Pesticidal compositions containing 4-phenoxyphenyl 2-(2-pyridyloxy)propyl ether and 2-(2,6-difluorophenyl)-4-(2-ethoxy-4-tert-butyl-phenyl)-2-oxazoline as active ingredients have excellent pesticidal efficacy.

The present invention relates to pesticidal compositions.
The development of pesticides has been widely carried out for the control of many kinds of pests including agricultural and forest pests and hygienically unfavorable pests, and a wide variety of chemical agents have been put to practical use. All conventional pesticides, however, cannot be said to give satisfactory results; for example, they may lack at least one of lethal efficacy, immediate effect, and residual effect, or they may have poor results on the specific kinds of pests or on the specific growth stage of pests. Accordingly, there has been a demand for the development of more excellent pesticides.
Under these circumstances, the present inventors have concentrated on the study and consequently found that pesticidal compositions comprising 4-phenoxyphenyl 2-(2-pyridyloxy)propyl ether and 2-(2,6-difluorophenyl)-4-(2-ethoxy-4-tert-butyl-phenyl)-2-oxazoline as active ingredients, when used to control agricultural and forest pests or hygienically unfavorable pests, can have unpredictably high pesticidal efficacy and exhibit excellent immediate effect and residual effect as compared with the separate application of each compound, making it possible to solve the above problems, which leads to the present invention.
Thus the present invention provides pesticidal compositions (hereinafter referred to as the present compositions) comprising 4-phenoxyphenyl 2-(2-pyridyloxy)propyl ether (hereinafter referred to as compound A) and 2-(2,6-difluorophenyl)-4-(2-ethoxy-4-tert-butyl-phenyl)-2-oxazoline (hereinafter referred to as compound B) as active ingredients; pest control methods comprising application of the present compositions to pests or their habitats; and plant protection methods comprising application of the present compositions to plants or their neighborhood, which may be infested with agricultural and forest pests.
The active ingredients in the present compositions are well known in the art; compound A (common name: pyriproxyfen) from U.S. Pat. No. 4,751,225 and compound B (common name: etoxazole) from WO 93/22297.
The present compositions can be applied as control agents against many kinds of pests including agricultural and forest pests and hygienically unfavorable pests. Specific examples of the pests which can be controlled by the present compositions are the following insects, acarines, and nematodes.
Hemiptera
Delphacidae such as Laodelphax striatellus, Nilaparvata lugens, and Sogatella furcifera; Deltocephalidae such as Nephotettix cincticeps and Nephotettix virescens; Aphididae such as Aphis gossypii, Myzus persicae, Aphis citricola, Lipaphis pserudobrassicae, Nippolachnus piri, Toxoptera aurantii, and Toxoptera ciidius; Pentatomidae such as Nezara antennata, Cletus punctiger, Riptortus clavetus, and Plautia stali; Aleyrodidae such as Trialeurodes vaporariorum, Bemisia tabaci, and Bemisia argentifolii; Diaspididae such as Aonidiella aurantii, Comstockaspis perniciosa, Unaspis citri, Pseudaulacaspis pentagons, and Lepidosaphes beckii; Coccidae such as Saissetia oleae and Ceroplastes rubens; Margarodidae such as Icerya purchasi; Tingidae; Psyllidae, etc.
Lepidoptera
Pyralidae such as Chilo suppressalis, Cnaphalocrocis medinalis, Ostrinia nubilalis, Parapediasia teterrella, Notarcha derogata, and Plodia interpunctella; Noctuidae such as Spodoptera litura, Pseudaletia separata, Mamestra brassicae, Agrotis ipsilon, Trichoplusia spp., Heliothis spp., and Helicoverpa spp.; Pieridae such as Pieris rapae crucivora; Tortricidae such as Adoxophyes spp., Grapholita molesta, and Cydia pomonella; Carposinidae such as Carposina niponensis; Lyonetiidae such as Lyonetia spp.; Lymantriidae such as Lymantria spp. and Euproctis spp.; Yponomeutidae such as Plutella xylostella; Gelechiidae such as Pectinophora gossypiella; Arctiidae such as Hyphantria cunea; Tineidae such as Tinea translucens and Tineola bisselliella, etc.
Diptera
Calicidae such as Culex pipiens pallens and Culex tritaeniorhynchus; Aedes spp. such as Aedes aegypti and Aedes albopictus; Anopheles spp. such as Anopheles sinensis; Chironomidae; Muscidae such as Musca domestica and Muscina stabulans; Calliphoridae; Sarcophagidae; Finnia spp.; Anthomyiidae such as Delia platura and Delia antiqua; Tephritidae; Drosophilidae; Psychodidae; Simuliidae; Tabanidae; Stomoxyinae; Agromyzidae, etc.
Coleoptera
Diabrotica spp. such as Diabrotica virgifera virgifera and Diabrotica undecimpunctata howardi; Scarabaeidae such as Anomala cuprea and Anomala rufocuprea; Curculionidae such as Sitophilus zeamais, Lissorhoptrus oryzophilus, Hypera pastica, and Callosobruchuys chienensis; Tenebrionidae such as Tenebrio molitor and Tribolium castaneum; Chrysomelidae such as Aulacophora femoralis, Phyllotreta striolata, and Leptinotarsa decemlineata; Anobiidae; Epilachna spp. such as Epilachna vigintioctopunctata; Lyctidae; Bostrychidae; Cerambycidae; Paederus fuscipes, etc.
Dictyoptera
Blattella germanica, Periplaneta fuliginosa, Periplaneta americana, Periplaneta brunnea, Blatta orientalis, etc.
Thysanoptera
Thrips palmi, Thrips tabaci, Thrips hawaiiensis, Scirtothrips dorsalis, Frankliniella intonsa, Frankliniella occidentalis, Ponticulothrips diospyrosi, etc.
Hymenoptera
Formicidae, Vespidae, Bethylidae, Tenthredinidae such as Athalia japonica, etc.
Orthoptera
Gryllotalpidae, Acrididae, etc.
Aphaniptera
Ctenocephalides felis, Ctenocephalides canis, Purex irritans, etc.
Anoplura
Pediculus humanus corporis, Phthirus pubis, etc.
Isoptera
Reticulitermes speratus, Coptotermes formosanus, etc.
Acarina
Tetranychidae such as Tetranychus urticae, Tetranychus kanzawai, Panonychus citri, Panonychus ulmi, and Oligonychus spp.; Eriophyidae such as Aculops pelekassi and Calacarus carinatus, Tarsonemidae such as Polyphagotarsonemus latus; Tenuipalpidae; Tuckerellidae; Ixodidae such as Haemaphysalis japonica, Haemaphysalis flava, Haemaphysalis Longicornis, Boophilus microplus, Ixodes ovatus, and Ixodes persulcatus; Acaridae such as Tyrophagus putresceutiae; Epidermoptidae such as Dermatophagoides farinae and Dermatophagoides ptrenyssnus; Cheyletidae such as Cheyletus eruditus, Cheyletus fortis, Cheyletus malaccensis, and Cheyletus moorei; Dermanyssidae, etc.
Nematoda
Pratylenchus coffeae, Pratylenchus fallax, Pratylenchus loosi, Pratylenchus vulnus, Heterodera glycines, Globodera rostochiensis, Meloidogyne hapla, Meloidogyne incognita, etc.
The present compositions, although they may consist of compound A and compound B, can be made suitable for practical use by allowing various solid, liquid, or gaseous carriers to hold the present compositions, to which surfactants, dispersants, fixing agents, stabilizers, propellants, or other auxiliaries are added, if necessary, followed by formulation into various forms including oil sprays, emulsifiable concentrates, wettable powders, flowables such as aqueous suspensions and aqueous emulsions, microcapsule formulations, spot-on or pour-on formulations, shampoo formulations, granules, dusts, aerosols, ULV agents, poison baits, sheet-shaped formulations, and resin formulations.
The solid carrier which can be used in the formulation may include, for example, fine powder or granules of clay materials such as kaolin clay, diatomaceous earth, synthetic hydrated silicon oxide, bentonite, Fubasami clay, and acid clay; various kinds of talc, ceramics, and other inorganic minerals such as sericite, quartz, sulfur, activated carbon, calcium carbonate, and hydrated silica; and chemical fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, and ammonium chloride.
The liquid carrier may include, for example, water; alcohols such as methanol and ethanol; ketones such as acetone and methyl ethyl ketone; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and methylnaphthalene; aliphatic hydrocarbons such as hexane, cyclohexane, kerosene, and light oil; esters such as ethyl acetate and butyl acetate; nitrites such as acetonitrile and isobutyronitrile; ethers such as diisopropyl ether and dioxane; acid amides such as N,N-dimethylformamide and N,N-dimethylacetamide; halogenated hydrocarbons such as dichloromethane, trichloroethane, and carbon tetrachloride; dimethyl sulfoxide; and vegetable oils such as soybean oil and cottonseed oil.
The gaseous carrier or propellant may include, for example, fluoro-carbons, butane gas, LPG (liquefied petroleum gas), dimethyl ether, and carbon dioxide.
The surfactant may include, for example, alkylsulfates, alkylsulfonates, alkylarylsulfonates, alkyl aryl ethers and their polyoxyethylene derivatives, polyethylene glycol ethers, polyhydric alcohol esters, and sugar alcohol derivatives.
The auxiliaries such as fixing agents or dispersants may include, for example, casein, gelatin, polysaccharides such as starch, arabic gum, cellulose derivatives, and alginic acid; lignin derivatives, bentonite, sugars, and synthetic water-soluble polymers such as polyvinyl alcohol, polyvinyl pyrrolidone, and polyacrylic acid.
The stabilizer may include, for example, PAP (isopropyl acid phosphate), BHT (2,6-di-tert-butyl-4-methylphenol), BHA (mixtures of 2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol), vegetable oils, mineral oils, surfactants, fatty acids and their esters.
The base materials of poison baits may include, for example, bait ingredients such as grain powder, vegetable oils, sugars, and crystalline cellulose; antioxidants such as dibutylhydroxytoluene and nordihydro-guaiaretic acid; preservatives such as dehydroacetic acid; substances for preventing erroneous eating, such as red pepper powder; and attractants such as cheese flavor, onion flavor, and peanut oil.
The base materials of resin formulations may include, for example, olefin polymers, vinyl chloride polymers, and polyurethanes. To these base materials, there can be added, if necessary, plasticizers such as phthalates and stearic acid; pest-attractive substances such as pheromones; dyes or pigments with pest-attractive colors; and any other additives.
The resin formulations can be obtained, for example, by kneading the present compositions into the base materials with a conventional kneader and then forming into a desired shape by injection, extrusion, or compression molding. The present compositions may be supported on the base materials which do not contain them, by impregnation, coating, printing, or any other techniques. In the operation, for example, impregnation, coating, or printing of the present compositions, compounds as the active ingredients may be used in the form of previously-prepared formulations or their dilutions, including oil sprays, emulsifiable concentrates, and flowables.
The resin formulations thus obtained can be formed through further steps, if necessary, such as shaping and cutting, into plates, sheets or films, tapes or ribbons, nets, strings or cords, or any other shapes, and can also be formed into final products such as materials for mulching, strings or cords for training, supports for horticultural use, sheet-shaped formulations, films for wrapping use, collars for animals, and ear tags for animals.
The formulations as flowables (e.g., aqueous suspensions or aqueous emulsions) can usually be obtained by finely dispersing 1-75% active ingredients in water containing 0.5-15% dispersants, 0.1-10% suspension aids (e.g., protective colloids, thixotropy-conferring compounds), and 0-10% suitable auxiliaries (e.g, antifoaming agents, rust preventives, stabilizers, spreading agents, penetration aids, antifreezing agents, antiblastic agents, antifungal agents). The replacement of water with oils in which the active ingredients can hardly be dissolved makes it possible to produce oily suspensions.
As the protective colloids, there can be used, for example, gelatin, casein, various kinds of gum, cellulose ethers, polyvinyl alcohol, or other similar materials. The thixotropy-conferring compounds may include, for example, bentonite, aluminum magnesium silicate, xanthan gum, and polyacrylic acid.
The mixing ratios of compound A and compound B in the present compositions are not strictly limited, but they can be changed over a wide range depending upon types of formulations, uses, and other factors. The mixing ratios are usually in the range of 0.01 to 30 parts, preferably 0.5 to 10 parts, of compound B for 1 part of compound A, and the total amounts of compound A and compound B contained in the present compositions are usually in the range of 0.01% to 90% by weight, preferably 0.1% to 80% by weight.
The present compositions can also be used in admixture or together with other insecticides, nematocides, acaricides, bactericides, fungicides, herbicides, plant growth regulators, synergists, fertilizers, soil conditioners and/or feeds for animals. The insecticides, acaricides, and nematocides may include, for example, pyrethroid compounds such as permethrin, cypermethrin, fenvalerate, esfenvalerate, fenpropathrin, bifenthrin, deltamethrin, fluvalinate, flucythrinate, allethrin, d-allethrin, prallethrin, cyphenothrin, phenothrin, resmethrin, tefluthrin, empenthrin, acrinathrin, cyhalothrin, cyfluthrin, etofenprox, halfenprox, silafluofen, tralomethrin, cycloprothrin, esbiothrin, transfluthrin, terallethrin, imiprothrin, and 1-ethynyl-2-fluoro-2-pentenyl 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate; organo-phosphorus compounds such as cyanophos, fenthion, fenitrothion, parathion, methyl parathion, pirimiphos-methyl, diazinon, isoxathion, pyridaphenthion, chlorpyriphos, chlorpyriphos-methyl, oxydeprofos, vamidothion, malathion, phenthoate, dimethoate, thiometon, disulfoton, phosalone, phosmet, methidathion, prothiofos, sulprofos, profenofos, azinphos-methyl, pyraclofos, salithion, tetrachlorvinphos, dichlorvos, monocrotophos, naled, dimethylvinphos, propaphos, acephate, methamidophos, and ethion; carbamate compounds such as carbaryl, metolcarb, isoprocarb, fenobucarb, propoxur, XMC, ethiofencarb, bendiocarb, pirimicarb, carbosulfan, carbofuran, benfuracarb, furathiocarb, methomyl, thiodicarb, oxamyl, alanycarb, metoxadiazone, and fenothiocarb; neo-nicotinoids including nitroiminoimidazolidine derivatives, nitrovinylidenediamine derivatives such as N-(6-chloro-3-pyridylmethyl)-N-ethyl-Nxe2x80x2-methyl-2-nitrovinylidenediamine (common name: nitenpyram), nitroguanidine derivatives such as 1-methyl-2-nitro-3-[(3-tetrahydrofuryl)-methyl]guanidine, cyanoacetoamidine derivatives such as N1-[(6-chloro-3-pyridyl)methyl]-N2-cyano-N1-methylacetoamidine (common name: acetamiprid), cyanoiminothiazoline derivatives such as 1-(2-chloro-5-pyridylmethyl)-2-cyanoiminothiazoline (common name: thiacloprid), nitroiminotetrahydro-1,3,5-oxadiadine derivatives such as 3-[(2-chloro-5-thiazolyl)methyl]-5-methyl-4-nitroiminotetrahydro-1,3,5-oxadiadine (common name: thiamethoxam), and nitroiminohexahydro-1,3,5-triazine derivatives such as 3,5-dimethyl-1-[(2-chloro-5-thiazolyl)methyl]-2-nitroiminohexahydro-1,3,5-triazine; nereistoxin derivatives such as cartap, bensultap, and thiocyclam; chlorinated hydrocarbon compounds such as benzoepin, dicofol, and tetradifon; formamidine derivatives such as amitraz and chlordimeform; phenylpyrazole derivatives such as ethiprole; benzoylphenyl urea compounds such as diflubenzuron, teflubenzuron, chlorfluazuron, flufenoxuron, triflumuron, hexaflumuron, lufenuron, and novaluron; triazine derivatives such as cyromazine; thiadiazine derivatives such as buprofezin; juvenoid compounds such as methoprene, hydroprene, fenoxycarb, and diofenolan; tebufenozide, methoxyfenozide, halofenozide, chromafenozide, chlorfenapyr, phenisobromolate, chinomethionat, propargite, fenbutatin oxide, hexythiazox, clofentezine, pyridaben, fenpyroximate, tebufenpyrad, pyrimidifen, polynactin, milbemectin, avermectin, ivermectin, and azadirachtin.
When the present compositions are applied for use in the control of agricultural and forest pests, their amounts for application are usually in the range of 1 g to 1000 g, preferably 10 g to 100 g, per 10 ares in terms of the total amounts of active ingredients. For emulsifiable concentrates, wettable powders, flowables, or other similar formulations, which are used after dilution with water, their concentrations for application are usually in the range of 10 ppm to 1000 ppm in terms of the total amounts of active ingredients. In contrast, granules, dusts, or other similar formulations are applied as such. These formulations may be sprayed over the foliage of plants such as crop plants to be protected from pests or may be used in the soil treatment for the control of pests inhabiting the soil. The present compositions may also be formed into sheet-shaped, or string- or cord-shaped formulations, which are applied by directly winding around plants, disposing in the neighborhood of plants, or spreading on the soil surface at the root.
When the present compositions are applied for use in the control of hygienically unfavorable pests, emulsifiable concentrates, wettable powders, flowables, or other similar formulations are usually applied after dilution with water to the total amounts of active ingredients ranging from 0.01 ppm to 10,000 ppm, and oil sprays, aerosols, smoke formulations, ULV agents, poison baits, or other similar formulations are applied as such. When the present compositions are used in the direct treatment of animal bodies for the control of ectoparasites on small animals such as cats and dogs, they may be applied by the known veterinary methods: for example, as tablets, by feed incorporation, as suppositories, or by injection (intramuscular, subcutaneous, intravenous, intraperitoneal, or any other routes) for systemic control; or by spraying oily or aqueous solutions, by spot-on or pour-on treatment, or as shampoo formulations or resin formulations such as collars and ear tags for non-systemic control. For such direct application to animal bodies, the amounts for application are usually in the range of 0.1 mg to 500 mg per kg of a host animal in terms of the total amounts of active ingredients.
These amounts or concentrations for application may vary depending upon types of formulations, times, places, and methods of application, kinds of pests, degree of damage, and other factors; they can therefore be increased or decreased without limitation to the above ranges.


A method for manufacturing a microporous film comprising the steps of:

This invention relates to microporous films and methods of manufacturing thereof, and to image receptors which are particularly suitable for use in ink-jet imaging using either aqueous or nonaqueous inks.
Microporous films and membranes are well-known materials, and may be regarded as polymer films in which a significant proportion of the volume of the film comprises microscopic pores and voids. The pores and voids normally connect with each other and with at least one surface of the film. Microporous films find use in a wide range of fields, including filtration, reverse osmosis, battery separators, breathable fabrics, surgical dressings and, when the pores have been filled with a suitable substance, sustained-release systems. Recently, there has been growing interest in the use of microporous films as printable surfaces, and in particular as receptors for ink jet printing.
The manufacture and uses of microporous films are reviewed, for example, in Synthetic Polymeric Membranes (R. E. Kesting), McGraw-Hill, 1971, and described in numerous patents.
In a widely-used manufacturing process, a mixture comprising a thermoplastic polymer and a particulate filler and/or a second polymer, which is incompatible with the first polymer, is melt extruded as a heterophasic film, then stretched in at least one direction so as to form voids at the phase boundaries.
This method is described, for example, in U.S. Pat. Nos. 3,903,234; 3,967,978; 4,472,328; 4,585,604; and 4,613,643.
In another widely-used process, a blend of two incompatible polymers, or a mixture of a polymer and a low molecular weight additive, often in combination with a filler, is melt extruded as a film and then washed with a suitable solvent so as to remove one of the polymers or the additive, thereby creating voids in the film. This is described, for example, in U.S. Pat. Nos. 3,351,495; 3,729,332; 3,862,030; 4,237,083; 4,335,193; 5,326,391 and WO 97/20885. A combination of washing and stretching may be employed, e.g., as disclosed in U.S. Pat. Nos. 4,833,172 and 4,861,644.
Methods involving casting of the film from a solution or dispersion are also known. For example, U.S. Pat. No. 5,374,475 and EP 555,398 disclose the formation of microporous films by coating dispersions of polymer microparticles on a support, followed by drying in a manner which does not cause coalescence of the particles. EP 156,532 and U.S. Pat. No. 5,374,475 disclose formation of microporous films by the process known as polymer phase inversion. In this method, a polymer is dissolved in a solvent mixture comprising a good solvent for the polymer and a less-volatile poor solvent for the polymer, then coated on a support and dried. Voids are formed in the resulting film as the residual poor solvent is driven off.
Formation of microporous polyester membranes by xe2x80x9cpolymer assisted phase inversionxe2x80x9d is described in the above-referenced book Synthetic Polymeric Membranes and in U.S. Pat. No. 3,957,651. In this process, a polyester derived from an aromatic dibasic acid and an xe2x80x9cassistingxe2x80x9d polymer are dissolved in a mutual solvent, then coated on a support and dried. The resulting film is washed in a solvent capable of selectively dissolving the assisting polymer, thereby forming voids in the film. Only expensive and/or noxious fluorinated solvents such as hexafluoroisopropanol and trifluoroacetic acid are said to be suitable as the mutual solvent.
There is a growing interest in the use of ink jet printing for the output of high quality images, e.g., of a quality rivalling conventional photographic images. In ink jet printing, tiny droplets (e.g., of a volume measured in picolitres) of colored ink are expelled from an array of nozzles onto a receptor, in accordance with digitally-stored image information. The process may be repeated several times using inks of different colors to build a full color image, and has the potential to provide images of photographic quality in a cost-effective manner using relatively simple apparatus suitable for use in the home or office environment, without the need for light-sensitive materials or the use of processing chemicals. However, the quality and throughput obtainable is largely dependent on the properties of the receptor on which the image is printed. The jetting process generally demands the use of low viscosity inks with a low solids content, and so large volumes of liquid must be absorbed by the receptor, especially in the case of 4-color imaging. The liquid must be absorbed rapidly, to enable successive printing of the different colors without bleeding, and to provide an image that resists smearing, without extended drying times. Furthermore, the ink must not diffuse sideways after contacting the receptor, otherwise the resolution is degraded. Finally, so as to obtain bright, dense images, the dyes or pigments in the ink preferably should be retained at or near the surface of the receptor, but in a manner which does not render the image susceptible to physical damage.
Two techniques are currently employed in the art in pursuit of higher quality images. One is to jet a normal density ink and a low density ink (from separate printheads) so that the number of available grey levels is increased. The second is to jet multiple droplets of ink from a single nozzle into a particular pixel area in order to obtain multiple grey levels. A combination of the two techniques can provide even more grey levels, and hence even higher image quality. However, such techniques place great demands on the image receptor. Even larger volumes of ink must be absorbed, and the rate of absorption must be commensurate with the ever-increasing firing rate of commercial ink jet printheads, otherwise the image-forming process becomes limited by the absorption rate and capacity of the receptor.
Piezoelectric ink jet printheads are most suitable for multiple droplet jetting, owing to the superior control they afford over the droplet size and placement. In particular, the shared-wall type of piezoelectric ink jet printheads, as exemplified by the Xaarjet(trademark) printheads supplied by Xaar Ltd., Cambridge, UK and described in U.S. Pat. Nos. 4,887,100 and 4,879,568, have advantages in this respect. Such printheads are not limited to the use of aqueous inks (which are used by most, if not all, of the commercially-available ink jet printers), and indeed many advantages are to be gained by the use of oil-based inks. These include the ease with which pigmented inks can be designed, since pigmented inks can provide a more accurate and stable color rendition than their dye-based counterparts.
Although a large body of literature exists on the design and manufacture of receptors for ink jet printing, there is still a need for improved receptors, suitable for use in high quality multilevel printing. In particular, Applicants are unaware of any published art addressing the particular demands of multilevel printing using oil-based inks.
In the context of conventional ink jet printing, many patents describe the use of microporous films as receptors. The pores of such materials potentially provide a means of absorbing substantial amounts of liquid, and at the same time channelling it downwards (away from the surface) rather than sideways. Patents disclosing microporous receptors include WO97/29916; WO97/20885; EP 555,398; EP 409,440; EP 156,532; and U.S. Pat. Nos. 3,729,332; 4,460,637; 4,481,244; 4,496,629; 4,780,356; 4,861,644; 5,002,825; 5,104,730; 5,326,391; 5,374,475; 5,445,868; 5,635,291 and 5,647,935. Many patents teach the use of a two-layer system in which an ink-absorbing layer is overlaid by an ink-transporting layer, one or both of said layers being microporous (see, for example, WO97/33758; Japanese Patent Publication Nos. 61-035276; 61-035277; 61-035278 and 05-051470; and U.S. Pat. Nos. 4,785,313; 4,832,984; 4,954,395; 5,027,131; 5,059,983; 5,275,867; 5,374,475; 5,463,178 and 5,605,750. A variety of different microporous layer compositions are disclosed, including many composed predominantly of inorganic materials such as alumina or silica, as in U.S. Pat. Nos. 5,647,935; 5,104,730; 5,002,825; 5,463,178; 5,635,291; 5,445,868; 5,275,867; and 4,780,356. Print-accepting members comprising a microporous poly(vinyl butyral) layer are disclosed in Japanese Published Patent Application Nos. 08-090944 and 58-136479.
The majority of the above-referenced patents refer to aqueous ink jet printing, and few patents describe receptors tailored specifically for nonaqueous inks, although one example is Japanese Published Patent Application JPO8-324095, which discloses an ink jet recording medium comprising a base material, a porous layer with high affinity for nonaqueous solvents, and a transparent top layer which is permeable to the relevant solvents.
A number of microporous materials are marketed as ink jet receptors for use with aqueous inks, including the materials sold under the tradename Teslin(trademark) Microporous Membrane by PPG Industries Inc., Pittsburgh, Pa. The manufacture of this and similar materials is described in several patents, notably U.S. Pat. No. 5,326,391, which refers to a sheet-form microporous material which on a coating-free, printing ink-free and impregnant-free basis comprises: (a) a matrix consisting essentially of substantially water-insoluble thermoplastic organic polymer, (b) finely divided substantially water-insoluble filler particles, of which at least 50% by weight are siliceous particles, the filler particles being distributed throughout the matrix and constituting from 40 to 90% by weight of the microporous material, and (c) a network of interconnecting pores communicating substantially throughout the microporous material, the pores constituting from 35 to 95% by volume of the microporous material. U.S. Pat. No. 4,861,644 describes the utility of such materials as image receptors, including their use in ink jet printing using aqueous inks. There is no mention of multilevel ink jet printing, or of the use of oil-based inks.
U.S. Pat. No. 5,605,750 and WO97/33758 disclose the formation of topcoats consisting (respectively) of boehmite and nonporous poly(N-vinyl pyrrolidone) on Teslin(trademark) Microporous Membrane. The resulting materials show improved properties as receptors for ink jet printing using aqueous inks, giving brighter images of higher density than the unmodified Teslin(trademark) sheet. Again, neither patent mentions multilevel printing or oil-based inks.
Applicants have discovered that unmodified Teslin(trademark) sheet fulfills many of the requirements for high-speed multilevel ink jet printing, in that it has the ability to absorb both aqueous and nonaqueous inks in the necessary volumes and at the necessary rates to give xe2x80x9cinstant-dry,xe2x80x9d non-bleeding, well-resolved images. However, the resulting images still show a number of deficiencies. When aqueous inks are used, the images are dull and of low density. When oil-based inks are used, the images have a mottled appearance, which can be traced to the ragged, uneven shape of the individual image pixels, caused by the rough texture of the sheet. With either type of ink, the images are excessively matt in appearance.
There is therefore a need for improved receptors for ink jet printing, capable of giving glossy, high quality images by multilevel printing with both aqueous and nonaqueous inks.
According to a first aspect of the invention, there is provided a method for manufacturing a microporous film comprising the steps of:
(a) providing a first polymer which is a hydrophobic thermoplastic polymer and a second polymer which is a hydrophilic polymer or copolymer of N-vinylpyrrolidone;
(b) dissolving said first and second polymers in a solvent system which is compatible with both polymers, said solvent system comprising a blend of an aprotic organic solvent and an alcohol,
(c) coating the resulting solution on a support;
(d) effecting at least a partial drying of the resulting coating; and
(e) washing the coating in an aqueous medium so as to extract at least 50% by weight of the said second polymer.
Optionally, the microporous film may be removed from the support in a subsequent step. Optionally, a finely-divided particulate filler (such as silica) may be dispersed in the solution prior to coating, and optionally one or more low molecular weight additives (such as crosslinkers, hardeners or levelling agents) may be co-dissolved with the polymers in step (b).
xe2x80x9cAprotic organic solventsxe2x80x9d are organic solvents which neither release nor accept protons. For the purpose of the invention, this may be regarded as excluding from the invention any solvent whose molecules comprise one or more hydrogen atoms bonded directly to oxygen, sulfur or nitrogen, unless the nitrogen forms part of an amide group.
In a second aspect of the invention there is provided an image accepting member, preferably an ink accepting member, comprising a microporous film made by the above method.
In a third aspect, the invention is an ink accepting member comprising a support which is a sheet-form microporous material which on a coating-free, printing ink-free and impregnant-free basis comprises: (a) a matrix consisting essentially of substantially water-insoluble thermoplastic organic polymer, (b) finely divided substantially water-insoluble filler particles, of which at least 50% by weight are siliceous particles, the filler particles being distributed throughout the matrix and constituting from 40 to 90% by weight of the microporous material, and (c) a network of interconnecting pores communicating substantially throughout the microporous material, the pores constituting from 35 to 95% by volume of the microporous material, the support bearing on at least one side thereof a microporous organic polymer film comprising a network of pores which communicate with the pores in said support. Preferably the microporous organic polymer film is made by the above method.
In a fourth aspect of the invention there is provided an imaging method wherein an ink image is deposited on the image accepting member defined above.
The invention provides a novel and versatile method for the manufacture of microporous films, affording an unprecedented level of control over the physical and chemical properties of the said films, such as the size and distribution of the pores, and their affinities for aqueous and nonaqueous media. The resulting films find particular use as receptors for colorant transfer and ink jet imaging, and may be tailored for use with aqueous or nonaqueous inks, providing images superior in one or more attributes such as gloss, density, smear-resistance and fade-resistance compared to images obtained using prior art receptors.
Image accepting members in accordance with the second aspect of the invention are capable of providing bright, high density, glossy, durable images of high quality by means of multilevel ink jet printing at high speeds (e.g., 2 minutes or less per A4 sheet). Furthermore, they are compatible with both aqueous and oil-based inks.
At the heart of the inventive method lies Applicants"" discovery that polymers and copolymers of N-vinylpyrrolidone form microphasic dispersions with a wide range of host polymers when codissolved with them in a particular solvent system, then cast as films from the resulting solutions. Pores of controlled size and uniformity are then created by washing the films in aqueous media, which selectively extracts the N-vinylpyrrolidone polymers.
Polymers and copolymers of N-vinylpyrrolidone appear to be unique in their ability to form microphasic dispersions with a wide range of hydrophobic thermoplastic host polymers when blended with them and cast as films from suitable solvent systems. Attempts to use alternative hydrophilic polymers, such as poly(vinyl alcohol), polyacrylamide, etc., typically result in grossly incompatible mixtures which cannot be cast as coherent films.
The first stage in the process requires the dissolution of two different polymers in a solvent system which is compatible with both polymers, and which comprises a blend of an aprotic organic solvent and an alcohol. xe2x80x9cCompatible with bothxe2x80x9d means that both polymers must be retained in solution or suspension by the solvent system, preferably at a loading of at least 1% solids by weight, as a system which is homogeneous (i.e., clear and non-turbid) at least to the naked eye.
The first polymer is a hydrophobic thermoplastic polymer, and as such has a minimal affinity for water, i.e., it neither dissolves nor swells appreciably in water at ambient or moderately elevated temperatures. It must be soluble in the particular solvent system used, and must be capable of being cast as a film from solution. In particular, it should be readily soluble in the aprotic organic component of the solvent system, but less soluble (preferably insoluble) in the hydroxylic component of the solvent system. As discussed in greater detail below, the aprotic organic solvent is typically a cheap and readily available ketone, ester, ether or hydrocarbon solvent, and so preference is given to polymers which dissolve readily in such media. Thermoplastics which are insoluble in aprotic organic solvents, or soluble only in xe2x80x9cexoticxe2x80x9d highly polar solvents (e.g., aromatic polyesters such as poly(alkylene terephthalates), and engineering plastics such as aromatic polysulphones, polyetherketones, polyimides, etc.) are not suitable for use in the invention. Apart from these constraints, there are no particular restrictions on the identity of the first polymer. Thus, it may be selected from a wide range of thermoplastic homopolymers and copolymers (ordered or random), including both addition and step-growth (condensation) polymers. Suitable examples may be selected from a variety of structural classes, including vinyl polymers, acrylate and methacrylate polymers, cellulose esters, polyethers, polyesters, and polycarbonates. Preferred materials include poly(vinyl acetal)s such as poly(vinyl butyral); cellulose acetate butyrate; poly(methyl methacrylate); and vinyl chloride/vinyl acetate copolymers such as those available under the tradenames VAGH(trademark) and VYNS(trademark) from Union Carbide.
Particularly preferred hydrophobic thermoplastics are those comprising a limited number of pendant hydroxyl groups per polymer chain. The pendant hydroxyl groups facilitate crosslinking or hardening reactions, which may be employed to optimize the physical and chemical properties of the final product, as described in greater detail below. Furthermore, the hydroxyl groups may assist in the dispersion of a particulate filler such as silica, which is present in the preferred embodiments of the invention, described in greater detail below. It is also possible that the hydroxyl groups promote hydrogen-bonding or other interactions between the hydrophobic and hydrophilic polymers which favor production of the necessary microphasic dispersion, and may control the rate and extent of extraction of the hydrophilic polymer in the washing step. However, the number of hydroxyl groups per chain should not be so great as to alter the essentially hydrophobic character of the polymer, or to render it highly soluble in the hydroxylic component of the solvent system. A useful indicator of the hydroxyl content of the polymer is its hydroxyl number, which is the weight (in grams) of the polymer equivalent to one mole of hydroxyl groups, and hence a relatively high value indicates a relatively low hydroxyl content, and vice-versa. To maintain hydrophobic character, the OH number is preferably not less than 300, more preferably not less than 350. While there is no particular upper limit for the OH number, little benefit is obtained from the very low concentrations of hydroxyl groups corresponding to OH numbers of 1000 or more. Preferred hydroxy-functional polymers include cellulose esters such as cellulose acetate butyrate, which are prepared by esterification of cellulose, but typically comprise an average of 0.2-0.5 unreacted OH groups per repeating unit; and poly(vinyl acetal)s such as poly(vinyl formal) and poly(vinyl butyral), which are prepared by reacting poly(vinyl alcohol) with an aldehyde, but which invariably comprise unreacted OH groups. A particularly preferred material is Butvar(trademark) B76 (supplied by Solutia, formerly Monsanto) which is nominally poly(vinyl butyral), but comprises approximately 12 wt % unreacted poly(vinyl alcohol).
The second polymer is a hydrophilic polymer or copolymer of N-vinylpyrrolidone, and therefore shows a high affinity for water, i.e., it should swell on contact with water, and preferably should be soluble in water. At the very least, it must be soluble in aqueous organic mixtures (e.g., aqueous ethanol) to enable it to be selectively extracted from the coating without dissolving or swelling the first polymer. Most preferably, the second polymer is soluble in pure water. Preferred materials are homopolymers of N-vinylpyrrolidone or copolymers of N-vinylpyrrolidone and vinyl acetate comprising up to 50% by weight vinyl acetate. Homopolymers of N-vinylpyrrolidone are available in a variety of molecular weights from International Specialty Products (ISP) (Wayne, NJ) under the tradenames K-15, K-30, K-60, K-80, K-90 and K-120. Homopolymers of different molecular weights give rise to different pore sizes and distributions in the final product, with higher molecular weights generally leading to larger numbers of smaller pores, with a more uniform size distribution. Thus, for the preparation of ink jet receptors, relatively high molecular weights (greater than 100,000, preferably greater than 200,000, most preferably greater than 300,000, e.g., 630,000 as in the K-90 product) are preferred. However, the most preferred material is a copolymer comprising 70% N-vinylpyrrolidone and 30% vinyl acetate by weight, available as a 50 wt % solution in ethanol from International Specialty Products (ISP) (Wayne, N.J.) under the tradename GAF E735(trademark).
The relative proportions of the first and second polymers may vary widely, depending on the identity of the materials involved and the degree or type of porosity desired in the final product. Most commonly, however, the weight ratio of the first and second polymers is in the range 2:1-1:3. In the preferred embodiments, where the first and second polymers are (respectively) Butvar(trademark) B-76 and GAF E735(trademark), weight ratios of 1:1 or less (and preferably about 1:2) are found to lead to a high density of pores of average diameter less than 1 xcexcm, which is desirable for image receptor applications.
The solvent system in which the first and second polymers are co-dissolved comprises an aprotic organic solvent and an alcohol. Depending on the choice of polymers, the aprotic organic solvent may be selected from a wide variety of organic solvents, but preference is given to the cheaper, readily-available solvents having a boiling point of less than 120xc2x0 C. at normal atmospheric pressure, preferably less than 100xc2x0 C. These include ketones, such as acetone, methyl ethyl ketone (MEK), cyclohexanone etc.; ethers, such as diisobutyl ether, tetrahydrofuran, dioxan, glycol ethers, etc.; esters, such as ethyl acetate and propyl acetate; and hydrocarbons, such as hexane, toluene, etc., Chlorinated hydrocarbons may also be used (e.g., chloroform, dichloroethane, etc.), but are less preferred for environmental reasons and on grounds of cost. Mixtures of two or more aprotic organic solvents may be used, if desired. The aprotic organic solvent should be a good solvent for the first polymer (i.e., the hydrophobic thermoplastic polymer). In the preferred embodiments of the invention, best results are obtained when MEK is used as the aprotic solvent.
The other essential component of the solvent system, namely the alcohol, must be miscible with the aprotic organic solvent, and should be a good solvent for the second polymer (i.e., the polymer or copolymer of N-vinylpyrrolidone). Preferably, the alcohol is of similar volatility to the aprotic organic solvent. Most commonly the alcohol is a lower alcohol, such as methanol, ethanol, 1-propanol, 2-propanol etc. Ethanol is a particularly preferred example. Mixtures of two or more alcohols may be used, and water may also be present. For example, it is quite acceptable to use commercial grades of ethanol which typically comprise several wt % of water, and are typically denatured with about 5 wt % of other alcohols, such as methanol and 2-propanol.
The relative proportions of aprotic solvent and alcohol may vary depending on the identities of the solvents and of the polymers, and with the microstructure required in the final product. A notable feature of the invention is the ability to vary the size and number of pores formed from a given polymer blend by varying the relative proportions of the aprotic solvent and alcohol(s) used to dissolve the polymer blend. Typically, the weight ratio of aprotic solvent to alcohol is in the range 30:1 to 1:2, more commonly in the range 20:1 to 1:1. In the case of the preferred embodiments, where the first and second polymers are (respectively) Butvar(trademark) B-76 and GAF E735(trademark), increasing proportions of aprotic solvent lead to smaller pores, while increasing proportions of alcohol lead to larger pores. In the preferred embodiments of the invention, the weight ratio of MEK to ethanol is in the range 5:1 to 2:1, more preferably about 3:1. Use of pure ethanol or pure MEK as the solvent leads to a mainly non-porous film.
In a typical procedure, the first polymer is dissolved in the aprotic organic solvent, the second polymer is dissolved in the alcohol, and the two solutions are mixed. Prior to coating on a suitable substrate, further quantities of one or both of the solvents may be added for final adjustment of the aprotic/hydroxylic ratio, or for adjustment of the solids content (and hence viscosity) of the coating solution. The substrate is typically a flexible, self-supporting sheet-form material such as resin-coated paper, aluminium foil or plastic film. A preferred substrate is polyester film of about 25-250 xcexcm thickness. If necessary, it may comprise subbing layers, or be corona treated, to increase the adhesion of the coating. Alternatively, it may comprise a release layer to facilitate subsequent removal of the coating, if this is desired. The substrate may itself be microporous. For the purposes of this embodiment of the invention, a nonporous support (such as polyester film) bearing a microporous coating prepared by any method known in the art may be regarded as a microporous substrate. Image accepting members comprising a microporous organic polymer film on a microporous support of a particular defined type constitute a separate aspect of the invention, as described in greater detail hereinafter.
Any known coating method may be used, such as slot coating, knife coating, bar coating, roller coating, etc. The coating weight may vary depending on the intended end use, but is typically consistent with a dried coating thickness in the range 5 to 100 xcexcm.
The next step is drying of the coating. As a result of solvent evaporation, the coating solidifies in the form of a film which appears clear and homogeneous to the naked eye. However, subsequent aqueous extractive treatment reveals it to be phase-separated on a microscopic scale. It is not clear whether the phase separation takes place during the drying process or at an earlier stage, but both these mechanisms are within the scope of the invention. In the practice of the invention, drying must proceed at least to the point at which the coating solidifies, but it is not necessary to remove all traces of solvent before the washing step, especially if washing is carried out in-line, in which case there is less risk of physically damaging the coating while it remains relatively soft.
Optimum drying conditions may vary widely depending on the materials used, and may be established by routine experimentation, but generally speaking, drying (at least initially) at ambient temperatures or at moderately elevated temperatures (e.g., less than 50xc2x0 C.) is preferred.
The final step in the process according to the invention is washing of the coating in an aqueous medium so as to extract at least 50% by weight of the hydrophilic polymer, and thereby render the coating microporous. For a given loading of hydrophilic polymer in the initial coating, the degree of porosity of the final product is determined by the proportion of the hydrophilic polymer that is removed by the wash. Preferably, at least 75% by weight of the hydrophilic polymer is removed, more preferably at least 85% by weight.
The wash preferably uses plain water at ambient temperature, but higher temperatures and/or aqueous-organic mixtures may be employed to obtain a more rapid or complete extraction, as long as the hydrophobic polymer component does not dissolve or swell appreciably under those conditions. If surfactants are added to the aqueous wash medium, they may deposit on the interior surface of the pores that are formed, and modify the wettability thereof. Similarly, functional materials such as mordents, UV absorbers, antioxidants, etc., may be deposited in the pores from the wash medium. Washing may be carried out by any suitable means, such as spraying or immersion, optionally with agitation, and is conveniently carried out using apparatus of the type used for the processing of photographic film. The washed coating may be dried at ambient or moderately elevated temperature, and is then ready for use.
When the coating (prior to washing) comprises a 1:2 w/w mixture of Butvar(trademark) B-76 and GAF E735(trademark), washing in distilled water for 30 seconds or more at ambient temperature or below results in a maximum weight loss of about 60 wt %, indicating that about 10% by weight of the GAF E735(trademark) remains in the coating.
In a variant of the above-described process, the solution of hydrophobic and hydrophilic polymers in the prescribed blend of solvents is coated on a temporary carrier, dried, laminated to a desired substrate, and the temporary carrier peeled off and discarded. Thereafter, washing the coating in an aqueous medium provides a microporous film attached to the desired substrate. This method may be advantageous in the situation where the desired substrate is highly porous, and direct solvent coating thereof might result in unwanted filling of its pores.
Various additives may be incorporated in the microporous films prepared in accordance with the invention, such as particulate fillers, chemical modifiers (including crosslinkers and hardeners) and fluorocarbon- or silicone-based levelling agents. One or more of such ingredients may be used to optimize the properties of the film for particular end uses.
Particulate fillers, especially silica-based fillers and/or alumina-based fillers, may advantageously be incorporated in microporous films intended for use in ink jet imaging (with either aqueous or nonaqueous inks). Siliceous fillers are particularly effective absorbers of the liquid solvents or dispersants found in the relevant aqueous or nonaqueous inks. Suitable materials include fumed silica, precipitated silica and calcium silicate, including the materials commercially-available under the trade names Aerosil OX50(trademark) and Extrusil(trademark) (Degussa), and Syloid ED74(trademark) (W. R. Grace, N.Y.). The average particle size of such materials is preferably less than 1.0 xcexcm, more preferably less than 0.5 xcexcm, and most preferably less than 0.1 xcexcm. The loading is preferably in the range of from 5 to 40 wt % of the first (hydrophobic) polymer. The siliceous filler is typically added to the solution of the first (hydrophobic) polymer in the aprotic organic solvent and subjected to conventional milling treatments to reduce the particle size (if necessary), prior to mixing with the solution of the hydrophilic polymer in the alcohol. Conventional dispersing aids such as Disperbyk(trademark) 161 (available from Byk Chemie) may be added prior to milling to improve the quality of the dispersion.
Alumina-based fillers (especially boehmite) find particular use in films intended for use in aqueous ink jet imaging, where it is believed that they act as mordents for the dyes commonly used in aqueous inks. A preferred material is Cerasol CD(trademark), supplied by Alcan Chemicals. It may be co-dispersed with the siliceous filler, and/or may be coated separately on top of the microporous film as an aqueous dispersion.
When the hydrophobic polymer has suitable reactive pendant groups, especially hydroxyl groups, a chemical modifier such as a hardener or crosslinking agent may advantageously be added to the formulation. It is preferably added to the solution of the hydrophobic polymer in the aprotic solvent prior to admixture of the solution of the second polymer in the alcohol. The quantity of any crosslinking agent should not be so great as to cause gelling of the solution prior to coating. Chemical modifiers suitable for use with the preferred hydroxy-functional hydrophobic polymers (such as Butvar B76(trademark)) include isocyanates, acid chlorides, active esters and the like, especially polyfunctional derivatives thereof, but isocyanates are preferred, as no by-products are formed during the relevant reactions. Suitable isocyanates include 4,4xe2x80x2-methylenebis(phenyl isocyanate), hexamethylene diisocyanate, toluene diisocyanate and the like, and are preferably added to the extent of 0.05-0.5 wt % of the hydrophobic polymer, preferably together with dibutyl tin dilaurate or a similar catalyst.
The use of a modifier such as a polyfunctional isocyanate provides another means of controlling the pore size in the final film, with increasing amounts of modifier leading to smaller diameter pores. The resulting films are also harder, more abrasion resistant, and thermally stable, which is particularly important for use as receptors in thermal transfer imaging, where softening or melting of the film during the imaging process is undesirable. The use of chemical modifiers also improves the performance of the films as receptors in aqueous ink jet imaging, but not in solvent-based ink jet imaging. It is believed that for good results with nonaqueous inks, the polymeric film must absorb substantial quantities of the ink solvent (with concomitant swelling), and that crosslinking or excessive hardening hinders this process.
As an alternative to irreversible chemical hardening and crosslinking by additives such as the isocyanates described above, reversible xe2x80x9cphysicalxe2x80x9d crosslinking or hardening of the films may be effected by incorporation of additives capable of ionic or dipolar interactions (e.g., hydrogen bonded interactions) with the polymer chains. This results in a microporous film of increased durability and abrasion resistance, but which retains the ability to swell on contact with nonaqueous inks, and hence is particularly well suited to nonaqueous ink jet imaging applications. Preferred additives of this type, suitable for use in Butvar B76(trademark) based films, are of the following general formula:
in which
R1 represents hydrogen, an alkyl group, a cycloalkyl group or an aryl group;
R2 represents an alkyl group, a cycloalkyl group or an aryl group;
each R3 represents an alkyl group or an alkoxy group; and
each R4 represents hydrogen, an alkyl group or an aryl group.
In preferred embodiments, R1 represents hydrogen; R2 represents an aryl group such as phenyl, tolyl, 3,4-dihydroxyphenyl, etc.; each R3 represents an alkyl or alkoxy group of up to 5 carbon atoms such as methyl, ethyl, butyl, methoxy, ethoxy, isopropoxy, etc.; and each R4 represents an alkyl group of up to 5 carbon atoms such as methyl, ethyl, etc.
A particularly preferred compound of this type is:
whose preparation is described in J. Med. Chem. (1974), 17(9), 956-65.
The mechanism by which compound (1) and similar species interact with polymers such as Butvar B76(trademark) is not well understood, but is believed to involve hydrogen bonding. They are typically added to the formulation in the range of about 1-10 wt % of the Butvar B76(trademark) or similar polymer, preferably about 3-5 wt %.
Other additives behaving similarly to Compound (1) include xcex1-D-glucose pentaacetate and diethyl terephthalate.
Other additives which may usefully be incorporated in the microporous films include surfactants, levelling agents, UV absorbers, antioxidants, free radical scavengers and mordents, all of which are materials known in the prior art. UV absorbers, antioxidants, free radical scavengers and mordents may improve the light-fastness and/or substantivity of colorants (especially dyes) subsequently deposited on the films. Typical UV absorbers include benzotriazoles and o-hydroxybenzophenones, typical antioxidants include hindered phenols and phenidone, typical radical scavengers include hindered tertiary amines, and typical mordents include quaternarized vinylpyridine polymers. Such materials may be added to the solution prior to coating, typically at loadings of up to 3 wt % of the Butvar B76(trademark) or similar polymer.
The use of levelling agents, particularly silicone- or fluorocarbon-based levelling agents, produces smoother coatings and glossier films. Preferred materials include N-methyl perfluorooctanesulfonamide (at a loading of up to 10 wt % of the Butvar B76(trademark) or similar polymer), and EFKA-30 and EFKA-3032 (at a loading of about 1 wt %). (EFKA-30 and EFKA-3032 are organosiloxane-based coating aids supplied by EFKA Chemicals.)
High surface gloss is a desirable attribute in ink jet receptors, but the microporous receptors of the prior art generally suffer from a matt appearance. It is a particular advantage of the present invention that it can provide microporous receptors that combine all the advantages of microporosity (such as shorter drying times and reduced image spread) with a relatively high degree of surface gloss, comparable to that shown by nonporous receptors. While the use of the aforesaid levelling agents is important in obtaining high gloss values, control over the size and uniformity of the pores, and over the particle size of any filler present, is equally important.
The microporous films made by the process of this invention are particularly suitable for use in imaging processes involving the deposition of one or more colorants on selected areas of the microporous film. The colorants typically comprise one or more dyes or pigments, which most commonly (but not necessarily) are dissolved or dispersed in a binder or a liquid carrier. The dyes or pigments may be chosen on the basis of their ability to absorb radiation of selected wavelengths (e.g., in the UV, visible or infrared regions), or for other physical properties, such as electrical conductivity, magnetic properties, etc. The colorants may be deposited on the film by any conventional means, including pens, pencils, crayons, typographic printing, planographic printing, intaglio printing, screen printing, electrophotographic printing, and thermal transfer imaging. However, the benefits of the invention are realized most fully when the colorants are deposited by ink jet printing.
Ink accepting members in accordance with the third aspect of the invention comprise a support which is typically an opaque, white, microporous sheet form material comprising: (a) a matrix of thermoplastic organic polymer; (b) a large proportion of finely divided water-insoluble siliceous filler; and (c) interconnecting pores. More specifically, the support comprises: (a) a matrix consisting essentially of substantially water-insoluble thermoplastic organic polymer, (b) finely divided substantially water-insoluble filler particles, of which at least 50% by weight are siliceous particles, the filler particles being distributed throughout the matrix and constituting from 40 to 90% by weight of the microporous material, and (c) a network of interconnecting pores communicating substantially throughout the microporous material, the pores constituting from 35 to 95% by volume of the microporous material. The manufacture of such materials is described in U.S. Pat. Nos. 5,326,391 and 4,861,644, the disclosures of which are incorporated herein by reference.
A preferred support for use in this aspect of the invention comprises the microporous material supplied commercially by PPG Industries Inc., Pittsburgh, under the tradename Teslin(trademark). Such materials are typically supplied in the form of a self-supporting sheet or web (e.g., of thickness 150-360 xcexcm), and may be used without further modification as the support in the manufacture of the image accepting members of the invention. If desired, however, one side of the Teslin(trademark) sheet or equivalent material may be adhered to an auxiliary support such as paper, card, polyester film, etc., as described in U.S. Pat. No. 5,605,750.
Alternatively, a coating of adhesive (such as a hotmelt adhesive or a pressure-sensitive adhesive) may be deposited on one side of the Teslin(trademark) sheet or equivalent material, enabling the sheet subsequently to be adhered to any desired surface.
The support carries on at least one of its major surfaces a microporous organic polymer film. When unmodified Teslin(trademark) sheet or similar material is used as the support, both sides may have deposited thereon a microporous organic polymer film. The microporous organic polymer film preferably has a thickness in the range 5 to 100 xcexcm, most preferably from about 20 to 80 xcexcm, and has a porosity in the range 30 to 80% by volume, most preferably from 50 to 70% by volume. The average pore size is preferably in the range 0.2-2.0 xcexcm, and the pore density preferably in the range 104-107 pores/mm2, most preferably about 106 pores/mm2. Best results are obtained when the distribution of pore sizes is such that a major proportion of the pores are less than 1.0 xcexcm in diameter, but a minor proportion of the pores have diameters greater than this, e.g., in the range 1.5-2.5 xcexcm. It is believed that the smaller pores enable the dyes and pigments of inks to be retained close to the surface of the film, whereas the larger pores facilitate rapid draining of the carrier fluid into the porous support.
In principle, the microporous organic polymer film may comprise any organic polymeric material capable of being fabricated as a microporous film. In practice, preference is given to materials which (prior to being formed into microporous films) are hydrophobic thermoplastics. (However, in the course of being fabricated as microporous films, the polymers may become crosslinked and/or acquire a degree of hydrophilic character.) Polymers with a high affinity for the solvents used in oil-based inks are particularly preferred. Said solvents typically comprise high boiling hydrocarbons, glycol ethers, glycol esters, alkyl esters, long chain alcohols, and the like, including mixtures of two or more of such species, and preferred polymers are those which swell and/or dissolve in such media. Examples of suitable polymers include acrylics, such as poly(methyl methacrylate), cellulose esters, such as cellulose acetate butyrate, and vinyl polymers, such as poly(vinyl acetal)s and vinyl chloride/vinyl acetate copolymers. Particularly preferred materials include the grade of poly(vinyl butyral) supplied by Solutia (formerly Monsanto) under the tradename Butvar(trademark) B-76, and the vinyl chloride/vinyl acetate copolymers supplied by Union Carbide under the tradenames Vinylite(trademark) VYNS and Vinylite(trademark) VAGH.
In principle, the microporous organic polymer film may be formed on the support by any method known in the art, provided the method of fabrication does not prevent the pores of the microporous organic film from communicating with the pores already present in the support. Thus, for example, bonding a pre-formed microporous film to the support by means of a layer of adhesive would not be a suitable manufacturing method. The preferred method, however, is the method described above in relation to the first aspect of the invention.
Various additives may be incorporated in the microporous organic polymer film, such as the chemical modifiers (including crosslinkers and hardeners) and fluorocarbon- or silicone-based levelling agents described above. The manufacturing process described above readily accommodates the incorporation of such additives, one or more of which may be used to optimize the properties of the film for particular end uses. However, the incorporation of particulate fillers, such as silica-based fillers and/or alumina-based fillers, is not preferred in this aspect of the invention.
The ink receiving element of the third embodiment of this invention is useful in any ink receiving process, but is especially useful for ink jet printing. xe2x80x9cInkxe2x80x9d as used herein means a colorant (e.g., dye or pigment) dispersed in a fluid or liquid carrier.
Suitable ink jet printers include those employing solid, phase-change inks, such as Tektronix Phaser(trademark) printers, those employing aqueous inks, such as the Epson Photo Stylus(trademark) printer, the Epson Stylus(trademark) 800 printer, the HP Photosmart(trademark) printer and the HP Deskjet(trademark) 870 printer, as well as those employing nonaqueous inks. Image accepting members in accordance with the invention are particularly suited to high quality multilevel ink jet printing, wherein multiple droplets of ink of a given color are jetted on individual pixel areas, and/or normal density and low-density inks of the same color are jetted from separate printheads. Printers suitable for this type of imaging include those equipped with piezoelectric shared-wall printheads as described, for example, in U.S. Pat. Nos. 4,887,100 and 4,879,568, and exemplified by the Xaarjet(trademark) printheads available from Xaar Ltd, Cambridge, UK.
A surprising feature of the microporous films prepared by the method of the invention, and of the image accepting members in accordance with the invention, is their high affinity for both aqueous and nonaqueous inks. With both types of ink, they show improvements in one or more attributes such as gloss, image density, resolution, drying time and image durability, compared to currently-available ink jet receptors (microporous or otherwise). Particularly striking is their apparent ability to retain the dyes and pigments from the inks at or near the surface of the microporous organic polymer film, and at the same time protect the said dyes and pigments against damage or removal by rubbing or wiping, even under wet conditions.
The brightness and sharpness of ink-jetted images are greatly enhanced when the colorants constituting the image are retained near the surface of the image accepting member. However, this is frequently at the expense of the durability of the image, since the dyes and pigments are susceptible to physical removal or displacement. Thus, many ink jet receptors of the prior art provide images which, although bright and sharp initially, have a poor resistance to smearing or pick-off, especially under damp conditions. Certain other ink jet receptors of the prior art are designed so that the ink is transported away from the surface and held in an underlayer. While this provides a well-protected image, its brightness and sharpness are inevitably degraded.
The mechanism by which the image accepting members of the invention retain and protect the image near the surface is not well understood, but the ability of the microporous organic polymer film to swell or distort on contact with the ink solvent is believed to be important. One possibility is that the colorant is held in micropores near the surface, but swelling of the polymer matrix causes collapse of these pores and effectively encapsulates the colorant. In the case of imaging with nonaqueous inks, evidence has been found for the formation of microscopic pits or depressions on the surface of the film where droplets of ink have been deposited. In such situations, the pigment resides at the bottom of the pits or depressions, and thus enjoys a degree of protection from smearing or other mechanical damage.
Microporous organic polymer films, and, in particular, microporous poly(vinyl butyral) films, have the desirable property of swelling or distorting on contact with the solvents (both aqueous and nonaqueous) used in commercially available inks. The behavior towards aqueous inks is particularly surprising, given that poly(vinyl butyral) is normally regarded as a hydrophobic polymer. However, most aqueous inks contain water-miscible organic solvents, such as glycols, alcohols, etc., in addition to water, and such materials may have a high affinity for poly(vinyl butyral). Furthermore, if the microporous films are prepared by the method described earlier herein, they are likely to contain residual amounts of a hydrophilic polymer or copolymer of N-vinyl pyrrolidone, whose presence may promote the desired interactions.
The invention is illustrated by the following non-limiting examples.

Method of preparing a microporous film, and imaging method

Abstract: (b) dissolving said first and second polymers in a solvent system which is compatible with both polymers, said solvent system comprising a blend of an aprotic organic solvent and an alcohol;


Disclosed is a touch screen display with an electric field shielding layer arranged between a liquid crystal layer of an LCD device and a glass substrate, having a touch sensing layer arranged on a top surface thereof, so that the electric field shielding layer isolates signal interference between the touch sensing layer and the liquid crystal layer.

An LCD (Liquid crystal display) device with a touch screen display integrated thereinto has been widely applied as, for example, the display for portable notebook computer, and the input device for cellular phone, electric household appliances, public information systems, office automated apparatus, etc.
A conventional touch screen display mainly includes a glass substrate being coated on one surface with a layer of transparent conductive layer, such as an indium-tin oxide conductive layer; a thin film being coated on a bottom surface with a transparent conductive layer corresponding to the transparent conductive layer on the glass substrate; and a plurality of insulating dot spacers provided between the transparent conductive layer on the glass substrate and the transparent conductive layer below the thin film for spacing the two transparent layers from each other. When the touch screen display is touched during an operation, a touch signal is generated and transmitted to a controller via a signal line. There is also another type of conventional touch screen display that adopts a capacitive touch sensing structure.
Among different structural designs for conventional LCD devices, there is a thin film transistor (TFT) LCD that mainly includes a glass substrate, a liquid crystal layer, two polarizing plates, a color filter layer, a backlight source, a pixel electrode layer located below the liquid crystal layer, and a common electrode layer located atop the liquid crystal layer. The common electrode layer and the pixel electrode layer together form a liquid crystal driving electrode layer for driving the liquid crystal layer.
Another type of LCD device is referred to as an in-plane switching mode (IPS mode) LCD, which is structurally similar to the TFT LCD, except that it adopts a horizontally arranged liquid crystal driving electrode structure formed between the glass substrate and a bottom surface of the liquid crystal layer. The liquid crystal driving electrode layer includes a plurality of staggered pixel electrodes and common electrodes for driving the liquid crystal layer.
While the integrated touch screen display and LCD device provides high practicability, it has the problem of mutual interference between the touch signal and the liquid crystal driving signal due to a extremely close distance between the touch screen display and the liquid crystal layer, the pixel electrode, and the common electrode of the LCD.
Further, in an analysis on capacitive effect, it is found the interference of capacitive coupling exists between the pixel and common electrodes of the LCD device and a touch sensing layer of the touch screen display. In addition, there is also interference of high-frequency signal between the LCD module and the touch sensing layer. These interferences are noise interferences in terms of the capacitive coupling formed between the touch sensing layer and a part of human body, and would adversely affect the accuracy in detecting the position of a touched point on the touch screen display. Meanwhile, a relatively high driving voltage used to obtain enhanced brilliance further intensifies the problem of noise interference.
The above-mentioned problems of signal interference occur in both the general TFT LCD and the IPS mode LCD.

Touch screen display with electric field shielding layer


A charging apparatus for a mobile robot enabling the mobile robot to move relatively freely even during charging using a wiring member, while preventing occurrence of an inconvenience such as damage to the wiring member, is provided. The charging apparatus includes a charging power source, a control board which controls the charging power source, and a wiring members for use in supplying electric power from the charging power source to a battery mounted on the mobile robot. The wiring member is connected to the mobile robot to follow the movement of the robot. The charging apparatus further includes a detector which detects tension applied to the wiring member. When the wiring members is pulled, an appropriate measure to stop the mobile robot or disconnect the wiring member from the robot is taken in accordance with a signal from the tension detector.

1. Field of the Invention
The present invention relates to an apparatus for charging a battery mounted on a mobile robot.
2. Description of the Related Art
There is conventionally known an apparatus for charging a mobile robot wherein a power-receiving connector is provided in place of the mobile robot and connected to a battery mounted on the robot, and a charging station including a charging power source and a power-feeding connector connected to the charging power source is installed within a range reachable by the mobile robot. With movement of the mobile robot, the power-receiving connector is connected to the power-feeding connector at the charging station for charging the battery by the charging power source (see, for example, Japanese Patent Application Laid-Open No. 2001-179663).
According to this apparatus, when the battery level is lowered, the mobile robot is capable of autonomously moving to the place where the charging station is installed, and having the power-receiving connector connected to the power-feeding connector for automatic charging.
In this conventional apparatus, however, the power-feeding connector is fixedly provided in the charging station. This means that the mobile robot has its movement restricted by the power-feeding connector via the power-receiving connector during charging, resulting in a considerably lowered degree of freedom in movement of the mobile robot. As such, the entertaining property of the mobile robot cannot be exerted effectively during charging, which would make the audience disappointed.
If a wiring member having one end connected to a charging power source has its other end connected to the mobile robot to allow the wiring member to follow the movement of the robot, the mobile robot will be able to move in a relatively wide range during charging. The restricted length of the wiring member, however, may cause an inconvenience such as damage to the wiring member when the mobile robot makes a movement large enough to pull the wiring member.


A web-based voice messaging system uses an application server, configured for executing a voice application defined by XML documents, that accesses subscriber attributes from a standardized information database server (such as LDAP), and messages from a standardized messaging server (such as IMAP). The application server, upon receiving a request from a browser serving a subscriber, accesses an IP based messaging server to obtain a stored message for the subscriber from a second party. The stored message identifies a text-based form. The application server converts the text-based form into an audible format. The application server generates an HTML document to present to the subscriber the form in audible format with audible prompts, based on the HTTP request and the text-based form. The application server then updates the text-based form based on an input from the subscriber. Thus, text-based forms can be retrieved and acted on via a telephone.

1. Field of the Invention
The present invention relates to generating and executing voice enabled web applications within a hypertext markup language (HTML) and hypertext transport protocol (HTTP) framework.
2. Description of the Related Art
The evolution of the public switched telephone network has resulted in a variety of voice applications and services that can be provided to individual subscribers and business subscribers. Such services include voice messaging systems that enable landline or wireless subscribers to record, playback, and forward voice mail messages. However, the ability to provide enhanced services to subscribers of the public switched telephone network is directly affected by the limitations of the public switched telephone network. In particular, the public switched telephone network operates according to a protocol that is specifically designed for the transport of voice signals; hence any modifications necessary to provide enhanced services can only be done by switch vendors that have sufficient know-how of the existing public switched telephone network infrastructure.
An open standards-based Internet protocol (IP) network, such as the World Wide Web, the Internet, or a corporate intranet, provides client-server type application services for clients by enabling the clients to request application services from remote servers using standardized protocols, for example hypertext transport protocol (HTTP). The web server application environment can include web server software, such as Apache, implemented on a computer system attached to the IP network. Web-based applications are composed of HTML pages, logic, and database functions. In addition, the web server may provide logging and monitoring capabilities.
In contrast to the public switched telephone network, the open standards-based IP network has enabled the proliferation of web-based applications written by web application developers using ever-increasing availability of web development tools. Hence, the ever-increasing popularity of web applications and web development tools provides substantial resources for application developers to develop robust web applications in a relatively short time and an economical manner. However, one important distinction between telephony-based applications and web-based applications is that telephony-based applications are state-aware, whereas web-based applications are stateless.
In particular, telephony applications are state-aware to ensure that prescribed operations between the telephony application servers and the user telephony devices occur in a prescribed sequence. For example, operations such as call processing operations, voicemail operations, call forwarding, etc., require that specific actions occur in a specific sequence to enable the multiple components of the public switched telephone network to complete the prescribed operations.
The web-based applications running in the IP network, however, are state-less and transient in nature, and do not maintain application state because application state requires an interactive communication between the browser and back-end database servers accessed by the browsers via a HTTP-based web server. However, an HTTP server provides asynchronous execution of HTML applications, where the web applications in response to reception of a specific request in the form of a URL from a client, instantiate a program configured for execution of the specific request, send an HTML web page back to the client, and terminate the program instance that executed the specific zo request. Storage of application state information in the form of a xe2x80x9ccookiexe2x80x9d is not practical because some users prefer not to enable cookies on their browser, and because the passing of a large amount of state information as would normally be required for voice-type applications between the browser and the web application would substantially reduce the bandwidth available for the client.
Commonly-assigned, copending application Ser. No. 09/559,637, filed Apr. 28, 2000, entitled Browser-Based Arrangement For Developing Voice Enabled Web Applications Using Extensible Markup Language Documents, the disclosure of which is incorporated in its entirety herein by reference, discloses an application server that executes a voice application defined by extensible markup language (XML) documents and dynamically generates an HTML form specifying selected application parameters from an XML document executable by the voice application. The HTML form is supplied to a browser, enabling a user of the browser to input or modify application parameters for the corresponding XML document into the form. The application server, upon receiving the form from the web browser, inserts the input application parameters into the XML document, and stores the application document for execution. Since voice applications are executed by the application server based on runtime parsing of the XML document, a user can concurrently use the HTML form to create or modify an XML document, post the HTML to the application server, and then execute the XML document to validate the inputs supplied to the HTML form. Thus, a user can easily generate XML documents and verify the corresponding voice application operation using a forms-based application development methodology.
Hence, web programmers can write voice-enabled web applications, using the teachings of the above-incorporated application Ser. No. 09/559,637, by writing XML pages that specify respective voice application operations to be performed. The XML documents have a distinct feature of having tags that allow a web browser (or other software) to identify information as being a specific kind or type of information. Hence, the XML documents define the application to be executed by the application server within the runtime environment, enabling voice enabled web applications to be generated and executed without the necessity of programming language environments.
The use of forms has been a significant contribution to the utility of HTML for the World Wide Web. Anyone can go to a web site and fill out a form to purchase, take a survey, request information, schedule an appointment, and so on. The forms are then posted to a common gateway interface (CGI) which interprets the organized information and stores it accordingly. In the business world, such forms can eliminate the drudgery of paperwork. In many cases, these forms are processed automatically. However, some forms such as vacation requests, cell phone or pager purchase request, purchase orders, capital expense requests, etc., require human approval.
A conventional way of simplifying the request approval is to e-mail the approving party a URL that specifies a CGI request for retrieval of a submitted form. The retrieved form is then presented by the web server enabling the approving party to click on the retrieved form to accept or deny the request. The updated form is then posted to the web server for storage. This method, however, is practical only when the approving party has access to a web browser and an e-mail client on a personal computer.
There is a need for an arrangement that enables users to deploy a scalable, open standards based form approval system on an open standards based network such as an Internet Protocol (IP) network by using a telephone.
This and other needs are attained by the present invention, where an application server, configured for executing a messaging application, includes an application runtime environment configured for dynamically generating a hypertext markup language (HTML) document to present to a subscriber a text-based formn, identified in a stored message from a second party, in audible format with audible prompts, by converting the text based form into audible format and providing the prompts. The application run time environment is configured to update the text-based form based on an input from the subscriber.
Another aspect of the present invention provides a method in an application server for executing a messaging application. The method includes receiving an HTTP request for execution of a prescribed messaging application operation for a subscriber. A stored message for the subscriber from a second party is accessed from an IP-based messaging server. The stored message identifies a text-based formn. The application server converts the text-based form into an audible format. The application server generates an HTML document to present to the subscriber the form in audible format with audible prompts, based on the HTTP request and the text based message. The application server then updates the text-based form based on an input from the subscriber.
Thus, by use of the application server, a subscriber or approving party can receive a text-based form, identified by a second party, converted to audio format and take action with regard the form contents by use of a telephone or a computer having a web browser.
Additional advantages and novel features of the invention will be set forth in part in the description which follows and in part will become apparent to those skilled in the art upon examination of the following or may be learned by practice of the invention. The advantages of the present invention may be realized and attained by means of instrumentalities and combinations particularly pointed out in the appended claims.

Voice IP approval system using voice-enabled web based application server