A topical ointment pharmaceutical composition that uses a lipophilic base, a pharmaceutical active and, dispersed in the base, from about 1% to about 50% by weight of the total composition of hydrogenated non-melted castor oil in powder form. The result of using hydrogenated non-melted castor oil in powder form is a surprising pharmaceutical elegance perceived to be smoother in texture and more spreadable than an ointment made by melting the hydrogenated castor oil.

This invention relates to topical pharmaceutical compositions.
Topical pharmaceutical compositions are, of course, well known. They can be used as water proofing agents, sunscreens, skin conditioning agents, lip balms, wound dressings, hair pomades, etc. Regardless of the specific use, common to pharmaceutically satisfactory topical actives are that they must stay on the skin for a sufficient period of time to allow the active to perform; they must not irritate the skin; and, they must be perceived by the patient as pharmaceutically elegant or the patient will simply not use them. By xe2x80x9cpharmaceutically elegantxe2x80x9d, as those skilled in the art know, one means the feel to the patient is good. It must not be too watery or too greasy. Some say it relates to the creaminess or lubricity properties as well.
There is a continual need for improvements in topical carrier systems, particularly for those that are lipophilic in nature, most of which are perceived by consumers as too waxy or greasy when smeared on the skin.
As a result of the unique properties of the cream/ointments of the present invention, the preparation can be dosed effectively and conveniently from a squeeze-type dispenser, which is a desirable objective.
Accordingly, it is a primary object of the present invention to prepare a topical application or pharmaceutical composition which is of wide-spread applicability (i.e. useful with many drug actives) and which is at the same time perceived by the patient/user as pharmaceutically elegant.
Another objective of the present invention is to achieve the primary objective with a composition especially adapted for lipophilic bases and which can provide effective delivery in squeeze tube formats.
An even further objective is to achieve each of the above objectives in a cost effective manner so that the price can be maintained at reasonable levels, without the need for using expensive cosmetic carrier systems to achieve elegance.
A yet further objective is to provide a method of preparation of a topical ointment that achieves each of the above composition objectives or attributes.
The method and manner of achieving the above objectives will become apparent from the detailed description of the invention which follows.
A topical ointment pharmaceutical composition that uses a lipophilic base, a pharmaceutical active and, dispersed in the base, from about 1% to about 50% by weight of the total composition of hydrogenated non-melted castor oil in powder form. The result of using hydrogenated non-melted castor oil in powder form is a surprising pharmaceutical elegance perceived to be smoother in texture and more spreadable than can ointment mad e by melting the hydrogenated castor oil.
For describing the compositions certain definitional terms are appropriate. xe2x80x9cPharmaceutically elegantxe2x80x9d has been previously defined. The xe2x80x9cpharmaceutical compositionxe2x80x9d as used throughout the present specification and the accompanying claims is to be understood as defining compositions of which the individual components or ingredients are themselves pharmaceutically acceptable, e.g. that is they are topically acceptable. Put another way, they are non-irritants, and they are either FDA approved or on the GRAS safe list. The term xe2x80x9ctopically active pharmaceuticalxe2x80x9d is intended to be non-limiting and includes those pharmaceutical active agents that are commonly applied topically such as waterproofing agents, skin barrier/skin protectant agents, skin conditioning agents, solvents, bio-adhesives, acne actives, analgesics, anesthetics, anorectals, antihistamines, anti-inflammatory agents, antibiotics, antifungals, antivirals, antimicrobials, scabicides, pediculicides, antineoplastics, antiperspirants, antipruritics, antisporadics, antiseborrheics, biologically active proteins and peptides, burn actives, cauterizing agents, depigment agents, diaper rash agents, enzymes, hair growth actives, kerotolytics, canker sore actives, cold sore actives, dental actives, saliva actives, photosensitizing actives, steroids, sunburn actives, sunscreens, wart actives, wound dressings and retinol, retinoic acid and retinoic acid derivatives. It is understood that this list is by way of example and not a limitation with respect to the active.
In the present compositions, there are three essential ingredients. The first is a lipophilic base normally selected from the group of vegetable oils, fatty acids, glycerides, or combinations thereof, including reaction combinations thereof. Thus, for example, fatty acid esters and fatty alcohols are included. The term xe2x80x9cfattyxe2x80x9d refers to higher carbon, generally C8 to C22. Suitable vegetable oils can include for example sunflower oil, safflower oil, castor oil, rapeseed oil, corn oil, Balsam Peru oil and soybean oil. Suitable fatty acids are generally C8 to C22 mono-and dicarboxylic fatty acids. They can include for example, stearic acid, oleic acid, myristic acid etc. Suitable fatty acid esters can include diisopropyl adipate, diisopropyl sebacate, diethyl sebacate, middle-length fatty acid triglycerides, middle-length acid propylene glycols, isopropyl myristate, and the like. Fatty alcohols can include cetanols, stearyl alcohol, cetostearyl alcohol, oleyl alcohol, behenyl alcohol, and the like.
The amount of the lipophilic base used is from about 20% to about 99% by weight of the total composition.
The second essential ingredient is the topically active pharmaceutical or in other words, the drug active. Suitable drug active categories have been previously listed. Generally the drug actives are present in amounts of from about 0.01% to about 10% by weight of the total composition.
The third essential ingredient and the one on which the discovery of the new invention is premised is, from about 1% by weight to about 50% by weight of the total pharmaceutical composition of hydrogenated, non-melted castor oil in powder form dispersed throughout the topical ointment. This changes dramatically the characteristics of the ointment. In particular, the ointment is smoother, more spreadable, perceived as less greasy or waxy in feel and functions effectively when dose dispensed from a squeeze tube. It does not happen if this is either not used or melted.
Critical to the invention, therefore, is that the hydrogenated castor oil powder be in a non-melted form. If it has been melted, it will not achieve the desired creaminess and lubricity of the present invention. Hydrogenated castor oil is itself known and can be obtained from a variety of sources, for example Henkel. Henkel has it available under the trademark CUTINA(copyright) HR NF and describes it as a slightly yellow fine free-flowing powder. It has an acid value of less than 3, a saponification value of 180, an iodine value of 5.0 and a hydroxy value of 160 with a melting range of 85xc2x0 C. to 88xc2x0 C. For further technical data and properties and application uses, see the technical data sheet of Henkel dated July 1999, a copy of which is being provided with the Information Disclosure Statement herein.
As earlier mentioned, the manner of preparation of the composition is equally important. It must be below the melt temperature of the hydrogenated castor oil and it must be prepared by dispersing under high shear mixing. Unexpectedly, when this occurs a matrix is formed in the lipophilic lipid base resulting in a semi-solid structure that is smoother, and more spreadable than a compound formulation made by simply melting hydrogenated castor oil into a lipid such as is conventional with, for example, lipstick. There are several advantages to a low temperature process. Exposures to high temperatures, which can degrade some ingredients such as active pharmaceutical ingredients or preservatives, can be avoided in a low temperature process. Temperature sensitive ingredients can be incorporated into the product at low temperatures prior to the formation of the semisolid structure. Exposing vegetable oils to high temperatures, especially unsaturated oils, can accelerate degradation and oxidation reactions resulting in the need for addition of antioxidants. Heating and cooling utility costs can be saved with a low temperature process. Manufacturing process times can be reduced with a low temperature process. The high shear mixing is achievable in a variety of mixing apparatus but one that is especially suitable is a high speed dispersator-type mixer. Another that is suitable is a rotor/stator-type emulsifier mixer. Yet a further one that provides satisfactory results is a high pressure-type emulsifier/mixer. By high shear mixing, it is meant that mixing occurs under high power per unit mass through rotating high shear forces. It is intended to distinguish this from more conventional formulary mixing apparatus such as planetary or anchor mixers.
The composition may contain other ingredients as well. These include viscosity modifiers, solvents, surfactants, preservatives, fragrances, waterproofing and skin barrier agents, etc.
Suitable viscosity adjusting agents (i.e., thickening and thinning agents) for use in the formulations of the present invention include, but are not limited to silica, microcrystalline wax, beeswax, paraffin, and cetyl palmitate. In addition, appropriate combinations or mixtures of these viscosity adjusters may be utilized according to the present invention.
Suitable solvents for use in the formulations of the present invention include, but are not limited to, water, ethanol, butylene glycol, dimethyl isosorbide, propylene glycol, isopropyl alcohol, glycerin, ethoxydiglycol, Pharmasolve, Carbowax 200, Carbowax 400, Carbowax 600, and Carbowax 800. In addition, combinations or mixtures of these solvents may be used according to the present invention.
Suitable surfactants for use in the formulations of the present invention include, but are not limited to nonionic surfactants like Surfactant 190 (dimethicone copolyol), Polysorbate 20 (Tween 20), Polysorbate 40 (Tween 40), Polysorbate 60 (Tween 60), Polysorbate 80 (Tween 80), lauramide DEA, cocamide DEA, and cocamide MEA, amphoteric surfactants like oleyl betaine and cocamidopropyl betaine (Velvetex BK-35), and cationic surfactants like Phospholipid PTC (Cocamidopropyl phosphatidyl PG-dimonium chloride). Appropriate combinations or mixtures of such surfactants may also be used accordingly to the present invention.
Suitable preservatives for use in the formulations of the present invention include, but are not limited to, antimicrobials such as Germaben II (manufactured by ICI; propylene glycol, diazolidinyl urea, methylparaben, and propylparaben), methylparaben, propylparaben, imidazolidinyl urea, benzyl alcohol, sorbic acid, benzoic acid, sodium benzoate, dichlorobenzyl alcohol, and formaldehyde, as well as physical stabilizers and antioxidants such as alphatocopherol (vitamin E), sodium ascorbate/ascorbic acid, ascorbyl palmitate and propyl gallate. In addition, combinations or mixtures of these preservatives may also be used in the formulations of the present invention.
Suitable moisturizers for use in the formulations of the present invention include, but are not limited to, lactic acid and other hydroxy acids and their salts, glycerin, propylene glycol, butylene glycol, sodium PCA, Carbowax 200, Carbowax 400, and Carbowax 800. Suitable emollients for use in the formulations of the present invention include, but are not limited to, PPG-15 stearyl ether, lanolin alcohol, lanolin, lanolin derivatives, cholesterol, petrolatum, isostearyl neopentanoate, octyl stearate, mineral oil, isocetyl stearate, Ceraphyl 424 (myristyl myristate), octyl dodecanol, dimethicone (Dow Corning 200-100 cps), phenyl trimethicone (Dow Corning 556), Dow Corning 1401 (cyclomethicone and dimethiconol), and cyclomethicone (Dow Corning 344), and Miglyol 840 (manufactured by Huls; propylene glycol dicaprylate/dicaprate). In addition, appropriate combinations and mixtures of any of these moisturizing agents and emollients may be used in accordance with the present invention.
Suitable fragrances and colors, such as FDandC Red No. 40 and FDandC Yellow No. 5, may be used in the formulations of the present invention. Other examples of fragrances and colors suitable for use in topical products are known in the art.
Suitable waterproofing and skin barrier agents include but are not limited to aluminum/magnesium hydroxide stearate, calcium stearate, aluminum stearate, magnesium stearate, dimethicone, and PTFE compounds.
Other suitable additional and adjunct ingredients which may be included in the formulations of the present invention include, but are not limited to, abrasives, absorbents, anti-caking agents, anti-foaming agents, anti-static agents, astringents (e.g., witch hazel, alcohol, and herbal extracts such as chamomile extract), binders/excipients, buffering agents, chelating agents (e.g., Versene EDTA), film forming agents, conditioning agents, opacifying agents, and protectants. Examples of each of these ingredients, as well as examples of other suitable ingredients in topical product formulations, may be found in publications by The Cosmetic, Toiletry, and Fragrance Association (CTFA). See, e.g., CTFA Cosmetic Ingredient Handbook, 2nd edition, eds. John A. Wenninger and G. N. McEwen, Jr. (CTFA, 1992).
Examples of various formulations taking advantage of the hydrogenated castor oil in non-melted form system of the present invention, and each having various rhealogical properties, are set forth below.
The following example is offered to further illustrate but not limit the invention. An anhydrous lipophilic pharmaceutical topical ointment comprised of a lipid and powdered hydrogenated castor oil (such as CUTINA(copyright) HR from the Henkel Corporation) that can be used as a vehicle for pharmaceutical actives was prepared.
The ointment was prepared by dispersing the powdered hydrogenated castor oil into the lipid at a temperature less than the melting point of the hydrogenated castor oil in particular at below 42xc2x0 C. The dispersion of the fine particles of the hydrogenated castor oil forms a semisolid structure in the lipid when subjected to the high shear mix.
The texture of this ointment is smoother and more spreadable than that of an ointment made by melting hydrogenated castor oil into the lipid, which obtains its structure by the crystallization of the hydrogenated castor oil upon cooling.
The lipid used was a vegetable oil (castor oil) but could be a fatty acid, a glyceride, an ester or mixtures thereof.

Elegant hydrogenated castor oil ointments


The present invention refers to an ink jet receiving sheet for ink-jet printers comprising a support and at least one ink receiving layer, wherein said ink receiving layer comprises a binder selected from the group consisting of gelatin and gelatin derivatives and at least one saccharide derivative selected from the group consisting of mono-, oligo-, or poly-saccharides as additive agents to improve glossiness.

The invention relates to an ink receptor for ink jet printers, and more particularly, to ink receptor containing a combination of gelatin binder and a saccharide as additive agent to improve glossiness.
Ink jet printing has become increasingly popular, particularly for so-called xe2x80x9cdesk-top publishingxe2x80x9d, because of its capability to produce small volumes of printed matter from digital input at high throughput speeds. Recent equipment developments have led to the introduction of multi-color ink jet printers that integrate colored graphics and text. To some extent, however, the applications of ink jet printing have been limited due to the demanding requirements the ink receptors must meet in order to provide high quality text and graphics.
Glossiness is associated with the capacity of a surface to reflect more light in some directions than in others and is defined as the quantity of reflected light measured at a predetermined angle (generally at 20xc2x0, 60xc2x0 or 85xc2x0) respect to incident light and is expressed in percentage.
JP Patent Application 5-16517, 2-289375 and 6-64306, DE Patent Application 2,234,823, and U.S. Pat. No. 4,379,804 disclose methods in which gelatin is used in ink-receiving layers of ink-jet receiving sheets. From these, it has become clear that gelatin has an advantageous function for the absorption of ink solvents. The gelatin is to improve smudge resistance and increase definition quality.
U.S. Pat. No. 5,141,599 discloses a receiving material for ink-jet printing including a polyolefin coated base paper and an ink receiving layer applied on the front face thereof, and the receiving layer containing a mixture of gelatin and starch of a grain size of less than about 20 xcexcm, and wherein the ratio of gelatin to starch ranges from 1:1 to 10:1. The receiving material so produced has a glossy surface achieved by as few work processes as possible, avoiding the necessity for additional smoothing processes. One of the forms preferred for the ink receiving layer additionally contains a copolymer containing polar groups such as an acrylate copolymer containing carboxyl groups, metal combined carboxyl groups and/or nitrile groups or a carboxylized vinylidene copolymer.
U.S. Pat. No. 5,804,320 discloses a receiving medium which comprises an ink-receiving layer comprising a pigment and an alkali-process gelatin, wherein said gelatin has no sol-gel reversibility at room temperature and has an average molecular weight within the range from 50,000 to 150,000. High image density and resolution, sharp color tone and good ink absorptivity are obtained.
U.S. Pat. No. 5,254,403 describes a receiving sheet which comprises a substrate and an image receiving layer comprising a mixture of (a) a polymer (b) a polysaccharide; and (c) a polymer containing oxyalkylene monomers to provide receiving sheets that enable the formation of images with high optical density with minimum intercolor bleed.
EP Patent Application 667,245 describes receiving sheets for ink jet printing containing monosaccharides, oligosaccharides or alcohols, having rapid drying times and being resistant to curling.
U.S. Pat. No. 5,474,843 discloses an ink receiving sheet forming quick-drying, water-resistant, light-stable ink prints with aqueous inks. The material comprises a support such as a polyester film and a coated layer containing a water-soluble mordant that forms insoluble compounds with and immobilizes the dyestuffs of the inks and a hardened polymer, preferably, hardened gelatin, which contains polymeric beads that protrude from the layer. A highly preferred hardenable polymer is gelatin. Other preferred polymers include chitosan and 100% hydrolyzed polyvinyl alcohol. Chitosan is a linear biopolymer, specifically a polysaccharide which comprises two monosaccharides, N-acetyl-D-glucosamine and D-glucosamine linked by xcex2-glycosidic bonds. Said polymers can yield a finished surface of high gloss.
U.S. Pat. No. 5,472,930 discloses a thermosensitive receiving material containing a mono-, oligo- or polysaccharide and a catalyst in one or more binder layers arranged on a transparent support. A black-and-white image with high optical density, good gray step reproduction, great sharpness and good stability is formed when the material is heated imagewise, e.g. by means of a thermohead.
The present invention relates to an ink jet receiving sheet comprising a support and at least one ink receiving layer, wherein said ink receiving layer comprises a binder selected from the group consisting of gelatin and gelatin derivatives and at least one saccharide derivative selected from the group consisting of mono-, oligo-, or poly-saccharides as additive agent to improve glossiness.
A first essential element of the ink jet receiving sheet according to the present invention is the use of gelatin or gelatin derivatives as binder component of the ink receiving layer(s).
Any gelatin made from animal collagen can be used, but gelatin made from pig skin, cow skin or cow bone collagen is preferable. The kind of gelatin is not specifically limited, but lime-processed gelatin, acid processed gelatin, amino group inactivating gelatin (such as acetylated gelatin, phthaloylated gelatin, malenoylated gelatin, benzoylated gelatin, succinoylated gelatin, methyl urea gelatin, phenylcarbamoylated gelatin, and carboxy modified gelatin), or gelatin derivatives (for example, gelatin derivatives disclosed in JP Patent Publications 38-4854/1962, 39-5514/1964, 40-12237/1965, 42-26345/1967 and 2-13595/1990, U.S. Pat. Nos. 2,525,753, 2,594,293, 2,614,928, 2,763,639, 3,118,766, 3,132,945, 3,186,846 and 3,312,553 and GB Patents 861,414 and 103,189) can be used singly or in combination.
The gelatin binder is preferably added to the ink receiving layer(s) in a total amount of from 1 to 20 g/m2, and more preferably from 2 to 10 g/m2. When preparing the ink jet receiving sheet by coating a plurality of ink receiving layers, each ink receiving layer comprises an amount of gelatin binder ranging from 0.5 to 10 g/m2.
The second essential element according to the present invention is the use of mono-, oligo-, and poly-saccharides as additive agents to improve glossiness in the ink receiving layer(s). The saccharide derivatives can comprise a recurring unit comprising five or six carbon atoms. The saccharide derivatives can be hydrogenated or non-hydrogenated. Preferred recurring units include, for example, glucose, xylose, mannose, arabinose, galactose, sorbose, fructose, fucose, adonitol, arbitol, inositol, xylitol, dulcitol, iditol, lactitol, mannitol, sorbitol, and the like. The average molecular weight of the saccharide derivatives ranges from 1,000 to 500,000, preferably from 1,000 to 30.000.
Hydrogenated and non-hydrogenated saccharide derivatives useful in the present invention are commercially available, for example, under the trade designation POLYSORB(trademark) or GLUCIDEX(trademark), from Roquette, Lille, France. The preparation of hydrogenated and non-hydrogenated saccharides usually starts from natural products (such as starch, agar, tragacanth gum, xanthan gum, guar gum, and the like) by means of enzymatic processes (to reduce the average molecular weight) and of reducing processes (to saturate the molecule, in case of hydrogenated saccharides).
The above mentioned saccharide derivatives are added to the ink receiving layer(s) in an amount ranging from 0.1 to 5 g/m2, preferably from 0.5 to 3 g/m2. When preparing the ink jet receiving sheet by coating a plurality of ink receiving layers, each ink receiving layer comprises an amount of saccharide derivatives ranging from 0.05 to 2.5 g/m2.
Examples of suitable polysaccharides as additive agents to improve glossiness include (1) cellulose ester salts, such as sodium salts of cellulose phosphate ester (including those available from James River Chemicals), cellulose phosphate, available from CTC organics, sodium cellulose sulfate, available from Janssen Chimica, cellulose carbonate, available from Sigma Chemicals, sodium ethyl cellulose (which can be obtained by the reaction of alkali cellulose with sodium chloroethane sulfonate), and the like; (2) cellulose ethers and their salts, such as sodium carboxymethylcellulose (including CMC 7HOF, available from Hercules Chemicals Company), sodium carboxymethylhydroxyethyl cellulose (including CMHEC 43H.TM. and 37L, available from Hercules Chemical Company; CMHEC 43H(trademark) is believed to be a high molecular weight polymer with carboxymethyl cellulose (CMC)/hydroxyethyl cellulose (HEC) ratio of 4:3, and CMHEC 37L is believed to be a lower molecular weight polymer with a CMC/HEC ratio of 3:7, carboxymethylmethyl cellulose, available from Aqualon Company, carboxymethyl cellulose calcium salt, available from Pfaltz and Bauer Inc., carboxymethyl cellulose ether sodium salt, available from E. M. Science Company, carboxymethyl cellulose hydrazide, available from Sigma Chemicals, sodium sulfoethyl cellulose (which can be prepared by the reaction of sodium vinyl sulfonate with alkali cellulose), and the like; (3) cationic cellulose ethers, such as diethyl aminoethyl cellulose (including DEAE cellulose, available from Poly Sciences Inc.), cationic hydroxyethyl celluloses, such as diethyl ammonium chloride hydroxyethylcellulose and hydroxypropyl triethyl ammonium chloride hydroxyethylcellulose (available as Celquat H-100 and L-200 from National Starch and Chemical Company and as Polymer JR series from Union Carbide Company), and the like; (4) hydroxyalkyl celluloses, such as hydroxyethyl cellulose (Including Natrosol 250 LR, available from Hercules Chemical Company), hydroxypropyl methyl cellulose, such as Methocel(trademark) K35LV, available from Dow Chemical Company, hydroxypropyl hydroxyethyl cellulose, available from Aqualon Company, dihydroxypropyl cellulose (which can be prepared by the reaction of 3-chloro-1,2-propandiol with alkali cellulose), and the like; (5) substituted deoxycelluloses, such as chlorodeoxycellulose (which can be prepared by the reaction of cellulose with sulfuryl chloride in pyridine and CHCl3 at 25xc2x0 C.), amino deoxycellulose (which can be prepared by the reaction of chlorodeoxycellulose with a 19% alcoholic solution of ammonia for 6 hours at 160xc2x0 C.), deoxycellulose phosphate (which can be prepared by the reaction of tosyl cellulose with triethyl phosphate in dimethyl formamide at 85xc2x0 C.), deoxy cellulose phosphonium salt (which can be prepared by the reaction of tosyl cellulose with tris(hydroxy methyl) phosphine), and the like; (6) dextran polymers, such as carboxymethyl dextran (including #16058, available from Poly Sciences Inc.), diethyl aminoethyl dextran, such as #5178, available from Poly Sciences Inc., dextran sulfate, available from Sigma Chemical Company, dextran sulfate potassium salt, available from Calibiochem Corporation, dextran sulfate sodium salt, available from Poly Sciences Inc., amino dextran, available from Molecular Probes Inc., dextran polysulfonate sodium salt, available from Research Plus Inc., and the like; (7) natural ionic gums and their modifications, such as alginic acid sodium salt (including #032, available from Scientific Polymer Products), alginic acid ammonium salt, available from Fluka Chemie AG, alginic acid calcium salt, available from Fluka Chemie AG, alginic acid calcium sodium salt, available from American Tokyo Kasel Inc., gum arabic, available from Sigma Chemicals, Carrageenan sodium salt, available from Gallard-Schless Inc., carboxymethyl hydroxypropyl guar, available from Aqualon Company, cationic gum guar, available as Celanese Jaguars C-14-S, C-15, and C-17 from Celanese Chemical Company, karaya gum, available from Sigma Chemicals, xanthan gum, available as Keltrol-T from Kelco division of Merck and Company, chitosan, available from Fluka Chemie AG, n-carboxymethyl chitin, and the like; (8) protein polymers, such as dimethylammonium hydrolyzed collagen protein, available as Croquats from Croda, agar-agar, available from Pfaltz and Bauer Inc., amino agarose, available from Accurate Chemical and Scientific Corporation, and the like; (9) n-carboxymethyl amylose sodium salt, available from Sigma Chemicals; and the like, as well as mixtures thereof.
The supports used in the ink jet receiving sheet of the invention include any conventional support for ink jet receiving sheet. A transparent or opaque support can be optionally used according to its final use. Useful examples of transparent support include films of polyester resins, cellulose acetate resins, acryl resins, polycarbonate resins, polyvinyl chloride resins, poly(vinylacetal) resins, polyether resins, polysulfonamide resins, polyamide resins, polyimide resins, cellophane or celluloid and glass plates. The thickness of the transparent support is preferably 10 to 200 xcexcm. Useful examples of opaque supports include paper, coated paper, synthetic paper, resin-covered paper, pigment-containing opaque films or expanded films, even if synthetic papers, resin-covered papers or various films are preferred in view of glossiness or smoothness, or polyester films are preferred in view of touchiness or luxuriousness.
The base paper constituting the resin-covered paper useful in the invention is not specifically limited, and any conventional paper can be used, but a smooth paper used as a conventional photographic support is preferable. The pulp used for the preparation of the base paper, singly or in admixture, is constituted by natural pulp, reproduction pulp, chemical pulps such as hardwood bleached kraft pulp, softwood bleached kraft pulp, high yield pulps such as groundwood pulp or thermo-mechanical pulp, recycled pulps and non-wood pulps such as cotton pulp or synthetic pulp. These base papers may contain additives usually employed in paper manufacture such as a sizing agent, binders, fixing agents, yield-improving agents, cationated agents, paper stiffness enhancing agents, reinforcing agents, fillers, anti-static agents, fluorescent brightening agents or dyes. A surface sizing agent, a surface reinforcing agent, a fluorescent brightening agent, an antistatic agent and an anchoring agent may be coated on the surface of the material.
The thickness of the base paper is not specifically limited, but is preferably 10 to 200 xcexcm. A base paper having a smooth surface is preferable, which is obtained by applying a pressure to or calendering the paper during or after papering. The weight of the base paper is preferably 30 to 250 g/m2. The resin used in the manufacturing of resin-covered paper is preferably a polyolefin resin or a resin capable of being hardened with an electron beam. The polyolefin resin includes an olefin homopolymer such as a low density polyethylene, a high density polyethylene, polypropylene or polypentene, an olefin copolymer such as ethylene-propylene copolymer or their mixture, each having various densities or melt viscosity indexes (melt index). These resins can be used singly or in combination.
The resin for the resin-covered paper preferably contains various additives, for example, white pigments such as titanium oxide, zinc oxide, talc or calcium carbonate, a fatty acid amide such as stearic acid amide or arachidic acid amide, a fatty acid metal salt such as zinc stearate, calcium stearate, aluminum stearate or magnesium stearate, an anti-oxidant such as Irganox(trademark) 1010 or Irganox(trademark) 1076, blue pigments or dyes such as cobalt blue, ultramarine or phthalocyanine blue, magenta pigments or dyes such as cobalt violet, fast violet or manganese violet, a brightening agent and a UV absorber. These additives may be all suitably used in combination.
The resin-covered paper, which is the support preferably used in the present invention, is manufactured by the so-called extrusion method casting a thermally fused resin (for example, fused polyolefin) on the moving paper, whereby both surfaces of the paper are covered with the resin. When the paper is covered with a resin capable of being hardened with electron beam irradiation, the resin itself is coated with a conventional coater such as a gravure coater or a blade coater and then is irradiated with electron beam to harden the coated resin. Before the paper is coated with a resin, the surface of the paper is preferably subjected to an activation treatment such as a corona discharge treatment or a flame treatment. The surface of the support on the ink receiving layer side is glossy or matted depending upon its usage, but a glossy surface is preferable. The back side of the support is not necessarily covered with a resin, but it is preferably covered with a resin to prevent curling. The back surface of a support is ordinarily non-glossy, but the back surface or both surfaces of the support are optionally subjected to activation treatments such as a corona discharge treatment or a flame treatment. The thickness of a covered resin is not specifically limited, but ordinarily ranges from 5 to 50 xcexcm.
A subbing or primer layer may be provided to improve the adhesion between the film support and the ink receiving layer. Subbing layers useful to this purpose are widely known in the photographic art and include, for example, vinylidene chloride polymers, such as vinylidene chloride/acrylo-nitrile/acrylic acid terpolymers or vinylidene chloride/methylacrylate/itaconic acid terpolymers.
In addition to the above mentioned ingredients, the ink receiving layer(s) can comprise other adjuvants dispersed in a binder. Useful additional adjuvants are represented by fillers, surfactants, mordants, matting agents, hardeners, plasticizers, and the like.
Organic and inorganic particles can be used as fillers. Useful filler examples are represented by silica (colloidal silica), alumina or alumina hydrate (aluminazol, colloidal alumina, a cation aluminum oxide or its hydrate and pseudo-boehmite), a surface-processed cation colloidal silica, aluminum silicate, magnesium silicate, magnesium carbonate, titanium dioxide, zinc oxide, calcium carbonate, kaolin, talc, clay, zinc carbonate, satin white, diatomaceous earth, synthetic amorphous silica, aluminum hydroxide, lithopone, zeolite, magnesium hydroxide and synthetic mica. Among these inorganic pigments, porous inorganic pigments are preferable such as porous synthetic silica, porous calcium carbonate and porous alumina.
Useful examples of organic fillers are represented by polystyrene, polymethacrylate, polymethyl-methacrylate, elastomers, ethylene-vinyl acetate copolymers, polyesters, polyester-copolymers, polyacrylates, polyvinylethers, polyamides, polyolefines, polysilicones, guanamine resins, polytetrafluoroethylene, elastomeric styrene-butadiene rubber (SBR), urea resins, urea-formalin resins. Such organic fillers may by used in combination, and/or instead of the above-mentioned inorganic fillers.
The above mentioned fillers are added to the ink receiving layer(s) in an amount from 0.1 to 5 g/m2, preferably from 0.2 to 3.0 g/m2, most preferably from 0.3 to 1 g/m2.
Preferred examples of surfactants include anionic surfactants, amphoteric surfactants, cationic surfactants, and nonionic surfactants.
Examples of anionic surfactants include alkylsulfocarboxylates, xcex1-olefin sulfonates, polyoxyethylene alkyl ether acetates, N-acylaminoacids and salts thereof, N-acylmethyltaurine salts, alkylsulfates, polyoxyalkylether sulfates, polyoxyalkylether phosphates, rosin soap, castor oil sulfate, lauryl alcohol sulfate, alkylphenol phosphates, alkyl phosphates, alkyl allyl sulfonates, diethylsulfosuccinates, diethylhexylsulfosuccinates and dioctylsulfosuccinates.
Examples of the cationic surfactants include 2-vinylpyridine derivatives and poly-4-vinylpyridine derivatives.
Examples of the amphoteric surfactants include lauryl dimethyl aminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine, propyldimethylaminoacetic acid betaine, polyoctyl polyaminoethyl glycine, and imidazoline derivatives.
Useful examples of non-ionic surfactants include non-ionic fluorinated surfactants and non-ionic hydrocarbon surfactants. Useful examples of non-ionic hydrocarbon surfactants include ethers, such as polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene alkyl allyl ethers, polyoxyethylene oleyl ethers, polyoxyethylene lauryl ethers, polyoxyethylene alkyl ethers, polyoxyalkylene alkyl ethers; esters, such as polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate and polyoxyethylene stearate; and glycol surfactants. Specific examples of nonionic surfactants include octylphenoxy polyethoxy ethanols, such as Triton(trademark) X-100, X-114 and X-405, available from Union Carbide Co., Danbury, Conn.; acetylenic diols such as 2,4,7,9-tetramethyl-5-decyn-4,7-diol and the like, such as Surfynol(trademark) GA and Surfynol(trademark) CT-136, available from Air Products and Chemicals Co., Allentown, Pa.; trimethyl nonylpolyethylene-glycol ethers, such as Tergitol(trademark) TMN-10 (containing 10 oxyethylene units, believed to be of formula C12H25O(C2H4O)5H), available from Union Carbide Co., Danbury, Conn.; non-ionic esters of ethylene oxide, such as Merpol(trademark) SH (believed to be of formula CH3(CH2)12(OC2H4)8OH), available from E. I. Du Pont de Nemours and Co., Wilmington, Del.; non-ionic esters of ethylene oxide and propylene oxide, such as Merpol(trademark) LFH (believed to be of formula CH3(CH2)n(OC2H4)8(OC3H6)8OH, where n is an integer from 12 to 16), available from E. I. Du Pont de Nemours and Co., Wilmington, Del., and the like, as well as mixtures thereof. Non-limiting examples of non-ionic fluorinated surfactants include linear perfluorinated polyethoxylated alcohols (e.g., Zonyl(trademark)FSN, Zonyl(trademark)FSN-100, Zonyl(trademark)FSO, and Zonyl(trademark)FSO-100 available from DuPont Specialty Chemicals, Wilmington, Del.), fluorinated alkyl polyoxyethylene ethanols (e.g., Fluorad(trademark) FC-170C available from 3M, St. Paul, Minn.), fluorinated alkyl alkoxylate (e.g., Fluorad(trademark) FC-171 available from 3M, St. Paul, Minn.), fluorinated alkyl esters (e.g., Fluorad(trademark) FC-430, FC-431, and FC-740 available from 3M, St. Paul, Minn.) and fluorine-substituted alkyl esters and perfluoroalkyl carboxylates (for example, the F-tergent series manufactured by Neos Co., Ltd., the Lodyne series manufactured by Ciba-Geigy, the Monflor series manufactured by ICI, the Surfluon series manufactured by Asahi Glass Co., Ltd., and the Unidyne series manufactured by Daikin Industries, Ltd.). Preferred nonionic fluorocarbon surfactants include Zonyl(trademark) FSO, Fluorad(trademark) FC-170C, and Fluorad(trademark) FC-171.
The above mentioned non-ionic surfactants are added to the ink receiving layers in an amount from 0.01 to 1.0 g/m2, preferably from 0.05 to 0.50 g/m2.
Mordants may be incorporated in the ink-receptive layer of the present invention. Such mordants are represented by cationic compounds, monomeric or polymeric, capable of complexing with the dyes used in the ink compositions. Useful examples of such mordants include quaternary ammonium block copolymers, such as Mirapol A-15 and Mirapol WT available from Miranol Inc., Dayton, N.J., prepared as disclosed in U.S. Pat. No. 4,157,388, Mirapol AZ-1 available from Miranol Inc., prepared as disclosed in U.S. Pat. No. 4,719,282, Mirapol AD-1 available from Miranol Inc., prepared as disclosed in U.S. Pat. No. 4,157,388, Mirapol 9, Mirapol 95, and Mirapol 175 available from Miranol Inc., prepared as disclosed in U.S. Pat. No. 4,719,282, and the like. Other suitable mordants comprise diamino alkanes, ammonium quaternary salts (such as poly(vinylbenzyl quaternary ammonium salts disclosed in U.S. Pat. No. 4,794,067), and quaternary acrylic copolymer latexes.
Other suitable mordants are fluoro compounds, such as tetra ammonium fluoride hydrate, 2,2,2-trifluoroethylamine hydrochloride (Aldrich #18,038-6); 2,2,2-trifluoroethyl-toluene sulfonate (Aldrich #17,782-2); 1-(xcex1,xcex1,xcex1-trifluoro-m-tolyl) piperazine hydrochloride, 4-bromo-xcex1,xcex1,xcex1-trifluoro-o-toluidine hydrochloride, difluorophenylhydrazine hydrochloride, 4-fluorobenzylamine hydrochloride, 4-fluoro-xcex1,xcex1-dimethylphenethylamine hydrochloride, 2-fluoroethylaminehydrochloride, 2-fluoro-1-methyl pyridinium-toluene sulfonate, 4-fluorophenethylamine hydrochloride, fluorophenylhydrazine hydrochloride, 1-(2-fluorophenyl) piperazine monohydrochloride, 1-fluoro pyridinium trifluoromethane sulfonate.
Further mordants are monoammonium compounds as disclosed, for example, in U.S. Pat. No. 5,320,902, including (A) tetradecyl ammonium bromide (Fluka 87582), tetradodecyl ammonium bromide (Fluka 87249), tetrahexadecyl ammonium bromide (Fluka 87298), tetraoctadecyl ammonium bromide (Aldrich 35,873-8), and the like; (B) 2-coco trimethyl ammonium chloride (Arquad C-33, C-33W, C-50 from Akzo Chemie), palmityl trimethyl ammonium chloride (Adogen 444 from Sherex Chemicals), myristyl trimethyl ammonium bromide (Cetrimide BP Triple Crown America), benzyl tetradecyl dimethyl ammonium chloride (Arquad DM 14B-90 from Akzo Chemie), didecyl dimethyl ammonium bromide (Aldrich 29,801-8), dicetyl dimethyl ammonium chloride (Adogen 432CG, Sherex Chemicals), distearyl dimethyl ammonium methyl sulfate (Varisoft 137, 190-100P from Sherex Chemicals, Arosurf TA-100 from Sherex Chemicals), difatty acid isopropyl ester dimethyl ammonium methyl sulfate (Rewoquat CR 3099 from Rewo Quimica, Loraquat CR 3099 from Dutton and Reinisch), tallow dimethyl trimethyl propylene diammonium chloride (Tomah Q-D-T from Tomah), and N-cetyl, N-ethyl morpholinium ethosulfate (G-263 from ICI Americas).
Additional mordants are phosphonium compounds, such as, for example, those disclosed in U.S. Pat. No. 5,766,809, including bromomethyl triphenyl phosphonium bromide (Aldrich 26,915-8), 3-hydroxy-2-methyl propyl triphenyl phosphonium bromide (Aldrich 32,507-4), 2-tetraphenyl phosphonium bromide (Aldrich 21,878-2), tetraphenyl phosphonium chloride (Aldrich 21879-0), hexadecyl tributyl phosphonium bromide (Aldrich 27,620-0), and stearyl tributyl phosphonium bromide (Aldrich 29,303-2).
Additional examples of mordants include those disclosed in U.S. Pat. Nos. 5,760,809; 5,457,486; 5,314,747; 5,320,902 and 5,441,795.
The ink receiving layer can be hardened with a hardener in order to improve water resistance or dot reproduction. Examples of the hardener include aldehyde compounds such as formaldehyde and glutaraldehyde, ketone compounds such as diacetyl and chloropentanedion, bis(2-chloroethylurea), 2-hydroxy-4,6-dichloro-1,3,5-triazine, reactive halogen-containing compounds disclosed in U.S. Pat. No. 3,288,775, carbamoyl pyridinium compounds in which the pyridine ring carries a sulfate or an alkylsulfate group disclosed in U.S. Pat. Nos. 4,063,952 and 5,529,892, divinylsulfones, reactive olefin-containing compounds disclosed U.S. Pat. No. 3,635,718, N-methylol compounds disclosed in U.S. Pat. No. 2,732,316, isocyanates disclosed in U.S. Pat. No. 3,103,437, aziridine compounds disclosed in U.S. Pat. Nos. 3,017,280 and 2,983,611, carbodiimides disclosed in U.S. Pat. No. 3,100,704, epoxy compounds disclosed in U.S. Pat. No. 3,091,537, halogencarboxyaldehydes such as mucochloric acid, dioxane derivatives such as dihydroxy dioxane, and inorganic hardeners such as chromium alum, potash alum and zirconium sulfate. These hardeners can be used singly or in combination. The addition amount of hardener is preferably from 0.01 to 10 g, and more preferably from 0.1 to 5 g based on 100 g of a binder contained in the ink receiving layer.
The ink receiving layer may contain a matting agent in an amount of 0.005 to 0.3 g/m2 in order to prevent adhesion defects such as blocking. The matting agents may be defined as particles of inorganic or organic materials capable of being discontinuously dispersed in a hydrophilic organic colloid. The inorganic matting agents include oxides such as silicon oxide, titanium oxide, magnesium oxide and aluminum oxide, alkali earth metal salts such as barium sulfate, calcium carbonate and magnesium sulfate, light-insensitive silver halide particles such as silver chloride and silver bromide (each of which may contain a small amount of iodine) and glass particles. Besides these substances there may be used inorganic matting agents which are disclosed in DE Patent 2,529,321, in GB Patents 760,775 and 1,260,772, U.S. Pat. Nos. 1,201,905, 2,192,241, 3,053,662, 3,062,649, 3,257,296, 3,322,555, 3,353,958, 3,370,951, 3,411,907, 3,437,484, 3,523,022, 3,615,554, 3,635,714, 3,769,020, 4,021,245 and 4,029,504. The organic matting agents include starch, cellulose esters such as cellulose acetate propionate, cellulose ethers such as ethyl cellulose and synthetic resins. The synthetic resins are water insoluble or sparingly soluble polymers which include an alkyl(meth)acrylate, alkoxyalkyl(meth)acrylate, glycidyl(meth)acrylate, (meth)acrylamide polymer, a vinyl ester such as vinyl acetate and acrylonitrile, an olefin such as ethylene or styrene and a copolymer of the above described monomers with other monomers such as acrylic acid, methacrylic acid, xcex1,xcex2-unsaturated dicarboxylic acid, hydroxyalkyl(meth)acrylate, sulfoalkyl(meth)acrylate and styrene sulfonic acid. Further, a benzoguanamin-formaldehyde resin, an epoxy resin, nylon, polycarbonates, phenol resins, polyvinyl carbazols or polyvinylidene chlorides can be used. Besides the above there may be used organic matting agents which are disclosed in GB Patent 1,055,713, in U.S. Pat. Nos. 1,939,213, 2,221,873, 2,268,662, 2,322,037, 2,376,005, 2,391,181, 2,701,245, 2,992,101, 3,079,257, 3,262,782, 3,443,946, 3,516,832, 3,539,344,554, 3,591,379, 3,754,924 and 3,767,448, in JP Patents 49-106821/1974 and 57-14835/1982. These matting agents may be used alone or in combination.
The ink-receiving layer of the present invention can also comprise a plasticizer such as ethylene glycol, diethylene glycol, propylene glycol, polyethylene glycol, glycerol monomethylether, glycerol monochlorohydrin, ethylene carbonate, propylene carbonate, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, urea phosphate, triphenylphosphate, glycerolmonostearate, propylene glycol monostearate, tetramethylene sulfone, N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, and polymer latices with low Tg-value such as polyethylacrylate, polymethylacrylate, etc.
The ink receiving layer can comprise biocides. Examples of suitable biocides include (A) nonionic biocides, such as 2-bromo-4xe2x80x2-hydroxyacetophenone (Busan 90 available from Buckman Laboratories); 3,5-dimethyl tetrahydro-2H-1,3,5-thiadiazine-2-thione (Slime-Trol RX-28 available from Betz Paper Chem Inc.; a nonionic blend of 5-chloro-2-methyl-4-isothiazoline-3-one, 75% by weight and 2-methyl-4-isothiazolin-3-one, 25% by weight (available as Amerstat 250 from Drew Industrial Division; Nalcon 7647 from Nalco Chemical Company; Kathon LX from Rohm and Haas Company); and the like, as well as mixtures thereof; (B) anionic biocides, such as anionic potassium N-hydroxymethyl-N-methyl-dithiocarbamate (available as Busan 40 from Buckman Laboratories Inc.); an anionic blend of methylene bis-thiocyanate, 33% by weight, sodium dimethyl-dithiocarbamate, 33% by weight, and sodium ethylene bisdithiocarbamate, 33% by weight, (available as Amerstat 282 from Drew Industrial Division; AMA-131 from Vinings Chemical Company); sodium dichlorophene (G-4-40 available from Givaudan Corporation); and the like, as well as mixtures thereof; (C) cationic biocides, such as cationic poly(oxyethylene(dimethylamino)ethylene(dimethylamino)ethylene dichloride) (Busan 77 available from Buckman Laboratories Inc.); a cationic blend of bis(trichloromethyl) sulfone and a quaternary ammonium chloride (available as Slime-Trol RX-36 DPB865 from Betz Paper Chem. Inc.); and the like, as well as mixtures thereof. The biocide can be present in any effective amount; typically, the biocide is present in an amount of from 0.1 to 3% by weight of the coating, although the amount can be outside this range.
The ink receiving layer in the invention may further contain various conventional additives such as colorants, colored pigments, pigment dispersants, lubricants, permeating agents, fixing agents for ink dyes, UV absorbers, anti-oxidants, dispersing agents, anti-foaming agents, leveling agents, fluidity improving agents, antiseptic agents, brightening agents, viscosity stabilizing and/or enhancing agents, pH adjusting agents, anti-mildew agents, anti-fungal agents, agents for moisture-proofing, agents for increasing the paper stiffness and anti-static agents.
The above-mentioned various additives can be added ordinarily in a range of 0 to 10% by weight based on the solid content of the ink receiving layer composition.
As a coating method of an ink receiving layer coating solution, any conventional coating method (for example, a curtain method, an extrusion method, an air-knife method, a slide coating, a roll coating method, reverse roll coating, solvent extrusion, dip coating processes and a rod bar coating method) can be used.
The ink-receiving layer of the present invention is preferably coated on one side of the support as a plurality of at least two distinct layers, coated from different coating solutions. Most preferably, the ink-receiving layer of the present invention is coated on one side of the support as a plurality of three distinct layers, coated from different coating solutions. When preparing an ink-jet receiving sheet according to this invention, by coating two or more ink-receiving layers onto a support, it is possible to prepare an ink-receiving sheet with excellent properties, especially with respect to bleeding and mottle.

Receiving sheet for ink-jet printing comprising a gelatin and saccharides combination


A sun shade having an elongated member laterally supported from the end of a pole by a universal joint permitting rotational and angular movement of the member with respect to the longitudinal axis of the pole itself. The pole includes a telescoping arrangement whereby the pole can be lengthened or shortened at the discretion of the user. The end of the pole opposite to its end carrying the member includes a universal mount connected to a firm anchor or support by a suitable clamp.

1. Field of the Invention
The present invention relates to the field of sun shades, and more particularly to a novel sun shade having an extended and elongated panel supported on the end of a pole by a universal joint and which further includes means for detachably connecting or supporting the pole on such items as lawn chairs, window ledges, ground support or the like.
2. Brief Description of the Prior Art
In the past, it has been the conventional practice to employ sun shades which are of a large area so that a maximum amount of shade is produced beneath an umbrella, stretched membrane or diaphragm or flexible cover material. Such shades, such as umbrellas; usually provide elaborate mechanisms for opening and closing the sheet material serving as a shade and usually such prior umbrellas are supported in cement anchors or are supported through openings in the center of a table or other support mechanisms.
Problems and difficulties have been encountered with conventional shade umbrellas and the like which stem from the fact that the shade cover itself is not adjustable throughout a variety of positions so as to be responsive to movement of the sun over the earth""s surface which causes a need for change in shading area. Even if conventional umbrellas include pivots in the supporting pole, the pivots are unidirectional and permit only raising or lowering of the shade in either a vertical direction or at an angle, and such pivots are not of a universal nature. Other difficulties are encountered because the conventional shades, such as umbrellas, are intended to cover a wide shaded area and are not applicable for use in connection with individuals who wish to spot shade portions of their body, such as the face or even solely the eye area. In such situations, the sunbather wishes to have the sun cover as much of his body as possible except for the very small portion to be shaded.
Therefore, a long-standing need has existed to provide a sunshade which can readily be used for spot shading on a sunbather""s body and which may include a rigid shade panel which is mounted on a pole by a universal joint means and which may be detachably supported on a variety of furniture, equipment or even on the ground.
The above problems and difficulties are avoided by the present invention which provides a novel sun shade having an elongated member or panel which is laterally supported from the end of a pole by means of a universal joint which permits not only rotational movement of the member or panel but permits angular movement with respect to the longitudinal axis of the pole itself. The pole includes a telescoping arrangement so that the pole may be lengthened or shortened at the discretion of the user. The end of the pole opposite to its end carrying the panel includes a universal mount connected to a support means for supporting the sun shade from lawn furniture, window sills, such as the window ledge of an automobile, or which may be supported directly on the ground. Such a means may include a suitable clamp or may include a spike or ground support. A feature of the invention involves providing a storage cavity in the end of the post for storing a spike that may be used as an alternate support to a clamp for ground support purposes. Means are also provided for attaching a clamp support to the arm of furniture such as lawn furniture so that marring of the arm will not occur and scratching as well as damage is avoided. Such means may include rollers whereby the entire assembly can be moved on the arm to a selected position. The clamp and/or universal joint securing the end of the post to the arm of furniture may be detachably connected from the post so as to permit access to the compartment for storing the support spike. The support spike can be removed from the compartment and then threadably attached to the end of the post.
Therefore, it is among the primary objects of the present invention to provide a novel sun shade for sunbathing use which will selectively shade a portion of a sunbather""s body while permitting the sun""s rays to be applied against a major portion of a sunbather""s skin.
Another object of the present invention is to provide a novel sun shade which will selectively shade a portion of a sunbather""s body from the sun""s rays while permitting the major body area to receive the sun rays.
Still a further object of the present invention is to provide a novel sun shade which includes a rigid elongated member or panel which is attached to a post by a universal joint so that the panel may be articulated to a variety of selected positions for selectively shading a portion of a sunbather""s body.
A further object resides in providing a portable sun shade which includes an extendable post having a variety of support means for detachably connecting the sun shade to furniture, mobile vehicles such as autos or golf carts, and, alternately, which may be supported directly on the ground.
Other objects and features reside in providing an elongated telescoping post for supporting a rigid sun shade by means of a universal joint at one end of the post while employing a second universal joint for supporting a clamp for detachably connecting the post to a variety of supports.


A coating composition for forming abrasion-resistant coatings is described. It has been found that sol gel process aluminum oxide grain can be added to a film-forming resin composition for producing coatings exhibiting exceptional abrasion resistance.

This invention relates to a composition and method for forming abrasion resistant coatings. More particularly, this invention is directed to novel coating compositions containing a sol gel aluminum oxide grain in amounts sufficient to provide coatings exhibiting enhanced abrasion resistance.
The application of protective or decorative coatings is a common processing step in many manufacturing protocols. One important functional property of such coatings, whether they be applied for a decorative or a protective function, is abrasion resistance. Disruption of the integrity of the applied coatings by abrasive contact with other surfaces during shipment or in the ordinary use of the coated surfaces can affect the appearance of the coatings and their effectiveness in protecting the underlying surface. Accordingly, there has been a significant research and development effort directed to the formulation of coating compositions which exhibit abrasion resistance along with other desirable coating characteristics such as flexibility, hardness, adhesion, transparency, translucency, and the like.
Abrasion resistance is a particularly important and desirable property for coating formulations used on surfaces which in use are subjected to abrasive contacts with other objects, such as flooring, shelving and the like. The use of coatings exhibiting good abrasion resistance on such surfaces prolongs both the appearance and the functionality of the coating compositions.
Therefore, in accordance with this invention there is provided a coating composition for forming abrasion resistant coatings. The invention is based, at least in part, on the discovery that the use of a sol gel process grain or grain composition as an additive at effective levels in a resin coating composition provide coatings exhibiting surprisingly enhanced abrasion resistance.
Typical coating compositions in accordance with this invention comprise a film-forming resin composition and a sol gel process ceramic grain composition wherein the ceramic grain contains aluminum oxide and wherein the aluminum oxide grain forms about 1 to about 60 percent by weight of the coating. The film-forming resin component of the present coating composition is preferably a thermosetting or UV-curable resin of the type used in decorative and protective coating compositions.
In another embodiment of the present invention improved abrasion resistant surface finishes are applied in a coating protocol utilizing at least one sealer or primer coating composition to form a sealer coat and at least one top coat composition to form a surface top coat. The improved surface finish and method comprises using an improved sealer and/or top coating composition comprising a film-forming resin composition and a sol gel processed ceramic grain in an amount effective to impart abrasion resistance to the surface finish.
In accordance with one embodiment of this invention there is provided a curable coating composition for forming abrasion-resistant coatings. The coating composition comprises a film-forming resin composition, most typically a thermosetting resin or a UV-curable resin, and a sol gel processed grain composition. The film-forming resin composition is formulated to include an amount of a sol gel ceramic grain composition sufficient to enhance the abrasion resistance in the resulting cured coatings.
In one embodiment of the invention the film-forming resin of the present coating composition is a thermosetting resin composition comprising epoxy resins, acrylic resins, polyester resins, urea resins, melamine resins or polyurethane resins.
In another embodiment of the invention the film-forming resin composition comprises a UV-curable resin, typically a UV-curable resin comprising olefin-functional monomers and olefin-functional oligomers and polymers. Typically such formulations include a combination of mono- and multi-functional olefin oligomers or polymers. See, for example, the disclosures of U.S. Pat. Nos. 4,600,649; 4,902,975; 4,900,763; and 4,065,587, the disclosures of which are incorporated herein by reference. In one preferred embodiment of the invention there is provided a coating for forming abrasion resistant coating compositions, particularly for wood floor applications, wherein the coating composition comprises mono-olefin functional and multi-olefin functional polyurethane monomers, oligomers and polymers.
Typically the present coating compositions comprise about 40 to about 90 percent by weight of a film-forming resin composition and about 10 to about 60 weight percent of a sol gel process ceramic grain, typically an aluminum oxide composition. Of course, such coating compositions can, and typically do, include other standard coating additives such as resin-dependent curing agents or catalysts, flow aids, wetting agents, dispersing agents, pigments, dyes, fillers, fibers, antistatic agents, lubricants, surfactants, plasticizers, rheology modifiers, and coupling agents. Thus, for example, coating compositions of this invention utilizing UV-curable resins typically include effective amounts (about 0.1 to about 3 percent by weight) of one or more photoinitiators. Such compositions can be cured by electron beam irradiation without photoinitiators.
The coating composition may also, for example, contain a coupling agent. Exemplary of such coupling agents suitable for use in this invention include organo silanes, zircoaluminates and titanates. The coupling agent may be added directly to the coating composition. Alternatively, the ceramic grain may be pre-treated with the coupling agent before the grain is added to the coating composition. The coupling agent is added in an amount typically between 0.1 to 5% by weight of the ceramic particle weight.
The mineral component of the present coating compositions comprises a form of alumina made by sol gel processing. These products, sometimes referred to as sol gel process ceramic grain are commercially available from several sources. In one embodiment of the invention the sol gel processed alumina grain is a product sold under the name Cubitron(copyright) by 3M Corporation.
Sol gel processed grain compositions such as those for use in accordance with this invention are often specified, inter alia, by grain size, ranging from about JIS 240 down to JIS 8000. These grain sizes correspond to a particle size range from about 130 xcexcm down to about 0.5 xcexcm. The sol process grain component of the present composition can be of a homogeneous grain size or several grain sizes in combination. In one embodiment of the present invention, the sol gel process grain forms about 1 to about 60 percent by weight of the coating, more typically about 10 to about 40 percent by weight of the coating with a grain size of JIS 320 or smaller. In one embodiment, JIS 400 sol gel process aluminum oxide grain is used alone or in combination with smaller and/or larger grain size material. Sealer coats/primer coats in accordance with the present invention typically have higher weight percents of the grain composition than grain-filled top coat compositions. Top coat compositions are usually formulated to contain about 1 to about 15 percent of the sol gel processed grain while sealer/primer coat composition are most typically formulated to contain about 10 to about 40, more preferably about 10 to about 30 percent by weight of the sol gel process grain.
The ceramic grain particles may also contain a surface coating. Surface coatings are known to improve the adhesion between the ceramic particle and the film-forming resin composition binder in abrasive articles. Such surface coatings are described in U.S. Pat. Nos. 5,011,508; 1,910,444; 3,041,156; 5,009,675; 4,997,461; and 5,213, 951.
The coating compositions of the present invention are applied using art-recognized coating application techniques including spray coating, curtain coating, reverse roll coating, vacuum coating, extrusion coating, or direct or differential roll coating applications. The viscosity of the coating compositions of the present invention is not critical; thus, the present invention encompasses coating compositions of any given viscosity containing a film-forming resin composition and a sol gel processed ceramic grain. Typically, the viscosity of the coating compositions can range from about 200 centipoise up to about 8000 centipoise depending on the grain loading the nature of the film-forming resin components of the composition. The compositions are prepared utilizing standard coating formulation techniques. Thus, the ceramic grain composition can be blended into or sifted onto, for example, floor finishing compositions for providing coatings with enhanced abrasion resistance without compromise of other functionally significant properties such as flexibility, hardness, adhesion and the like.
Most surface finishing protocols comprise the steps of applying at least one sealer/primer coating composition to form a sealer/primer coat and one top coating composition to form a surface top coat. The finished surfaces can be prepared to have improved abrasion resistance using an improved sealer coating or top coating composition in accordance with this invention, i.e., one comprising a film-forming resin composition and a sol gel process ceramic grain in an amount effective to impart enhanced abrasion resistance to the sealer coat. In some coating protocols, for example, those used in applying coatings for wood flooring, the wood surface is coated with at least two sealer coats, more typically two to five sealer coats prior to application of one or more top coat compositions. The surface finish can be formed to have exceptional abrasion resistance wherein, during the coating process, at least one of the applied sealer coats is a sol process grain filled coating composition of the present invention. In one embodiment, at least two sealer coats of the present invention are applied to the surface before application of the top coat.
In still another embodiment of this invention, the top coat is a sol gel process grain filled coating composition in accordance with this invention. Top coat formulations typically are formulated to contain lower levels of grain, generally in the range of about 1 to about 15 percent by weight of fine grain, typically JIS 400 or finer. In one embodiment, the surface being coated is a wood surface intended for use in flooring applications and the film-forming resin composition of both the sealer and top coats are UV-curable 100 percent solids compositions comprising a combination of mono-olefin functional and multi-olefin functional monomers, oligomers and polymers.
Preparation: Sol gel processed ceramic grain for use in this invention may be made according to the following procedure:
Mixing step: An alumina-based mixture is prepared that comprises an alumina precursor, optionally an acid, and liquid medium. The alumina precursor is capable of being sintered into alpha alumina. The preferred alumina precursor is alpha alumina monohydrate, commonly referred to as boehmite. Examples of other alumina precursors include alpha alumina powders, gamma alumina powders, aluminum formoacetate, aluminum nitrofomoacetate and aluminum salts.
One useful alpha alumina monohydrate is commercially available from the Alcoa Company. Other alpha alumina monohydrates are commercially available from Condea GmbH, Hamburg, Germany. Preferred alumina monohydrates are in the alpha form, and include relatively little, if any, hydrated phases other than monohydrates (although very small amounts of trihydrate impurities can be present in some commercial grade boehmite, which can be tolerated). These monohydrates typically have a low solubility in water and have a high surface area (typically at least about 180 m2/g).
The liquid medium in which the boehmite mixed is typically water. The water may be tap water, distilled water or deionized water. In some instances, it is preferable to heat the aqueous medium (e.g., 30-70xc2x0 C.) to improve the mixing of the boehmite.
The mixture may further comprise peptizing agents; these peptizing agents are generally soluble ionic compounds which are believed to cause the surface of a particle or colloid to be uniformly charged in the liquid medium (e.g., water). Preferred peptizing agents are acids or acid compounds. Examples of typical acids include monoprotic acids such as acetic, hydrochloric, formic, and nitric acid, with nitric acid being preferred. Typically, the mixture contains at least 0.1 to 20% by weight, preferably 1% to 10% by weight acid and most preferably 3 to 8% by weight acid, based on the weight of boehmite in the mixture. In some instances, the acid may be applied to the surface of the alpha alumina monohydrate particles prior to being combined with the water.
The mixture may further comprise a nucleating material or nucleating material precursor such as alpha alumina, alpha iron oxide, an alpha iron oxide precursor and/or chromia. Additional details regarding nucleating materials are disclosed, for example, in U.S. Pat. Nos. 4,623,364; 4,744,802; 4,964,883; 5,139,978; and 5,219,806. An example of a nucleating material is iron oxide or an iron oxide precursor. Sources of iron oxide, which in some cases may act as or provide a material that acts as a nucleating material, include hematite (i.e., xcex1-Fe2O3), as well as precursors thereof (i.e., goethite (xcex1-FeOOH), lepidocrocite (xcex3-FeOOH), magnetite (Fe3O4), and maghemite (xcex3-Fe2O3)).
The alumina mixture may further comprise other metal oxide precursors, sometimes referred to as a metal oxide modifier. The term precursor means that the material is capable of being converting into metal oxide under appropriate sintering conditions. The amount of the metal oxide precursor added to the mixture is calculated and determined based upon the desired amount in the final sintered mineral particle. These other metal oxides may alter the physical and chemical properties of the resulting mineral particle. The metal oxide precursor may be added to the mixture as 1) a metal salt, 2) a metal oxide particle or 3) a colloidal suspension of the metal oxide. Preferably these precursors are added as a metal salt and examples of metal salts include metal nitrate salts, metal acetate salts, metal citrate salts, metal formate salts, and metal chloride salts. For metal oxide particles, it is generally preferred that the particles are less than 5 microns, preferably less than 1 micron, in size. Colloidal metal oxides are discrete finely divided particles of metal oxide having one or more of their dimensions within a range of about 3 nanometers to about one micrometer. Examples of these colloidal metal oxides include lithium oxide, manganese oxide, zirconium oxide, silica, chromium oxide, praseodymium oxide, dysprosium oxide, samarium oxide, cobalt oxide, zinc oxide, neodymium oxide, yttrium oxide, ytterbium oxide, magnesium oxide, nickel oxide, silica, manganese oxide, lanthanum oxide, gadolinium oxide, dysprosium oxide, europium oxide, ferric oxide, hanium oxide, and erbium oxide.
Typically, the use of a metal oxide modifier can decrease the porosity of the sintered mineral particle and thereby increase the density. Additionally certain metal oxide precursors may reduce the temperature at which transitional aluminas transform into alpha alumina. Certain metal oxides may react with the alumina to form a reaction product which may be beneficial in enhancing the physical properties of the mineral particle. Thus, the selection and amount of metal oxide will depend, in part, upon the processing conditions and the desired properties of the mineral particle.
Oxides of cobalt, nickel, zinc, and magnesium typically react with alumina to form a spinel, whereas zirconia and hafnia do not react with the alumina. Alternatively, the reaction products of dysprosium oxide and gadolinium oxide with alumina oxide are generally garnet. The reaction products of alumina with praseodymium oxide, ytterbium oxide, erbium oxide, and samarium oxide generally have a perovskite and/or garnet structure. Yttria can also react with alumina to form Y3Al5O12 having a garnet crystal structure. Certain rare earth oxides and divalent metal cations react with alumina to form a rare earth aluminate represented by the formula LnMA111O19, wherein Ln is a trivalent metal ion such as La3+, Nd3++, Ce3+, Pr3+, Sm3+, Gd3+, Er3+, or Eu3+, and M is a divalent metal cation such as Mg2+, Mn2+, Ni2+, Zn2+, or CO2+. Such aluminates have a hexagonal crystal structure; these aluminates are sometimes referred to as a magnetoplumbite platelets. For additional details regarding the inclusion of metal oxide (and/or precursors thereof) in a boehmite mixture see, for example, in U.S. Pat. Nos. 4,314,827; 4,770,671; 4,881,951; 5,429,647; and 5,551,963.
The alumina-based mixtures typically comprise greater than 15% by weight (generally from greater than 30% to about 80% by weight) solids, based on the total weight of the mixture. Certain mixtures, however, comprise 35% by weight or more, 45% by weight or more, 50% by weight or more, 55% by weight or more, 60% by weight or more, as well as 65% by weight or more solids, based on the total weight of the mixture.
The mixture may be prepared, for example, by gradually adding a liquid medium to a component(s) that is non-soluble in the liquid medium, while the latter is mixing or tumbling. For example, a liquid medium containing water, nitric acid, and metal salt may be gradually added to boehmite, while the latter is being tumbled such that the liquid medium is more easily distributed throughout the boehmite. Alternatively, the mixture may be formed by combining boehmite, water and acid and then mixed to form essentially a homogeneous mixture. Next, nucleating agents and/or metal oxide precursors may be added to this mixture.
Suitable mixers include pail mixers, sigma blade mixers, ball mill and high shear mixers. Other suitable mixers are available from Eirich Machines, Inc., Gurnee, Ill.; Hosokawa-Bepex Corp., Minneapolis, Minn. (including a mixer available under the trade designation xe2x80x9cSCHUGI FLEX-O-MIXxe2x80x9d, Model FX-160); and Littleford-Day, Inc., Florence, Ky.
After the alumina-based mixture is formed, the mixture may be heated to increase the dispersibility of the alpha alumina monohydrate and/or to create a homogeneous mixture. The temperature may vary, for example, the temperature may range from about 20 to 80xc2x0 C., usually between 25 to 75xc2x0 C. Alternatively, the mixture may be heated under a pressure ranging from 1.5 to 130 atmospheric pressure.
The mixture may gel prior to or during the drying step. The addition of most modifiers may result in the mixture gelling faster. The pH of the mixture and concentration of ions in the gel generally determines how fast the mixture gels. Typically, the pH of the mixture is within a range of about 1.5 to about 4. The gelled mixture may be extruded.
Drying Step: In general, techniques for drying the mixture are known in the art, including heating to promote evaporation of the liquid medium or simply drying in air. The drying step generally removes a significant portion of the liquid medium from the mixture; however, there still may be a minor portion (e.g., about 10% or less by weight) of the liquid medium present in the dried mixture. Typical drying conditions include temperatures ranging from about room temperature to over about 200xc2x0 C., typically between 50 to 150xc2x0 C. The times may range from about 30 minutes to several days.
Converting Step: After drying, the dried mixture may be converted into precursor particles. One typical means to generate these precursor particles is by a crushing technique. Various crushing or comminuting techniques may be employed such as a roll crusher, jaw crusher, hammer mill, ball mill and the like. Coarser particles may be recrushed to generate finer particles.
Alternatively, the dried mixture is shaped into lumps with a high volatilizable content which then are explosively communited by feeding the lumps directly into a furnace held at a temperature above 350xc2x0 C., usually a temperature between 600 to 900xc2x0 C.
Calcining Step: In general, techniques for calcining the dried mixture or ceramic precursor particles, wherein essentially all the volatiles are removed and the various components that were present in the mixture are transformed into oxides, are known in the art. Such techniques include using a rotary or static furnace to heat dried mixtures at temperatures ranging from about 400 to 1000xc2x0 C. (typically from about 450 to 800xc2x0 C.) until the free water, and typically until at least about 90% by weight of any bound volatiles, is removed.
Impregnating Step: A metal oxide modifier precursor can be impregnated into a calcined precursor particle, although this impregnation step is not required. The metal oxide modifier precursor is selected to provide the desired characteristic of the mineral particle. Typically, the metal oxide precursor is in the form of metal salts. Metal oxide precursors and metal salts are described above.
Methods of impregnating sol gel-derived mineral particles are described in general, for example, in U.S. Pat. No. 5,164,348. In general, ceramic precursor materials (i.e., dried alumina-based mixtures, dried ceramic precursor material, calcined alumina based mixtures or calcined ceramic precursor material) are porous. For example, a calcined ceramic precursor material typically has pores about 5 to 10 manometers in diameter extending into the material from an outer surface. The presence of such pores allows an impregnation composition comprising a mixture of liquid medium (typically water) and appropriate metal precursor to enter into ceramic precursor material. The impregnation process is thought to occur through capillary action.
The liquid medium used for the impregnating composition is preferably water (including deionized water), an organic solvent (preferably a non-polar solvent), or mixtures thereof. If impregnation of a metal salt is desired, the concentration of the metal salt in the liquid medium is typically in the range from about 5% to about 40% dissolved solids, on a theoretical metal oxide basis. Preferably, there is at least 50 ml of solution added to achieve impregnation of 100 grams of porous ceramic precursor material.
After the impregnation step, the resulting impregnated precursor particle is typically calcined a second time to remove any volatiles prior to sintering. Typical calcining conditions are described above.
Sintering Step: After the precursor particle is formed or optionally calcined, the precursor particle is sintered to provide a dense ceramic alpha alumina-based mineral particle. In general, techniques for sintering calcined material, which include heating at a temperature effective to transform transitional alumina(s) into alpha alumina, cause all of the metal oxide precursors to either react with the alumina or form metal oxide, and increase the density of the ceramic material, are known in the art. The calcined material may be sintered by heating (e.g., using electrical resistance, microwave, plasma, laser, or gas combustion both in batch or continuous processes). Sintering temperatures usually range from about 1200 to 1650xc2x0 C., typically, from about 1200 to 1500xc2x0 C. The length of time which the calcined material is exposed to the sintering temperature depends, for example, on particle size, composition of the particles, and sintering temperature. Typically, sintering times range from a few seconds to about 60 minutes (preferably, within about 3 to 30 minutes). Sintering is typically accomplished in an oxidizing atmosphere, although neutral or reducing atmospheres may also be used.
Crushing and Classification Steps: In some instances, the mineral particle is sintered to about the desired particle size and about the desired particle size distribution. The mineral particle may be further classified using screening techniques, air classification techniques or water classification techniques to further refine the particle size distribution. In some cases, the mineral particle is first crushed to a smaller particle size. This crushing may be accomplished for example, by roll crushing, jet milling, hammer milling, ball milling and the like. After crushing, the resulting particles are typically classified using screening techniques, air classification techniques or water classification techniques to further refine the particle size distribution.
The aluminum sol gel ceramic grain can also be made by other procedures known in the art and described in each of the following U.S. Patents which are specifically incorporated herein by reference: U.S. Pat. Nos. 4,623,364; 4,314,827; 4,744,802; and 4,800,685.
Sintered Alumina Mineral Particle Properties
The sintered alumina mineral particles have a true density of at least about 3.70 grams/cm3, preferably at least about 3.80 grams/cm3, more preferably at least about 3.85 grams/cm3, and most preferably at least about 3.90 grams/cm3. Likewise, it is preferred that the sintered alumina mineral particles have a theoretical density of at least about 90%, preferably at least about 93% and more preferably at least about 95%. The densities of the particles may be determined with a helium gas pycnometer (available under the trade designation xe2x80x9cMicromeritics AccuPyc 1330xe2x80x9d from Micromeritics Instruments Corp., Norcross, Ga.).
The sintered alumina mineral particles have a hardness of at least about 16 GPa, preferably at least about 17 GPa, more preferably at least about 18 GPa and most preferably at least about 19 GPa. In some instances, the hardness may be greater than about 20 GPa or greater than about 22 GPa. The hardness may be measured according to a Vicker""s indentation method using a 500 gram weighted stylus. This test procedure is further described in accordance with ASTM (American Society of Testing Methods) Test Method E3 84.
The sintered alumina mineral particles have a toughness of at least about 2 MPa-m0.5, preferably at least about 2.2 MPa-m0.5, more preferably at least about 2.5 MPa-m0.5, and most preferably at least about 2.8 MPa-m0.5. In some instances, the toughness may be greater than about 3.0 MPa-m0.5, or greater than about 4.0 MPa-m0.5. The toughness may be measured according to a Vicker""s indentation method using a 500 gram weighted stylus. The toughness may be measured according to a test procedure outlined in xe2x80x9cEquilibrium Penny-Like Cracks in Indentation Fracturexe2x80x9d by B R Lawn and E R Fuller published in the Journal of Material Science, Volume 10, 1974, pages 2016-2024.