The present invention provides a method and composition for treating skin disorders, skin pathologies and pruritus, which includes applying a compound of formula (I) in a suitable formulation to the affected area.

Not Applicable
The milieu of the skin is normally of acidic pH, i.e. the stratum corneum layer of the human skin is normally acidic. The stratum corneum is the thin outer cornified lipophilic epidermal layer of the skin, which functions as a barrier to the external environment. It is now generally accepted that this outer layer of the skin has a natural pH in the range of 4.0 to 6.0, normally 5.0. Ten to fifteen micrometers below the stratum corneum, the pH quickly rises to a neutral pH of 7.0.
Within the thin stratum corneum resides a diverse array of hydrolytic, proteolytic, esterifying, and lipid active enzymes which all appear to function optimally in an acidic range of pH 4.5-6.0, which is typical of this layer. Disruption of the pH of this layer by a vast array of etiologies is associated with numerous well-described pathologic entities. In other words, abnormally high pH, or abnormal alkalization, of the skin is often associated with many pathologic dermatological states.
For example, abnormal alkaline surface pH has been noted in atopic dermatitis. Atopic dermatitis is a chronic, itching, superficial inflammation of the skin, frequently associated with related disorders, such as hay fever and asthma. Atopic dermatitis may begin in the first few months of life, with red, weeping, crusted lesions on the face, scalp, diaper area and extremities. In older children or adults, it may be more localized and chronic. Although the dermatitis often improves by age 3 or 4, exacerbations are common during childhood, adolescents or adulthood. Itching is a constant feature, and consequent scratching and rubbing lead to an itch-scratch-rash-itch cycle.
Another pathology generally associated with abnormally high alkalinity of the skin is ichthyosis. Ichthyosis is a symptom in several rare hereditary syndromes and in several systematic disorders. It usually occurs in the lower legs of middle aged or older patients, most often in cold weather and in patients who bathe frequently. Mild to moderate itching may exist in an associated dermatitis due to detergents or other irritants. Xeroderma is the mildest form of ichthyosis.
Another example is seborrheic dermatitis. Seborrheic dermatitis is an inflammatory scaling disease of the scalp, face and occasionally more generalized areas. Onset in adults is gradual, and the dermatitis usually is apparent only as dry or greasy diffused scaling of the scalp (dandruff) with variable itching. In severe disease, yellow-red scaling papules appear along the hairline, behind the ears, and external auditory canals, on the eyebrows, on the bridge of the nose, the nasolabial folds, and over the sternum. Dry yellow crusting and conjunctival irritation may also be present. Neonates under one month old may develop seborrheic dermatitis, with thick, yellow, crusted scalp lesions, fissuring and yellow scaling behind the ears and red facial papules. Newborns may also have an associated stubborn diaper rash, while older children may develop thick, tenacious, scaly plaques in the scalp that may measure 1 to 2 centimeters in diameter. Very rarely, in infants or adults, the condition may become generalized.
Contact dermatitis, another example of a skin disorder associated with abnormally basic skin, is characterized as an acute or chronic inflammation, produced by substance contact with the skin. Contact dermatitis may be caused by marginal irritants such as soap, detergents, acetone or even water. It may take several days of exposure to cause clinically recognizable changes. Strong irritants, for example, acids and alkalines, cause observable changes within a few minutes. More specifically, allergic contact dermatitis is a delayed hypersensitivity reaction. It takes between 6 and 10 days to years for individual to become sensitized. Often times, ingredients in topical drugs constitute a major cause of allergic contact dermatitis. Other commonly implicated substances include plants, many potential sensitisers used in the manufacture of shoes and clothing, p-phenylenediamine and other dyes and cosmetics. Contact dermatitis ranges from redness to severe swelling and itching. Any exposed skin surface in contact with the sensitizing or irritating substance may be involved.
Pemphigus is an uncommon, potentially fatal, autoimmune skin disorder characterized by bullae on apparently healthy skin and mucus membranes that has been demonstrated to have an abnormally high pH. The primary lesions associated with pemphigus often occur first in the mouth, where they soon rupture and remain as chronic, often painful, erosions for variable periods of time before the skin is affected. On the skin, the bullae typically arise from normal appearing skin to leave a raw, denuded area and crusting when they rupture later.
Dermatitis herpetiformis is a chronic eruption characterized by clusters of intensely pruritic vesicles, papules and urticaria-like lesions. With this dermatitis, itching and burning are severe, and scratching often obscures the primary lesions. This form of dermatitis is also associated with abnormally alkaline skin.
Psoriasis is a common, chronic, recurrent disease characterized by dry, well-circumscribed, silvery, scaling papules and plaques of various sizes that is associated with high alkaline skin surface conditions. Psoriasis varies in severity from one or two lesions to a widespread dermatitis with disabling arthritis or exfoliation. It is generally caused by increased epidermal cell proliferation from abnormally alkaline stratum corneum. Psoriasis characteristically involves the scalp, the extensor surfaces of the extremities, particularly at elbows and knees and the back. The nails, eye brows and other regions may also be affected. Occasionally the disease is generalized.
Candidiasis, or yeast infections, may also be related to an abnormally high pH in the skin or mucous membranes. The symptoms of candidiasis vary from the site of the infection. However, symptoms usually include itchiness and inflammation.
Other skin disorders or pathologies that may be linked with an abnormally basic stratum corneum are acne, dermatophytosis, diaper rash, eczema and skin damage from a variety of causes including wounds, burns and fecal and urinary incontinence. In addition, a more alkaline surface pH has been shown to promote Staphylococcal skin colonization and the invasion of Nector americanus, i.e. human hookworm. Alopecia, or baldness, may also result from abnormal alkaline surface skin pH.
Many of these skin disorders or pathologies are accompanied by pruritus, a condition involving localized or general itching. Although usually occurring in the skin, pruritus can also occur in non-cutaneous sites such as mucous membranes. A variety of causes for the condition of pruritus are known including external and endogenous causes, localized skin disorders and systemic diseases. As previously discussed, many systemic and skin diseases are accompanied by persistent or recurrent itch attacks. Itch can also be produced by a variety of chemical, mechanical, thermal and electrical stimuli.
Research into the etiology of and treatment of many skin pathologies including pruritis has been limited both by the lack of animal models and by patient populations that at present would not support the perceived research and development and clinical testing costs. Treatment involves diagnosis of the underlying condition that causes pruritus and these skin disorders and pathologies and intervening therapeutically to alleviate these conditions. For example, developments leading to drugs to threat these conditions have been, for the most part, a bonus of anti-inflammatory drugs. Such treatments are not considered to be direct treatments of these conditions and are of limited efficacy, only occasionally and indirectly relieving the itching. In many cases, however, either the underlying cause for the condition cannot be determined or cannot be eliminated. In such cases, the direct treatment of the pruritic condition or the accompanying skin disorder is required.
Generally, options for effectively treating these disorders are limited. Currently available treatment modalities for these pathologies include nonspecific topical agents such as emollients and counterirritants, topical and oral drugs such as steroids, local anesthetics and antihistamines, and physical modalities such as ultraviolet phototherapy and thermal stimulation. Some of these treatments are effective in pruritic conditions of a particular etiology, while others may show general but nonspecific benefit. It is known that many corticosteroids, e.g., hydrocortisone, fluocinide, betamethasone valerate, fluocinolene acetonide, triamcinolone acetonide and others, have antiprutitic properties and may be effective in treating some skin disorders. However, prolonged use of such corticosteroids is associated with both cutaneous and systemic toxic side effects (e.g., fluid and electrolyte disturbances, impaired wound healing, musculoskeletal, gastrointestinal, neurological and endocrine disturbances) and their widespread use is limited without medical supervision. Selenium sulfide, sulfur and salicylic acid or tar shampoo have also been employed to treat these skin conditions. In any event, remission of the pathology or pruritus is often slow and frequently incomplete.
Nonspecific topical preparations can act as moisturizing lotions or creams or as oil-based ointments that are occlusive and serve to soften dry skin as well as provide a protective layer. While such preparations may have valuable moisturizing and skin softening properties, they also possess undesirable effects in that they generally impart to the skin an uncomfortable feeling of warmth in addition to a sticky, oily, greasy or waxy feel. More importantly, these materials alone have little effect, if any, on reducing itching.
Topical formulations containing pharmacologically active agents are often useful in particular conditions but many may not be generally useful in all conditions. For example, topical corticosteroids are not indicated for symptomatic treatment unless a steroid responsive disorder is diagnosed.
Thus, there is a continuing need for development of new and improved, nontoxic antipruritic and pH-adjusting agents that are effective in treating and alleviating skin disorders, pathologies and pruritus resulting from a wide variety of causes or causes different than those that can be treated by currently available agents.
The present invention provides a method of treating skin pathologies, disorders and pruritus which includes topically applying a fatty acid esterified with glycerol (or another suitable alcohol) in combination with a dermatologically acceptable vehicle to adjust, regulate or control the skin pH. Examples of suitable fatty acids, as defined herein, include, but are not limited to, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, etc. The compounds of formula (I), described hereinafter, are examples of suitable fatty acids esterified with glycerol that can be applied to the skin to adjust pH and treat the various skin disorders described above. For example, it has been found that the esters in accordance with the present invention can be applied topically at affected sites and are surprisingly therapeutically effective such that the pruritus is rapidly and completely relieved.
The invention provides a simple, safe and effective way to control skin pH. By normalizing abnormally alkaline skin, i.e. returning the stratum corneum to a more typical acid milieu, many of the skin disorders and pathologies listed above can be treated. Triacetin is one example of a glyceryl fatty acid ester. When applied to abnormally alkaline skin, triacetin is enzymatically hydrolyzed in the alkaline milieu found therein to form glycerol and acetic acid. The acetate ion is a two-carbon moiety that contributes to fatty acid synthesis and ultimately to tissue healing and repair. In other words, the application of triacetin and the other esters provide a safe way to apply an acid to normalize the pH of the skin, and return it to its more natural acid milieu. This results in the normalization of the pH in the stratum corneum and subsequent skin healing. As the skin pH returns to its normal acidic pH, the cleavage of triacetin is halted leading to a simple control mechanism.
The compound of formula (I) is suitably the compound of formula (II) described hereinafter, which is glyceryl triacetate or 1, 2, 3 propanetriol triacetate or, commonly, triacetin. It is again, noted however, that any of the esters described herein that is capable of adjusting the pH of the skin will suffice. Triacetin has been used as a pharmaceutical plasticizer (U.S. Pharmacopoeia National Formulary 1075-76, 1492 (1985)), as an antifungal drug and a fixative in perfumery (see, The Merck Index (12th ed.) p. 1636 (1996); U.S. Pat. No. 3,070,497 issued to Knight), listed as one of many general pharmaceutical carriers/diluents for primarily systemic administration of specific compounds (see, e.g., U.S. Pat. No. 4,543,360 issued to von Angerer et al.; U.S. Pat. No. 4,218,447 issued to Isaac et al.; U.S. Pat. No. 4,055,653 issued to Offermanns et al.; U.S. Pat. No. 4,847,297 issued to Chandra; U.S. Pat. No. 5,061,700 issued to Dow et al.), as an alkalinity reducing agent in permanent waving treatments for hair (see, e.g., U.S. Pat. No. 3,975,515 issued to Wajaroff et al.), and as an ingredient in a vaginal tampon (see, U.S. Pat. No. 3,091,241 issued to Kellett). It is noted that despite disclosure that triacetin is a general antifungal agent, a U.S. Food and Drug Administration Over-the-Counter (OTC) Drug Review Panel has concluded that there is no evidence that triacetin is effective in any fungal disease other than the soggy toeweb form of athlete""s foot. The OTC panel also concluded that triacetin was safe for topical use (see, Federal Register, vol. 47, 12553 (Mar. 23, 1982)). It has not heretofore been known that triacetin, the compounds of formula (I) and other esterified fatty acids can be effectively used in the treatment of pruritic conditions and other skin disorders related to pH imbalance.
The foregoing and other advantages of the present invention are realized in one aspect thereof in a method of treating pruritus, skin disorders and skin pathologies which comprises applying a compound of formula (I) in an inert vehicle to the affected area to treat the related skin disorder.
In another aspect, the invention provides a method of treating skin disorders, skin pathologies and pruritus which includes applying a composition to the pathologically or pruritically affected area, which composition essentially consists of a pH modifying substance, self regulating at the molecular level, that stabilizes the desirable healthy skin pH, namely a glyceryl fatty acid ester, e.g. a compound of formula (I).
In a further aspect, the invention provides a topical anti-pathologic or antipruritic composition consisting of 5-100%, preferably 5-50%, by weight of a glyceryl fatty acid ester, e.g. a compound of formula (I), and 0%-95% by weight a dermatologically acceptable vehicle. The glyceryl fatty acid ester in accordance with the present invention acts as an essential active ingredient for normalizing the skin pH to treat the skin pathology.
In yet a further aspect, the invention provides a prodrug composition for treating skin disorders, skin pathologies and pruritus which consists essentially of 5-100% by weight of a glyceryl fatty acid ester, e.g. a compound of formula (I), and 0%-95% by weight a dermatologically acceptable vehicle.
The present invention relates to a method of treating pruritus and other skin disorders which is highly effective in providing rapid and sustained relief. Accordingly, the present invention will now be described in detail with respect to such endeavors. Those skilled in the art will appreciate that such a description of the invention is meant to be exemplary only and should not be viewed as limitative of the full scope thereof.
The term xe2x80x9cpruritusxe2x80x9d is meant to refer to itching which can range from a mild sensation to an intense sensation of itching pain. The itching may accompany primary skin disease or may be a symptom of systemic diseasexe2x80x94sometimes the only symptom. Skin diseases in which itching can be most severe include, among others, scabies, pediculosis, insect bites, urticaria, atopic dermatitis, contact dermatitis, lichen planus, miliaria and dermatitis herpetiformis. Also, dry skin (especially in the elderly) is often a cause of severe generalized itching.
The terms xe2x80x9cskin disorderxe2x80x9d and xe2x80x9cskin pathologyxe2x80x9d are meant to refer to and include skin conditions such as atopic dermatitis, ichthyosis, xeroderma, seborrheic dermatitis, allergic contact dermatitis, alopecia, pemphigus, dermatitis herpetiformis, psoriasis, candidiasis, acne, dermatophytosis, diaper rash, cradle cap, eczema, hookworm and skin damage from, e.g., wounds, burns, and fecal and urinary incontinence. These examples are purely illustrative and are not meant to limit the scope of the invention.
The term xe2x80x9ccompound of formula (I)xe2x80x9d is meant to refer to the following
wherein R1, R2 and R3 are each independently RCOOxe2x80x94 or H provided that R1, R2 and R3 are not all H. With regard to RCOOxe2x80x94, R is a saturated or unsaturated, straight or cyclic, C2-C22 alkyl group. For saturated fatty acids, R is suitably represented by CnH2n+1, such as CH3COOxe2x80x94, CH3CH2COOxe2x80x94 or CH3(CH2)2COOxe2x80x94, etc. For unsaturated fatty acids, R is suitably represented by the formula CnH2nxe2x88x92m, wherein n is an integer from 1 to 23, and m is an odd integer from 1 to 7, provided that m is less than 2n. Examples of suitable unsaturated fatty acids include, but are not limited to oleic acid, linolenic acid, linoleic acid and arachidonic acid. Positional and geometric isomers of unsaturated fatty acids are considered within the scope of formula I.
The term xe2x80x9cfatty acidxe2x80x9d as used herein is meant to refer to saturated and unsaturated acids composed of a chain of alkyl groups and characterized by a terminal carboxyl group xe2x80x94COOH. Fatty acids may contain from 2 to 24 carbon groups. The term xe2x80x9cfatty acidxe2x80x9d includes, but is not limited to, acetic acid, butyric acid, propionic acid, valeric acid and caproic acid. The compound of formula (I) shows a variety of both saturated and unsaturated fatty acids.
The term xe2x80x9cglyceryl fatty acid esterxe2x80x9d is meant to refer to a fatty acid, as described above, esterified with glycerol.
The present invention is also suitably used for the relief of epidermal or dermal itching associated with any condition such as a systemic disease or allergy that affect epidermal and/or dermal nerve endings, an injury resulting in localized trauma affecting the epidermal or dermal nerve endings, or localized dermatitis. In a preferred method, the invention includes a method of relief of pruritic symptoms associated with dermatitis including actinic dermatitis, contact dermatitis such as an allergic dermatitis or contact dermatitis caused by irritating substances of plant, animal, mineral or synthetic origin.
The method of the present invention includes applying to an affected area an effective amount of a glyceryl fatty acid ester, for example, the compound of formula (I):
wherein R1, R2 and R3 are each independently RCOOxe2x80x94 or H provided that R1, R2 and R3 are not all H and R is a saturated or unsaturated, straight or cyclic, C2-C22 alkyl group. For saturated fatty acids, R is suitably represented by CnH2n+1. For example, When n is 1, R1, R2 and R3 are each independently CH3COOxe2x80x94 or H. When R1 is CH3COOxe2x80x94 and R2 and R3 are H, the compound of formula (I) is glycerol monoacetate or monacetin. When R1 and R2 are CH3COOxe2x80x94 and R3 is H, the compound of formula (I) is glycerol diacetate or diacetin. When R1, R2 and R3 are all CH3COOxe2x80x94, the compound of formula (I) is glycerol triacetate or triacetin. Triacetin or 1,2,3-propanetriol triacetate or glycerol triacetate is given by formula (II):
Besides triacetin, diacetin and monoacetin, other esters are suitable for adjusting skin pH, thereby treating and alleviating certain skin disorders. Other suitable fatty acids that can be esterified to glycerol include, but are not limited to, acetic acid, propionic acid, butyric acid, valeric acid and caproic acid. Again, these compounds are illustrated again by formula (I),
wherein R1, R2 and R3 are each independently RCOOxe2x80x94 or H provided that R1, R2 and R3 are not all H. With regard to RCOOxe2x80x94, R is a saturated or unsaturated, straight or cyclic, C2-C22 alkyl group. For saturated fatty acids, R is suitably represented by CnH2n+1. RCOOxe2x80x94 is suitably, for example, CH3COOxe2x80x94, CH3CH2COOxe2x80x94 or CH3(CH2)2COOxe2x80x94, etc. For unsaturated fatty acids, R is suitably represented by the formula CnH2nxe2x88x92m wherein n is an integer from 1 to 23, and m, which is the number of double bonds in R, is an odd integer from 1 to 7, provided that m is less than 2n.
Compounds of formula (I) and other esters formed from the esterification of an acid with glycerol have not previously been recognized as undergoing biotransformation to exhibit a desired pharmacological effect i.e., they are, in effect, prodrugs. These compounds are readily broken down by enzymes, namely esterases, present in or on the skin, in mucus membranes and in body fluids, into glycerol (a skin protectant) and a fatty acid, which is ionized to an anion and a hydrogen ion. When R1, R2 and/or R3 are CH3COOxe2x80x94, for example, the ester is broken down by esterase to glycerol, acetate ion and hydrogen ion. Again, many skin disorders and pathologies are caused by abnormally alkaline conditions in skin and membranes. The hydrogen ions tend to normalize and return the skin pH to a more normal acidic milieu. The action of the esterases continues until the pH of the environment is changed to about 4.0 to 6.0 which is the normal range for healthy skin. At this pH level, the activity of the esterases is inhibited until the pH rises again to a level where the esterases again become active. Also present in the skin and other bodily environments is a protease enzyme that signals the itch sensation. This protease is also pH sensitive in the same range, and it is believed that pH balance that is possible with application of compounds of formula (I) provides a dramatic and surprising effect on pruritus.
The compounds of formula (I) are commercially available. For example, triacetin is commercially available in USP grade from Eastman Chemical Company, Kingsport, Tenn. It is a colorless, somewhat oily liquid with a slight fatty odor with a density at 25xc2x0 C. of 1.156 g/mL. It is prepared by acetylation of glycerol. Triacetin, diacetin and monacetin are miscible in water, alcohol, ether and chloroform.
For topical application, suitable viscous, semi-solid or solid forms can be employed which include a carrier compatible with topical application. Suitable formulations include, but are not limited to, solutions, suspensions, emulsions, creams, ointments, powders, liniments, salves, sprays, aerosols and gels. Preferably, compounds of formula (I), e.g., triacetin, are formulated as an ointment in which the vehicle is Aquaphor(copyright), commercially available from Beiersdorf Inc., Norwalk, Conn., US. Aquaphor(copyright) is a composition of petrolatum, mineral oil, mineral wax and wool wax alcohol. Compounds of formula (I) are also suitably formulated as up to a 6% solution in water, and a 25% solution in 50% alcohol, suitably isopropyl alcohol.
Optionally, the skin treating compositions of the present invention may suitably include auxiliary agents such as plasticizing agents, preservatives, stabilizers, demulsifiers, wetting agents, opacifiers, surfactants, fragrances, sunscreens, antibiotics, insect repellants, preservatives, emollients, humectants, emulsifiers, thickeners, moisturizers, astringents, deodorants as well as other compatible materials which may be desired to enhance the properties of the compositions.
Other suitable emollient vehicles include hydrocarbon oils and waxes and volatile silicone fluids such a low molecular weight dimethyl siloxanes.
For topical treatment of skin disorders associated with alkaline skin pH, the concentration of the glyceryl ester in accordance with the present invention in a locally applied composition is about 5% to about 100% by weight, preferably about 5% to about 50% by weight, i.e., about 0.05 g/g to 0.5 g/g of composition, and most preferably, the concentration is about 20% by weight. An ester concentration of 55-100% is also acceptable.
These compounds, particularly, triacetin, have been found of value in the relief and treatment of pruritus due to leukoclastic vasculitis, macular lesion from drug allergies, skin conditions associated with renal disease, dry skin, dandruff, anal itch, poison ivy, poison oak, poison sumac, insect bites, vaginitis, bladder infection, diaper rash, cradle cap and eczema. Administering these compounds as a vaginal cream can normalize vaginal acidity. As a result, this controls and help maintain the normal healthy vaginal flora, thereby preventing bacteria and viruses that cause sexually transmitted diseases from becoming established. These compounds of formula (I) are also of value in treating psoriatic lesions. Triacetin has been found to improve psoriatic lesions, applied as a topical, episodic treatment for psoriasis. As previously discussed, these compounds can also treat and provide relief for other skin disorders and pathologies, including atopic dermatitis, ichthyosis, xeroderma, seborrheic dermatitis, allergic contact dermatitis, alopecia, pemphigus, dermatitis herpetiformis, psoriasis, candidiasis, acne, dermatophytosis and other skin damage caused from a variety of wounds, burns and incontinence.
The skin treating compositions of the present invention when applied to the skin, e.g., up to four times per day as needed, provide reduction in and relief from itching within about 24-36 hours, and relief may even be evident after the first dose. For treatment of psoriasis, improvement is often seen within a day, with complete healing occurring within about 5 to 7 days.
The skin treating composition of the present invention is suitably formulated by simply mixing the compounds of formula (I) with the vehicle at room temperature. The composition is formulated to provide delivery of the antipruritic compound at a suitable rate and concentration. The composition may be in the form of any formulation that provides the compound as bioavailable to esterase action.


A pesticidal composition in the form of an aqueous suspoemulsion, comprising at least two pesticides A and B which are substantially insoluble in water, wherein pesticide A is solid and pesticide B is liquid or dissolved in a hydrophobic organic solvent, and a combination of surfactants comprising

The present invention relates to pesticidal compositions in form of aqueous suspoemulsions, comprising at least two pesticides which are substantially insoluble in water, wherein one pesticide A is solid and the other pesticide B is liquid or is dissolved in a hydrophobic organic solvent, and a combination of surfactants comprising
(1) a tristyrylphenol-ethoxylate having 6-14 mol ethoxylate, in nonionic form, and
(2) a tristyrylphenol-ethoxylate having 14-18 mol ethoxylate in form of its sulfate or phosphate, in anionic or acid form, and
(3) a dialkyl-sulfosuccinate salt.
Suspoemulsions according to the invention consist of at least three phases: an aqueous phase, comprising pesticide A in solid dispersed form, and an organic phase comprising pesticide B, either in liquid form or dissolved in an organic hydrophobic solvent. Normally the aqueous phase is the continuous phase. Such suspoemulsions are very sensible systems regarding physical and chemical stability.
Suspoemulsions comprising pesticides are described for example in EP 88,049, EP 143,099 and EP 261,492.
However, the known suspoemulsions do not always satisfy the needs of agricultural practice in many incidents and aspects: some suspoemulsions are not suitable for certain pesticide combination due to lacking stability. For example, they become inhomogeneous on storage, pH or viscosity are not remaining constant, particle size is growing which may plug the nozzle of the spray device, or the active ingredient may decompose. As a result the handling is rendered difficult and the biological efficacy is reduced. Furtheron, some of the surfactants used in the known suspoemulsions, as alkylphenol ethoxylates, for example nonylphenol ethoxylates, are not entirely satisfactory with respect to their ecological and toxicological properties, and their replacement is desirable.
The suspoemulsions provided herewith are storage stable, easy to apply, ecological and toxicological favourable and have good pesticidal efficacy. The compositions according to the invention are stable for at least 12 months at 25xc2x0 C.
Suitable salts of the surfactants are, for example, metal salts, such as alkali metal or alkaline earth metal salts, for example sodium, potassium calcium or magnesium salts, or salts with ammonia or an organic amine, such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower alkylamine, for example ethyl-, diethyl-, triethyl- or dimethyl-propylamine, or a mono-, di- or tri-hydroxy-lower alkylamine, for example mono-, di- or tri-ethanolamine. Preferred combinations of surfactants are
(1) a tristyrylphenol-ethoxylate having 8-12, preferably 10 mol ethoxylate, and
(2) a tristyrylphenol-ethoxylate having 16 mol ethoxylate, in form of its sulfate or phosphate, preferably in form of its ammonuim sulfate, and
(3) a dioctyl-sulfosuccinate salt, preferably the sodium salt.
Pesticides which are substantially insoluble in water means their solubility at room temperature is less than 2%, preferably less than 0.2%. Liquid means the melting point is below 30xc2x0 C.
The term pesticide is understood to encompass herbicides, insecticides, acaricides, nematicides, ectoparasiticides, fungicides and plant growth regulators; many of them are described in The Pesticide Manual, 11th Ed, British Crop Protection Council. Preference is given to herbicides.
Suitable herbicides A, which are solid and substantially insoluble water are for example triazine derivatives, as atrazine, terbutryn, prometryn, terbuthylazine, ametryn, cyanazine, desmetrine, propazine, simazine, simetryn, terbumeton; preferred ar atrazine, terbutryn, prometryn, and terbuthylazine; or urea derivatives, as isoproturon, chlorobromuron, chlorotoluron, diuron, metobromuron, metoxuron. Suitable herbicides B, which are liquid or soluble in a hydrophobic organic solvent, are acetanilide derivatives, as alachlor, metolachlor or S-metolachlor (S-enantiomer of racemic metolachlor); preferred are metolachlor and S-metolachlor. Particularly preferred are the combinations atrazinelmetolachlor and atrazine/S-metolachlor. It may be advantageous to combine the herbicides with a safener, for example with benoxacor.
Suitable fungicides A are for example sulfur, copperhydroxide, mancozeb, folpet, chlorthalonil, carbendazim, acibenzolar-S-methyl. Suitable fungicides B are for example benomyl, cyprodinil, dimethomorph, edifenphos, fenpropimorph, metalaxyl, (R)-metalaxyl (enantiomer), oxadixyl, pyrifenox, thiabendazol, tridemorph, azoxystrobin, kresoxim-methyl or triazoles such as propiconazol, difenoconazol, bromoconazol, cyproconazole, epoxyconazol, hexaconazol, ipconazol, fenbuconazol, myclobutanil, penconazol, tebuconazol, triadimefon, triadimenol, tetraconazol, triticonazol, or uniconazol; furtheron famoxadone, quinoxyfen, spiroxamin, fludioxonil, fenpiclonil, fenhexamid and 2-[xcex1-{[(xcex1-methyl-3-trifluoromethyl-benzyl)imino]-oxy}-o-tolyl] -glyoxylic acid-methylester-O-methyloxim.
Suitable insecticides/acaricides are benthiocarb, diflubenzuron, teflubenzuron, lufenuron, diafenthiuron or pyrethroide such as bifenthrin, bioallethrin, tau-fluvalinate, resmethrin, permethrin, cypermethrin, cyfluthrin, cyhalothrin, deltamethrin, tefluthrin or tetramethrin; furtheron pymetrozin, thiocyclam, fenoxycarb, methopren, abamectin and emamectin.
Suitable hydrophobic organic solvents in which the pesticides may be dissolved are aliphatic and aromatic hydrocarbons such as hexane, cyclohexane, benzene, toluene, xylene, mineral oil or kerosin, mixtures or substituted naphthalenes, mixtures of mono- and polyalkylated aromatics, halogenated hydroarbons such as methylene chloride, chloroform and o-dichlorobenzene; phthalates, such as dibutyl phthalate or dioctyl phthalate; ethers and esters, such as ethylene glycol monomethyl or monoethyl ether, fatty acid esters; pyrrolinones, such as N-octylpyrrolidone, ketones, such as cyclohexanone; plant oils such as castor oil, soybean oil, cottonseed oil and possible methyl esters thereof; as well as epoxidised coconut oil or soybean oil.
The amount of organic solvent is not critical and can vary from 0 to 50%, depending on the solubility of the respective pesticide.
The average size of the suspended particles is 0.5 to 20, preferably 1 to 5 microns when measured with a laser particle analyzer, e.g a CILAS 920 apparatus.
The viscosity of the suspoemulsion is 100 to 2000, preferably 200 to 1500, most preferably 300 to 1000 mPas when measured with a BROOKFIELD viscosymeter with spindle 3 at 30 rpm and 20xc2x0 C.
Suitable concentrations in relation to the composition are (% weight/weight): 1 to 95%, preferably 5 to 90%, more preferably 10 to 80% by weight of pesticides A and B, 3 to 90%, preferably 5 to 80%, more preferably 10 to 60% by weight of water, and 1 to 40%, preferably 2 to 20%, more preferably 4 to 12%, most preferably 6-8% by weight of the surfactants (1), (2) and (3) in total.
The ratio of the pesticide A: pesticide B is 1:99 to 99:1, preferably 1:5 to 5:1 and 1:2 to 2:1. The concentration of the surfactants is
0.5 to 20%, preferably 1 to 10%, more preferably 1 to 5% by weight of surfactant (1)
0.2 to 15%, preferably 0.5 to 10%, more preferably 1 to 5% by weight of surfactant (2)
0.2 to 20%, preferably 0.5 to 15%, more preferably 1 to 5% by weight of surfactant (3).
The composition according to the invention may comprise additional dispersants and adjuvants, as (in % by weight)
a dispersing agent, 0 to 20%, preferably 0.2 to 5%, e.g. fatty alcohole ethers, fatty acid esters, arylsultonates as polynaphtalensulfonate, alkylarylsulfonates as dodecylbenzene sulfonate, alkylsulfonates as sodium sulfosuccinate, polyalkyleneglycol ethers, acrylic Graft Co-Polymer, N-methly-N-oleyl-taurin Na salt or polyvinylalkohol, preferably 0.2 to 5% dodecylbenzene sulfonate calcium;
a thickening agent, 0 to 2%, preferably 0.1 to 1%, e.g. xanthan gum, heteropolysaccharides, oxypropylated cellulose, precipitated or fused silica (hydrophobizised or non-hydrophobizised), gelatine, polysaccharides, tetramethyl decyne diol, ethoxylated dialkyl phenol, methylated clay, propylene carbonate, hydrogenated castor oil, ethoxylated vegetable oil, sodium benzoate or hexanediol;
an antifreeze agent, 0 to 20%, preferably 1 to 10% , e.g. 1,2-propyleneglycol, glycerine, ethyleneglycol or freezing point-lowering salts;
a defoaming agent, 0 to 5%, preferably 0.1 to 2%, e.g. silicone oil, alcohols, fluoroorganics or mineral oils;
a preservative/biocide, 0 to 10%, preferably 0.1 to 3% , e.g. formaldehyde, 1,2 benzisothiazol-3(2H)-one or its salts, or benzoic acid;
a buffer, 0 to 5%, preferably 0.1 to 3%, e.g. acetic acid (AcOH)/NaOH or AcOH/KOH, H3PO4/NaOH or H3PO4/KOH, citric acid/NaOH or citric acid/KOH, or KH2PO4/Borax; as well as further wetting, dispersing and emulsifying agents, organic solvents, cosolvents and oils.
Another object of the invention is a process for preparing a composition as herein described, by grinding or milling the solid pesticide and then intimateley mixing, optionally by warming, the components, until a homogeneous phase is achieved.
In another aspect of the invention the composition is an aqueous spray mixture. Before the application, the composition of the invention may be diluted with water by simple mixing at ambient temperature in order to get a ready for use spray mixture.
The resulting spray mixtures are stable, i.e. they remain as a homogeneously dispersed phase on standing without agitation for at least one hour to 12 hours or even more. Preferred concentrations of the spray mixture are 0.05 to 10%, more preferred 0.2 to 5% pesticide in relation to the spray mixture.
A further aspect of the invention is a method of preventing or combatting undesirable plant growth, infestation of plants or animals by pests and regulating plant growth by diluting the composition according to claim 1 with water and applying a pesticidally effective amount to the cultivation area, to the plant or animal.

Abstract: (1) a tristyrylphenol-ethoxylate having 6-14, in nonionic form and

Abstract: (2) a tristyrylphenol-ethoxylate having 14-18 mol ethoxylate, in form of its sulfate or phosphate, in anionic or acid form, and

Abstract: (3) a dioctyl-sulfosuccinate salt.


A crankcase lubricant containing a Group III basestock in a major amount and a Group V basestock in the form of an ester in a minor amount. The lubricant also comprises a dispersant, a metal detergent, one or more other additives, and a viscosity modifier.

This invention relates to lubricating oil compositions such as multigrade lubricants that, in particular, give enhanced performance in diesel engine piston cleanliness and piston ring-sticking tests.
Lubricating oil compositions (or lubricants) for the crankcase of internal combustion engines are well-known and it is also well-known for them to contain additives (or additive components) to enhance their properties and performance.
Increasingly, the demands of original equipment manufacturers (OEM""s) to meet performance criteria dictate the properties of lubricants. One such performance criterion concerns the sticking of piston rings during operation of a compression-ignited (diesel) internal combustion engine. This is usually referred to briefly as xe2x80x9cring-stickingxe2x80x9d; it may be measured by the VWTDi test (CEC L-78-T-99). A second performance criterion that is measured in this test is piston cleanliness.
Other performance criteria of interest include the volatility of the lubricant, the fuel economy performance of the lubricant, and the chlorine content of the lubricant.
The various criteria clearly constrain formulators of lubricants in terms of additive components and amounts, and of basestocks, that may be used.
EP-A-1 087 008 describes a way of meeting xe2x80x9cring-stickingxe2x80x9d test requirements by provision of certain additive components.
The present invention provides a different approach, i.e. by providing a specific basestock mixture in order to meet the above mentioned requirements.
In a first aspect, the invention is a crankcase lubricating oil composition, such as an SAE 5W-20, 5W-30 or 5W-40 composition, comprising, or made by admixing, a major amount of
(A) a basestock of lubricating viscosity comprising a Group III basestock, in a major amount, and a Group V basestock, in the form of an ester, in a minor amount, such as 3 to 5, preferably 3 to 10, mass % based on the mass of the composition, other than basestocks that arise from provision of additive components in the composition; and minor amounts of lubricant additive components comprising
(B) a dispersant, such as an ashless dispersant;
(C) a metal detergent;
(D) one or more other lubricant additive components selected from anti-oxidants, anti-wear agent and friction modifiers; and
(E) a viscosity modifier.
The data contained in the specification demonstrate that the use of the basestock mixture (A) unexpectedly improves the performance of lubricating oil compositions in the TDi test.
In a second aspect, the invention is a method of lubricating a compression-ignited internal combustion engine comprising operating the engine and lubricating the engine with a lubricating oil composition according to the first aspect of the invention.
In a third aspect, the invention is a method of reducing the ring-sticking tendencies of a compression-ignited internal combustion engine comprising adding to the engine a lubricating oil composition according to the first aspect of the invention.
In a fourth aspect, the invention is a combination comprising the crankcase of a compression-ignited engine and a lubricating oil composition according to the first aspect of the invention for lubricating the crankcase.
In this specification:
xe2x80x9ccomprisingxe2x80x9d or any cognate word is taken to specify the presence of stated features, integers, steps or components, but does not preclude the presence or addition of one or more other features, integers, steps, components or groups thereof;
xe2x80x9cmajor amountxe2x80x9d means in excess of 50 mass % of the composition;
xe2x80x9cminor amountxe2x80x9d means less than 50 mass % of the composition both in respect of the stated additive and in respect of the total mass % of all of the additives present in the composition, reckoned as active ingredient of the additive or additives;
xe2x80x9coil-solublexe2x80x9d or xe2x80x9cdispersiblexe2x80x9d used herein do not necessarily indicate that the compounds or additives are soluble, dissolvable, miscible, or capable of being suspended in the oil in all proportions. These do mean, however, that they are, for instance, soluble or stably dispersible in oil to an extent sufficient to exert their intended effect in the environment in which the oil is employed. Moreover, the additional incorporation of other additives may also permit incorporation of higher levels of a particular additive, if desired.
The invention also provides the product obtained or obtainable as a result of any reaction between the various additive components of the composition or concentrates, essential as well as customary and optimal, under the conditions of formulation, storage or use:
The features of the invention will now be discussed in more detail as follows:
Multigrade Lubricants
Multigrade lubricants perform over wide temperature ranges. Typically, they are identified by descriptors such as SAE 10W-30 or SAE 5W-30. The first number in the multigrade descriptor is associated with a safe cranking temperature (e.g., xe2x88x9220xc2x0 C.) viscosity requirement for that multigrade oil as measured by a cold cranking simulator (CCS) under high shear rates (ASTM D5293). In general, lubricants that have low CCS viscosities allow the engine to crank more easily at lower temperatures and thus improve the ability of the engine to start at those ambient temperatures.
Multiviscosityxe2x80x94grade oils, commonly referred to as xe2x80x9cmultigradesxe2x80x9d are designed to operate over wide temperature ranges and are identified by descriptors such as SAE 10W-30 or SAE 5W-30,. Their properties are defined in the Society of Automotive Engineers document SAE J300. This publication defines multigrades in terms of two criteria:
Maximum low temperature cranking and pumping viscosities and
Maximum and minimum kinematic viscosities at 100xc2x0 C. and a minimum high-shear viscosity at 150xc2x0 C. and 108sxe2x88x921.
Low temperature properties define which xe2x80x9cWxe2x80x9d grade shall be assigned to a lubricant and high temperature properties define the xe2x80x9cnon Wxe2x80x9d part of the designation.
SAE J300 defines a series of W grades with SAE 0W representing the requirements for operation at lowest temperatures. SAE 5W, 10W, 15W, 20W and 25W are also defined, these grades are suitable for progressively higher minimum temperature of operation.
Non-W grades are also assigned a numerical designation, these define a scale of increasing high temperature viscosity. This scale starts with SAE 20 and goes through SAE 30, 40 and 50 to the most viscous grade, SAE 60.
This system of viscometric classification of automotive crankcase lubricants finds universal application with the vehicle and lubricant manufacturing industries.
(A) Basestock
The basestock (sometimes referred to as xe2x80x9cbase oilxe2x80x9d) is an oil of lubricating viscosity and is the primary liquid constituent of a lubricant into which additives and possibly other oils are blended to produce the final lubricant.
Basestocks may be categorised in Groups I to V according to the API Engine Oil Licensing and Certification System (EOLCS) API 1509 definitions, which definitions are used to define the basestocks of this invention. Thus:
a) Group I basestocks contain less than 90 percent saturates and/or greater than 0.03 percent sulfur and have a viscosity index greater than or equal to 80 and less than 120 using the test methods specified in Table E-1.
b) Group II basestocks contain greater than or equal to 90 percent saturates and less than or equal to 0.03 percent sulfur and have a viscosity index greater than or equal to 80 and less than 120 using the test methods specified in Table E-1.
c) Group III basestocks contain greater than or equal to 90 percent saturates and less than or equal to 0.03 percent sulfur and have a viscosity index greater than or equal to 120 using the test methods specified in Table E-1.
d) Group IV basestocks are polyalphaolefins (PAO).
e) Group V basestocks include all other basestocks not included in Group I, II, III, or IV.
As stated, the basestock (A) in the present invention comprises a major amount of a Group III basestock and a minor amount of Group V basestock in the form of an ester. Preferably, it consists essentially of such basestocks, but may contain minor amounts of Group I or Group II basestocks or both. Group III basestocks are commercially available.
Group V basestocks in the form of esters are also commercially available. Examples include polyol esters such as pentaerythritol esters, trimethylolpropane esters and neopentylglycol esters; diesters; C36 dimer acid esters; trimellitate esters, i.e. 1,2,4-benzene tricarboxylates; and pathalate esters, i.e. 1,2-benzene dicarboxylates. The acids from which the esters are made are preferably monocarboxylic acids of the formula RCO2H where R represents a branched, linear or mixed alkyl group. Such acids may, for example contain 6 to 18 carbon atoms.
(B) Dispersants
Dispersants, such as ashless dispersants i.e. non-metallic organic materials that form substantially no ash on combustio, hold solid and liquid contaminants in suspension and comprise long-chain hydrocarbons, to confer oil-solubility, with a polar head capable of associating with particles to be dispersed. A noteworthy group is hydrocarbon-substituted succinimides.
(C) Metal Detergents
A detergent is an additive that reduces formation of piston deposits, for example high temperature varnish and lacquer deposits, in engines; it normally has acid-neutralising properties and is capable of keeping finely-divided solids in suspension. Most detergents are based on metal xe2x80x9csoapsxe2x80x9d, that is metal surfactants or salts of acidic organic compounds.
Detergents generally comprise a polar head with a long hydrophobic tail, the polar head comprising a metal salt of an acidic organic compound. The salts may contain a substantially stoichiometric amount of the metal, in which case they are usually described as normal or neutral salts, and would typically have a total base number or TBN (as may be measured by ASTM D2896) of from 0 to 80. Large amounts of a metal base can be included by reacting an excess of a metal compound, such as an oxide or hydroxide, with an acidic gas such as carbon dioxide. The resulting overbased detergent comprises neutralised detergent as the outer layer of a metal base (e.g. carbonate) micelle. Such overbased detergents may have a TBN of 150 or greater, and typically of from 250 to 450 or more.
The detergents that may be used include oil-soluble neutral and overbased sulfonates, phenates, sulfurized phenates, thiophosphonates, salicylates, and naphthenates. Particularly convenient detergents are neutral and overbased calcium sulfonates having a TBN of from 20 to 450 TBN, and neutral and overbased calcium phenates and sulfurized phenates having a TBN of from 50 to 450.
(D) Other Lubricant Additives
anti-oxidants increase the composition""s resistance to oxidation and may work by combining with and modifying peroxides to render them harmless by decomposing peroxides or by rendering an oxidation catalyst inert. They may be classified as radical scavengers (eg sterically hindered phenols, secondary aromatic amines, and organo-copper salts); hydroperoxide decomposers (eg organo-sulfur and organophosphorus additives); and multifunctionals. In the practice of the present invention, the use or otherwise of certain anti-oxidants may confer certain benefits. For example, in one embodiment it may be preferred that the lubricating oil composition is free of any secondary aromatic amine anti-oxidants. In another embodiment, it may be preferred to employ in the lubricating oil composition a combination of one or more secondary aromatic amine anti-oxidants (eg in the range of 0.1 to 0.7, preferably 0.2 to 0.5, mass % of the composition) and one or more sterically hindered phenol anti-oxidants (eg in the range of 0.1 to 2, preferably 0.5 to 1.5 mass % of the composition); such composition may for example contain one or more molybdenum-containing additives in an amount providing from 50 or 100 to 500 or 700 ppm by mass of elemental molybdenum in the composition.
anti-wear agents reduce friction and excessible wear and are usually based on compounds containing sulfur or phosporus or both. Noteworthy are metal dihydrocarbyl dithiophosphates such as zinc dialkyl dithiophosphates (ZDDP""s). Preferably, the alkyl groups are essentially secondary alkyl groups.
friction modifiers include boundary additives that lower friction coefficients and hence improve fuel economy. Examples are esters of polyhydric alcohols such as glycerol monoesters of higher fatty acids, for example glycerol mono-oleate; esters of long chain polycarboxylic acids with diols, for example the butane diol esters of dimerized unsaturated fatty acids; oxazoline compounds; and alkoxylated alkyl-substituted mono-amines, and alkyl ether amines, for example, ethoxylated tallow amine and ethoxylated tallow ether amine. Preferably, in the practice of this invention, component(s) (D) includes one or more friction modifiers selected from esters of polyhydric alcohols and from alkoxylated amines.
(E) Viscosity Modifiers
Viscosity modifiers (or viscosity index improvers) impart high and low temperature operability to a lubricating oil. Viscosity modifiers that also function as dispersants are also known and may be prepared as described above for ashless dispersants. In general, these so-called dispersant viscosity modifiers are functionalized polymers (e.g. interpolymers of ethylene-propylene post-grafted with an active monomer such as maleic anhydride) which are then derivatized with, for example, an alcohol or amine.
Suitable compounds for use as viscosity modifiers are generally high molecular weight hydrocarbon polymers, including polyesters. Oil-soluble viscosity modifying polymers generally have weight average molecular weights of from 10,000 to 1,000,000, preferably 20,000 to 500,000, which may be determined by gel permeation chromatography or by light scattering.
Representative examples of suitable viscosity modifiers are polyisobutylene, copolymers of ethylene and propylene and higher alpha-olefins, polymethacrylates, polyalkylmethacrylates, methacrylate copolymers, copolymers of an unsaturated dicarboxylic acid and a vinyl compound, interpolymers of styrene and acrylic esters, and partially hydrogenated copolymers of styrene, isoprene, styrene/butadiene, and isoprene/butadiene, as well as the partially hydrogenated homopolymers of butadiene and isoprene and isoprene/divinylbenzene.
Other known additives may be incorporated into the lubricating oil compositions of the invention, being different from those defined in the invention. They may, for example, include other detergents; rust inhibitors; corrosion inhibitors; pour point depressants; anti-foaming agents; and surfactants. They can be combined in proportions known in the art.
As is known in the art, some additives can provide a multiplicity of effects; thus, for example, a single additive may act both as a dispersant and as an anti-oxidant.
Concentrates
In the preparation of lubricating oil compositions, it is common practice to introduce additive(s) therefor in the form of concentrates of the additive(s) in a suitable oleaginous, typically hydrocarbon, carrier fluid, e.g. mineral lubricating oil, or other suitable solvent. Oils of lubricating viscosity such as described herein, as well as aliphatic, naphthenic, and aromatic hydrocarbons, are examples of suitable carrier fluids for concentrates.
Concentrates constitute a convenient means of handling additives before their use, as well as facilitating solution or dispersion of additive in lubricating oil compositions. When preparing a lubricating oil composition that contains more than one type of additive, each additive may be incorporated separatelyxe2x80x94each in the form of a concentrate. In many instances, however, it is convenient to provide a so-called additive xe2x80x9cpackagexe2x80x9d (also referred to as an xe2x80x9cadpackxe2x80x9d) comprising two or more additives in a single concentrate.
A concentrate may contain 1 to 90, such as 10 to 80, preferably 20 to 80, more preferably 20 to 70, mass % active ingredient of the additive or additives.
Making Compositions
Lubricating oil compositions may be prepared by adding to an oil of lubricating viscosity a mixture of an effective minor amount of at least one additive and, if necessary, one or more co-additives such as described hereinafter. This preparation may be accomplished by adding the additive directly to the oil or by adding it in the form of a concentrate thereof to disperse or dissolve the additive. Additives may be added to the oil by any method known to those skilled in the art, either prior to, contemporaneously with, or subsequent to addition of other additives.
The lubricating oil compositions may be used to lubricate mechanical engine components, particularly an internal combustion, such as a compression-ignited engine, by adding the lubricating oil thereto. Particular examples of compression-ignited engine are those developed in recent years where the top ring groove temperature may exceed 150xc2x0 C. due to increases in specific power output to around 40 kW/liter or greater. These engines are more prone to suffer from ring-sticking problems in their operation.
When concentrates are used to make the lubricating oil compositions, they may for example be diluted with 3 to 100, e.g. 5 to 40, parts by mass of oil of lubricating viscosity per part of the concentrate.
When lubricating oil compositions contain one or more additives, each additive is typically blended into the base oil in an amount which enables the additive to provide its desired function. Representative effective amounts of such additives, when used in crankcase lubricants, are listed below. All the values listed herein are stated as mass percent active ingredient, unless otherwise indicated.
The final composition may contain from 5 to 25, preferably 5 to 18, typically 10 to 15, mass % of the concentrate, the remainder being oil of lubricating viscosity.


Asphalt emulsions containing emulsifiers comprising alkali metal or ammonium salts of solidified pyrolytic wood tar oil. Resinous compositions useful as asphalt emulsifiers comprising: (a) solidified pyrolytic wood tar oil and salts thereof, and (b) rosins and salts thereof.

This invention relates to asphalt emulsions and emulsifiers used in preparing asphalt emulsions.
In the manufacture of pale wood rosin from southern pine stumpwood, crude rosin is extracted from the wood and then refined using solvent/solvent partitioning between aliphatic hydrocarbon and polar solvents. One of the by-products of this operation is a dark, high melting, largely aliphatic hydrocarbon-insoluble resin, hereinafter referred to as AHI resin. AHI resin is a thermoplastic resin that chemically is a complex mixture of high molecular weight phenolic compounds, rosin acids, neutral materials and several minor components. An AHI resin is produced as described in U.S. Pat. No. 2,221,540, which patent is incorporated herein by reference in its entirety. A preferred AHI resin is Vinsol(copyright) resin available from Hercules Incorporated, Wilmington, Delaware.
AHI resin, particularly Vinsol(copyright) resin from Hercules Incorporated, Wilmington, Del., is used in a wide variety of industrial applications including asphalt emulsions. Asphalt emulsions are used in a variety of applications such as road building, road sealing, soil stabilization, mulching, surface coating of asphalt pavements, and built-up roofs. Because the amount of wood rosin produced relative to tall oil and gum rosin is declining, the supply of AHI resin available for industrial applications is also declining. Consequently, there is a need for a material which will perform in asphalt emulsions in a manner similar to AHI resin.
U.S. Pat. No. 5,656,733 describes resinous compositions comprising lignin and polymerized rosin, and the use of such compositions as asphalt emulsifiers and air entraining agents for concrete.
This invention pertains to asphalt emulsions containing an emulsifier comprising an alkali metal or ammonium salt of solidified pyrolytic wood tar oil.
In another embodiment the invention comprises a resinous composition comprising a first component selected from the group consisting of solidified pyrolytic wood tar oil and salts thereof, and a second component selected from the group consisting of rosins and salts thereof.
In yet a third embodiment the invention pertains to a method for preparing a resinous composition comprising: combining solid ingredients comprising solidified pyrolytic wood tar oil and a rosin selected from the group consisting of natural rosin, fortified rosin, polymerized rosin, hydrogenated rosin, disproportionated rosin, modified rosin and esterified rosin; and milling the combined solid ingredients until a substantially homogeneous particulate blend is obtained.
In yet another aspect, the invention pertains to a method for preparing an asphalt emulsion comprising dissolving ingredients comprising a rosin and solidified pyrolytic wood tar oil in an aqueous solution of alkali metal or ammonium hydroxide in water to form an aqueous solution of emulsifier, mixing the aqueous solution of emulsifier with asphalt to form a mixture, and milling the mixture to form an emulsion of the asphalt.
Solidified Pyrolytic Wood Tar Oil
The solidified wood tar oil for use in the current invention is produced by thermal destructive distillation, for example fast pyrolysis of biomass, e.g., wood. The controlled, rapid heating of the biomass material (e.g., wood) initiates depolymerization reactions in the lignin component while minimizing condensation reactions. In addition, the very short reaction times and rapid vapor quench employed in fast pyrolysis preserve the lignin polymer fragments by protecting them from prolonged exposure to high temperatures. In summary, the high intensity but very short xe2x80x9cthermal shockxe2x80x9d of fast pyrolysis causes the lignin component of the wood feedstock to depolymerize, yielding reactive polymer fragments in a molecular size range suitable for subsequent controlled crosslinking. Fast pyrolysis processes are described in U.S. Pat. Nos. 4,876,108; 5,792,340; 5,853,548 and 5,961,786, all of which are incorporated herein by reference in their entireties.
The rapid destructive distillation or fast pyrolysis involves the rapid heating of biomass material. Reaction temperatures of 500xc2x0 to 550xc2x0 C. allow maximization of the production of desired product vapors while minimizing byproduct gas and char. The product vapors are rapidly condensed and collected. This product, referred to as whole oil, bio-oil or pitch is used as a feedstock for further processing to produce solidified pyrolytic wood tar oil.
The subsequent processing of the whole oil involves the non-destructive distillation and evaporative treatment of the material. The non-destructive techniques for distillation-evaporation include wipe film evaporation, roto-evaporation, agitated film evaporation, vacuum distillation, falling film, etc. These non-destructive techniques remove or reduce the content of water, acids, odors and non-resin components by heat and/or vacuum distillation. In addition, the carefully controlled temperatures used during evaporation allow a controlled polymerization of the feedstock to occur while maintaining the reactive sites in the final product. In summary, distillation/evaporation can be controlled to product an optimized degree of crosslinking or polymerization, resulting in a solidified pyrolytic wood tar oil.
In the case of the solidified pyrolytic wood tar oil for this invention, the distillation/evaporation conditions are controlled to produce product with the following preferred property ranges: softening point (Fisher-Johns), from about 100xc2x0 to about 170xc2x0 C.; acid number, from about 10 to about 50; glass transition temperature (Tg) of from about 30xc2x0 to about 100xc2x0 C.; weight average molecular weight (size exclusion chromatography) of from about 1,500 to about 4,500; and number average molecular weight of from about 500 to about 1,000. More preferred property ranges are: softening point, from about 140xc2x0 to about 160xc2x0 C.;
acid number, from about 20 to about 30; glass transition temperature (Tg) of from about 70xc2x0 to about 100xc2x0 C.; weight average molecular weight (size exclusion chromatography) of from about 3,000 to about 4,000; and number average molecular weight of from about 750 to about 1,000.
Preferably, the solidified pyrolytic wood tar oil will contain from about 40% to about 60% of material of number average molecular weight less than about 1,000, and from about 20% to about 30% less than about 500.
Rosins
The rosins useful for the present invention can be any thermoplastic rosin, including unfortified rosin, fortified rosin, extended rosin, rosin esters, acid modified rosin esters, polymerized rosin, dimerized rosin, disproportionated rosin, hydrogenated rosin, hydrogenated rosin esters and mixtures and blends thereof. Preferred rosins for use in the invention are fortified rosins and polymerized rosin.
The rosin used in this invention can be any of the commercially available types of rosin, such as wood rosin, gum rosin, tall oil rosin, or mixtures of any two or more in their crude or refined state. Partially hydrogenated rosins and polymerized rosins, as well as rosins that have been treated to inhibit crystallization, such as by heat treatment or reaction with formaldehyde, can also be employed. Rosins for the invention preferably will have an acid number of at least about 100, more preferably at least about 150, and most preferably at least about 200.
Fortified rosin useful in this invention is the adduct reaction product of rosin and an acidic compound containing the
group and is derived by reacting rosin and the acidic compound at elevated temperatures of from about 150xc2x0 C. to about 210xc2x0 C.
The amount of acidic compound employed will be that amount which will provide fortified rosin containing from about 1% to about 16% be weight of adducted acidic compound based on the weight of the fortified rosin. Methods for preparing fortified rosin are well known to those skilled in the art. See, for example, the methods disclosed and described in U.S. Pat. Nos. 2,628,918 and 2,684,300, the disclosures of which are incorporated herein by reference.
Examples of acidic compounds containing the
group that can be used to prepare the fortified rosin include the xcex1,xcex2-unsaturated organic acids and their available anhydrides, specific examples of which include fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride and acrylic acid. Mixtures of acids can be used to prepare the fortified rosin if desired. Thus for example, a mixture of the acrylic acid adduct of rosin and the fumaric acid adduct can be used in the invention. Also, fortified rosin that has been hydrogenated after adduct formation can be used.
For use in the present invention fumaric acid and maleic anhydride are preferred, and fumaric acid is most preferred. When fumaric acid is employed as the fortifying agent, the preferred amount of fumaric acid employed will be that amount which will provide fortified rosin containing from about 1% to about 16% by weight of combined or adducted fumaric acid based on the weight of the fortified rosin. More preferably, the amount employed will provide fortified rosin containing from about 1% to about 10% by weight of adducted fumaric acid, and most preferably from about 1 % to about 5% by weight fumaric acid.
Various rosin esters of a type well known to those skilled in the art can also be used in the present invention. Esterified rosins comprise esters formed from any of the above mentioned rosins and an alcohol. Suitable exemplary rosin esters may be rosin esterified as disclosed in the U.S. Pat. Nos. 4,540,635, and 5,201,944, the disclosures of which are incorporated herein by reference. Suitable alcohols include polyhydric alcohols such as ethylene glycol, glycerol, diethylene glycol, triethylene glycol, pentaerythritol, 1,4-butanediol, sorbitol, and mannitol, aminoalcohols such as triethanolamine, triisopropanolamine, and tributanolamine, and polyethylene and polypropylene glycols.
Polymerized rosin useful in this invention is manufactured by acid catalyzed polymerization of rosin. It comprises predominantly dimeric rosin acids and is generally available as a mixture of dimerized and monomeric rosin acids. Commercially available polymerized rosin comprises a mixture of about 30 to about 90 wt. percent rosin dimer and about 10 to about 70 wt. percent rosin acids. The preferred polymerized rosin for this invention comprises a mixture of from about 30 to about 50 wt. percent dimerized rosin. The most preferred polymerized rosin is Poly-Pale(copyright) resin available from Hercules Incorporated, Wilmington, Del.
The asphalt emulsions of this invention contain an emulsifier comprising an alkali metal or ammonium salt of solidified pyrolytic wood tar oil. Preferably, the emulsifier will further comprise an alkali metal or ammonium salt of a rosin as described above, preferably fumaric acid fortified rosin or polymerized rosin. The asphalt emulsifiers are generally used at a level of from about 1 to about 2 weight percent based on the total weight of the emulsion.
In the preferred case, i.e., when an alkali metal or ammonium salt of a rosin is used together with solidified pyrolytic wood tar oil, the ratio of solidified pyrolytic wood tar oil to the rosin or mixture of rosins on a weight basis is from about 1:3 to about 3:1. Preferably the ratio is from about 1:2 to about 2:1, and more preferably from about 1:1.5 to about 1.5:1.
A preferred method for preparing the resin composition for use as an asphalt emulsifier comprises blending and mixing the solidified pyrolytic wood tar oil, the rosin or rosins, as well as any additional ingredients, in the form of lumps, flakes or powders, followed by grinding or milling the ingredients under conditions ensuring good mixing until a homogeneous mixture is obtained. Any high shear mixers suitable for blending solids are usable for this purpose. The resin composition prepared in this way may be converted into an asphalt emulsifier by solution of the blended composition in aqueous alkali metal or ammonium hydroxide.
Alternatively, the emulsifier may be prepared without the solid blending step by separately dissolving the ingredients in an aqueous solution of alkali metal or ammonium hydroxide to form an aqueous solution comprising a salt.
In most case the emulsifier solution will be used in the form of the aqueous solution. However, if desired, the water can be removed from the aqueous solution to form a solid, substantially dry salt. Preferred methods of water removal are distillation and spray drying.
The alkali metal for use in preparing the emulsifiers of the invention is selected from the group consisting of lithium, sodium and potassium. The preferred alkali metal is sodium.
Thus the resinous compositions of this invention may be in free acid form, in the form of a salt of an alkali metal or ammonium, or as mixtures of both. In the free acid form, properties of the compositions which are usually measured are the acid number and the Ring and Ball softening point. In the free acid form, the acid number of the resinous compositions of this invention is preferably from about 100 to about 130, more preferably from about 110 to about 120, and the Ring and Ball softening point is preferably from about 110xc2x0 C. to about 140xc2x0 C. and more preferably from about 120xc2x0 C. to about 130xc2x0 C.
This invention is illustrated by the following examples, which are exemplary only and not intended to be limiting. All percentages, parts, etc., are by weight, unless otherwise indicated.
Materials and Procedures
Softening points of solidified pyrolytic wood tar oil were determined on a Fisher-Johns Melting Point Apparatus. Softening points of all other materials were Ring and Ball softening points, determined by ASTM method E-28(1992). The acid number of a material is defined as the number of milligrams of KOH required to neutralize 1 gram of material.
Solidified pyrolytic wood tar oil: Wood was pyrolyzed at 500-550xc2x0 C. by the methods described in U.S. Pat. No. 5,792,340, which is incorporated herein by reference in its entirety. The bio-oil from the pyrolysis system was then heated at 150-250xc2x0 C. under vacuum in a wiped film evaporator until the product solidified pyrolytic wood tar oil had a Fisher Johns softening point of 130xc2x0 C.
Polymerized rosin: Poly-Pale(copyright) resin, available from Hercules Incorporated, Wilmington, Del. contains approximately 40 wt. % rosin dimer and 60 wt. % monomeric rosin
AHI resin: Vinsol(copyright) resin obtained from Hercules Incorporated, Wilmington, Del., acid number 90-105, Ring and Ball softening point 103-123xc2x0 C.
Fumaric acid adduct of rosin: For preparation of the fumaric acid adduct of rosin, gum rosin was heated to 170xc2x0 C. and then the desired quantity of fumaric acid was added. The resulting mixture was heated to 200xc2x0 C. and stirred for about 2 hours. In the examples presented herein the amount of fumaric acid was 4% by weight of the rosin. The acid number of the product was 196, and the Ring and Ball softening point 97xc2x0 C.

Asphalt emulsion containing solidified pyrolytic wood tar oil


A low voltage differential signaling driver is disclosed that is capable of supporting many different LVDS standards or signal level requirements. The low voltage differential signaling driver has a programmable offset voltage and a programmable differential output voltage, which may be programmed independently.

1. Technical Field
The present invention relates generally to electrical circuits and, more particularly, to interface circuits to support, for example, low voltage differential signaling.
2. Related Art
Low voltage differential signaling (LVDS) has emerged as a popular differential data transmission method. LVDS offers many advantages, such as low noise and low power while providing a robust and high-speed data transmission.
Because of its many advantages, LVDS has been deployed across market segments for numerous applications. As a result, there exist a number of different types of LVDS standards or signal level requirements. For example, IEEE standard 1596.3 and HyperTransport specifications employ LVDS, but have different signaling level requirements, such as for the offset voltage (or common mode voltage level) or the differential output voltage swing.
A drawback of having numerous LVDS signal level requirements is that a device is typically designed to support only one specific type of LVDS, which limits the device""s applicability. Alternatively, the device is implemented with a specific circuit to support each respective type of LVDS. A drawback of this approach is that it becomes difficult to select which combination of specific circuits should be incorporated into the device due to the number of existing LVDS signal level requirements and the rapid pace at which they continue to emerge and evolve. As a result, there is a need for systems and methods that address the various LVDS requirements.
Systems and methods are disclosed herein for supporting two or more LVDS signal level requirements. For example, in accordance with an embodiment of the present invention, an LVDS driver (or buffer) supports two different LVDS signal level requirements by having a programmable common mode voltage (offset voltage). Furthermore, other parameters, such as the bias current or differential output voltage may also be programmable. As a result, by utilizing the techniques discussed herein, one LVDS driver can support many different LVDS standards or signal level requirements. As an example, an LVDS driver in accordance with an embodiment of the present invention can be provided for a programmable device, such as a complex programmable logic device, a programmable logic device, or a field programmable gate array, to support various LVDS interface requirements.
More specifically, in accordance with one embodiment of the present invention, a driver includes a multiplexer adapted to select from a plurality of reference voltages; an amplifier, coupled to the multiplexer, adapted to receive the reference voltage selected by the multiplexer and set an offset voltage of the driver based on the reference voltage; a current source circuit, coupled to the amplifier, adapted to provide an output current for the driver; a plurality of transistors, coupled to the current source circuit and to a data line, adapted to route the output current to produce a positive voltage differential output or a negative voltage differential output based on a data value on the data line; and a current limiting circuit, coupled to the plurality of transistors, adapted to limit the output current to a value that provides a desired differential output voltage.
In accordance with another embodiment of the present invention, a driver includes means for selecting one of a plurality of offset voltages; means for providing a driver current to generate a positive differential voltage or a negative differential voltage based on a data signal; and means for selecting one of a plurality of values for the driver current to provide a desired differential voltage level for the positive differential voltage and the negative differential voltage.
In accordance with another embodiment of the present invention, a method of providing a plurality of low voltage differential signal levels from a single driver includes programming a desired offset voltage based on a plurality of selectable reference voltages; providing a programmable current source to generate a driver current; channeling the driver current to provide a positive differential output voltage or a negative differential output voltage based on a value of a data signal; and limiting the driver current to a specified value to provide a desired value for the positive differential output voltage and the negative differential output voltage.
The scope of the invention is defined by the claims, which are incorporated into this section by reference. A more complete understanding of embodiments of the present invention will be afforded to those skilled in the art, as well as a realization of additional advantages thereof, by a consideration of the following detailed description of one or more embodiments. Reference will be made to the appended sheets of drawings that will first be described briefly.

Low voltage differential signaling systems and methods


An apparatus for a firearm, the firearm having a user hand-gripable barrel portion. The apparatus has a U-shaped member with an outwardly extending cylindrical protuberance swivelably disposed thereto. An elongated handle is detachably secured to the cylindrical protuberance. An elevated contoured member is mountably disposed along the curved portion of the U-shaped member. The elevated contoured member is formed to receive a selected portion of the hand-gripable barrel of the firearm. An elongated strap is connectively disposed to the U-shaped member. The elongated strap traverses the hand-gripable barrel portion of the firearm thereby detachably securing the firearm to the U-shaped member. Whereby the user gripping the elongated handle enables swivelable firearm movement.

The invention relates, in general, to a hand gripable biomechanical tool. In particular, the invention relates to an apparatus mounted to a firearm stock containing a portion of the firearm""s barrel. More particularly the invention relates to a swivelable hand gripable apparatus mounted to a firearm stock containing a portion of the firearm""s barrel. A user of the swivelable apparatus is enabled to pivot the firearm while aiming the firearm.
Firearms are manufactured in various sizes, calibers, and physical configurations. In general, firearms used by sportsmen are pistols, rifles, or shotguns. The sportsman may engage in game hunting or target shooting i.e., stationary or moving targets. Sportsmen, regardless of the type of firearm they use or the sport they are engaged in, have one common thread that runs through the connection between the sportsman and his firearm. The common thread is aiming the firearm before discharging the weapon.
The standard or common practice for aiming a firearm, a rifle for example, is to place the rifle stock butt against either the right or left shoulder and grip a portion of the stock containing the firing mechanism with either the right or left hand. The sportsman""s other hand is positioned palm up along a portion of the stock containing the barrel of the rifle. The rifle is cradled in a position allowing the sportsman to raise the rifle and align the sights of the rifle with the intended target thus aiming the firearm at the target.
The palm of the hand facing upwards and grasping the stock portion containing the barrel causes the muscles in the forearm to tighten thus supporting the wrist and hand. The thumb and forefinger form a U-shaped cradle for the barrel-mounted stock. The remaining fingers of the hand provide no mechanical advantage in supporting the firearm. Various muscle groups of the shoulder, upper arm, forearm, and hand are tightened to support the firearm while the sportsman is aiming the firearm.
The tightening of the aforementioned muscle groups restricts the arcuate movement of the firearm while aiming. The arcuate movement required during aiming of the firearm or tracking a moving target while aiming the firearm is limited to a relatively short arcuate radius extending to either side of the centerline of the barrel of the firearm. If further arcuate movement is desired, the sportsman must traverse his upper torso in concert with his arm movement. The extended arc produced by the upper torso and arm movement only marginally extend the radius of the arc. If further extensions in the radius of the arc are desired the sportsman must physically change or move his stance i.e., his whole body relative to the target. The change of stance while aiming a firearm may be acceptable during target shooting but changing stance while game hunting may cause the game to bolt. The sportsman would be required to re-aim the firearm and possibly change his stance once again.
Attempts in the past to provide mechanical advantage to a firearm to increase the successful aiming of the firearm have been concerned with the vertical or horizontal position of the barrel relative to the target. One attempt is disclosed in U.S. Pat. No. 2,826,848 issued to T. E. Davis on Mar. 18, 1958. The Davis patent discloses a hand held elongated apparatus that has one end formed into a C-shape. The C-shaped end fits partially about the barrel of a firearm. A sportsman grasps the elongated portion and aims the firearm. The sportsman may, if desired, increase the elevation of the barrel by partially unscrewing the C-shaped end from the elongated apparatus. The Davis patent discloses an apparatus to increase the user""s ability to obtain a constant firearm barrel elevation but does not teach a method or apparatus to increase the sportsman""s arcuate movement of a firearm while aiming at a moving target.
Another attempt to remedy the problems of aiming a firearm at a moving target are disclosed in U.S. Pat. No. 879,052 issued to J. Jeranek on Feb. 11, 1908. The Jeranek patent discloses an elongated apparatus that has one end sharpened to assist in penetrating a surface or penetrating the ground to provide a stationary position for the elongated apparatus. The elongated apparatus has a sliding tubular section that may, if desired, be adjustably secured to select a desired elevation of the firearm. The elongated apparatus has a U-shaped member mounted at one end of the tubular section. The U-shaped member is rotatably mounted to the tubular section. The firearm is positioned within the confines of the U-shaped member and aimed by the sportsman. Presumably, if the sportsman desired to track a moving target he would rotate the U-shaped member by moving his body about the elongated apparatus.
It would be desirable to have an apparatus that enables a sportsman to aim a firearm utilizing a maximum arcuate radius to achieve maximum arcuate movement of the barrel while aiming the firearm. The apparatus would be biomechanical thereby enabling the sportsman to grasp the stock mounted barrel with either the right or left hand utilizing all of his fingers of the right or left hand. The palm holding the apparatus would be in a neutral position rather than a supinated position i.e., the palm facing upwards. The neutral position of the palm about the apparatus would provide stabilization from both the pronator teres as well as the supinator for improved elbow stabilization. The brachioradialis is at a mechanical advantage to aid in strength and stabilization of the elbow flexors with the palm in the neutral position. The shoulder is adjusted from the conventional external rotation to an increased internal rotation, allowing both the long and short head of the bicep to aid in shoulder flexion and stabilization. With the improved gripping of the finger flexors about the apparatus there would be an improved ability to stabilize the butt of the firearm into the shoulder of the sportsman. The desirable results of grasping an apparatus in the above discussed manner would enable the sportsman to biomechanically enhance the stability, mobility, comfort, and accuracy while engaged in target shooting or game hunting.
The present invention is a user operable and hand gripable tool or apparatus that incorporates biomechanical features enabling a user to aim a firearm. The present invention may be mounted on any barrel of any type of firearm. If desired, the present invention may be mounted to the firearm stock containing the portion of the firearm""s barrel. The user of the present invention is enabled to aim the firearm utilizing the maximum arcuate radius derived from the pivotal movement of the firearm while aiming or tracking an intended target.
The present invention is a biomechanical apparatus for a firearm wherein the firearm has a user hand-gripable barrel portion. The apparatus may, if desired, comprise a U-shaped member that has an outwardly extending cylindrical protuberance. The outwardly extending cylindrical protuberance is swivelably mounted to the U-shaped member. An elevated contoured member is connected along the curved portion of the U-shaped member. The elevated contoured member is sized to receive a selected portion of the user hand-gripable barrel portion of the firearm. An elongated handle has an aperture disposed in one end. The aperture is sized to receive a portion of the outwardly extending cylindrical protuberance. The elongated handle is detachably secured to the U-shaped member by a setscrew that adjoins the elongated handle and the outwardly extending cylindrical protuberance. The U-shaped member is now free to rotate 360xc2x0 (degrees) about one end of the elongated handle.
The present invention may, if desired, have an elongated connecting strap traversing the barrel or the barrel mount stock portion of the firearm and the U-shaped member. The elongated connecting strap may, if desired, be detachably securable to the barrel and the U-shaped member by a hook and loop fastener. The present invention may further have a pair of pads mounted onto the legs of the U-shaped member thus protecting the barrel or stock mount barrel from damage. The pads may be of any size or material composition and may serve as supporting ballast for varying sizes of barrels or stock mounted barrels.
A user of the present invention, once the apparatus was mounted to a firearm, would grip the elongated handle with either the right or left hand. The user""s other hand would be in proximity to the trigger mechanism. The butt of the firearm would be against the user""s shoulder. The firearm would be raised or positioned in the general direction of a selected target. If the target was moving the user would, if desired, aim the firearm by arcuately traversing the barrel of the firearm using the elongated handle. The stock of the firearm would pivot against the user""s shoulder thereby enabling arcuate movement of the barrel while the elongated handle remained stationary in the user""s hand as the barrel portion connected to the U-shaped member swiveled relative to the handle. The swivel action of the present invention provides maximum arcuate movement of the barrel of the firearm during the aiming process discussed herein.
When taken in conjunction with the accompanying drawings and the appended claims, other features and advantages of the present invention become apparent upon reading the following detailed description of embodiments of the invention.

Method and apparatus for a hand-gripable biomechanical tool