A stud snap system includes a pin, a receiver, and a stud. The receiver fixedly engages with the pin and also fixedly engages with the stud to attach of the stud snap system to a material. The material can include apparel, clothing, sportswear, outdoor gear, fabrics, coverings, and textiles. Use of the receiver affords a large selection of options for materials and geometries to be used for the stud since the pin is not directly engaged with the stud.

1. Field of the Invention
The present invention relates to apparel fasteners, and more particularly, to snap type fasteners.
2. Description of the Related Art
Related-art fasteners for material, such as apparel, clothing, sportswear, outdoor gear, fabrics, coverings, textiles, and so on include, snaps. Snaps generally include a stud and a portion to receive the stud and thereby fasten material.
The inventor named herein (xe2x80x9cinventorxe2x80x9d) has noticed deficiencies and/or unmet needs associated with related-art snap studs, a few of which will now be set forth (other related-art deficiencies and/or unmet needs will become apparent in the detailed description below).
The inventor has discovered that it would be advantageous for a snap stud to be attached to material without a requirement of first producing a hole in the material prior to attachment of the snap stud. The inventor has discovered that attachment of related-art snap studs to material conversely requires a hole to be first made in the material before one of the related-art snap studs is attached to the material. The inventor has thus recognized that a need exists in the art for snap studs that can be attached to material without need of first making a hole in the material prior to attachment of the snap stud.
The inventor has discovered that it would be advantageous for a snap stud to have an outside surface that is substantially unaffected as to how the snap stud is attached to the material. The inventor has discovered that attachment of related-art snap studs can affect one or more outside surfaces and consequently, the relative appearance of the snap studs. The inventor has thus recognized that a need exists in the art for a snap stud that can be attached to material without being substantially affected by how the snap stud is attached to the material.
The foregoing-described inventor discoveries constitute at least a part of the inventive content herein.
In one embodiment, a system includes but is not limited to: a pin including a shaft portion and a head portion, the shaft portion including a first end portion, a second end portion, and a longitudinal length, the head portion being adjacent the first end portion of the shaft portion, the second end portion of the shaft portion including a tip portion that is substantially pointed to pierce a material when the pin is in an unaltered state and that is substantially blunt when the pin is in an altered state; a receiver including a pin enclosure portion and a backing portion, the pin enclosure portion having first and second end portions, the first end portion having an opening and the second end portion being enclosed by a top portion, the opening so sized to receive the shaft portion of the pin, the pin enclosure portion having a longitudinal axis, the top portion of the receiver having a hardness so selected to change the pin from the unaltered state to the altered state when the tip portion of the pin is forced against the top portion, the top portion having a protrusion portion, the top portion so shaped that the protrusion portion moves from an un-extended position to an extended position in one or more directions away from the longitudinal axis of the pin enclosure portion when the pin is forced against the top portion and changed from the unaltered state to the altered state; and a stud including a stud top portion and a backing enclosure portion, the stud top portion having an opening so sized to receive the pin enclosure portion when its protrusion portion is in the un-extended position, the stud top portion having an internal surface so sized to fixedly engage with the pin enclosure portion when the protrusion portion is in the extended position, the backing enclosure portion so sized and positioned with respect to the stud top portion to receive the backing portion of the receiver when the stud top portion has received at least a portion of the pin enclosure portion of the receiver.
The foregoing is a summary and thus contains, by necessity, simplifications, generalizations and omissions of detail; consequently, those skilled in the art will appreciate that the summary is illustrative only and is NOT intended to be in any way limiting. Other aspects, inventive features, and advantages of the devices and/or processes described herein, as defined solely by the claims, will become apparent in the non-limiting detailed description set forth herein.


The discussion relates to visitor-driven, venue-specific media. One implementation can obtain a venue media profile of a venue and obtain visitor profiles of visitors at the venue. This implementation can generate a playlist of visitor-driven, venue specific media based on both the venue media profile and the visitor profiles.

A venue may wish to create an ambience to enhance an experience of visitors while the visitors are at the venue. For example, the venue, such as a restaurant or shop, can play music and/or video (e.g., media) to improve the visitor experience. Playing music or video that the visitors enjoy can make the visitors feel more comfortable and connected to the venue, and potentially increase visitor spending and/or increase re-visitation by the visitors. However, playing music or video that the visitors do not like can annoy the visitors, cause them to leave, and/or cause them to be less likely to revisit the venue. Therefore, selection of media to offer at the venue is important.


Provided is a method for identifying problematic input fields in a webform. The method comprises obtaining a set of user interaction data for a plurality of user interactions with input fields of a webform. The user interaction data for each input field includes data corresponding to at least one aspect. The method comprises assigning an aspect value to each aspect of each user interaction with each input field. The method comprises aggregating aspect values into an aggregated aspect value for each input field, generating a score for each input field based at least in part on the aggregated aspect field, ranking the input fields by their respective scores to identify at least one particular input field in the webform as problematic, and indicating that the at least one particular input field in the webform is problematic.

The present disclosure relates generally to the field of webforms, and more particularly to identification of problematic input fields in a webform.
A webform is an interactive form on a website that allows a user to enter data into one or more input fields. The data entered into the input field(s) is collected by the webform and sent to a server for processing. To promote intuitive interaction by users, a webform can resemble a paper form, including input fields that resemble checkboxes and text fields. Like paper forms, webforms may have some input fields that are easier for users to complete and some input fields that are more difficult for users to complete.

Identification of problematic webform input fields

International Business Machines Corporation


A printhead and a method of ejecting liquid droplets are provided. The method includes providing a printhead operable to eject liquid drops having a plurality of drop volumes Vi, for i equal to 1 through n, where n≧2, with Vj>Vi when j>i. One of the plurality of drop volumes is a minimum drop volume Vmin, and a difference in drop volumes between successively larger drops equals (Vk+1−Vk) which is less than Vmin, for k equal to 1 through n−1. The method also includes ejecting liquid drops through the printhead.

In traditional inkjet technology, image quality is related to the volume of individual ink droplets. With all else being equal, a smaller drop volume results in higher resolution and better image quality. For example, a drop volume for a 600 dpi×600 dpi resolution inkjet printer is about 16.0 pL, while that for a higher quality 1200 dpi×1200 dpi resolution inkjet printer is only about 4 pL. Sub-picoliter drops are required to obtain printed images at greater than 2400 dpi×2400 dpi resolution.
Printheads capable of producing sub-picoliter drops are challenging to manufacture. More specifically, extremely small orifice holes are needed to achieve such sub-picoliter drops. The dimensional accuracy and uniformity of such orifice holes is beyond the capability of existing micro fabrication technologies. Moreover, it is difficult to operate a printhead with small drop volumes due to problems such as jet straightness. In addition, small orifices tend to become clogged more easily by contaminants. Small orifices also have short latency and are difficult to recover after being idle for a period of time.
Due to finite size of spots made by inkjet droplets on the receiving substrate, a halftoning technique is used to produce various levels of gradation for mid-tone shades. Smaller drop volumes achieve higher image quality by producing a finer level of gradation in the mid-tone shades without introducing objectionable graininess or other noises associated with halftoning. Halftoning also reduces the printing speed due to the required processing time for rendering the halftone image.
Another approach for increasing color image quality uses diluted inks. Because less colorant is present in each diluted ink drop, the effect of smaller drops having higher concentration is achieved. However, certain drawbacks to this approach include a higher cost and more complex printing system, issues related to drying, and media cockle due to excess solvents.
The present invention provides a new and improved apparatus and method which addresses the above-referenced problems.

Inkjet printhead and method of printing with multiple drop volumes


Hydroxyethylated polyethyleneimine is added to jet ink having an anionic dye to prevent whisker forming overnight. To avoid excessive viscosity at start-up, the polyethyleneimine is low molecular weight or a low molecular weight hydroxyethylated amine is combined with high molecular weight polyethyleneimine.

This invention employs an ingredient known to improve waterfastness in printing of the jet ink to which it is added, that ingredient being either at a low molecular weight or in combination with a low molecular weight amine. That essential ingredient is hydroxyalkylated polyethyleneimine, preferably hydroxyethylated polyethyleneimine (HEPEI).
No novelty is claimed for the use of hydroxyalkylated polyethyleneimine itself in such inks, and U.S. Pat. Nos. 4,197,135 to Bailey; 4,789,400 to Solodar et al; and 5,017,644 to Fuller et al (Example XIII) disclose such use. The results may not be entirely satisfactory since the hydroxyethylation tends to reduce the effectiveness as a waterfastness aid.
This invention is directed to the elimination of solid whiskers which form spontaneously during inactivity of the ink. No prior art suggestion is known to employ a polyethyleneimine for such purpose. Indeed, no prior art expressly directed to solving the problem of such solid formation is known, although certain ink formulas with pH sensitive dyes have less tendency to solid formation. The common factor in such formulas appears to be that they have at least two dissimilar dyes present in major proportions.
Although this invention is not considered dependent on any factor of the ink formula other than the dye being base soluble, some details of a commercially suitable formula are given. Illustrative prior teachings of various ingredients of that formula are the following: U.S. Pat. Nos. 5,098,476 to Baker illustrating use of 2-pyrrolidone as a co-solvent; 5,062,892 to Halko disclosing buffers such as used in the formulation; 5,049,188 to Takimoto et al and 4,973,992 to Owatari mentioning amines as additives to jet inks.


A syringe assembly for fluid collection includes a housing having a sidewall defining a hollow bore therein, and an elongate plunger with the distal end of the plunger forming a chamber within the hollow bore for containing a fluid therein. The plunger is adapted for slideable movement within the hollow bore between an initial position and a retracted position. The assembly includes a hub disposed at least partially within the hollow bore and at least partially supporting a cannula therewith. The hub is adapted to automatically transition from an initial position in which at least a portion of the cannula is disposed external to the housing, to a retracted position in which the cannula is fully shielded by the housing, upon transition of the elongate plunger from the initial position to the retracted position.

Field of the Invention
The subject invention relates to a device for withdrawing a fluid specimen from a patient and subsequently dispensing the collected fluid into a collection container. More particularly, this invention relates to a safety syringe for withdrawing a fluid specimen, such as blood, from a patient, retracting the needle element of the device into the housing of the device, and subsequently dispensing the collected fluid into a separate collection container.
Description of Related Art
Hypodermic syringes are widely used in the medical arts for withdrawing fluid samples from a patient. Generally, hypodermic syringes have a metal needle that has a sharpened distal point for penetrating a patient's skin that is either fixedly or removably attached to a housing. With the recognition of fluid borne diseases that are transmitted by bodily fluids, and greater sensitivity of the need to protect healthcare workers from inadvertent contact with previously used needles (commonly referred to as "sharps"), as well as the need to reduce criminal misuse of improperly disposed needles and syringes, syringes that include provisions to prevent reuse and reduce exposure to healthcare workers have been developed.
A variety of shielding mechanisms have also been developed to reduce the incidence of inadvertent exposure of healthcare workers to sharps, however, most of these devices can be compromised by an individual determined to obtain and misuse a hypodermic syringe after its intended use. As a result, further developments in the art of hypodermic syringes have resulted in the advent of hypodermic syringes having needles that withdraw into the body of the syringe once their intended use is completed.
Most of the conventional syringe assemblies in which the needle is withdrawn into the body of the syringe require manufacture and assembly of parts with tight tolerance requirements. Many of the designs depend upon a careful application of forces by the practitioner to draw and/or expel fluids from the syringe. In these assemblies, deviance from the tight tolerances of the multiple components of the device during manufacture and assembly may result in premature activation of the retraction function of the syringe. In addition, conventional syringe assemblies, including a retraction aspect, have been developed for the limited purpose of injecting a medication into a patient, and do not address the need for a syringe used for bodily fluid collection having a retraction element.
Current conventional syringes are considered by users to be virtually fault-free and reliable. They are used for a variety of different procedures involving both "one-shot" fill and inject procedures, as well as more complex mixing, measuring, and delivery functions. In order for a retractable syringe to displace these functional, utilitarian, and reliable conventional syringes, the new retractable syringe should not interfere with current practices, should be cost-effective, and must be substantially reliable. Current conventional syringes are often manufactured at rates of several hundred per minute and their cost is generally not a significant factor in their usage. One skilled in the art of high volume manufacturing recognizes that assembling hundreds of millions of complex retraction syringes having retraction elements contained in a small space, for example on the order of a one-quarter inch diameter bore, is a daunting task.
Accordingly, a need exists for a retractable syringe that is suitable for use as a bodily fluid collection device for subsequent transfer to a collection container. A need further exists for a retractable syringe that is capable of being manufactured at high volumes, and is sufficiently reliable in use when produced at high volume. Such a device is disclosed herein below.

Safety syringe having an automatic activated retractable needle


A dual output buck-boost power converter operates with a single inductor to achieve high efficiency with automatic or inherent load balancing. Switches associated with the opposite polarity outputs are driven based on feedback signals, with one feedback signal being a reference voltage and another feedback signal being related to an opposite polarity output. The opposite polarity feedback signal is provided to a comparator with a reversed polarity to achieve a simple balanced control that maintains polarity outputs. The power converter delivers power to each output with each switching cycle and uses a single inductor to achieve high efficiency performance.

1. Field of the Invention
The present invention relates generally to power converters, and relates more particularly to a dual buck-boost power converter with independent regulation.
2. Description of Related Art
Dual buck-boost converter topologies are available for a number of applications. Typically, two different power supplies create two separate outputs. The two separate outputs are often a positive voltage output and a negative voltage output.
Referring to FIG. 1, a buck-boost converter with two inputs and two outputs is illustrated as circuit 10. Circuit 10 includes two of each component, such as two switches S1, S2, two diodes D1, D2, two inductors L1, L2 and two capacitors C1, C2. The two power supplies, indicated as circuit 12 and 13, each have a separate feedback circuit to provide a closed loop control. Circuit 12 and 13 each use a reference voltage in conjunction with a feedback voltage value to determine modulation of the voltage to duty cycle conversion. In circuit 10, two separate inputs of +/−5V are used to generate the two separate outputs, +Vout and −Vout. In addition, there are typically two separate loads, negative load 14 and positive load 15.
In circuit 10, switches S1 and S2 are operated to control power output to loads 14 and 15 according to the desired set point determined by voltage Vref. In controlling the output to loads 14 and 15, inductors L1 and L2 are separately charged or discharged. Accordingly, circuit 10 uses two separate inductors that typically are realized as external components due to their size. That is, the majority of components in circuit 10 can be formed in an integrated circuit with the noted exception of inductors L1 and L2. The use of two inductors also adds cost to the circuit in terms of component cost and increased size that is realized in constructing the converter.
An alternative to circuit 10 provides a buck-boost converter that drives a positive and negative output voltage on alternating cycles of the controller respectively. This alternate method uses one inductor, but suffers from being less efficient in power density and device utilization. The outputs of this alternative prior circuit using a single inductor also has very high ripple voltage on both outputs +Vout and −Vout.
In some buck-boost solutions that deliver dual outputs, a load balancer is sometimes used to help maintain the output voltages at consistent and opposite levels. However, the load balancer typically draws extra power by shunting voltage or current, and reduces the overall efficiency of the power converter.
Accordingly, it would be desirable to obtain a buck-boost converter with a dual output and single inductor with improved efficiency and performance.

Dual buck-boost converter with single inductor


A display structure is formed using patterned deposition of display materials. A substrate includes a plurality of distinct electrodes. A plurality of droplets including a material are formed and charged to a second polarity. First selected ones of the plurality of electrodes are charged to a first polarity opposite the second polarity to selectively attract the droplets including the material to the oppositely charged first selected ones of the plurality of electrodes.

The general concept of patterned deposition of a material onto a substrate has many applications. Some methods of patterned deposition are additive and others are subtractive. Additive methods deposit the material only where desired. In contrast, subtractive methods deposit the material and then selectively remove (subtract) the material exclusive of the desired pattern.
One application of patterned deposition is the patterned deposition of toner particles to reproduce images. Patterned deposition may also be used to deposit patterns of different colored phosphors to form color pixels on the screen of a cathode ray tube (CRT).
Shadowing is an additive method for depositing a pattern of a material onto a substrate. For shadowing, a shadow mask is formed above or on the substrate. The material is then directionally deposited onto the substrate through apertures in the shadow mask. As a result of the deposition being directional, the material is not deposited in the "shadows" of the structure. Thus, the material is deposited in a pattern defined by the portion of the substrate exclusive of the "shadows" and the structure. By varying the direction of deposition, this technique may be used to deposit different patterns of one or more different materials on a single substrate.
Another method of patterned deposition uses a patterned photoconductor to electrostatically attract charged particles of a material onto a pattern on a substrate. For example, as used in photocopiers, a photoconductor is first applied to the substrate. The photoconductor is then electrostatically charged. The charged photoconductor on the substrate is exposed to light in a desired pattern to selectively discharge the photoconductor. Particles of the material (toner), charged to an opposite polarity than the charge of the patterned photoconductor, are brought into proximity with the substrate. The attraction between opposite charges results in the deposition of the toner onto the substrate in the pattern formed by the charged photoconductor. Paper is then brought in contact with the substrate to deposit the patterned toner onto the paper. The paper may then be heated to fuse the toner to the paper.
Another method of patterned deposition may be used for forming patterns of different colored phosphors corresponding to different colors in pixels on the screen of a cathode ray tube (CRT). For example, a photoconductor may be deposited on the screen and then charged. The photoconductor may then be selectively exposed to form a pattern of charge. Oppositely charged phosphor particles of a first color are then formed. Electrostatic attraction causes the phosphor particles of the first color to attach to the screen positions where the charges were selectively deposited. The phosphors may then be secured to the screen by curing. The process may then be repeated to form patterns of additional colors of phosphor on the screen.
For some applications and for some materials it may be desirable to deposit a pattern while the material is in liquid form. Inkjet technology may be used to deposit a liquefied material in a pattern formed by a plurality of positions on a substrate. First, the liquefied material is supplied to the inkjet. The inkjet and the substrate are then positioned so the inkjet output is adjacent one of the plurality of positions on the substrate. The material in the inkjet is then discharged toward the one of the plurality of positions on the substrate. The inkjet is then repositioned and the process is repeated for each of the plurality of positions on the substrate.
The cost and complexity of an inkjet apparatus may increase when the positions on the substrate are small and when the deposition of material must be localized. Material discharged from an inkjet typically disperses once it exits from the inkjet. To localize deposition, the extent of dispersion may be limited by precisely locating the inkjet close to the substrate.
An inkjet method may also be costly when the number of positions on the substrate is large. When material is to be deposited on many distinct positions on the substrate, using an inkjet is costly due to the time necessary to reposition the inkjet in relation to the substrate for deposition at each of the positions. Alternatively, multiple inkjets may be used to simultaneously deposit material at more than one position. This alternative may be cost prohibitive due to the cost of the multiple ink jets and their operating and maintenance costs.
Inkjet deposition of a liquid may be undesirable for depositing a precise quantity of material. After repeated discharges, an inkjet may begin to clog. A clogged inkjet may not discharge as much material as an unclogged inkjet. Thus, the amount of material per discharge may vary from position to position on the substrate, depending on the extent to which the inkjet is clogged at the various positions.
To overcome the shortcomings of conventional methods of patterned deposition, a new method of deposition is provided.


Methods of predicting or detecting sensitivity to therapeutic effects of anti-PD-1 therapy in a patient suffering from melanoma, as well as for selecting somatic mutanomes and transcriptomes of melanoma biopsies. A tumor sample obtained from the patient is assayed for a measure of anti-PD-1 therapy sensitivity via, for example, whole transcriptome sequencing, antibody based protein quantifications, mass spectrometry based protein quantification, targeted mRNA sequencing, real-time RT-PCR, Sanger sequencing, targeted sequencing and/or whole exome/genome sequencing. Samples are selected that exhibit a higher first enrichment similarity score and/or a lower second enrichment similarity score, and/or at least one measure of sensitivity. A patient whose sample was selected herein as a candidate for anti-PD-1 therapy is thereby identified. The method of the invention can further comprise treating the patient with anti-PD-1 therapy, optionally in conjunction with combinatorial therapy.

PD-1 immune checkpoint blockade induces a high rate of anti-melanoma response and provides clinical benefits unprecedented with immunotherapy (Hamid et al., 2013; Topalian et al., 2012). This therapeutic approach has also been shown to be active against a growing list of human malignancies, and clinical testing of combinations of PD-1 with other treatment targets has already begun (Sharma and Allison, 2015). However, effective use of anti-PD-1 clinical agents is encumbered mostly by innate resistance, the mechanistic basis of which remains poorly characterized.
In melanoma, the extent of pretreatment and especially treatment-induced T cell infiltration correlates with clinical responses (Tumeh et al., 2014), supporting unleashing of tumor-specific T cells as a mechanistic basis of anti-PD-1 therapy. Preliminary retrospective analyses of clinical data hinted at prior failure of MAPK-targeted therapy being a negative factor for subsequent response to immune checkpoint blockade in melanoma (Puzanov et al., 2015; Ramanujam et al., 2015; Simeone et al., 2015). At the genomic level, the overall mutation load, which may reflect or lead to higher neoepitope load, a smoking signature, and impairment of DNA repair, have been correlated with anti-PD-1 response in non-small cell lung cancers (Rizvi et al., 2015). However, the lack of these response-related features do not robustly preclude response. Thus, there remains a need for an objective assessment of omic-scale features related to both response and resistance as an important step toward patient stratification and identification of combinatorial targets.
There remains a need for improved tools to permit the detection, identification and prognosis of drug resistant cancers, particularly anti-PD-1-resistant melanomas. There also remains a need for targets useful in the detection and treatment of cancer.

Detection and treatment of anti-PD-1 therapy resistant metastatic melanomas

THE REGENTS OF THE UNIVERSITY OF CALIFORNIA


A method and device for double-camera-based imaging are provided. The method includes the following actions. A first image is acquired by a main camera and a second image is acquired by an auxiliary camera. A main image resolution and an auxiliary image resolution are determined according to a determined shooting mode and resolutions of the main camera and the auxiliary camera respectively. The first image is converted into a main image with the main image resolution. The second image is converted into an auxiliary image with the auxiliary image resolution according to the second image. A required target image is obtained according to the main image and the auxiliary image.

More and more mobile terminal equipment is provided with double cameras. In a conventional art, one of double cameras is adopted to take a photo and the other camera is adopted to assist in calculation of depth information of the photo for subsequent image blurring processing.
However, for double cameras in a related art, after an image is shot, a fixed resolution is usually adopted for subsequent image processing. This results in a relatively undiversified function and makes it impossible for a user to regulate the resolution according to a requirement.

Method and device for double-camera-based imaging

GUANGDONG OPPO MOBILE TELECOMMUNICATIONS CORP., LTD.


This invention provides for, inter alia, a method for increasing the rainfastness of an agrochemical composition without increasing its spreading properties, which comprises adding to said agrochemical composition an effective amount of one or more silicone surfactants of the formula

1. Field of the Invention
The invention relates to a method of improving the performance of agricultural compositions particularly with respect to rainfastness, run-off properties and efficacy under conditions of low humidity, by using silicone surfactants that reduce the surface tension to less than about 30 mN/m in 0.10% (w/w) aqueous solution thereof without concomitant spreading of the spray solution.
2. Description of the Related Art
Foliar-applied pesticidal and plant growth modifying chemicals are widely used in agricultural, industrial, recreational and residential areas worldwide. These chemical agents illustratively include insecticides, fungicides, herbicides, plant growth regulators and plant nutrients among other chemicals. Such chemicals are typically applied by spraying on the foliage of vegetation to be protected, controlled, killed or modified, but other methods such as rope-wick application are known. Some of these agents show contact action, killing, controlling or modifying the growth of target organisms at the site of deposition. Other chemicals are systemic, translocating within the plant to a site of action remote from the site of deposition. Still other chemicals show both contact and systemic action.
Surfactant formulations are commonly used in forestry, agriculture, and horticulture as agricultural adjuvants to improve the efficacy of agrochemical active ingredients such as micronutrients, growth regulators, biologicals, pesticides such as herbicides, fungicides, insecticides, acaracides and miticides. Surfactants are often used as dispersants, wetting and spreading agents, and emulsifiers in a formulated product or package or in a tank mix. Prior art identifies spreading of spray solution on the weed leaf as an essential criterion for surfactant efficacy. Surfactants have been used to improve herbicide performance since organic herbicides were first developed in the 1940s. Spreading the spray solution on weed leaves has always been a major reason for the inclusion of surfactants. This is clearly expressed in the preface to xe2x80x9cAdjuvants for Herbicidesxe2x80x9d Weed Science Society of America Monograph Series Number 1, 1988, R. H. Hodgson (ed). It includes the statement xe2x80x9cExperience shows that successful weed control often depends on the appropriate use of adjuvants in herbicide sprays to ensure uniform application and target coveragexe2x80x9d.
Herbicides commonly have been formulated with surfactants. Organosilicone surfactants provide surface tension values significantly lower than other commonly used surfactants. For example, the use of an organosilicone surfactant such as BREAK-THRU(copyright) S240, Goldschmidt Chemical Corp., or Silwet(copyright) L-77, Crompton Corp., in combination with a pesticide results in increased foliar uptake of the pesticide and, hence, increased efficacy of the pesticide in control of weed growth.
Among the numerous studies of the foliar uptake of the herbicide glyphosate combined with such silicone surfactants are those reported by Field and Bishop in Pesticide Science, 1988, Vol. 24, pp. 55-62; Stevens et al. in Pesticide Science, 1991, Vol. 33, pp. 371-82; Gaskin and Stevens in Pesticide Science. 1993, Vol. 38, pp. 185-92; and Gaskin and Stevens in Pesticide Science, 1993. Vol. 38, pp. 193-200. An extensive review of 160 references relating to the use of organosilicones as adjuvants for agrochemicals was provided by Stevens in Pesticide Science, 1993, Vol. 38, pp. 103-22. It is well recognized in the art that trisiloxane ethoxylate surfactants with no more than about 10 ethylene oxide units have the ability to impart the property of superspreading to agricultural spray mixtures. The term xe2x80x9csuperspreadingxe2x80x9d means the ability of a drop of the mixture to spread to a diameter at least 9 times as great as a drop of distilled water on a hydrophobic surface such as the leaf of a plant.
The fact that superspreading has been considered an essential attribute of such silicone surfactants is confirmed by the fact that various patents have been issued with improved spreading as the main objective. For example, U.S. Pat. No. 5,104,647 to Policello and U.S. Pat. No. 5,558,806 to Policello and Murphy have as main objective maintaining the superspreading capability of organosilicone/organic surfactant blends.
U.S. Pat. No. 5,017,216 to Dow Corning discloses postemergent herbicide compositions containing silicone glycol adjuvants, comprising blends of trisiloxane surfactants of the structure Me3SiOxe2x80x94SiMeRxe2x80x2xe2x80x94Oxe2x80x94SiMe3 wherein Rxe2x80x2 is a short-chain polyether radical with typically 4.6 ethylene oxide units, in combination with siloxane dispersants.
WO 89/12394, WO 99/40785, U.S. Pat. No. 6,051,533, U.S. Pat. No. 6,040,272 and EP 0483095, all to Monsanto, disclose various herbicide compositions comprising silicone surfactants in combination with other adjuvants like humectants, oils, glycol esters and organic cosurfactants. For the silicone surfactants claimed to be useful in these inventions, the inventors disclose a very broad structural range and provide little direction to those skilled in the art about which of these siloxane surfactants are to be advantageously used to enhance the efficacy of herbicide compositions. However, the examples used in these inventions are trisiloxanes like Silwet(copyright) L77 or Silwet(copyright) 408, having typical structures like Me3SiOxe2x80x94SiMeRxe2x80x2xe2x80x94Oxe2x80x94SiMe3 wherein Rxe2x80x2 a radical xe2x80x94(CH2)3xe2x80x94(CH2CH2Oxe2x80x94)8xe2x80x94Z wherein Z is hydrogen or methyl. It is well known to a person skilled in the art that trisiloxane surfactants of that type convey superspreading properties to aqueous solutions thereof, as long as the polyether chain length does not exceed about 10 ethylene oxide units. The fact that only such superspreading siloxanes have been chosen to exemplify the invention shows that the inventors were following the common belief that enhanced spreading is an essential attribute for silicone surfactants to be useful as adjuvants in herbicide compositions for most applications.
It is equally well-known to the practitioner of the art that silicone surfactants can have antagonistic effects on the efficacy on herbicides on certain plant species. Gaskin, et al., (Pestic. Sci. 1993, 38, 185-192) demonstrated that some trisiloxane ethoxylates (TSE), such as Silwet(copyright) L-77 surfactant (available from Crompton), can antagonize cuticular penetration of a herbicide into grasses, when compared to the herbicide alone. The term antagonism is used to indicate that the treatment of herbicide plus adjuvant is less effective than the comparative herbicide treatment. This tendency to antagonize the activity of glyphosate on some species in the absence of rain can be mitigated by the addition of a humectant such as glycerin to the spray solution, as disclosed in WO 89/12394. This addition prevents rapid drying of the spray solution which commonly is experienced when using superspreading silicone surfactants under conditions of low humidity, such as, for example, a relative humidity of 30% or less.
Gaskin, et al., (Pest. Sci. 1993, 38, 192-200) also studied the antagonism of glyphosate by trisiloxane surfactants with 8 to 40 ethylene oxide units and found that the antagonism is reduced when using surfactants with increased ethylene oxide content. However, no information was provided on rainfastness, and run-off behaviour of the glyphosate compositions, or on efficacy under conditions of low humidity.
It is also common knowledge that surfactants with high content of ethylene oxide groups usually have melting points above common use temperatures and thus are impractical to handle during application. Therefore it is usually desirable to use adjuvants which are liquid at room temperature.
Great Britain Pat. No. 1,255,249 to Dow Corning Corporation, published Dec. 1, 1971, discloses herbicide compositions employing silicone glycol copolymers. Here, general utility of a large number of adjuvants is professed, as exemplified by two generic silicone glycol formulas which embrace structures having both diorganosiloxane units and alkyl-glycol siloxane units. There are also provided two examples employing a triazine herbicide in conjunction with an adjuvant having 1.8 siloxy units and bearing a glycol chain consisting exclusively of 12 ethylene oxide units showing enhanced efficacy of the herbicide. However, no information is disclosed on rainfastness, and run-off behaviour of the herbicide composition, or on efficacy under conditions of low humidity. In addition, it is well known to the practioner of the art that such surfactants with a large number of only ethylene oxide units are solid at low use temperatures, such as 45 to 50 F., and thus impractical to handle.
It has now surprisingly been found that the use of silicone surfactants which reduce the surface tension in 0.1% (w/w) aqueous solution to less than about 30 mN/m without increasing the spreading properties results in a significantly improved performance of agrochemical compositions, such as herbicide compositions. The use of said siloxanes can improve, for example, the rainfastness, run-off, efficacy under conditions of low humidity without the need for additional humectants, and they can even be used in combination with cosurfactants which have an adverse effect on the spreading properties of superspreading silicone surfactants, and therefore offer a wider latitude of formulations.
It has further been found that silicone surfactants which are liquid at use temperature and reduce the surface tension in 0.10% (w/w) aqueous solution to less than about 30 mN/m without increasing the spreading properties thereof can especially advantageously be used to enhance the performance of agrochemical compositions, such as herbicide compositions. The use of said siloxanes can improve the efficacy, rainfastness, run-off, performance under conditions of low humidity without the need for additional humectants, and they can also be used in combination with cosurfactants which have an adverse effect on the spreading properties of superspreading silicone surfactants.
It is an object of this invention to provide a method for enhancing the performance of agrochemical compositions with respect to rainfastness, run-off, efficacy under conditions of low humidity without the need for additional humectants, by using silicone surfactants capable of reducing the surface tension of 0.10% (w/w) aqueous solutions thereof to less than about 30 mN/m without enhancing the spreading properties. It is a further object to provide a method for enhancing the performance of agrochemical compositions with respect to efficacy, rainfastness, run-off, efficacy under conditions of low humidity without the need for additional humectants, by using silicone surfactants which are liquid at use temperature and capable of reducing the surface tension of 0.10% aqueous solutions thereof to less than about 30 mN/m without enhancing the spreading properties.
Silicone surfactants which can be used within the scope of this invention, are polysiloxane-based surfactants containing polyether groups having such structural features that they are capable of reducing the static surface tension of a 0.10% (w/w) aqueous solution of the silicone surfactant to less than about 30 mN/m without enhancing the spreading properties thereof. In this invention, a silicone surfactant surfactant is defined as xe2x80x9cnot enhancing the spreading properties of a 0.10% aqueous solution thereofxe2x80x9d or as a xe2x80x98non-spreading silicone surfactantxe2x80x99 if the spreading area of a 0.10% (w/w) aqueous solution of said silicone surfactant on a polypropylene test substrate is reduced by a factor of about 10 or more, compared to a conventional super-spreading silicone surfactant such as Silwet(copyright) L-77 or Breakthru(copyright) S240, which is well known to the practitioner of the art as a typical super-spreading surfactant.
Preferred silicone surfactants capable of reducing the static surface tension of a 0.10% (w/w) aqueous solution of the silicone surfactant to less than about 30 mN/m without enhancing the spreading properties have the general structure:
xe2x80x83R3Sixe2x80x94Oxe2x80x94[RRxe2x80x2Sixe2x80x94Oxe2x80x94]nxe2x80x94Oxe2x80x94SiR3xe2x80x83xe2x80x83(I),
wherein
n is 1 to 3,
R is an alkyl radical with 1 to 6 carbon atoms,
Rxe2x80x2 is a radical of the structure
xe2x80x94(CH2)mxe2x80x94Oxe2x80x94(C2H4O)y(C2H3Rxe2x80x3O)zxe2x80x94Z,
xe2x80x83wherein
m is 2 to 6,
Rxe2x80x3 is independantly methyl, ethyl or phenyl,
Z is hydrogen, an alkyl radical with 1 to 4 carbon atoms, or an acyl radical with 2 to 6 carbon atoms,
y is 6 to 30, and
z is 0 to 10,
with the proviso that the ratio y/z is 1 or greater, and that the total number of alkylene oxide groups n*(y+z) in the siloxane polymer (I) is at least 12.
Preferred alkyl radicals for R and Rxe2x80x3 are methyl, a preferred value for m is 3.
A preferred subclass (a) are silicone surfactants (I), wherein
n is 1, R and Rxe2x80x3 is methyl, m is 3, y is 13 to 30, z is 0 to 2, especially preferred 0, and Z is hydrogen, methyl or acetyl.
Another preferred subclass (b) are silicone surfactants (I), wherein
n is 2, R and Rxe2x80x3 is methyl, m is 3, y is 6 to 20, z is 0 to 2, especially preferred 0, and Z is hydrogen, methyl or acetyl.
Another preferred subclass (c) are silicone surfactants (I), wherein
n is 1, R and Rxe2x80x3 is methyl, m is 3, y is 8 to 30, z is 2 to 10, and Z is hydrogen, methyl or acetyl, and the ratio y/z is 2 to 10 (i.e., 2:1 to 10:1), especially preferred 2 to 6.
Another preferred subclass (d) are silicone surfactants (I), wherein
n is 2, R and Rxe2x80x3 is methyl, m is 3, y is 5 to 20, z is 1 to 6 and Z is hydrogen, methyl or acetyl and the ratio y/z is 2 to 10, especially preferred 2 to 6.
Further preferred are any mixtures of two or more of the preferred subclasses (a to d).
Surfactants of subclass (c) and (d) have the additional benefit that the presence of propylene oxide units tends to reduce the melting point of the silicone surfactants, compared to materials containing only ethylene oxide units, resulting in materials with the desirable property of being liquid even at low use temperature such as 45 to 50xc2x0 F. so they are easy to handle during application.
Illustrative examples of siloxanes showing the required physical properties are shown below. These structures are given as typical examples, without intending to limit the scope of the invention:
xe2x80x83Me3SiOxe2x80x94[MeRxe2x80x2SiO]1xe2x80x94OSiMe3 with Rxe2x80x2=xe2x80x94(CH2)3xe2x80x94Oxe2x80x94(CH2CH2Oxe2x80x94)13xe2x80x94H
Me3SiOxe2x80x94[MeRxe2x80x2SiO]1.2xe2x80x94OSiMe3 with Rxe2x80x2=xe2x80x94(CH2)3xe2x80x94Oxe2x80x94(CH2CH2O)12(CH2CH(CH3)Oxe2x80x94)3xe2x80x94H
Me3SiOxe2x80x94[MeRxe2x80x2SiO]1xe2x80x94OSiMe3 with Rxe2x80x2=xe2x80x94(CH2)3xe2x80x94Oxe2x80x94(CH2CH2O)15(CH2CH(CH3)Oxe2x80x94)2xe2x80x94Me
Me3SiOxe2x80x94[MeRxe2x80x2SiO]1.3xe2x80x94OSiMe3 with Rxe2x80x2=xe2x80x94(CH2)3xe2x80x94Oxe2x80x94(CH2CH2O)15(CH2CH(CH3)Oxe2x80x94)2xe2x80x94C(O)CH3
Me3SiOxe2x80x94[MeRxe2x80x2SiO]2xe2x80x94OSiMe3 with Rxe2x80x2=xe2x80x94(CH2)3xe2x80x94Oxe2x80x94(CH2CH2Oxe2x80x94)9xe2x80x94H
Me3SiOxe2x80x94[MeRxe2x80x2SiO]2.2xe2x80x94OSiMe3 with Rxe2x80x2=xe2x80x94(CH2)3xe2x80x94Oxe2x80x94(CH2CH2O)8(CH2CH(CH3)Oxe2x80x94)2xe2x80x94H
It is well known to the practioner of the art, that the polyalkyleneoxide polymers have a broad molecular weight distribution and that the indices stated above designate the average composition only. The distribution of the different alkylene oxide units can be random or in blocks.
The siloxane surfactants described above can be prepared by methods well known to the practioner of the art, such as, for example, by hydrosilylation reaction of a Sixe2x80x94H containing siloxane and an unsaturated polyoxyalkylene derivatives, such as an allyl derivative, in the presence of a platinum catalyst. The reaction conditions and catalysts employed have been described in detail, for example, by W. Noll in xe2x80x9cChemie und Technologie der Siliconexe2x80x9d, 2nd ed., Verlag Chemie, Weinheim (1968), by B. Marciniec in xe2x80x9cAppl. Homogeneous Catal. Organomet. Compd.1996, 1, 487)xe2x80x9d or by G. C. Davis et al. in U.S. Pat. No. 5,204,438. It is common knowledge in the art that the hydrosilylation products of SiH-containing siloxanes with unsaturated polyoxyalkylene derivatives may contain excess unsaturated polyoxyalkylene derivative, or an isomerization product thereof. It is equally well understood that the linear siloxane derivatives, and the mixtures thereof, may contain up to 10%, preferred less than 5%, of cyclic siloxanes.
The siloxane surfactants described above may further be modified by introduction of units of the type
xe2x80x94[RRxe2x80x3Sixe2x80x94Oxe2x80x94]
wherein R has the meaning as stated above, Rxe2x80x3 is a linear or branched alkyl radical with 6 to 30 carbon atoms which may be additionally substituted by nitrogen atoms. Preferred radicals Rxe2x80x3 are alkyl groups with 10 to 18 carbon atoms, aminopropyl and dimethylaminopropyl. Modified siloxane surfactants can be prepared by methods well-known to the practitioner of the art, for example by equilibration of siloxanes (I) with linear or cyclic siloxanes or mono- or di-alkoxysilanes containing the units xe2x80x94[RRxe2x80x3Sixe2x80x94Oxe2x80x94], in the presence of an equilibration catalyst such as, for example, a hydroxide, or alkoxide of sodium, potassium or tetraalkylammonium, or by equilibration of the precursor SiH-containing siloxanes with siloxanes or alkoxysilanes containing the units xe2x80x94[RRxe2x80x3Sixe2x80x94Oxe2x80x94] in the presence of an acid or base catalyst, followed by hydrosilylation with an unsaturated polyoxyalkylene compound.
The use of the non-spreading silicone surfactants described above provides a method for enhancing the efficacy and rainfastness of agrochemical compositions in general and for reducing run-off from the plant which is commonly experienced when using superspreading silicone surfactants. They may be used to enhance the efficacy of agrochemical compositions under adverse conditions such as low humidity without the need for further humectants. If the non-spreading silicone surfactants contain significant amounts of propylene oxide units in their polyoxyalkylene side chain, the user has the additional benefit of having adjuvants which are liquid at low use temperature and thus easy to handle, without the need for solvents or additional premixing/dissolving.
The non-spreading silicone surfactants of this invention can be advantageously used with a variety of agrochemical compositions, such as compositions comprising micronutrients, growth regulators, pesticides such as herbicides, fungicides, insecticides, acaracides and miticides. Especially advantageous is the use in compositions comprising herbicides. Suitable herbicides are, for example:
Growth regulators such as:
Phenoxy Acetic Acids, such as 2,4-D [(2,4-dichlorophenoxy)acetic acid];
Phenoxy Propionic Acids, such as Dichlorprop[(RS)-2-(2,4-dichlorophenoxy) propionic acid], Mecoprop [(RS)-2-(4-chloro-o-tolyloxy)-propionic acid];
Phenoxy Butyric Acids, such as 2,4-DB[4-(2,4-Dichlorophenoxy)butyric acid];
Benzoic Acids, such as Dicamba [3,6-dichloro-o-anisic];
Other growth regulators, such as Fluroxypyr [4-amino-3,5-dichloro-6-fluoro-2-pyridyloxy-acetic acid], Picloram [4-amino-2,3,5-trichlor-2-carboxylic acid], Triclopyr [3,5,6-trichloro-2-pyridyloxyacetic acid], Copyralid [3,6-dichloropyridine-2-carboxylic acid];
Pigment Inhibitors: such as Amitrole, [1H-1,2,4-triazol-3-ylamine; 3-amino-1H-1,2,4triazole], Clomazone [2-(2-chlorobenzyl)-4,4-dimethyl-1,2-oxazolidin-3-one;2-(2-chlorobenzyl)-4,4-imethylisoxazolidin-3-one], Fluridone [1-methyl-3-phenyl-5-(a,a,a-trifluoro-m-tolyl)4-pyridone], Norflurazone [4-chloro-5-methylamino-2-(a,a,a-trifluoro-m-tolyl)pyridazin-3(2H)-one];
Mitotic disruptors, for example: Dinitroanilines, such as Isopropalin [4-isopropyl-2,6-dinitro-N,N-dipropylaniline], Oryzalin [3,5-dinitro-N4N4-dipropylsulfanilamide], Pendimethalin [N-(1-ethylpropyl)-2,6-dinitro-3,4-xylidine], Prodiamine [5-dipropylamino-a,a,a-trifluoro-4,6-dinitro-toluidine; 2,6-dinitro-N1N1-dipropyl-4-trifluoromethyl-m-phenylenediamine], Trifluralin [a,a,a-trifluoro-2,6-dinitro-N,N-dipropyl-p-toluidine];
Inhibitors of lipid biosynthesis, such as Clethodim [(xc2x1)-2-[(E)-3-chloroallyloxyimino]propyl]-5[2(ethylthio)-propyl]-3-hydroxycyclohex-3-enone], Diclofop-methyl [(RS)-2-[4-(2,4-dichlorophenoxy)phenoxy]propionic acid], Fenoxaprop-ethyl [(xc2x1)-2-[4-(6-chloro-1,3-benzoxazol-2-yloxy)phenoxy]propionic acid; (xc2x1)-2-[4-(5-chlorobenzoxazol-2-yloxy)phenoxy]propionic acid], Fluazifop-P-butyl [(R)-2-[4-(5-trifluoromethyl-2-pyridyloxy)phenoxy)propionic acid, Haloxyfop-methyl [(RS)-2-(4-(3-chloro-5-trifluoromethyl 2-pyridyloxy)phenoxy]propionic acid], Quizalofop[.(RS)-2[4-(6-chloroquinoxalin-2-yloxy)phenoxy]propionic acid], Sethoxydim[.(xc2x1)-(EZ)-2-(1-ethoxyininobutyl)-5-[2(ethylthio)propyl]-3-hydroxycyclohex-2-enone];
Photosynthesis Inhibitors:
Triazines and s-Triazines such as Hexazinone [3-cyclo-hexyl-6-dimethylamino-1-methyl-1,3,4-triazine-2,4(1H,3H)-dione], Metribuzin [4-amino-6-tert-butyl-3-methylthio-1,2,3-triazine-5(4H)-one], Atrazine [6-chloro-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine], Simazine [6-chloro-N2,N4-diethyl-1,3,5-triazine-2,4-diamine], Cyanazine 2-[4-chloro-6-ethylamino-1,3,5-triazin-2-yl]amino]-2-methylpropanenitrile, Prometon [N2,N24-di-isopropyl-6-methoxy-1,3,5-triazine-2,4,diamine], Ametryn [N2-ethyl-N4-isopropyl-6-methylthio-1,3,5-triazine-2,4-diamine];
Substituted ureas, such as Diuron [3-(3,4-dichlorophenyl)-1,1-dimethylurea], Fluometuron [1,1-dimethyl-3-(a,a,a-trifluoro-m-tolyl) urea], Linuron [3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea], Tebuthiuron [1-(5-tert-butyl, 1,3,4-thiadiazol-2-yl)-1,3-dimethylurea], Uracils, such as Bromacil [5-bromo-3-sec-butyl-6-methyluracil], Terbacil [3-tert-butyl-5-chloro-6-methlyuracil];
Other photosynthesis inhibitors, such as Bentazon [3-isopropyl-1H-2,1,3-benzothiadiazin-4(3H)-one 2,2-dioxide], Desmedipham [ethyl 3xe2x80x2-phenylcarbamoyloxycarbanilate; ethyl 3-phenylcarbamoyloxyphenylcarbamate; 3-ethoxycarbonylaminophenyl phenylcarbamate], Methazole [2-(3,4-dichlorophenyl)-4-methyl-1,2,4-oxadiazolidine-3,5-dione], Phenmedipham [methyl 3-(3-methylcarbaniloyloxy) carbanilate, 3-methoxycarbonylaminophenyl 3xe2x80x2-methylcarbanilate], Propanil [3xe2x80x2,4xe2x80x2-dichloropropionanilide], Pyridate [6-chloro-3-phenylpyridazin-4-yl S-octyl thiocarbonate];
Inhibitors of amino acid synthesis, such as Glyphosate, Sulfosate and other salts of N-(phosphonomethyl)glycine;
Sulfonylureas, such as Bensulfuron [a-(4,6-dimethoxypy-rimidin-2-ylcarbamoylsulfamoyl)-o-toluic acid], Chlorimuron [2-(4-chloro-6-methoxypyrimidin-2-ylcarbamoylsulfamoyl)benzoic acid], Chlorsulfuron [1-(2-chlorophenylsulfonyl)-3-(4-methoxy-6-methyl-1,3,5-triazin-2-yl) urea], Metsulfuron [2-(4-methoxy-6-methyl-1,3,5-triazin-2-ylcarbamoylsulfamoyl)benzoic acid], Nicosulfuron [2-(4,6-dimethoxypyrimidin-2-ylcarbamoylsulfamoyl)-N,N-dimethylnicotinamide; 1-(4,6-dimethoxypyrimidin-yl)-3-(3-dimethylcarbamoyl-2-pyridylsulfonyl)urea], Primisulfuron [2-(4,6-bis(difluoromethoxy)pyrimidin-2-ylcarbamoylsulfamoyl)benzoic acid], Sulfometuron [2-(4,6-dimethylpyrimidin-2-ylcarbamoylsulfamoyl)benzoic acid; 2-[3-(4,6-dimethylpyrimidin-2yl)ureidosulfonyl)]benzoic acid], Thifensulfuron [3-(4-kethoxy-6-methyl-1,3,5-triazin-2ylcarbamoylsulfamoyl)thiophen-2-carboxylic acid], Triasulfuron [1-(2-(2-chloroethoxy)phenylsulfonyl)-3(4-methoxy-6-methyl-1,3,5-triazin-2yl)urea], Tribenuron [2-(4-methoxy-6-methyl-1,3,5-triazin-2-yl(methyl)carbamoylsulfamoyl)benzoic acid];
Imidazolinones, such as Imazamethabenz [a reaction product comprising(xc2x1)-6-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-m-toluic acid and (xc2x1)-2-(4-isopropyl-4methyl-5-oxo-2-imidazolin-2-yl)-p-toluic acid], Imazapyr [2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2yl)nicotinic acid], Imazaquin [(RS)-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)quinoline-3-carboxylic acid], Imazethapyr [(RS)-5-ethyl-2-(4-isopropyl-4-methyl-5-oxo2-imidazolin-2-yl)nicotinic acid];
Cell membrane disruptors: Bipyridylium compounds, such as Diquat [9,10-dihydro-8a-diazoniaphenanthrene; 6,7-dihydrodipyrido[1,2-a:2xe2x80x2,1xe2x80x2-c]pyrazine-5,8-dium; 1,1xe2x80x2-ethylene-2,2xe2x80x2-bipyridyldiylium], Paraquat [1,1xe2x80x2-dimethyl-4,4xe2x80x2-bipyridinium(I)],
Diphenylethers, such as Acifluorfen [5-(2-chloro-a,a,a-trifluro-p-tolyoxy)-2-nitrobenzoic acid], Fomesafen [5-(2-chloro-a,a,a-trifluro-p-tolyloxy)-N-mesyl-2-nitrobenzamide; 5-(2-chloro-a,a,a-trifluoro-p-tolyoxy)-N-methylsulfonyl-2-nitrobenzamide], commercially available as REFLEX(copyright), Lactofen [ethyl 0-(5-(2-chloro-a,a,a-trifluoro-p-tolyl-oxy)-2-nitrobenzoyl)-DL-lactate], Oxyfluorfen [2-chloro-a,a,a-trifluoro-p-tolyl 3-ethoxy-4-nitrophenyl ether];
Cell wall inhibitors like Dichlobenil [2,6-dichlorobenzonitrile], Isoxaben [N-[3-(1-ethyl-1-methylpropyl)-1,2-oxazol-5-yl]-2,6-dimethoxybenzamide; N[(3-(1-ethyl-1-methylpropyl)isoxazol-5-yl]-2,6-dimethoxybenzamide];
Other herbicides such as Glufosinate [4-(hydroxy(methyl)phosphinoyl]-DL-homoalaine; DL-homoalanin-4-yl-(methyl)phosphinic acid], Bromoxynil, [3,5-dibromo-4-hydroxybenzonitrile]; 3,5-dibromo-4-hydroxyphenyl cyanide, 2,6-dibromo-4-cyanophenyl octanoate].
Aryltriazoliones such as carfentrazone-ethyl.
Especially preferred herbicides are N-(phosphonomethyl)glycine and its salts.
It is understood by those skilled in the art that the use of co-surfactants and co-adjuvants is common practice in spray tank mixes, pesticide formulations and within adjuvant blends. Therefore the scope of this patent is understood to include the use of the present invention in combination with other adjuvants, including but not limited to, surfactants, stickers, humectants, solvents, oils, drift control agents, buffers, extenders, deposition and retention aids, defoamers and antifoams, compatibility agents, and herbicide activity enhancers such as ammonium sulfate and nitrogen-containing fertilizers. Blends of other surfactants with these novel siloxanes is especially beneficial when a variety of properties may be desired from the adjuvant. Co-surfactants can include nonionic, cationic, anionic, and zwitterionic surfactants. Examples of potential co-surfactants include, but are not limited to the following: alkanolamides, alkyl aryl alkoxylates and their derivatives, alkoxylated amines and their derivatives, quaternary ammonium surfactants, alkoxylated quaternary ammonium surfactants and their derivatives, amine oxides, betaines and their derivatives, copolymers containing ethylene oxide, propylene oxide, butylene oxide, styrene oxide or any combination thereof, linear alcohol alkoxylates and their derivatives, branched alcohol alkoxylates and their derivatives, alkoxylated amides, alkoxylated fatty acids, alkoxylated fatty esters and oils, glycerol esters, alkoxylated glycerol esters, imidazolines and their derivatives, propoxylated quaternary amines, lignin and its derivatives (such as lignosulfonate salts), mono- and di-glycerides, olefin sulfonates, phosphate esters, alkyl polyglycosides, other siloxane surfactants (such as alkoxylated siloxanes, alkyl siloxanes, siloxanes containing betaine and quaternary ammonium groups, amino siloxanes, and alkoxylated amino siloxanes), sorbitan esters, ethoxylated sorbitan esters, sulfonate surfactants, sulfosuccinates and their derivatives, salts of fatty acids, and sarcosinates. By definition, the term xe2x80x98fattyxe2x80x99 as used in this invention includes materials of animal and plant origin.
In addition to being useful with the surfactants having no adverse effects on the spreading properties of herbicide compositions containing superspreading silicone surfactants, which are disclosed in U.S. Pat. Nos. 5,558,806 and 5,104,647 and are herein included by reference, the non-spreading siloxanes of the present invention can also be advantageously blended with surfactants that are known to antagonize super-spreading siloxanes. Examples of these include, but are not limited to: ethoxylated alkyl amines (such as Varonic(copyright) surfactants produced by Goldschmidt Chemical Corporation), ethoxylated alkyl quaternary ammonium surfactants, propoxylated quaternary ammonium surfactants (such as the Variquat(copyright) surfactants produced by Goldschmidt Chemical Corporation), ethoxylated alkyl aryl alcohols and their derivatives, linear and branched alcohol ethoxylates. By definition, the term alkyl as used in this patent can refer to both saturated and unsaturated hydrocarbon chains.
The method of this invention can be used for liquid and solid agrochemical compositions. They can be used in spray tank mixes, pesticide formulations, adjuvant blends, and in applications where the silicone surfactant is administered in a sequential addition after the application of the herbicide, such as disclosed in U.S. Pat. Nos. 5,985,793 and 5,821,195 which are incorporated herein by reference. Typical use temperatures are about 45xc2x0 F. to 100xc2x0 F.
Typical agrochemical formulations comprising non-spreading siloxanes and effective amounts of active ingredients can comprise, for example, 1 to 50% of siloxane(s), preferably 2 to 20% siloxane by weight of the total formulation.
If containing additional co-surfactants, typical adjuvant formulations comprising non-spreading siloxanes can comprise, about 1 to about 99% by weight of siloxane(s) and 0 to about 99% of co-surfactant(s), preferred about 10 to about 70% by weight of siloxane(s) and 30 to 90% of co-surfactant(s), especially preferred about 25 to about 50% siloxane(s) and about 50 to about 75% co-surfactant(s).

Use of non-spreading silicone surfactants in agrochemical compositions

Abstract: wherein

Abstract: n is 1 to 3,

Abstract: Rxe2x80x2 is a radical of the structure

Abstract: m is 2 to 6,

Abstract: y is 6 to 30,

Abstract: z is 0 to 10,


Embodiments of the disclosed technologies provide solutions for automatically reading digital electronic documents that contain tables and correctly extracting table data, rows and columns from the documents with high accuracy and high throughput. Embodiments are capable of converting a table portion of a read-only document to a searchable, editable data record using text rectangle (TR)-level numerical data that indicates probabilities of TRs belonging to canonicals and at least one convolutional neural network (CNN) that processes the TR-level numerical data to produce table-level numerical data.

The developments described in this section are approaches that could be pursued, but not necessarily approaches that have been previously conceived or pursued. However, unless otherwise indicated, it should not be assumed that any of the developments described in this section qualify as prior art, or that these developments are generally known to a person of ordinary skill in the art.
Table extraction is a process by which a computer automatically recognizes a table that contains rows and columns of data in a read-only document and converts the table to a structured data record. Known automated table extraction algorithms are image-based; that is, they rely on the detection of visual cues in the raw image data of the read-only document, such as printed or typed visual lines or other markings that separate the rows and columns of a table, to locate and extract the table data from the read-only document. Rule-based extraction relies heavily on human-derived, fixed heuristics to inspect text and detect tables. Other known approaches use optical character recognition (OCR). Still other known techniques are template-driven, where the template is created by a human manually identifying the types and location of data in the table. Template-driven and OCR approaches are not fully automated as end-to-end solutions.

Text-based machine learning extraction of table data from a read-only document


A compound, or a pharmaceutically acceptable salt thereof, having a structure of

The hallmark of pulmonary fibrosis is thickening and scarring of the tissue caused by increased deposition of extracellular matrix (ECM) proteins such as collagen and fibronectin. Fibrosis is the final stage of many diseases such as idiopathic pulmonary fibrosis, liver cirrhosis, and certain autoimmune disorders. Scarring causes irreversible damage that usually leads to low quality of life, transplantation or death. Fibroproliferative disorders such as idiopathic pulmonary fibrosis and systemic sclerosis have no effective therapies and result in significant morbidity and mortality due to progressive organ fibrosis. For example, IPF is a devastating and relentlessly progressive lung disorder. Currently available therapies are largely ineffective in reversing the lung damage, and lung transplantation is the only effective treatment for end-stage disease.
Excessive deposition of extra cellular matrix (ECM) components such as fibronectin (FN) and type I collagen (Col1α1) by organ fibroblasts is defined as fibrosis. Organ fibrosis is the final common pathway for many diseases that result in end-stage organ failure. However, an effective therapy for organ fibrosis is still unavailable (see, for example, Bjoraker et al., Am. J. Respir. Crit. Care. Med 2000; 157:199-203). Uncontrollable wound-healing responses, including acute and chronic inflammation, angiogenesis, activation of resident cells, and ECM remodeling, are thought to be involved in the pathogenesis of fibrosis (Wynn, J Clin Invest 2007; 117:524-29; Kalluri et al., Curr Opin Nephrol Hypertens 2000; 9:413-8). TGF-β is the prototype fibrotic cytokine that is increased in fibrotic organs and contributes to the development of fibrosis by stimulating the synthesis of ECM molecules, activating fibroblasts to α-smooth muscle actin (α-SMA)-expressing myofibroblasts, and downregulating matrix metalloproteinases (MMPs) (see, for example, Branton et al., Microbes Infect 1999; 1:1349-65). Despite high expectations, a clinical trial of a monoclonal anti-TGF-β antibody in patients with early SSc failed to show any efficacy (Varga et al., Nature Reviews Rheumatology 2009; 5:200-6). Thus, a need remains for other treatments of fibrosis.

Antifibrotic effects of oxetanyl sulfoxides

Abstract: wherein Z is aryl or substituted aryl, heteroaryl, or substituted heteroaryl;        X is —S—, —S(O)—, or S(O)2—;        R20 and R21 are each independently H, alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, aryl, substituted aryl, or halogenated alkyl;        one of R22, R23, and R24 is —O— and the others of R22, R23 and R24 are independently —CH2—, or —C(R13)— wherein R13 is alkyl, alkenyl, alkynyl, trialkylsilyl group, or —(CH2)mOR15, wherein R15 is alkyl or an aryl and m is an integer in the range of 1 to 10; and        R25 is H, alkyl, substituted alkyl, halogen, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, C1-C3 alkoxy, aryloxy, or —(CH2)qOR17, wherein R17 is alkyl an aryl and q is an integer in the range of 1 to 10.

University of Pittsburgh—Of the Commonwealth System of Higher Education

MUSC Foundation for Research Development


Methods, apparatuses, and devices for processing a service, including computer programs encoded on computer storage media are provided. One of the methods includes: receiving an application sent from a user terminal of a first user comprising a commitment; verifying a credit value of the first user; in response to the credit value reaching a predetermined credit value, accepting the application of the first user; and in response to the first user failing to fulfill the commitment, triggering a balance compensation process to cause the first user to send a balance resource to the second user by a deadline.

Service processing often involves various service interaction scenarios. With a network data sharing scenario as an example, different users can share their own network data with one another. For example, a first user may set a standard amount resources for network data to be available for sharing. Thereby any other user has to share an amount of network data corresponding to the standard amount resources to obtain a corresponding network data from the first user. In this way, long-term, sustainable sharing can be maintained between the users, helping increasing data sharing activities.

Service processing method and apparatus, and electronic device


Techniques are described herein for processing queries comprising joins specifying a plurality of tables. The techniques involve partitioning the tables by assigning rows to partitions. One or more partition maps may be generated to indicate the partitions. Subsequent tables may be partitioned based on the generated partition maps. The partitions may be used to determine results for the joins.

Database servers commonly receive commands that require the performance of a class of operations known as "join operations." A join operation is used to combine multiple tables, so data from those tables may be selected in a query. A query that joins two tables specifies how the tables are joined using one or more join criteria. Generally speaking, a join operation comprises merging each row in a first table with each row of a second table that matches the join criteria. For example, a query may specify that rows in the first table only join with rows in a second table when rows in the first table have a value in a particular column that matches the value in a particular column of rows in the second table. The corresponding columns that contain the values that determine which rows of the first table join with which rows of the second table are referred to as the "join keys."
Database servers may rely on an algorithm known as a "hash join" to efficiently perform join operations. The "hash join" operation typically comprises two phases. In the first phase, known as the "build phase," the database server generates a hash table by hashing each row of the first table according to a hash function on the join key. In the second phase, known as the "probe phase," the database server iteratively scans through each row of the second table. For each row in the second table, the database server uses the hash function and the hash table to identify rows in the first table with equivalent join key values. When matching rows are identified, the rows are merged and added to the result set for the join operation.
A hash join operation merges two tables at a time. For a query that specifies a join of more than two tables, a query optimizer may determine an order for joining pairs of tables. Each pair of tables may be merged with their respective join keys, using a hash join, to produce intermediate results. The intermediate results may be merged with other tables or other intermediate results to produce the query results. However, if the tables in the join operation are relatively large, the database server may be unable to fit an intermediate join result in volatile memory. In that situation, a portion or all of the intermediate join result must be written to a storage disk. Reading and writing from a disk takes longer than reading and writing results only from volatile memory.
The approaches described in this section are approaches that could be pursued, but not necessarily approaches that have been previously conceived or pursued. Therefore, unless otherwise indicated, it should not be assumed that any of the approaches described in this section qualify as prior art merely by virtue of their inclusion in this section.


By-product materials are processed to mitigate undesirable effects. In some embodiments, industrial waste by-products are recycled using calcium polysulfide and used in building materials. In certain implementations, toxins are rendered non-viable as human pathogens by reaction with calcium polysulfide to create non-soluble sulfide crystals locked in the material as hydration is completed. The sulfides are not soluble in water and are locked into position within the resulting hydrate material, which mitigates escape of or changes of state in the toxins.

A variety of processes are generated by-products that are harmful or otherwise undesirable. For example, the production of electricity by coal fired production plants creates by-product materials containing toxic waste. As coal is burned, toxic heavy metals such as Mercury, Arsenic, Cadmium, Lead and other substances become gases. Molecules of these gases cool in exhaust systems and collect with fine ash particles to make fly ash. Heavy ashes fall during coal combustion to create bottom ash. These materials are often stored in piles or in ponds at production facilities. The presence of these sites creates a potential hazard to human populations, at least in part due to the ability of toxins to dissolve in water supplies. Once in water supplies, the toxins can become a threat.
As another example, slag piles and other by-products of industrial processes such as mining, metal smelting and refining can pose potential problems. For instance, toxic lead, arsenic, copper, selenium and other contamination may be generated from such processes. These and other matters have presented challenges to managing by-products of a variety of applications.

By-product treatment via calcium polysulfide


A wireless communication system includes a wireless host and a wireless device. The wireless device includes a user authentication unit that authenticates a requesting user that is using the wireless host based on a result of comparison between a requesting-user ID of the requesting user received from the host and a user ID of a user that is permitted to establish communication with the wireless device. When the requesting user is authenticated by the user authentication unit, information required prior to connection is stored in the wireless device and the wireless host. The wireless device permits to continue the association process with the wireless host, when the information required prior to connection received from the wireless host and the information required prior to connection stored in the wireless device match.

1. Field of the Invention
The present invention is directed generally to a wireless communication system, a wireless host, and a wireless device, in particular, is directed to a wireless USB host, and a wireless USB device for carrying out wireless communication in compliance with wireless USB standard.
2. Description of the Related Art
Wireless universal serial bus (USB) is a technical standard that is introduced as an extension of the USB, which is widely used as a standard for wired, short-range communications, and that provides ease of use of wireless communication while preserving security and speed of wired communications. Specification for wireless USB has been defined by the Wireless USB Promoter Group, which is a lower branch of the USB-Implementers Forum (USB-IF).
Wireless USB employs a wireless technology called Ultra-wideband (UWB). UWB operates in a broad spectrum of 3.1 to 10.6 gigahertz (GHz). IEEE 802.15.3a Task Group in the Institute of Electrical and Electronic Engineers (IEEE) formulating standards works for standardization of the physical layer of UWB. There are two modulation approaches, specifically Direct Spread-UWB (DS-UWB) and Multiband-Orthogonal Frequency Division Multiplexing (MB-OFDM), for the physical layer of UWB.
In DS-UWB, two bands (dual band), or specifically, a low band of from 3.1 to 4.9 GHz and a high band of from 6.2 to 9.7 GHz are used. Data transmission is performed by performing primary modulation by using quadrature phase shift keying (QPSK) or binary phase shift keying (BPSK), and thereafter secondary modulation by using code division multiple access (CDMA). At this time, the data transmission is performed by using direct-sequence spread-spectrum technique.
In MB-OFDM, the spectrum of from 3.1 to 10.6 GHz is divided into 14 bands (frequency bands). For each band, primary modulation is performed by QPSK to thereby superimpose digital signals on radio waves first. Subsequently, secondary modulation is performed by OFDM to realize communication that is highly tolerant to interference with other radio waves. Specification for MB-PFDM physical (PHY) layer has been defined as the WiMedia PHY by a group called the WiMedia Alliance.
By performing modulation by using these modulation methods, transmitting electric power consumption per megahertz (MHz) is lowered in the UWB. Specifically, the Federal Communications Commission (FCC) has defined that the equivalent isotropic radiated power (EIRP), which denotes a limit of transmitting electric power consumption level for UWB communications, per megahertz is to be equal to or below −41.25 decibel per milliwatt (dBm). This can be converted into total electric power of approximately 0.5 milliwatt (mW), which is approximately one-twentieth of that of IEEE 802.11b wireless LAN and personal handy-phone system (PHS), which is 10 [mW].
The WiMedia Alliance has defined protocol for the media access control (MAC) layer as the WiMedia MAC. Wireless USB is based on wireless technologies, or specifically the WiMedia PHY and the WiMedia MAC, and incorporates USB technology based on the Universal Serial Bus Specification Revision 2.0 (USB 2.0 specification) defined by the USB-IF for wired communication. Accordingly, if the communication range is equal to or less than three meters, wireless USB allows data transfer of 480 megabits per second (Mbps), which is the maximum data transfer rate of the wired USB 2.0.
Wireless USB has low transmitting power consumption, which is one of characteristics of UWB. Hence, wireless USB is ranked as a personal area network (PAN) where radio waves are assumed to reach a range of up to 10 meters. Wireless USB can be said to be, in addition to providing higher data throughput, less susceptible to eavesdropping, and more secure than wireless LAN.
However, because wireless USB is one of the wireless communications technologies, a disadvantageous case that, for instance, a user that has not an access right or a permission accesses a file in a storage, which corresponds to a wireless USB device, without being noticed by an authorized user can occur. To this end, a wireless USB desirably has a function of authenticating an authorized user.
In wireless USB, the authentication is performed by using what is called a 4-way handshake scheme illustrated in FIG. 15 between a wireless USB host and a wireless USB device. The 4-way handshake is performed using four messages, or specifically, a message 1, a message 2, a message 3, and a message 4. The wireless USB host and the wireless USB device shares a connection key (CK) before the 4-way handshake is started. The wireless USB host generates a random number called HNonce; the wireless USB device generates a random number called DNonce. As the message 1, the wireless USB host transmits the HNonce to the wireless USB device (Step S400). The wireless USB device calculates a pairwise temporary key (PTK) by combining its own DNonce, the received HNonce, and the CK together (Step S402) based on a predetermined equation. The thus-obtained PTK is utilized as an encryption key in data transfer to be performed later.
Similarly, as the message 2, the wireless USB device transmits the DNonce to the wireless USB host (Step S404). The wireless USB host calculates a PTK by combining the received DNonce, its own HNonce, and the CK together (Step S406) based on the same equation. Thereafter, the PTK calculated by the wireless USB host is sent out by the wireless USB host as the message 3 (Step S408), and the PTK calculated by the wireless USB device is sent out by the wireless USB device as the message 4 (Step S410). The wireless USB host and the wireless USB device individually determine whether the calculated PTK and the received PTK has match (Step S412, Step S414). If the two PTKs match (Yes at Step S412, Yes at Step S414), communication between the wireless USB host and the wireless USB device is started. Authentication by using the 4-way handshake is performed in this manner. In this way, the 4-way handshake premises that a CK is pre-shared between a wireless USB host and a wireless USB device.
As illustrated in FIG. 16, a CK is defined in the Wireless Universal Serial Bus Specification, Revision 1.0 (hereinafter, "wireless USB 1.0 specification") as a component that, together with a connection host identifier (CHID) serving as an identifier of the wireless USB host and a connection device identifier (CDID) serving as an identifier of the wireless USB device, constitutes a connection context (CC). The CK is shared between the host and the device as a result that the CC is shared therebetween prior to authentication. In the wireless USB 1.0 specification, the term "association" is used to describe a series of operations that are performed to share a CC. Specification of the association is defined in Association Models Supplement to the Certified Wireless Universal Serial Bus Specification (hereinafter, "association specification"), which is a supplemental document of wireless USB.
In the association specification, two association models, more specifically the Cable Association Model and the Numeric Association Model, are described.
In the Cable Association Model, first-time association between a wireless USB host and a wireless USB device is performed by using a USB cable in a wired manner. The wireless USB host provides the wireless USB device with a CC via the USB cable. This causes the CC to be shared between the host and the device.
In contrast, in the Numeric Association Model, at first-time association between a wireless USB host and a wireless USB device, buttons, provided on each of the device and host, for starting association are pressed, and then each of the wireless USB host and the wireless device generates a random number. The host and the device exchange the random numbers by radio waves. Each of the wireless USB host and the wireless USB device displays a numeric value calculated from the random number generated by itself and the received random number by using a predetermined equation. A user checks whether the numeric values displayed on the wireless USB host and the wireless USB device match. If the numeric values match, buttons, which are provided on the wireless USB host and the wireless USB device, for permitting association are independently pressed. Thereafter, the wireless USB host provides the wireless USB device with a CC by radio waves, whereby the CC is shared between the device and the host.
However, each of the two association model has disadvantage discussed below. With the Cable Association Model, it is an essential condition that a wired USB port is additionally provided on each side of the wireless USB host and the wireless USB device. Furthermore, connection with a cable is troublesome. Meanwhile, with the Numeric Association Model, it is an essential condition that each of the wireless USB host and the wireless USB device includes a display. This makes the Numeric Association Model less appropriate for adoption into a small device, such as USB memory.
In view of the above circumstances, Near Field Communication Association Model (hereinafter, "NFC") is defined as a new association model in the wireless USB 1.1 specification, which is a currently drafted specification as a succeeding version of the wireless USB 1.0. NFC is a short-range two-way wireless communication standard that allows communication at a rate of from 100 to 400 kilobits per second (Kbps) over a short distance of approximately 10 centimeters by using radio waves of the 13.56 MHz. NFC is a communication technology that has originally been used in contactless IC cards for use in an automatic checking and collecting machine in a station, or the like. Because NFC was approved as an international standard as ISO/IEC 18092, NFC can proliferate in electronics products, such as audio equipment, for general end consumers.
Using NFC as one of association models for providing a CC from a wireless USB host to a wireless USB device is contemplated in wireless USB technology. Specifically, this scheme is performed such that, if it is desired that data in a notebook personal computer (PC) corresponding to a wireless USB host is printed by a printer corresponding to a wireless USB device, the notebook PC and the printer are brought into a range of 10 centimeters or less, thereby causing the notebook PC and the printer to share a CC by NFC.
As one of such techniques that use NFC, a technique directed to wireless local area network (LAN) technology is disclosed in Japanese Patent Laid-open Publication No. 2007-166538. According to this technique, communication methods supported by two wireless LAN communication devices are determined by using NFC, first. If the communication methods match, communication is carried out by using the communication method; if the communication methods do not match, communication is carried out by NFC. Another technique of causing two wireless communication devices to carry out communication by NFC first, and, if the two wireless communication devices support higher-speed communication protocol, such as Bluetooth®, switching communication protocol to the higher-speed communication protocol is disclosed in Japanese Patent Laid-open Publication No. 2008-160856. A technique that uses NFC in Device Wire Adapter (DWA) is disclosed in Japanese Patent Laid-open Publication No. 2008-72533. DWA acts as an adapter that converts data, in order to communicate data from external equipment, which is connected to a USB connector, by wireless USB communication.
As discussed above, NFC is an association model that complements disadvantages of the Cable Association Model and the Numeric Association Model. However, operation to be performed to verify whether a wireless USB host that has attempted association is an authorized wireless USB host is not defined in NFC.
Hence, such a situation that a user of a wireless USB host who is not given an access right to a wireless USB device that employs NFC as its association model establishes association with the wireless USB device by NFC in a sneaky manner when the user is unaccompanied by other people can occur. This allows the user that is not given an access right to deliver a CC to the wireless USB device and carry out communication between the wireless USB host and the wireless USB device, which is undesirable.
For instance, assume that a laboratory in a university has a printer corresponding to a wireless USB device that employs NFC for an association model. It is highly possible that a room where the printer is installed is left unlocked in many cases because of the way the printer is used. Under such a condition, there can occur such an undesirable situation that, for instance, due to a meeting attended by all members of the laboratory held in another room, the room where the printer is installed is emptied continuously for several hours, during which an outsider, such as a staff of another laboratory, carries a notebook PC into the room, establishes association with the printer without permission, and performs a large amount of printing by using the printer.
The present invention has been conceived in view of the above circumstances and aims at providing a wireless communication system, a wireless host, a wireless device, and a wireless communication method capable of restricting association to be established between a wireless host and a wireless device in response to an instruction issued by a user of a wireless host who does not have an access right to the wireless device.

Wireless communication system, wireless host, and wireless device


A spherical crocheted object includes a portion that contains high quality embroidery and is made beginning with a fabric piece called an initial disc. By initially knitting the spherical crocheted object into a flat, round disc of specific and limited dimensions, this initial disc is created for the introduction of an external embroidery process. The crocheted initial disc is tied off to maintain durability during the embroidery step, which is usually performed on specialized embroidery equipment. Thereafter, by vigilantly following specific construction techniques, a ball will be produced that retains its spherical shape resulting in an end product with characteristics similar to that of a spherical crocheted object that does not contain embroidery.

1. Technical Field
The present invention related to crocheted balls and, more particularly, relates to crocheted balls having an embroidered portion thereof.
2. Related Art
The utilization of spherical crocheted objects for toys, games and recreations have been increasingly popular over the past several years. Initially, crocheted balls were made and sold as toys through many retailers. Now crocheted balls have many additional uses in sports and recreational activities because they are soft, colorful and inexpensive to produce. Crocheted balls and bags have become very popular for use in sports that utilize soft balls including footbag, juggling, toss ball, kick ball, dodge ball and others. Thus, due to their popularity and wide distribution, spherically crocheted objects make an excellent item for advertising and promotional purposes.
One of the more popular utilizations of the spherical crocheted objects is for the game of footbag. An originating patent, U.S. Pat. No. 4,151,994, for the game was issued in May 1979 to Robert J. Stahlberger, Jr. the inventor of the game of footbag (Hacky Sack™). The original ball that was used for this game was a leather paneled style of ball shaped like a baseball. Years later, this original invention was improved upon with the introduction of several newer styles of footbags that touted improved characteristics for the playing of the game. These improved characteristics included a softer style of ball and low bounce characteristics that allowed for greater control and ease of use by the footbag players, who enjoyed the ability to "catch" the ball with the foot and perform a much wider array of athletic footbag tricks. One of the more popular ball types for the game has become the crocheted footbag.
Crochet is a fabric construction that utilizes needlework consisting of the interlocking of looped stitches formed with a single thread and a hooked needle. The popular crocheted ball is a successful implementation of crochet stitching in a round form. Thread types used include cotton, rayon, dacron, polyester or a combination of several thread types. The thread used is of varying degrees of thickness. Depending on the thickness and type of the thread, a crocheted ball will contain larger or smaller stitches which give the ball an appearance of being fuzzier, thicker or rougher. Crocheted balls are made of varying sizes, weights and looseness based on the game played, preference of the participants of the sport, durability and cost. All spherical crocheted objects can be woven by machine or by hand.
Spherical crocheted objects are woven such that rows contain increasing numbers of stitches expanding outward in a spiral form. Thus, the start of a crocheted ball (the "bottom") starts with a single stitch; which is added to in a spiral pattern. This spiral construction soon forms a round disc. The spherical shape forms as the disc construction expands and the stitches are tightened to create a curvature. In the middle of the crocheted ball, the rows contain their maximum number of stitches and determine the diameter of the crocheted ball. For instance, if there are 10 stitches per inch then a ball 8 inches in diameter will contain 80 stitches.
As a crocheted sphere is woven, and after it reaches its maximum diameter, the number of stitches per row is reduced. Thereafter the reduction of each successive row gives the ball its shape and the stitches get tighter and closer together. Before the crocheted sphere weaving is completed, a small hole remains. Before the final closure, the ball is filled with a filling type, which is often plastic resin pellets, bird seed or other types of small or inert filling; then the crocheted object is sealed shut with the final crocheted weave and tied off in a knot. A spherical crocheted object is usually seamless and durable with the final sewing termination.
The filling of a crocheted ball determines its characteristics: slackness, feel and the best utility.
Manufacturers have chosen many different filling types and sizes. Crocheted balls are quite durable, seldom rupture and thus can be used in the most active and aggressive games with little chance of breaking open.
The simplicity and low production cost of the crocheted ball is ideal for many applications in games, sports and toys. Crocheted balls are superior for the purpose of game balls because they are very durable while being malleable and soft at the same time. This offers a longevity not found with paneled balls which tend to break open at the seams. The stresses on the fabrics during the use of crocheted balls are dissipated throughout the stitches of the ball as compared to that of a paneled ball which have limited stitches.
Prior to this invention, spherical crocheted objects have been limited in their ability to purport messages. Previous utilizations were predominantly limited to fabricating crocheted balls with designs built entirely into the crocheted construction. Thus, the primary method has been to directly crochet images into the actual weaving by means of changing the colors of the threads on each individual stitch, usually by hand, to create the necessary contrast to create such images. Although images and logos implemented on existing crocheted balls can be quite complicated and intricate, the fact remains that crocheted balls are limited by the number of stitches per inch inherent in the manufacture of such balls, usually 10 stitches per inch or less, depending on the thickness of the thread used.
Alternative utilizations applied to crocheted balls for the purpose of creating a more useful advertising medium have included other attempts to modify their construction. One known attempt has been the addition of a round panel of fabric sewn into the crocheted ball. This panel, which can be of imitation suede or another durable material, is suitable for screen printing and other suitable advertising purposes; however, there are problems with this incarnation. The basic strength of the ball is dubious due to a fixed fabric seam that is incapable of handling the stresses of hard play, and has been known to come undone. Additionally, the fabric is less flexible than the original crocheted stitches so the ball does not function as well for the preferred active sports that require a softer ball.
Still other manufacturers have attempted variants on crocheted balls to enhance the ability to purport messages or logos. Directly dyeing the crocheted threads is a less successful method of applying words, logos or advertising messages since it is often messy and unprofessional in outcome. Further still, a panel of fabric has been sewn to the exterior of crocheted balls as a means of applying a logo or message. This application is also limited because the size of these fabric pieces must be very small and do not stick well to spherical objects when glued or sewn.
In summary, spherical crocheted objects are inexpensive and mass-produced items used for various sporting, recreational and advertising purposes. To date, the several known attempts to extend the message-carrying functionality of these crocheted objects have had limited success.

This patent is subject to a terminal disclaimer.