines can be readily obtained from various worldwide commercial sources of chemicals.
- each useful silver complex can be represented by the following Structure X):
- L represents the a-oxy carboxylate
- P represents an oxime compound
- b is 1 or 2
- c is 1, 2, 3, or 4, provided that when a is 1, b is 1, and when a is 2, b is 2.
- the "P" compound is an oxime compound (or a mixture of two or more different oxime compounds).
- the term “oxime compound” is meant to include such compounds as well as compounds in which the hydrogen is replaced with a suitable monovalent radical.
- the oxime compounds useful herein are not polymeric in nature and each has a molecular weight of 200 or less, or of 150 or less.
- c is 1, 2, 3, or 4, and in the embodiments where c is 2, 3, or 4, the P molecules within the single complex molecule can be the same or different oxime compounds.
- P can be an oxime compound that can be represented by the following Structure (XI):
- Rs and R 6 are independently hydrogen or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms (linear or branched), provided that at least one of Rs and R 6 is one of such alkyl groups.
- Rs and R 6 can together represent the carbon atoms sufficient to provide a substituted or unsubstituted 5- or 6-membered, saturated carbocyclic ring, such as a substituted or unsubstituted pentane ring or substituted or unsubstituted cyclohexane ring.
- oxime compounds useful in the practice of the present invention include but are not limited to, acetoxime (acetone oxime), acetaldoxime, Aldicarb, dimethylglyoxime, methylethyl ketone oxime, propionaldehyde oxime, cyclohexanone oxime, cyclopentanone oxime, heptanal oxime, acetone-O-methyl oxime, acetaldehyde-O-methyl oxime,
- the amounts of the (b) reducible silver ions can be varied depending upon the particular manner in which the composition is to be used.
- the (b) reducible silver ions are present at a weight ratio to the one or more (a) polymers of at least 5: 1 and up to and including 50: 1, or even at least 5: 1 and up to and including 20: 1, as described above.
- each (c) organic solvent used in the non-aqueous silver precursor composition or the non-aqueous silver-containing dispersion has a boiling point greater than or equal to 90°C, or at least 100°C, at least 150°C and at least > 200°C but generally less than 500°C. If two or more different organic solvents are used, the difference of the boiling points of any two organic solvents can be greater than >10°C.
- the (c) organic solvents useful in the practice of this invention can be selected to have a total Hansen parameter that is compatible with the total Hansen parameter of the one or more (a) polymers (such as one or more cellulosic polymers) that are to be incorporated into the silver nanoparticle composite. It is desirable that the total Hansen parameters of the one or more (a) polymers and the one or more (c) organic solvents lie within a certain range, and it is especially desirable to maintain the desired total Hansen parameter as the organic solvent profile changes during the deposition processes.
- the (c) organic solvents have a total Hansen parameter equal to or greater than the total Hansen parameter of the one or more (a) polymers (such as one or more cellulosic polymers).
- the total Hansen parameter of the organic solvent mixture is equal to or greater than the total Hansen parameter of the one or more (a) polymers (such as one or more cellulosic polymers) to be incorporated within the silver nanoparticle composite.
- Some useful dispersions comprise organic solvent blends that maintain desirable total Hansen parameters even as the (c) organic solvents are removed during and after the deposition processes (described below).
- the (a), (b), and (d) components are dispersed or dissolved in an (c) organic solvent medium that consists of one or more organic solvents described herein, and especially one or more hydroxylic organic solvents, each of which has an a-hydrogen atom and properties defined below. It is particularly useful that the (a) polymer(s) are soluble in the one or more (c) organic solvents.
- Useful hydroxylic solvents can be alcohols having an a-hydrogen atom. Accordingly, primary and secondary alcohols are useful and they can be monohydric or polyhydric. While either saturated or unsaturated alcohols can be used, it is desirable that the alcohol used be free from olefinic unsaturation.
- Suitable alcohols can be of either straight-chain or branched-chain configuration, and can contain in their structure either or both of alicyclic or aromatic carbon-to- carbon moieties.
- suitable straight-chain primary alcohols include but are not limited to, ethanol, «-propanol, «-butanol, «-pentanol, «-hexanol, 1-octanol, 2-ethyl-l-hexanol, «-decanol, ethylene glycol, propylene glycol, and benzyl alcohol.
- Representative examples of branched-chain alcohols include isobutyl alcohol, isoamyl alcohol, and secondary butyl carbinol.
- Secondary alcohols have greater reactivity.
- Representative examples of secondary alcohols include but are not limited to, isopropyl alcohol, secondary butyl alcohol, secondary amyl alcohol, diethyl carbinol, methyl isobutyl carbinol, methyl-3- heptanol, diisobutyl carbinol, dodecanol-Z, methyl allyl carbinol, cyclohexanol, methyl cyclohexyl carbinol, phenyl methyl carbinol, and similar materials.
- glycol ethers with both an ether and alcohol functional group in the same molecule are particularly useful in the practice of the present invention.
- Representative examples of such glycol ethers include but are not limited to, 2- methoxyethanol, 2-ethoxyethanol, diethylene glycol monoethyl ether (carbitol), and methoxy isopropanol. Mixtures of these compounds can be used if desired.
- Such glycol ethers are commercially available.
- Another essential component of the non-aqueous silver precursor compositions according to the present invention is a nitrogenous base having a pKa in acetonitrile of at least 15 and up to and including 25 at 25°C.
- Such one or more nitrogenous bases are generally present in an equimolar amount or molar excess relative to the amount of (b) reducible silver ions, described above.
- the nitrogenous bases can be cyclic or acyclic alkyl amines. All primary amines, secondary amines, or tertiary amines are useful in the present invention. Some especially useful amines are 1,4- diazabicyclo[2.2.2]octane (DABCO), cyclohexylamine, pipperidine, N-methyl pipperidine, N-methyl-3-piperidinol, and others that would be readily apparent to one skilled in the art. Combinations of two or more of these compounds can be used if desired.
- DABCO 1,4- diazabicyclo[2.2.2]octane
- the nitrogenous base can be an alkanolamines including but are not limited to, ethanol amine, 2-(ethylamino)ethanol, 2-(methylamino)ethanol, 2- (butylamino)ethanol, methyldiethanolamine (MDEA), diethanolamine (DEA), diglycolamine (DGA), diethylaminoethanol (DEAE), and others that would be readily apparent to one skilled in the art. Combinations of two or more of these compounds can be used if desired.
- alkanolamines including but are not limited to, ethanol amine, 2-(ethylamino)ethanol, 2-(methylamino)ethanol, 2- (butylamino)ethanol, methyldiethanolamine (MDEA), diethanolamine (DEA), diglycolamine (DGA), diethylaminoethanol (DEAE), and others that would be readily apparent to one skilled in the art. Combinations of two or more of these compounds can be used if desired.
- Nitrogen-containing heterocyclic compounds are also useful as nitrogenous bases in the present invention.
- Such compounds can be are aromatic and heterocyclic in nature and comprise at least one nitrogen atom in the aromatic heterocyclic ring.
- Such compounds can also be substituted or unsubstituted as desired.
- aromatic heterocyclic, nitrogen-containing bases useful in this invention include but are not limited to, substituted or unsubstituted, non- polymeric pyridine, picolines, lutidines, quinoline, purine, isoquinoline, imidazole, benzimidazole, benzthiazole, thiazole, oxazole, benzoxazole, 4,4'- bipyridine, pyrazine, triazine, pyrimidine, nicotinic acid, and isonicotinic acid compounds. Mixtures of two or more these or other unnamed compounds can be used if desired, in any useful proportion.
- the substituted or unsubstituted pyridines are particularly useful.
- ami dines such as 1,8- diazabicyclo[5.4.0]undec-7-ene (DBU).
- the nitrogenous base has a pKa of at least 15 and up to and including 20, or more typically of at least 18 and up to and including 25, as measured in acetonitrile.
- An experimental method for measuring pKa, and the pKa values of some aromatic heterocyclic and amine nitrogenous bases are known (for example, see Kalijurand et al. J. Org. Chem. 2005, 70, 1019; and Cantu et al. Journal of Chromatography A, 2005, 1068, 99).
- each nitrogenous base used in the present invention is in liquid form and has a boiling point equal to or higher than each of the one or more (c) organic solvents, for example, each of the one or more hydroxylic solvents.
- the boiling point of the nitrogenous base at atmospheric pressure is at least 100°C and up to but less than 500°C, or at least 120°C and up to and including 350°C, or up to and including 250°C.
- Non-Aqueous Silver-Containing Dispersions can be readily obtained from commercial sources.
- reducible silver ions in a non-aqueous silver precursor composition according to the present invention can be converted into silver nanoparticles in silver nanoparticle composites to provide a corresponding non- aqueous silver-containing dispersion using the operations described below for the methods according to this invention.
- Such non-aqueous silver-containing dispersions comprise one or more silver nanoparticle composites, each comprising silver and one or more of the (a) polymers described above.
- the amount of such silver nanoparticle composites in the non-aqueous silver-containing dispersion would generally be the total weight of silver and (a) polymers in the non-aqueous silver-containing dispersion but it could be less, depending upon how much of the (b) reducible silver ions are reduced and how much free silver, (b) reducible silver ions, and free (a) polymers are present in the non-aqueous silver-containing dispersion after silver ion reduction, silver nanoparticle composite isolation, and re-dispersion (described below).
- the non-aqueous silver- containing dispersion would contain silver in an amount of up to and including 100 mol % of the original (b) reducible silver ions in the non-aqueous silver precursor composition.
- the non-aqueous silver-containing dispersion contains one or more (c) organic solvents (such as hydroxylic organic solvents) as described above.
- organic solvents can be same or different as those used to make the non- aqueous silver precursor compositions.
- organic solvents can be those originally in the non-aqueous silver precursor composition (that is, before isolation and re-dispersion of the silver nanoparticle composite), or they can be added during re-dispersion of the silver nanoparticle composite.
- Nitrogenous base is also generally present in the non-aqueous silver-containing dispersion although much of the original amount that was present in the non-aqueous silver precursor composition may be washed out during isolation of the silver nanoparticle composite. However, it is evident that some (d) nitrogenous base remains with the silver nanoparticle composite upon its re-dispersion in one or more (c) organic solvents. The amount of such
- nitrogenous base(s) in the non-aqueous silver-containing dispersion is generally up to and including 10 weight %, based on the total weight of silver metal (not including any remaining reducible silver ions).
- (e) carbon black can be incorporated into the non-aqueous silver-containing dispersions at a suitable time.
- Carbon black can be obtained commercially in various forms.
- the (e) carbon black can be added so that it is present in an amount of at least 5 weight %, based on (or relative to) the total weight of the one or more (a) polymers.
- the amount of (e) carbon black is at least 5 weight % and up to and including 50 weight %, or more typically in an amount of at least 5 weight % and up to and including 25 weight %, based on (or relative to) the total weight of the one or more (a) polymers.
- non-aqueous silver-containing dispersions prepared according to the present invention can be used to provide articles that can then be used in various operations or devices.
- An article is typically designed to have a substrate having thereon a dry layer or dry pattern comprising a silver nanoparticle composite composition.
- the article has silver nanoparticles and no appreciable amounts of (b) reducible silver ions. That is, the (b) reducible ions are generally present in an amount of less than 5 mol %, based on the total amount of silver in the dry layer or dry pattern.
- each article comprises a substrate (described below), and can have disposed on at least one supporting surface (or side) thereof a dry layer or dry pattern of a dry silver nanoparticle composite composition comprising:
- a silver nanoparticle composite comprised of silver and one or more (a) polymers selected from one or more of cellulose acetate, cellulose acetate phthalate, cellulose acetate butyrate, cellulose acetate propionate, cellulose acetate trimellitate, hydroxypropylmethyl cellulose phthalate, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropylmethyl cellulose, carboxymethyl cellulose, and combinations thereof; and one or more nitrogenous bases as described above.
- polymers selected from one or more of cellulose acetate, cellulose acetate phthalate, cellulose acetate butyrate, cellulose acetate propionate, cellulose acetate trimellitate, hydroxypropylmethyl cellulose phthalate, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropylmethyl cellulose, carboxymethyl cellulose, and combinations thereof; and one or more nitrogenous bases as described above.
- These silver nanoparticle composites generally have a mean particle size (d50) of at least 10 nm and up to and including 1500 nm, or of at least 20 nm and up to and including 500 nm, or even of at least 50 nm and up to and including 350 nm.
- d50 mean particle size
- Carbon black can also be present in the dry silver nanoparticle composite composition in an amount of up to and including 50 weight %, or at least 5 weight % and up to and including 50 weight %, or even at least 5 weight % and up to and including 25 weight %, all based on (or relative to) the total weight of the one or more (a) polymers.
- Such dry layers or dry patterns generally contain less than 5 mol %, or less than 2 mol %, or even less than 1 mol %, of (b) reducible silver ions, all based on the total molar amount of silver in the dry pattern or dry layer.
- At least one of the patterns can comprise a combination of fine lines, each fine line having an average dry width of at least 1 ⁇ and up to and including 20 ⁇ , which combination of fine lines can be arranged in parallel, crossing at any desired angle, a combination thereof, or in a random arrangement.
- Each dry pattern can be designed to have any
- predetermined grid pattern that can be achieved in the art.
- the presence of the (e) carbon black in the dry patterns is particularly advantageous when the substrate (described in detail below) is transparent, such as a transparent continuous polymeric film (for example a transparent continuous polycarbonate, polystyrene, or polyester film).
- a transparent continuous polymeric film for example a transparent continuous polycarbonate, polystyrene, or polyester film.
- the substrate has a first supporting surface (or side) and a second opposing supporting surface (or side), and one or more dry patterns of the silver nanoparticle composite composition are disposed on the first supporting surface, and optionally, one or more dry patterns of the same or different silver nanoparticle composite composition are disposed on the second opposing supporting surface.
- the dry patterns can be disposed on the two opposing supporting surfaces of the substrate in any opposing arrangement, that is either directly opposite one another, or offset in some desired arrangement.
- the substrate is a transparent continuous polymeric (such as polyester) film (or web) that has a first supporting surface and a second opposing supporting surface,
- the article further comprising multiple (two or more) individual dry patterns formed on the first supporting surface comprise the same or different silver nanoparticle composite composition, and further comprising multiple (two or more) individual dry patterns formed on the second opposing supporting surface which opposing multiple dry patterns comprise the same or different silver nanoparticle composite composition.
- all of the multiple individual dry patterns on both the first supporting surface and the second opposing supporting surface can comprise the same silver nanoparticle composite composition
- the silver nanoparticle composite composition in each individual dry pattern comprises silver nanoparticle composite(s) having a mean particle size (d50) of at least 50 nm and up to and including 300 nm
- each of the multiple individual dry patterns comprises fine lines having an average dry width of at least 1 ⁇ and up to and including 20 ⁇ .
- the articles described herein comprise a suitable substrate that generally has two planar surfaces: a first supporting side (or surface) and a second opposing supporting side (or surface).
- Such substrates can have any suitable form such as sheets of any desirable size and shape, webs of metals, films, and elongated fibers or woven fibers (such as in webs of textiles) or other porous materials, and especially continuous webs of various transparent, translucent, or opaque polymeric materials (such as polycarbonates and polyesters) that can be supplied, used, or stored as rolls.
- Such continuous webs or films can be used in continuous roll-to-roll manufacturing operations where the continuous web is unrolled from a supply roll and taken up using a take-up roll.
- a uniform thin film or one or more thin film patterns of a silver nanoparticle composite composition are provided in a suitable manner on one or more supporting sides of a suitable substrate to provide an article as described according to the methods described below.
- such articles have an initially "wet" non-aqueous silver-containing dispersion layer or pattern during and immediately after application to the substrate but the hydroxylic organic solvents can be removed as described below to provide the desired uniform thin film layer or one or more thin film patterns.
- Suitable substrates can be composed of any suitable material that does not inhibit the purpose of the present invention and eventual uses of the articles.
- substrates can be formed from materials including but are not limited to, polymeric films, metals, glasses (untreated or treated for example with tetrafluorocarbon plasma, hydrophobic fluorine, or a siloxane water-repellant material), silicon or ceramic materials such as ceramic wafers, fabrics, papers, and combinations thereof (such as laminates of various films, or laminates of papers and films) provided that a uniform thin film or thin film pattern can be formed thereon in a suitable manner and followed by thermal treatment (heating) on at least one supporting surface thereof.
- the substrate can be transparent, translucent, or opaque, and rigid or flexible.
- the substrate can include one or more auxiliary polymeric or non-polymeric layers or one or more patterns of other materials before the non-aqueous dispersion is applied according to the present invention.
- suitable substrate materials for forming precursor and product articles according to the present invention include but are not limited to, metallic films or foils, metallic films on polymer, glass, or ceramic materials, metallic films on electrically conductive film supports, semi-conducting organic or inorganic films, organic or inorganic dielectric films, or laminates of two or more layers of such materials.
- Useful substrates can include transparent polymeric films such as poly(ethylene terephthalate) films, poly(ethylene naphthalate) films, polyimide films, polycarbonate films, polyacrylate films, polystyrene films, poly olefin films, and polyamide films, silicon and other ceramic materials, metal foils such as aluminum foils, cellulosic papers or resin- coated or glass-coated papers, glass or glass-containing composites, metals such as aluminum, tin, and copper, and metalized films. Porous fabrics, glasses, and polymeric webs can also be used.
- Useful continuous flexible polymers films include transparent continuous polymeric films such as transparent continuous polyester films such as films of poly(ethylene terephthalate), polycarbonate films, or poly(vinylidene chloride) films with or without surface- treatments or coatings as noted below.
- either or both supporting surfaces of the substrate can be treated with a primer layer or receptive layer, or with electrical or mechanical treatments (such as graining) to improve adhesion of the silver nanoparticle composite composition.
- An adhesive layer can be thermally activated, solvent activated, or chemically activated.
- a separate receptive layer can have any suitable dry thickness of at least 0.05 ⁇ when measured at 25°C.
- the two supporting surfaces of the substrate can be treated by exposure to corona discharge, mechanical abrasion, flame treatments, or oxygen plasmas, or coated with various polymeric films, such as poly(vinylidene chloride) or an aromatic polysiloxane.
- Useful substrates can have a desired dry thickness depending upon the eventual use of the articles. For example, the substrate dry thickness
- the substrate dry thickness can be at least 0.008 mm and up to and including 0.2 mm.
- the substrate used in the articles described herein can be provided in various forms, such as for example, individual sheets of any size or shape, and continuous webs such as continuous webs of transparent substrates (including transparent continuous polyester films).
- continuous webs can be divided or formed into individual first, second, and additional portions on a first supporting surface and a second opposing supporting surface on which can formed the same or different corresponding silver nanoparticle composite composition patterns in the different (or individual) portions of a supporting side (such as the first supporting sides).
- Non-aqueous silver-containing dispersions according to the present invention comprising the silver nanoparticle composite described above can be provided using either of two methods (Methods I and II) according to the present invention.
- Methods I and II the one or more (a) polymers (as described above) are mixed (or dissolved) in one or more (c) organic solvents (described above) using suitable stirring and mixing conditions.
- one or more (d) nitrogenous base(s) (as described above) are mixed within the one or more (c) organic solvents (as described above) along with the one or more (a) polymers (as described above), to form a premix solution.
- This premix solution can be heated to a temperature of at least 75°C and more likely to a temperature of at least 75°C and up to and including 125°C using any suitable heating means. During this heating operation, the premix solution can be continuously stirred using suitable stirring mechanism or apparatus.
- a solution of (b) reducible silver ions in any silver ion-containing form as described above) in one or more (c) organic solvents (same or different from those already in premix solution) can be added to the premix solution.
- the rate of addition of (b) reducible silver ions can be varied, for example, by using a peristaltic pump. This addition process is generally at a rate sufficient at the noted temperature to promote the extensive reduction of the (b) reducible silver ions, for example at least 90 mol % reduction based on the original amount of (b) reducible silver ions.
- the final amount of added (b) reducible silver ions in the premix solution is equimolar or less in relation to the (d) nitrogenous base(s) present in the premix solution.
- the final weight ratio of the (b) reducible silver ions to the one or more (a) polymers is at least 5: 1 and up to and including 50: 1, or at least 60: 1 and up to and including 75: 1.
- reducible silver ions in any silver ion containing-form as described above
- This premix solution can be heated to a temperature of at least 75°C and more likely to a temperature of at least 75°C and up to and including 125 °C using any suitable heating means. Stirring can also be carried out during this heating operation using any suitable stirring mechanism or apparatus and in the following addition of the (d) nitrogeneous base(s).
- This addition process is generally at a rate sufficient at the noted temperature to promote the extensive reduction of the (b) reducible silver ions, for example at least 80 mol % reduction based on the original amount of (b) reducible silver ions.
- the final amount of added (d) nitrogenous base(s) in the premix solution is equimolar or in molar excess in relation to the (b) reducible silver ions present in the premix solution.
- the result of this addition operation is the relatively rapid formation of one or more silver nanoparticle composites in a reaction mixture.
- carbon black is to be included in the non-aqueous silver- containing dispersion, it can be incorporated and dispersed within at any suitable point during either Method I or Method II in appropriate amounts described above using a suitable mixing means such as a shear mixer.
- a suitable mixing means such as a shear mixer.
- shear mixers are commercially available from various sources such as Silverson, Admix, and Ross.
- the resulting silver nanoparticle composite in the reaction mixture can be cooled generally to room temperature.
- the cooled silver nanoparticle composite is then isolated from the reaction mixture by either of the following two methods: 1) gravity precipitation followed by filtration of the precipitate; or
- the isolated silver nanoparticle composite can be dried, if desired, and stored for later use.
- the silver nanoparticle composite can be immediately re-dispersed in one or more suitable (c) organic solvents (same as or different from those used above) to provide a non-aqueous silver-containing dispersion containing up to 80 weight % of silver nanoparticle composite.
- Particularly useful (c) organic solvents used for this dispersing operation have a total Hansen parameter that is compatible with the total Hansen parameter of the one or more (a) polymers (such as one or more cellulosic polymers) that have been incorporated into the silver nanoparticle composite.
- these (c) organic solvents have a total Hansen parameter equal to or greater than the total Hansen parameter of the one or more (a) polymers (such as one or more cellulosic polymers).
- the total Hansen parameter of the organic solvent mixture is equal to or greater than the total Hansen parameter of the one or more (a) polymers (such as one or more cellulosic polymers) that have been incorporated within the silver nanoparticle composite.
- non-aqueous silver-containing dispersion resulting from the method described herein can be stored for later use or immediately employed in various additional operations, for example, to provide an article as described above.
- a non-aqueous silver-containing dispersion can be disposed onto a substrate (as described above) using any suitable equipment and method as described below, and the one or more (c) organic solvents can be removed in a suitable manner.
- the non-aqueous silver-containing dispersion disposed onto one or more supporting sides of a substrate to provide, upon drying, either a dry uniform film (usually thin), or one or more dry patterns of silver nanoparticle composite composition.
- Disposition of the non-aqueous silver- containing dispersion can be achieved in a variety of means known in the art for applying solutions or dispersions to a solid substrate.
- a variety of films including polymeric films composed of polyethylene, polypropylene, biaxially-oriented polypropylene, polyethylene terephthalate, polybutylene terephthalate and polyamide, can be utilized as suitable transparent substrates.
- the choice of substrate structure is not, however, limited to films but includes any material that can be formed into bags, shrink wrap, plates, cartons, boxes, bottles, crates, and other containers.
- the disposition on or application to a substrate can be carried out for example, using uniform inkjet printing, gravure printing, screen printing, flexographic printing, or by using a blade coating, gap coating, slot die coating, X- slide hopper coating, or knife on roll operations.
- a non-aqueous silver-containing dispersion can be disposed on the substrate (one or both supporting surfaces) in a patternwise manner using techniques described below such as flexographic printing, screen printing, gravure printing, or inkjet printing to provide one or multiple (two or more) silver nanoparticle composite composition patterns on the substrate.
- the method according to this invention can also comprise disposing the non-aqueous silver-containing dispersion containing the silver nanoparticle composite onto the substrate in a patternwise manner to form at least one pattern (or multiple patterns) of the non-aqueous silver-containing dispersion on at least the first supporting side.
- the method according to the present invention is also possible for the method according to the present invention to be used to further dispose the same or different non-aqueous silver-containing dispersion onto the substrate in a patternwise manner to form multiple patterns of the non-aqueous silver-containing dispersion on the second opposing supporting side, or in a manner to form multiple patterns of a non-aqueous silver-containing dispersion on both the first supporting side and the second opposing supporting side using one or more flexographic printing members.
- the present invention lends itself to rapid conversion of (b) reducible silver ions to electrically-conductive silver metal in an economical way so the process can be incorporated into the manufacture of various devices containing electrically-conductive silver patterns. Such operations can often be achieved using a substrate that is a continuous web that is unrolled from a supply roll and is taken up using a take-up roll, and the method is carried out in a continuous roll-to-roll manner.
- Any applied pattern of silver nanoparticle composite composition can comprise a grid of electrically-conductive fine lines (or other shapes including circles or an irregular network) as described above and the optimal dry thickness (or width) can be tailored for an intended use.
- the same or different silver nanoparticle composite pattern (after drying) can be provided in a suitable manner in different portions on both the first supporting side and the second opposing supporting side of the substrate to form a "duplex" or dual-sided article, and such patterns can be provided using the same or different non-aqueous silver-containing dispersion.
- a non-aqueous silver-containing dispersion can be applied on one or both supporting surfaces of the substrate (for example as a roll-to-roll web) using flexographic printing with one or more elastomeric relief elements such as those derived from flexographic printing plate precursors, many of which are known in the art.
- Some such precursors are commercially available, for example as the CYREL ® Flexographic Photopolymer Plates from DuPont and the Flexcel SR and NX Flexographic plates from Eastman Kodak Company.
- Useful elastomeric relief elements are derived from flexographic printing plate precursors and flexographic printing sleeve precursors, each of which can be appropriately imaged (and processed if needed) to provide the elastomeric relief elements for "printing" suitable electrically-conductive silver nanoparticle composite patterns.
- Useful precursors of this type are described for example, in U.S. Patents 7,799,504 (Zwadlo et al.) and 8,142,987 (Ali et al.) and U.S. Patent Application Publication 2012/0237871 (Zwadlo).
- Such flexographic printing precursors can comprise elastomeric photopolymerizable layers that can be imaged through a suitable mask image to provide an elastomeric relief element (flexographic printing plate or flexographic printing sleeve).
- the resulting relief layer can be same or different depending upon whether the same or different patterns are to be formed on one or both supporting sides of the substrate.
- an elastomeric relief element can be provided from a direct (or ablation) laser-engraveable elastomeric relief element precursor, with or without integral masks, as described for example in U.S.
- Patents 5,719,009 (Fan), 5,798,202 (Cushner et al.), 5,804,353 (Cushner et al.), 6,090,529 (Gelbart), 6,159,659 (Gelbart), 6,511,784 (Hiller et al.), 7,811,744 (Figov), 7,947,426 (Figov et al.), 8, 114,572 (Landry-Coltrain et al.), 8,153,347 (Veres et al.), 8,187,793 (Regan et al.), and U.S.
- Patent Application Publications 2002/0136969 (Hiller et al.), 2003/0129530 (Leinenback et al.), 2003/0136285 (Telser et al.), 2003/0180636 (Kanga et al.), and 2012/0240802 (Landry-Coltrain et al.).
- the non-aqueous silver-containing dispersion can be applied in a suitable manner to the uppermost relief surface (raised surface) in the elastomeric relief element. Then, application to a substrate can be accomplished in a suitable procedure while as little as possible is coated from the sides (slopes) or recesses of the relief depressions.
- Anilox roller systems or other roller application systems, especially low volume Anilox rollers, below 2.5 billion cubic micrometers per square inch (6.35 billion cubic micrometers per square centimeter) and associated skive knives can be used.
- the non-aqueous silver- containing dispersion can be designed to have optimal viscosity for flexographic printing. When a substrate is moved through the roll-to-roll handling system from a flexographic printing plate cylinder to an impression cylinder, the impression cylinder applies pressure to the flexographic printing plate cylinder that transfers an image from an elastomeric relief element to the substrate.
- a substrate can be "printed" one or more times using inkjet printing, gravure printing, screen printing, or flexographic printing along a web (for example, a roll-to-roll continuous web) that can contain multiple patterns (or individual precursor articles after cutting) in multiple portions of the continuous web that is passed through various stations.
- a web for example, a roll-to-roll continuous web
- the same or different non-aqueous silver-containing dispersions can be applied (for example, printed) on one or both supporting sides of the substrate in the continuous roll-to-roll production operation.
- At least 75 weight % and up to and including 100 weight % of the (c) organi solvent(s) can be removed in any suitable manner to form an article.
- ambient drying can be carried out in an open environment, or the article can be subject to "active" drying operations and apparatus (for example, heated drying chamber).
- Useful drying conditions can be as low as room temperature for as little as 5 seconds and up to and including several hours depending upon the manufacturing process.
- drying conditions can be employed at any suitable temperature, for example greater than 50 °C to remove at least 75 weight % and up to 100 weight % of all remaining organic solvents within at least 1 second and up to and including 10 seconds or even within 5 seconds.
- a method comprising, in sequence:
- reducible silver ions present in an amount of a weight ratio of (b) reducible silver ions to the one or more (a) polymers of at least 5: 1 and up to and including 50: 1;
- the one or more (c) organic solvents is one or more hydroxylic organic solvents each having an a-hydrogen atom and is chosen from the group consisting of ethanol, n- propanol, «-butanol, «-pentanol, «-hexanol, «-octanol, 2-ethyl-l-hexanol, n- decanol, ethylene glycol, propylene glycol, benzyl alcohol, isobutyl alcohol, isoamyl alcohol, secondary butylcarbinol, isopropyl alcohol, secondary butyl alcohol, secondary amyl alcohol, diethyl carbinol, methyl isobutyl carbinol, methyl-3-heptanol, diisobutyl carbinol, dodecanol-Z, methyl allyl carbinol, cyclohexanol, methyl cyclohexyl carb
- the nitrogenous base is an aromatic cyclic compound.
- the nitrogenous base is selected from the group consisting of 1,4- diazabicyclo[2.2.2]octane (DABCO), cyclohexylamine, piperidine, N-methyl pipperidine, N-methyl-3 -piped dinol, ethanol amine, 2-(ethylamino)ethanol, 2- (methylamino)ethanol, 2-(butylamino)ethanol, methyldiethanolamine (MDEA), diethanolamine (DEA), diglycolamine (DGA), diethylaminoethanol (DEAE), substituted or unsubstituted non-polymeric pyridine, picolines, lutidines, quinoline, purine, isoquinoline, imidazole, benzimidazole, benzthiazole, thiazole, oxazole, benzoxazole, 4,4'-bipyr
- DABCO 1,4- diazabicyclo[2.2.2]octane
- non-aqueous silver-containing dispersion further contains (e) a carbon black.
- a silver nanoparticle composite comprising silver and one or more (a) polymers selected from one or more of cellulose acetate, cellulose acetate phthalate, cellulose acetate butyrate, cellulose acetate propionate, cellulose acetate trimellitate, hydroxypropylmethyl cellulose phthalate, methyl cellulose, ethyl cellulose, hydroxy ethyl cellulose, hydroxypropylmethyl cellulose, and
- carboxymethyl cellulose wherein silver is present in the silver nanoparticle composite at a weight ratio to the one or more (a) polymers of at least 5: 1 and up to and including 50: 1;
- a nitrogenous base having a pKa in acetonitrile of at least 15 and up to and including 25 at 25°C, the nitrogenous base being present in an equimolar amount or molar excess in relation to the amount of silver.
- the median silver nanoparticle composite particle diameter [Dv (50%)] was 90 nm. (see FIG. 1).
- the silver content of the silver nanoparticle-cellulose acetate composite was measured using thermogravimetric analysis (TGA) using a small amount of obtained gray solid that was scanned at temperatures ranging from room temperature to 700°C in air. Organic materials are burnt and removed during the TGA scan. The residual weight at 700°C corresponded to the amount of silver in the solid. Consistent with the starting weight ratios, the gray solid comprised 89% by weight of silver and 11% weight total of cellulose acetate and nitrogenous base.
- the cooled gray-colored silver nanoparticle composite (4 g) thus obtained was added to 1-methylamino ethanol (10 ml) and re-dispersed by using a a high shear mixer (Silverson L4R) to provide a non-aqueous silver-containing dispersion containing containing the silver nanoparticle composite at 40 weight %.
- a pattern of fine lines of nominal width of 7-10 ⁇ was successfully formed from this non-aqueous silver-containing dispersion on a poly(ethylene terephthalate) film substrate using a flexographic test printer IGT Fl and flexographic printing members obtained from commercially available Kodak Flexcel NX photopolymer plates that had been imaged using a mask that was written using the Kodak Square Spot laser technology at a resolution of 12,800 dpi.
- a TE-TGS detector was used for IR detection. The data showed an initial weight loss of about 0.24% due to water as the sample was initially heated. From about 105°C into the isotherm at 150°C, a weight loss of 0.21% is seen due to the nitrogenous base. As the dispersion was heated to 250°C, a weight loss of about 0.7% was seen due to carbon dioxide and propionic acid, possibly mixed with an ester. A major weight loss of >5% was seen above 250°C due to a mixture of carbon dioxide, carbon monoxide, water, and what is likely cellulose acetate propionate.
- the gray colored silver nanoparticle composite (6 g) thus obtained was added to l-methoxy-2-propanol (10 ml) and re-dispersed using a a high shear mixer (Silverson L4R) to obtain a non-aqueous silver-containing dispersion containing 60 weight % silver nanoparticle composite.
- a pattern of lines of nominal width 2-20 mm was successfully formed from this non-aqueous silver-containing dispersion were on a
- a mixture of cellulose acetate propionate (0.375 g; Aldrich, Mol. wt. of 50,000, Acetyl content 39%) and 2- methoxyethanol (7 ml) was heated at 85°C with stirring until all cellulose acetate propionate was dissolved.
- a solution of silver nitrate (5 g) dissolved in 2- methoxyethanol (15 ml) was added into the reaction vessel and the resulting premix solution was stirred while being heated at 85°C.
- Particle size distribution was measured using a dynamic light scattering method (Malvern Instruments Ltd. Zetasizer Nano-ZS (ZEN) Dynamic Light Scattering or QELS: Quasi-Elastic Light Scatter).
- ZEN Zetasizer Nano-ZS
- QELS Quasi-Elastic Light Scatter
- ethyl cellulose [0.42 g, Scientific Polymer Products Cat#463 ethyl cellulose (10 cps), ethoxyl content 48%] was dissolved in 2-methoxyethanol (36.24 g) by stirring at 80°C for 30 minutes.
- 2-Methylamino ethanol (7.79 grams) was added to the solution as a nitrogenous base to form a premix solution.
- a solution of silver nitrate in 2- methoxy ethanol (105 g, 8 weight % silver salt) was then added to the premix solution over two hours. Heating and stirring were continued for another thirty minutes.
- the resulting slurry was poured into 800 ml water to form a precipitate that was filtered and dried.
- ZEN Particle Sizing of another aliquot of the premix solution prior to precipitation determined a silver nanoparticle composite particle size distribution having a mean size of 1200 nm.
- the resulting precipitate was re- dispersed in l-methoxy-2-propanol (50 % solids) using a a high shear mixer (Silverson L4R) to obtain a printable non-aqueous silver-containing dispersion.
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Abstract
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US15/713,786 US10246561B1 (en) | 2017-09-25 | 2017-09-25 | Method of making silver-containing dispersions with nitrogenous bases |
US15/713,795 US20190092647A1 (en) | 2017-09-25 | 2017-09-25 | Non-aqueous silver-containing dispersions |
PCT/US2018/050353 WO2019060166A1 (en) | 2017-09-25 | 2018-09-11 | Method of making silver-containing dispersions with nitrogenous bases |
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