The invention includes a method of patterning radiation. The radiation is simultaneously passed through a structure and through a subresolution assist feature that is transmissive of at least a portion of the radiation. The subresolution assist feature alters a pattern of radiation intensity defined by the structure relative to a pattern of radiation intensity that would be defined in the absence of the subresolution assist feature. The invention further includes methods of forming radiation-patterning tools, and the radiation-patterning tools themselves.

Photolithography is commonly used during formation of integrated circuits on semiconductor wafers. More specifically, a form of radiant energy (such as, for example, ultraviolet light) is passed through a radiation-patterning tool and onto a semiconductor wafer. The radiation-patterning tool can be, for example, a photomask or a reticle, with the term "photomask" being sometimes understood to refer to masks which define a pattern for an entirety of a wafer, and the term "reticle" being sometimes understood to refer to a patterning tool which defines a pattern for only a portion of a wafer. However, the terms "photomask" (or more generally "mask") and "reticle" are frequently used interchangeably in modern parlance, so that either term can refer to a radiation-patterning tool that encompasses either a portion or an entirety of a wafer. For purposes of interpreting the claims that follow, the terms "photomask" and "reticle" will be given their historical distinction such that the term "photomask" will refer to a patterning tool that defines a pattern for an entirety of a wafer, and the term "reticle" will refer to a patterning tool that defines a pattern for only a portion of a wafer.
Radiation-patterning tools contain light restrictive regions (for example, totally opaque or attenuated/half-toned regions) and light transmissive regions (for example, totally transparent regions) formed in a desired pattern. A grating pattern, for example, can be used to define parallel-spaced conductive lines on a semiconductor wafer. The wafer is provided with a layer of photosensitive resist material commonly referred to as photoresist. Radiation passes through the radiation-patterning tool onto the layer of photoresist and transfers the mask pattern to the photoresist. The photoresist is then developed to remove either the exposed portions of photoresist for a positive photoresist or the unexposed portions of the photoresist for a negative photoresist. The remaining patterned photoresist can then be used as a mask on the wafer during a subsequent semiconductor fabrication step, such as, for example, ion implantation or etching relative to materials on the wafer proximate the photoresist.
Advances in semiconductor integrated circuit performance have typically been accompanied by a simultaneous decrease in integrated circuit device dimensions and a decrease in the dimensions of conductor elements which connect those integrated circuit devices. The demand for ever smaller integrated circuit devices brings with it demands for ever-decreasing dimensions of structural elements on radiation-patterning tools, and ever-increasing requirements for precision and accuracy in radiation-patterning with the tools.
An exemplary prior art radiation-patterning tool 12 is shown in FIG. 1. Radiation-patterning tool 12 comprises a substrate 14 which is at least partially transparent to radiation which is to be patterned, and a structure 16 joined to substrate 14 and formed of a material which is less transparent to the radiation than is substrate 14. Substrate 14 typically comprises fused silica (for example, quartz), and structure 16 typically comprises chrome.
FIG. 1 further illustrates radiation 18 being directed toward radiation-patterning tool 12, and shows a plot 20 of radiation intensity exiting from radiation-patterning tool 12. Plot 20 illustrates that structure 16 has attenuated the radiation intensity. Specifically, plot 20 comprises a region 22 of decreased intensity where radiation 18 has been at least partially blocked by structure 16, and higher intensity regions 24 where radiation 18 has not been blocked by structure 16. In particular embodiments of the prior art, structure 16 will comprise a material substantially opaque to radiation 18 (for example, chrome can be opaque relative to ultraviolet light), and substrate 14 will be substantially transparent to the radiation (for example, quartz can be transparent to ultraviolet light).
A problem associated with the radiation-patterning described with reference to FIG. 1 can be in accurately and reproducibly forming the dip in radiation intensity shown at region 22 of plot 20. Specifically, if radiation 18 is slightly defocused from an optimal focus position, the depth of region 22 (i.e., the change in intensity between region 22 and regions 24) can be altered, which can cause variation in a critical dimension of openings ultimately patterned into photoresist. Also, the shape of the intensity profile in graph 20 can be less precise than is desired. Specifically, it would be ideal if the intensity profile of plot 20 exactly mirrored the pattern defined by structure 16 (i.e., if the intensity profile had sharp corners at transitions between regions 24 and 22, and if region 22 had a flat bottom with a width corresponding to that of structure 16).
An improved prior art radiation-patterning tool 12a is described with reference to FIG. 2. In referring to FIG. 2, similar numbering is utilized as was used in referring to FIG. 1, with the suffix "a" used to indicate structures shown in FIG. 2. Radiation-patterning tool 12a is similar to the patterning tool 12 of FIG. 1 in that it comprises a substrate 14a which is at least partially transparent to incoming radiation 18a, and a structure 16a which is less transparent to radiation 18a than the substrate. However, radiation-patterning tool 12a differs from the patterning tool 12 of FIG. 1 in that subresolution assist features 30 are provided adjacent structure 16a. Subresolution assist features 30 are formed of an identical material as structure 16a (which simplifies processing, as a single material can be formed over substrate 14a and patterned to form features 30 and structures 16a). Features 30 are referred to as subresolution assist features because intensity variations caused by features 30 are not resolved from intensity variations caused by structures 16a at the resolution provided by the particular wavelength of incoming radiation 18a. This is shown in the intensity graph 20a. Specifically, graph 20a shows a dip 22a corresponding to a region wherein an intensity variation is caused by structure 16a, and shoulders 32 corresponding to regions wherein intensity variation is caused primarily by features 30. Since the intensity variations caused by features 30 are shoulders 32 along region 22a, rather than distinctly resolved elements, such intensity variations are subresolution variations.
Subresolution assist features 30 can alleviate some of the problems described above as being associated with the radiation-patterning tool 12 of FIG. 1. Specifically, subresolution assist features 30 can stabilize an intensity difference between non-blocked regions 24a and blocked region 22a relative to subtle variations in focus of radiation 18a. Further, subresolution assist features 30 can improve the overall shape of blocked region 22a in the intensity profile 20a relative to the shape of region 22 in intensity profile 20 of FIG. 1. Specifically, subresolution assist features 30 can flatten a bottom of region 22a, and sharpen the transition at corners of region 22a, such that region 22a has a width which better approximates a width of structure 16a than the width of FIG. 1 region 22 approximates a width of structure 16.
A problem associated with the formation of subresolution assist features is that as the dimension of semiconductor devices becomes smaller the desired dimension of subresolution assist features also becomes smaller. It is therefore becoming increasingly difficult to form satisfactory subresolution assist features as integrated circuit device dimensions decrease. It would accordingly be desirable to develop alternative methods of forming subresolution assist features.

Methods of patterning radiation, methods of forming radiation-patterning tools, and radiation-patterning tools


An apparatus for estimating a frequency of access to a storage device that includes a flash memory and a controller for controlling the flash memory includes interface. Data is written into the flash memory in units of a page and being erased from the flash memory in units of a block consisting of pages. The interface is supplied with an internal signal transferred between the flash memory and the controller, configured to recognize the internal signal, and outputs the internal signal as an input signal. An erasure sequence detection section outputs a detection signal when address data is followed by an erasure command requesting erasure of data in the block specified by the address data in the input signal. An address holding section holds address data in the internal signal, and outputs held address data as erasure address data when supplied with the detection signal.

1. Field of the Invention
The present invention relates to an access frequency estimation apparatus and an access frequency estimation method and, for example, to an apparatus and a method for estimating a frequency of access to a semiconductor storage device for each predetermined region.
2. Description of the Related Art
A high voltage is applied to each of memory cells of a flash memory at an insulating film constituting the memory cell when data is written to the memory cell. An accumulation of application of the high voltage deteriorates the characteristics of the insulating film. An accumulation of deterioration of the characteristics of the insulating film lowers reliability of the memory cell in retaining data. Accordingly, each memory cell has an upper limit of the number of rewritable times.
If writing is concentrated at a certain memory cell, the count of writing data to this memory cell reaches the upper limit earlier than the other memory cells. As a result, reliability of data retention of the whole flash memory is lowered. In order to avoid such a situation, it is desirable that the count of writing data to the memory cells be as even as possible in the entire memory cells.
In order to meet such requirements, most of controllers for controlling a flash memory try to level the count of writing as much as possible in all the memory cells wear leveling).
A flash memory controller for controlling a flash memory is gencrally composed of hardware for controlling a bus of the flash memory and software for controlling an operation of the hardware. The software performs the wear leveling.
It is necessary to verify whether the software of the flash memory controller performs appropriate wear leveling at the designing stage of the flash memory controller. As the verification methods, the following two methods are so far possible.
A first method involves visual verification of a flowchart representing an operation of the software, and confirming whether the hardware operates in accordance with the flowchart by means of a simulator or the like. The first method does not verify an actual operation of the flash memory controller upon a write operation. As a result, the method cannot find a defect in wear leveling resulting from an unpredictable problem that cannot be found by the flowchart and simulation. Furthermore, the method includes confirmation performed by a human being, resulting in possible mistakes.
A second method involves actual verification of signals on a bus of the flash memory manufactured on an experimental basis. A general-purpose measuring instrument such as a logic analyzer is used because a protocol analyzer exclusively used for a flash memory to detect a command or the like peculiar to the flash memory is not commercially available so far. A logic analyzer outputs signals on the bus, which is an object to be verified, at appropriate intervals, and numerating the signals, for example, on an image along the time base. However, as described above, since the general-purpose logic analyzer cannot recognize a command peculiar to the flash memory, and thus it takes in the state (for example, "0" or "1") of each signal at each point of time. Further, it is necessary to extract write commands and write addresses from the acquired data to analyze the write commands and the write addresses. Thus, the data to be taken in and stored and the resulting throughput are enormous. Accordingly, it is impossible to actually carry out the second method.
Jpn. Pat. Appln. KOKAI Publication No. 6-52694 discloses monitoring signals transferred to or from a flash memory from or to a memory controller, and measuring a period of time from a data erasure command, with data erasure completion or incompletion, to data erasure completion.

Access frequency estimation apparatus and access frequency estimation method


By forming a polyester film from a polyester resin composition including ketene imine compound represented by the following Formula (1) and polyester, the polyester film having excellent hydrolysis resistance in which volatilization of the ketene imine compound or the ketene compound can be suppressed. In Formula (1), R1 and R2 represent an alkyl group, an aryl group, an alkoxy group, an alkoxycarbonyl group, an aminocarbonyl group, an aryloxy group, an acyl group, or an aryloxycarbonyl group, and the R1—C(═C)—R2 substructure has a molecular weight of 320 or greater. R3 represents an alkyl group or an aryl group.

A solar cell module generally has a structure in which from the light-receiving surface side to which sunlight is incident, a glass or front sheet/a transparent filling material (sealing material)/a solar cell element/a sealing material/a back sheet are laminated in this order. Specifically, the solar cell element is generally embedded with a resin (sealing material) such as EVA (an ethylene-vinyl acetate copolymer) and the like, and a protective sheet for a solar cell is adhered thereto. The protective sheet for a solar cell, above all, a back sheet for a solar cell module, which becomes in particular an outermost layer, is considered to be under an environment exposed to weather outdoor or direct sunlight for a long period of time, and therefore, excellent weather resistance (wet heat resistance, heat resistance) is required.
As the back sheet for a solar cell module, in the related art, a polyester film, in particular, a polyethylene terephthalate (hereinafter, referred to as PET) film has been used. The polyester film has excellent heat resistance, mechanical characteristics, chemical resistance, and the like, and therefore, the polyester film is widely used industrially. However, since the film has poor hydrolysis resistance, the molecular weight is reduced by hydrolysis, and mechanical characteristics are reduced by progressively stiffening. Therefore, it was not possible to maintain a practical strength for a long period of time as a back sheet for a solar cell.
In order to solve the above problems, for example, Patent Document 1 discloses the use of a ketene imine compound as a terminal blocking agent of the polyester in order to suppress hydrolysis of polyester. Here, it is proposed that hydrolysis of polyester is suppressed by reacting the ketene imine compound with the terminal carboxyl group of polyester.

Ketene imine compound, polyester film, back sheet for solar cell module and solar cell module


A remotely controlled actuator for depressing a brake pedal so as to permit the brake system to be bled by a single operator. There is a pneumatic cylinder having attachment fittings mounted to its ends, and these engage the brake pedal and the rim of the steering wheel. Compressed air is supplied to the pneumatic cylinder by way of a portable control valve, so that as this extends, one attachment fitting depresses the brake pedal while the other reacts against the steering wheel. The portable control valve is connected to the cylinder by long, flexible air hoses, so as to permit the operator to move from wheel cylinder to wheel cylinder. A pressure regulator allows the operator to adjust the pressure which is exerted on the brake pedal.

Motor vehicles are very commonly equipped with hydraulic brake systems, and these are almost universally fitted to modern automobiles and light trucks. Such systems have a master cylinder which is connected to a brake pedal which is depressed by the foot of the vehicle operator; as this is done, hydraulic fluid is forced from the master cylinder (which also includes a reservoir for supplying fluid to the system) through brake lines to the several wheel cylinders, causing their actuation.
After maintenance has been performed on a hydraulic brake system of this type, it is typically necessary to remove any air which may have been introduced into the system as a result of the various fittings and components having been disturbed. If this air is not removed, the bubbles in the brake lines and elsewhere will tend to compress when the system is actuated, causing "sponginess" and a loss of braking effectiveness. The process of removing the air from the brake system is commonly referred to as "bleeding". Typically, bleed screws are mounted at each of the wheel cylinders (as well as elsewhere in some systems) for permitting the air to escape at these points as hydraulic fluid is forced into the system from the master cylinder. Normally, the bleeding process requires two people. The first person goes to a selected wheel cylinder and operates the bleed screw, while the second person sits in the car and pumps the brake pedal; the first person observes the brake fluid and air bubbles flowing from the bleed screw, and opens and closes this, and shouts instructions to the second person to operate the brake pedal as necessary.
This conventional approach to brake bleeding is obviously fraught with serious deficiencies. Firstly, it requires the services of a two personnel, thus requiring excessive expenditure of valuable time and labor. Furthermore, the shouted instructions may not always be correctly interpreted by the person operating the brake pedal, or precisely responded to, so that the effort may be poorly coordinated. Also, the traditional technique requires one of the mechanics to sit in the car, which presents the potential for damage to the interior from oil and grease on the mechanics' clothing, or from tools inadvertently left in a pocket. Still further, many modern brake systems require an application of a very even amount of pressure to the brake pedal during each part of the bleeding operation, and such very even pressure is simply very difficult for a human operator to apply manually.
Attempts have been made to overcome some of these deficiencies. One approach has taken the form of what are known to those skilled in the art as "power bleeders". These are typically cannister-like containers which are partially filled with brake fluid and then pressurized with air. The brake fluid is fed under pressure through a flexible conduit to a fitting which is sealingly mounted to the reservoir on the master cylinder. The fluid pressure from the pressure bleeder is communicated through the master cylinder and brake lines to the wheel cylinders, so as to force fluid through the brake lines and evacuate the air. Such power bleeders are not completely satisfactory. Among the practical disadvantages which they exhibit is the fact that they are invariably messy to use, and spilled brake fluid can cause serious damage to a vehicle's paint finish. Furthermore, a number of specialized parts are required; due to the many configurations of master cylinders, there is no one "universal" type of fitting which will sealingly mount to all of these, and so even a reasonably well-equipped mechanic may find himself without suitable fittings for anything but the most ubiquitous systems. The need for all these specialized fittings also contributes to increased costs. Perhaps even more importantly, ordinary power bleeders can supply only a steady fluid pressure to the brake system, and cannot provide any sort of "pumping" action; this is becoming a more and more serious deficiency in view of the fact that this "pumping" action is required for the proper bleeding of the many modern anti-lock braking systems which are coming into use in both automobiles and light trucks.
Accordingly, there exists a need for a device which selectively pumps the brake pedal of a vehicle while the brake system is being bled by an operator who is located adjacent one of the wheel cylinders, remote from the brake pedal. Furthermore, there exists a need for such a device which is substantially universal in nature so that it can be detachably installed in at least the great majority of vehicles without requiring specialized attachment fittings. Also, a need exists for such a device which is able to deliver an equal and even amount of pressure to the brake pedal as each part of the system is bled. Still further, there is a need for such a device which is economical to fabricate and reliable to operate.

Assembly for depressing a vehicle pedal for bleeding brakes


A housing for an electric tool has a plurality of spring arms for exerting a spring force on a brush holder that holds a brush for engaging a commutator. Preferably, the spring arms are integral with a tool housing end cap.

Electric power tools such as portable electric drills, circular saws, jigsaws, sanders, and the like are widely known in the art. Generally, they include an electric motor for rotatably driving a shaft, with a tool such as a drill bit, a saw blade, or the like attached to the shaft. The electric motor is often an AC or DC motor that includes a rotating armature with a commutator. Two non-rotating conducting brushes electrically contact the commutator. The motor assembly, including the armature, the commutator and the brushes, is enclosed in a housing. The brushes must be urged into engagement with the commutator with a spring to ensure good contact with the, provide some degree of tolerance, and also compensate for wear of the brush.
Because electrical current flows through each of the brushes, they are often movably held in an insulating brush box or holder. The brush holder insulates the brush from the housing. The spring which biases the brush into engagement with the commutator is typically contained in the brush holder, and the brush (or the spring) is electronically connected to have a power source such as an AC supply or a DC battery.
During manufacture of such tools in the prior art, the motor armature and commutator were provided pre-assembled, and installed in the housing at the time of final tool assembly. Each brush and brush holder were likewise provided as a pre-assembled unit and installed in the housing at the time of final tool assembly. To speed and simplify tool assembly, the brush holder may have been installed through an open end of the housing by placing it in a bracket that has been pre-formed in the housing. To retain the brush holder in place in the bracket, a housing end cap had either a brush holder locking assembly extending therefrom, so that when the end cap was attached to the housing, the holder locking assembly locked the brush holder in place, or a screw or screws that secure the brush holder to the housing.
To allow for some tolerance in housings and brush holders, and to provide for long service life of the tool, the brush holder locking assembly included a spring member such as a rubber-like polymer layer or pad for engaging the brush holder. By way of particular example, one known tool assembly included a housing end cap having a hollow brush assembly support tube connected thereto. A resilient polymer bumper pad with a barrel portion was inserted into the hollow tube, and had a brush holder-engaging portion that engaged the brush holder. The bumper pad held the brush holder in place, and also provided a degree of protective cushion to the holder to prevent holder breakage if the tool was dropped on its end cap. This known configuration, however, was time consuming to install in the housing.
The commercial market for such tools is competitive, with a large number of competitors vying for market share. In this competitive environment, there are strong business incentives to keep manufacturing costs low. Accordingly, it is desirable to reduce the number of parts and the number of steps required to manufacture the tools.
These and other needs remain unresolved in the art.


A powder detergent composition which is effective for removing and dispersing organic non-polar and polar soils from fabrics in wash liquors. The powder detergent composition comprises a polymer having a hydrophilic backbone and at least one hydrophobic moiety. The hydrophilic backbone is prepared from a monomer selected from ethylenically unsaturated hydrophilic monomers, polymerizable hydrophilic cyclic monomers, and non-ethylenically unsaturated polymerizable hydrophilic monomers selected from glycerol and other polyhydric alcohols. The hydrophobic moiety is prepared from a monomer selected from siloxanes, saturated or unsaturated alkyl and hydrophobic alkoxygroups, aryl and aryl-alkyl groups. The polymers also boost the cleaning performance of hard surface and dishware detergent compositions.

This invention relates to a powder detergent composition having enhanced soil suspending properties on organic non-polar and polar soils in wash liquors which comprises a polymer having a hydrophilic backbone and hydrophobic moieties.
Detergent formulators are faced with the task of devising products to remove a broad spectrum of soils and stains from fabrics. The varieties of soils and stains ranges from polar soils, such as proteinaceous, clay, and inorganic soils, to non-polar soils, such as soot, carbon-black, byproducts of incomplete hydrocarbon combustion, and organic soils. Detergent compositions have become more complex as formulators attempt to provide products which handle all types concurrently.
Formulators have been highly successful in developing traditional dispersants which are particularly useful in suspending polar, highly charged, hydrophilic particles such as clay. As yet, however, dispersants designed to disperse and suspend non-polar, hydrophobic-type soils and particulates have been more difficult to develop. Without wishing to be limited by theory, it is believed that the first step for dispersion formation is the adsorbance of the soil dispersing agent onto the soil of interest. For clay-like soils, the soil dispersing agent must adsorb onto a negatively charged surface. For organic particulates, the soil dispersing agent must adsorb onto a hydrophobic surface with little or no charge. Hence, for polar soils, like clay, a dispersing agent with some charge, such as charged polyacrylates, are employed. However, these charged dispersing agents have no driving force for adsorbing onto organic non-polar particulates.
U.S. Pat. No. 4,444,561 describes using copolymers prepared from 50 to 90 weight percent of a vinyl ester of C1-C4 aliphatic carboxylic acids, from 5 to 35 weight percent of a N-vinyl lactam, and from 1 to 20 weight percent of a monomer containing basic nitrogen capable of forming a salt or quaternized product, in detergent compositions to inhibit soil redeposition. The disadvantage of using such copolymers, however, is that they are capable of forming cations which may complex with anionic surfactants under certain wash conditions and cause a decrease in cleaning performance. In addition, the cationic copolymers may also undesirably promote fabric graying over multiple washing cycles.
U.S. Pat. No. 5,008,032 describes using copolymers prepared from C4-C28 olefins and xcex1,xcex2-ethylenically unsaturated dicarboxylic anhydrides in detergent formulations. The disadvantage of using such copolymers, however, is that the copolymers are not water-soluble unless hydrolyzed with NaOH.
U.S. Pat. No. 5,723,434 describes a soil removal and soil resistant detergent composition containing a vinyl amide polymer which is prepared from 5 to 100 weight percent of a vinyl amide monomer and from 0 to 95 weight percent of a vinyl ester monomer. While the detergent compositions are effective for removing soil from hydrophobic articles such as polyester, such compositions are not as effective for cleaning hydrophilic substrates such as cotton.
U.S. Pat. No. 5,565,145 describes detergent compositions containing ethoxylated/propoxylated polyalkyleneamine polymers, such as poly(ethyleneimine), which provide soil dispersing properties. While the detergent compositions are effective for removing nonpolar soils, such detergent compositions are not as effective for removing polar soils.
U.S. patent application Ser. No. 09/262,566, filed Mar. 4, 1999, describes isotropic liquid detergent compositions containing a polymer having pendant acid functionality and a terminal fragment of a chain transfer agent. Such polymers are used to stabilize the isotropic liquid detergent composition and produce clear solutions by preventing phase separation.
U.S. Pat. No. 5,147,576 describes liquid detergent compositions in the form of a lamellar droplets which contain a deflocculating polymer having a hydrophilic backbone and a hydrophobic moiety. However, no mention is made of the possibility of using such polymers in powdered laundry detergents.
While liquid detergents are gaining popularity over powder detergents in the United States, powders remain more popular than liquid detergents outside the United States. Moreover, there is a trend to reduce the amount of water in the wash liquor for environmental reasons, thereby increasing the amount of dirt and soil that needs to be suspended in the wash liquor. For these reasons, there continues to be a need for a powder detergent composition which can be used to provide effective soil dispersing on organic non-polar and polar soils in wash liquors.
It has now been discovered that powder detergent compositions comprising polymers having a hydrophilic backbone and at least one hydrophobic moiety are effective for removing and dispersing organic non-polar and polar soils from fabrics in wash liquors. Furthermore, said polymers boost the cleaning performance of hard surface and dishware detergent compositions.
The present invention provides a powder detergent composition comprising at least one surfactant and builder and from about 0.1 to about 75 weight percent, based on the total weight of the powder detergent composition, of a polymer having a hydrophilic backbone and at least one hydrophobic moiety, wherein said hydrophilic backbone is prepared from at least one monomer selected from the group consisting of ethylenically unsaturated hydrophilic monomers selected from the group consisting of unsaturated acids, amides, ethers, alcohols, aldehydes, ketones and esters; polymerizable hydrophilic cyclic monomers; non-ethylenically unsaturated polymerizable hydrophilic monomers selected from the group consisting of glycerol and other polyhydric alcohols; and combinations thereof. The hydrophilic backbone may optionally be substituted with one or more amino, amine, amide, sulfonate, sulfate, phosphonate, hydroxy, carboxyl or oxide groups. The hydrophobic moiety is prepared from a monomer selected from the group consisting of siloxanes, saturated or unsaturated alkyl and hydrophobic alkoxygroups, aryl and aryl-alkyl groups, and combinations thereof, provided that said polymer does not include partially esterified copolymers of maleic anhydride or substituted maleic anhydride.
According to an additional aspect the invention provides a method for cleaning textiles comprising preparing the powder detergent composition as described above; contacting the powder detergent composition with one or more textiles wherein at least one of the textiles contains soil; and removing at least a portion of the soil from the textile containing soil.
This invention provides a powder detergent composition which contains at least one surfactant and builder and from about 0.1 to about 75 weight percent, based on the total weight of the powder detergent composition, of a polymer having a hydrophilic backbone and at least one hydrophobic moiety. Preferably, the powder detergent composition contains from about 0.5 to about 25 weight percent, more preferably from about 1 to about 10 weight percent of the polymer.
The polymer having a hydrophilic backbone and at least one hydrophobic moiety comprises a hydrophilic xe2x80x9cbackbonexe2x80x9d component. The hydrophilic backbone may be linear or branched and is prepared from at least one ethylenically unsaturated hydrophilic monomer selected from unsaturated acids preferably C1-C6 acids, amides, ethers, alcohols, aldehydes, ketones and esters; polymerizable hydrophilic cyclic monomers; and non-ethylenically unsaturated polymerizable hydrophilic monomers selected from glycerol and other polyhydric alcohols. Combinations of hydrophilic monomers may also be used. Preferably the hydrophilic monomers are sufficiently water soluble to form at least a 1% by weight solution in water.
Preferably the ethylenically unsaturated hydrophilic monomers are mono-unsaturated. Examples of ethylenically unsaturated hydrophilic monomers are, for example, acrylic acid, methacrylic acid, ethacrylic acid, alpha-chloro-acrylic acid, alpha-cyano acrylic acid, beta methyl-acrylic acid (crotonic acid), alpha-phenyl acrylic acid, beta-acryloxy propionic acid, sorbic acid, alpha-chloro sorbic acid, angelic acid, cinnamic acid, p-chloro cinnamic acid, beta-styryl acrylic acid (1-carboxy-4-phenyl butadiene-1,3), itaconic acid, maleic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, fumaric acid, tricarboxy ethylene, 2-acryloxypropionic acid, 2-acrylamido-2-methyl propane sulfonic acid, vinyl sulfonic acid, vinyl phosphonic acid, 2-hydroxy ethyl acrylate, tri methyl propane triacrylate, sodium methallyl sulfonate, sulfonated styrene, allyloxybenzenesulfonic acid, dimethylacrylamide, dimethylaminopropylmethacrylate, diethylaminopropylmethacrylate, vinyl formamide, vinyl acetamide, polyethylene glycol esters of acrylic acid and methacrylic acid and itaconic acid, vinyl pyrrolidone, and vinyl imidazole. Combinations of ethylenically unsaturated hydrophilic monomers may also be used. Preferably, the ethylenically unsaturated hydrophilic monomer is selected from acrylic acid, maleic acid, and itaconic acid.
The polymerizable hydrophilic cyclic monomers may have cyclic units that are either unsaturated or contain groups capable of forming inter-monomer linkages. In linking such cyclic monomers, the ring-structure of the monomers may either be kept intact, or the ring structure may be disrupted to form the backbone structure. Examples of cyclic units are sugar units such as saccharides and glucosides, cellulose ethers, glycerols, and alkoxy units such as ethylene oxide and propylene oxide.
The hydrophilic backbone of the polymer may optionally be substituted with one or more amino, amine, amide, sulfonate, sulfate, phosphonate, hydroxy, carboxyl or oxide groups. The hydrophilic backbone of the polymer may also contain small amounts of relatively hydrophobic units, for example, units derived from polymers having a solubility of less than 1 g/l in water, provided that the overall solubility of the polymer in water at ambient temperature and at a pH of 3.0 to 12.5 is more than 1 g/l, more preferably more than 5 g/l, and most preferably more than 10 g/l. Examples of relatively water insoluble polymers are polyvinyl acetate, polymethyl methacrylate, polyethyl acrylate, polyethylene, polypropylene, and polyhydroxy propyl acetate.
The polymers can be linked by any possible chemical link, although the following types of linkages are preferred:
Preferably the hydrophobic moieties are part of a monomer unit which is incorporated in the polymer by copolymerising hydrophobic monomers and the hydrophilic monomers making up the backbone of the polymer. The hydrophobic moieties for this use preferably include those which when isolated from their linkage are relatively water insoluble, i.e. preferably less than 1 g/l more preferred less than 0.5 g/l, most preferred less than 0.1 g/l of the hydrophobic monomers, will dissolve in water at ambient temperature and a pH of 3.0 to 12.5.
Preferably the hydrophobic moieties are selected from siloxanes, saturated and unsaturated alkyl chains, e.g. having from 5 to 24 carbon atoms, preferably from 6 to 18, most preferred from 8 to 16 carbon atoms, and are optionally bonded to the hydrophilic backbone via an alkoxylene or polyalkoxylene linkage, for example a polyethoxy, polypropoxy or butyloxy (or mixtures of same) linkage having from 1 to 50 alkoxylene groups. Alternatively the hydrophobic moiety may be composed of relatively hydrophobic alkoxy groups, for example butylene oxide and/or propylene oxide, in the absence of alkyl or alkenyl groups. In some forms, the hydrophobic moieties will essentially have the character of a nonionic surfactant.
Examples of hydrophobic monomers include styrene, xcex1-methyl styrene, 2-ethylhexyl acrylate, octylacrylate, lauryl acrylate, stearyl acrylate, behenyl acrylate, 2-ethylhexyl methacrylate, octylmethacrylate, lauryl methacrylate, stearyl methacrylate, behenyl methacrylate, 2-ethylhexyl acrylamide, octylacrylamide, lauryl acrylamide, stearyl acrylamide, behenyl acrylamide, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, 1-vinyl naphthalene, 2-vinyl naphthalene, 3-methyl styrene, 4-propyl styrene, t-butyl styrene, 4-cyclohexyl styrene, 4-dodecyl styrene, 2-ethyl-4-benzyl styrene, and 4-(phenylbutyl) styrene. Combinations of hydrophobic monomers may also be used.
In one embodiment, the polymers of the invention are represented by Structure (I) as follows:
wherein
z is 1;
(x+y):z is from 0.1:1 to 1,000:1, preferably from 1:1 to 250:1; in which the monomer units may be in random order;
y is from 0 to a maximum equal to the value of x; and
n is at least 1;
R1 is selected from the group consisting of xe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94, xe2x80x94CH2xe2x80x94, and xe2x80x94COxe2x80x94NHxe2x80x94 or is absent;
R2 is from 1 to 50 independently selected alkyleneoxy groups, preferably ethylene oxide or propylene oxide groups, or is absent, provided that when R3 is absent and R4 is H or contains no more than 4 carbon atoms, then R2 is an alkyleneoxy group with at least 3 carbon atoms;
R3 is a phenylene linkage, or is absent;
R4 is H or a C1-C24 alkyl or C2-C24 alkenyl group, provided that
a) when R1 is xe2x80x94Oxe2x80x94COxe2x80x94 or xe2x80x94COxe2x80x94Oxe2x80x94 or xe2x80x94COxe2x80x94NHxe2x80x94, R2 and R3 are absent and R4 has at least 5 carbon atoms;
b) when R2 is absent, R4 is not H and when R3 is absent, then R4 has at least 5 carbon atoms;
R5 is H or xe2x80x94COOA4;
R6 is H or a C1-C4 alkyl; and
A1, A2, A3, and A4 are independently selected from the group consisting of H, alkali metals, alkaline earth metals, ammonium bases, amine bases, and C1-C4alkyl.
In one embodiment, the polymers of the invention are represented by Structure (II) as follows:
wherein
Q2 has the Structure (IIa) as follows:
wherein
z and R1-R6 are as defined for Structure (I);
A1-A4 are as defined for Structure (I) or (C2H4O)tH, wherein t is from 1-50, and wherein the monomer units may be in random order;
Q1 is a multifunctional monomer, allowing the branching of the polymer, wherein the monomers of the polymer may be connected to Q1 in any direction or order, therewith possibly resulting in a branched polymer, preferably Q1 is selected from trimethyl propane triacrylate (TMPTA), methylene bisacrylamide or divinyl glycol; n and z are as defined above;
r is 1; and
(x+y+p+q+r):z is from 0.1:1 to 1,000:1, preferably from 1:1 to 250:1; in which the monomer units may be in random order; and preferably either p and q are zero, or r is zero;
R7 and R8 are independently xe2x80x94CH3 or xe2x80x94H;
R9 and R10 are independently substituent groups selected from the group consisting of amino, amine, amide, sulfonate, sulfate, phosphonate, phosphate, hydroxy, carboxyl and oxide groups, preferably xe2x80x94SO3Na, xe2x80x94COxe2x80x94Oxe2x80x94C2H4xe2x80x94OSO3Na, xe2x80x94COxe2x80x94Oxe2x80x94NHxe2x80x94C(CH3)2xe2x80x94SO3Na, xe2x80x94COxe2x80x94NH2, xe2x80x94Oxe2x80x94COxe2x80x94CH3, and xe2x80x94OH.
In one embodiment, the polymers of the invention are represented by Structure (III) as follows:
wherein
x is from 4 to 1,000, preferably from 6 to 250;
n is 1,
z and R1-R6 are as defined in Structure (I), wherein the monomers units may be in random order;
A1 is as defined above for Structure (I) or xe2x80x94COxe2x80x94CH2xe2x80x94C(OH)CO2A1-CH2xe2x80x94CO2A1, or may be a branching point wherein other molecules of Structure (III) are attached.
Examples of molecules having Structure (III) are hydrophobically modified polyglycerol ethers or hydrophobically modified condensation polymers of polyglycerol and citric acid anhydride.
In one embodiment, the polymers of the invention are represented by Structure (IV) as follows:
wherein
z, n and A1 are as defined for Structure (I),
(x+y):z is from 0.1:1 to 1,000 to 1, preferably from 1:1 to 250:1; wherein the monomer units may be in random order;
R1 is as defined above for Structure (I) or R1 is selected from xe2x80x94CH2xe2x80x94Oxe2x80x94, xe2x80x94CH2xe2x80x94Oxe2x80x94COxe2x80x94, and xe2x80x94NHxe2x80x94COxe2x80x94; R2-R4 are as defined in Structure (I);
R11 is selected from the group consisting of xe2x80x94OH, xe2x80x94NHxe2x80x94COxe2x80x94CH3, xe2x80x94SO3A1 and xe2x80x94OSO3A1;
R12 is selected from the group consisting of xe2x80x94OH, xe2x80x94CH2OH, xe2x80x94CH2OSO3A1, COOA1, and xe2x80x94CH2xe2x80x94OCH3.
Examples of molecules having Structure (IV) are hydrophobically modified polydextran, -dextran sulfonates, -dextran sulfates and lipoheteropolysaccharides.
In one embodiment, the polymers of the invention are represented by Structure (V) as follows:
wherein:
z, n and R1-R6 are as defined above for Structure (I); and
x is as defined for Structure (III).
In one embodiment, the polymers of the invention are hydrophobically modified condensation polymers of -hydroxy acids. Examples of suitable polymer backbones are polytartronate, polycitrate, polyglyconate, and mixtures thereof. In another embodiment, the polymers of the invention are hydrophobically modified polyacetals.
In any particular sample of polymer materials in which polymers of the above Structures are in the form of a salt, usually, some polymers will be full salts (A1-A4 all other than hydrogen), some will be full acids (A1-A4 all hydrogen) and some will be part-salts (one or more of A1-A4 hydrogen and one or more other than hydrogen).
The salts of the polymers of the above formulas may be formed with any organic or inorganic cation defined for A1-A4 and which is capable of forming a water-soluble salt with a low molecular weight carboxylic acid. Preferred are the alkali metal salts, especially of sodium or potassium.
It is within the scope of the invention to use the polymer having a hydrophilic backbone and hydrophobic moiety in liquid detergents.
The polymers of the present invention are prepared by processes known in the art such as disclosed in U.S. Pat. No. 5,147,576. Preferably, the polymers are prepared using conventional aqueous polymerization procedures, but employing a process wherein the polymerization is carried out in the presence of a suitable cosolvent and wherein the ratio of water to co-solvent is carefully monitored so as to maintain the ratio of water to cosolvent equal or greater than unity during the reaction, thereby keeping the polymer, as it forms, in a sufficiently mobile condition and to prevent unwanted homopolymerization of the hydrophobic monomer and subsequent undesired precipitation thereof.
The polymers of the invention having a hydrophilic backbone and hydrophobic moieties when used in a powder laundry detergent exhibit enhanced soil suspending properties on organic non-polar and polar soils in wash liquors. Typically such laundry detergents are manufactured by a spray drying process in which surfactants and builders are incorporated into an aqueous crutcher slurry fed into a spray tower. Such processes are ideal for obtaining fluffy, light-density powders (approximately 0.3 g/cm3).
In another embodiment, the powder detergent composition is manufactured in more compact powder detergents which involves removal of inert fillers, control of spray drying to minimize porosity of powder granules, minimization of occluded volumes within both powder granules and the packed powder bed, and reformulation on the basis of the most volume-efficient materials. Compact powders also offers increased opportunities to utilize a wider range of processing techniques. Low-active aqueous solutions can be conveniently used in spray tower processes. In contrast, high-active surfactant forms are required for agglomeration and dry blending.
In another embodiment, the powder detergent compositions are prepared by dry blending which refers to the direct blending of dry powder ingredients. Although the process is quite simple in nature and can produce high-density products, the restrictions for dry forms of surfactant such as powders or flakes severely limits the usefulness of this technique for manufacture of compact detergent powders. In addition, component segregation can occur due to the varying densities of the ingredients. Bulk densities 0.6 g/cm3 are also easily achieved by agglomeration processes. Agglomeration processes, although more complex than drying blending, require less capital investment and are also much less energy intensive than spray-drying. In this case, liquid silicates and/or liquid surfactants such as alcohol ethoxylates act as the agglomeration agent to hold the builder particles together and increase particle size. Various types of agglomeration equipment are available to allow efficient mixing of the liquid and powder ingredients.
In another embodiment, combination processes are used to prepare the powder detergent composition in the form of a compact powder. For example, liquid nonionic surfactants can be sprayed onto spray-dried powders containing only builder or builder and anionic surfactant. By filling the voids within the spray-dried bead, the liquid surfactant, such as alcohol ethoxylate, increases the density of the final product. Similarly, increased density and improved powder flow properties have been reported for a detergent produced by first coating a spray-dried base powder with zeolite followed by spraying with a nonionic surfactant. Higher densities approaching 1.0 g/cm3 are achieved when the spray-dried powder is compressed and then extruded in the presence of non-ionic surfactant. New processes in which fluid bed drying is incorporated long with the spray dryer and agglomerator have also been developed which provide greater flexibility in density and composition.
Examples of surfactants useful in the powder detergent compositions herein typically at levels from about 1% to about 55%, by weight, include the conventional C11-C18 alkyl benzene sulfonates (xe2x80x9cLASxe2x80x9d) and primary, branched-chain and random C10-C20 alkyl sulfates (xe2x80x9cASxe2x80x9d), the C10-C18 secondary (2,3) alkyl sulfates of the formula CH3(CH2)x(CHOSO3xe2x88x92M+)CH3 and CH3(CH2)y(CHOSO3xe2x88x92M+) CH2CH3 where x and (y+1) are integers of at least about 7, preferably at least about 9, and M is a water-solubilizing cation, especially sodium, unsaturated sulfates such as oleyl sulfate, the C10-C18 alkyl alkoxy sulfates (xe2x80x9cAExSxe2x80x9d; especially EO 1-7 ethoxy sulfates), C10-C18 alkyl alkoxy carboxylates (especially the EO 1-5 ethoxycarboxylates), the C10-C18 glycerol ethers, the C10-C18 alkyl polyglycosides and their corresponding sulfated polyglycosides, and C12-C18 alpha-sulfonated fatty acid esters. If desired, the conventional nonionic and amphoteric surfactants such as the C12-C18 alkyl ethoxylates (xe2x80x9cAExe2x80x9d) including the so-called narrow peaked alkyl ethoxylates and C6-C12 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), C12-C18 betaines and sulfobetaines (xe2x80x9csultainesxe2x80x9d), C10-C18 amine oxides, and the like, can also be included in the overall compositions. The C10-C18 N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the C12-C18 N-methylglucamides. Other sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C10-C18 N-(3-methoxypropyl) glucamide. The N-propyl through N-hexyl C12-C18 glucamides can be used for low sudsing. C10-C18 conventional soaps may also be used. If high sudsing is desired, the branched-chain C10-C16 soaps may be used. Mixtures of anionic and nonionic surfactants are especially useful. Other conventional useful surfactants are listed in standard texts.
Builders used in the powder detergent compositions include organic and inorganic builders. The level of builder can vary widely depending upon the end use of the composition and its desired physical form. Granular formulations typically comprise from about 10% to about 80%, more typically from about 15% to about 50% by weight, of the detergent builder. Lower or higher levels of builder, however, are not meant to be excluded.
Inorganic or P-containing detergent builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric metaphosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulfates, and aluminosilicates. However, non-phosphate builders are required in some locales. The detergent compositions function well in the presence of the so-called xe2x80x9cweakxe2x80x9d builders (as compared with phosphates) such as citrate, or in the so-called xe2x80x9cunderbuiltxe2x80x9d situation that may occur with zeolite or layered silicate builders.
Examples of silicate builders are the alkali metal silicates, particularly those having a SiO2:Na2O ratio in the range 1.1:1 to 3.2:1 and layered silicates. NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst. Unlike zeolite builders, the Na SKS-6 silicate builder does not contain aluminum. NaSKS-6 has the delta-Na2 SiO5 morphology form of layered silicate. Other layered silicates, such as those having the general formula NaMSixO2x+1yH2O wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0 can be used herein. Various other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the alpha, beta and gamma forms. Other silicates may also be useful such as for example magnesium silicate, which can serve as a crispening agent in granular formulations, as a stabilizing agent for oxygen bleaches, and as a component of suds control systems.
Aluminosilicate builders are useful in the present invention. Aluminosilicate builders are important in most currently marketed heavy duty granular detergent compositions. Aluminosilicate builders include those having the formula:
Mz[(zAlO2)y].xH2O
wherein
z and y are integers of at least 6, the molar ratio of z to y is in the range from 1.0 to about 0.5, and
x is an integer from about 15 to about 264.
Useful aluminosilicate ion exchange materials are commercially available. These aluminosilicates can be crystalline or amorphous in structure and can be naturally-occurring aluminosilicates or synthetically derived. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In an especially preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula:
Na12[(AlO2)12(SiO2)12].xH2O
wherein
x is from about 20 to about 30, especially about 27. This material is known as Zeolite A. Dehydrated zeolites (x=0-10) may also be used herein. Preferably, the aluminosilicate has a particle size of about 0.1-10 microns in diameter.
Additional builders include the ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy benzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic acid, the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
Citrate builders, e.g., citric acid and soluble salts thereof (particularly sodium salt) can also be used in granular compositions, especially in combination with zeolite and/or layered silicate builders. Oxydisuccinates are also especially useful in such compositions and combinations.
Also suitable in the detergent compositions of the present invention are the 3,3-dicarboxy4-oxa-1,6-hexanedioates and related compounds. Useful succinic acid builders include the C5-C20 alkyl and alkenyl succinic acids and salts thereof. A particularly preferred compound of this type is dodecenylsuccinic acid. Specific examples of succinate builders include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. Laurylsuccinates are the preferred builders of this group.
Fatty acids, e.g., C12-C18 monocarboxylic acids, can also be incorporated into the compositions alone, or in combination with the aforesaid builders, especially citrate and/or the succinate builders, to provide additional builder activity. Such use of fatty acids will generally result in a diminution of sudsing, which should be taken into account by the formulator.
In situations where phosphorus-based builders can be used, and especially in the formulation of bars used for hand-laundering operations, the various alkali metal phosphates such as the well-known sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can be used. Phosphonate builders such as ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates.
The powder detergent compositions may include one or more enzymes. Such enzymes include, for example, lipases, proteases, amylases, peroxidases and the like which are well known in the art. The enzymes may be used together with cofactors required to promote enzyme activity. It should also be understood that enzymes having mutations at various positions (e.g., enzymes engineered for performance and/or stability enhancement) are also contemplated by the invention. Enzymes are normally incorporated at levels sufficient to provide up to about 5 mg by weight, more typically about 0.01 mg to about 3 mg, of active enzyme per gram of the composition.
The detergent compositions may optionally contain bleaching agents or bleaching compositions containing a bleaching agent and one or more bleach activators when formulated appropriately by those skilled in the art. When present, bleaching agents will typically be at levels of from about 1% to about 30%, more typically from about 5% to about 20%, of the detergent composition, especially for fabric laundering. If present, the amount of bleach activators will typically be from about 0.1% to about 60%, more typically from about 0.5% to about 40% of the bleaching composition comprising the bleaching agent-plus-bleach activator.
The bleaching agents used herein can be any of the bleaching agents useful for detergent compositions in textile cleaning, hard surface cleaning, or other cleaning purposes that are now known or become known. These include oxygen bleaches as well as other bleaching agents. Perborate bleaches, e.g., sodium perborate (e.g., mono- or tetra-hydrate) can be used herein.
Another category of bleaching agent that can be used without restriction encompasses percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of meta-chloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid. Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid.
Peroxygen bleaching agents can also be used. Suitable peroxygen bleaching compounds include sodium carbonate peroxyhydrate and equivalent xe2x80x9cpercarbonatexe2x80x9d bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide. Persulfate bleach (e.g., OXONE, manufactured commercially by DuPont) can also be used.
A preferred percarbonate bleach comprises dry particles having an average particle size in the range from about 500 micrometers to about 1,000 micrometers, not more than about 10% by weight of said particles being smaller than about 200 micrometers and not more than about 10% by weight of said particles being larger than about 1,250 micrometers. Optionally, the percarbonate can be coated with silicate, borate or water-soluble surfactants. Mixtures of bleaching agents can also be used.
Peroxygen bleaching agents, the perborates, the percarbonates, etc., are preferably combined with bleach activators, which lead to the in situ production in aqueous solution (i.e., during the washing process) of the peroxy acid corresponding to the bleach activator. The nonanoyloxybenzene sulfonate (NOBS) and tetraacetyl ethylene diamine (TAED) activators are typical, and mixtures thereof can also be used. Bleaching agents other than oxygen bleaching agents are also known in the art and can be utilized herein.
The powder detergent compositions may further comprise at least one additive. Suitable additives may include, for example, dye transfer inhibitors, anticorrosion materials, antistatic agents, optical brighteners, perfumes, fragrances, dyes, fillers, chelating agents, fabric whiteners, brighteners, sudsing control agents, buffering agents, soil release agents, fabric softening agents, and combinations thereof. In general, such additives and their amounts are known to those skilled in the art.
The following nonlimiting examples illustrate further aspects of the invention.

Polymer having a hydrophilic backbone and hydrophobic moieties as soil suspending agent in powder detergents

National Starch and Chemical Investment Holding Corporation


Provided herein is a composition and a method for removing CHG from textiles. The composition is an acid-surfactant-based composition that may be used to remove CHG from a textile that has not been exposed to chlorine subsequent to being exposed to CHG.

Soiled and/or stained textiles, especially hospital garments, have been a consistent and on-going problem for the laundry cleaning industry. For example, since the advent of various skin cleansers and disinfectants, textiles often come into contact with such compositions whereby permanent staining of the textile may result. In the healthcare textile laundries, the use of topical antiseptic agents on patients is of concern as the adjacent textiles, such as gowns and other clothing and bedding, are routinely exposed and stained by said agents.
Common to the market of skin cleansers and disinfectants are compositions that contain CHG, which tends to bind to protein in the stratum corneum of the skin. CHG is an antimicrobial agent that has bactericidal and bacteriostatic mechanisms of action via the disruption of bacterial membranes. It is used in oral rinses and skin cleansers and marketed under a variety of brand names. Because of its antimicrobial capabilities, CHG is often used in hospital settings as a surgical scrub, as a rubbing agent prior to the use of hypodermic or intravenous needles (in place of iodine), and/or as an agent for pre-operatively preparing skin for a medical procedure.
The protein binding characteristic of CHG results in a persistent residue on the surface of the skin, which can come into contact with textiles meant to cover the skin. As a result, CHG may become adsorbed onto the textile, which cannot be removed by washing and/or the application of chlorine bleach; traditional washing in the presence of one or more alkaline detergents and chlorine bleach will fix the CHG to the textile. When textiles stained with compositions containing CHG, are laundered initially in a traditional alkaline detergent wash, followed by a hydrogen peroxide or other similar oxygen-based bleaching solution, the CHG stain is not visible; however, a colorless residue may remain in the textile. If this CHG-bound textile is then ever exposed to chlorine bleach, a permanent dark stain will appear where the CHG is present. This is due to a chemical reaction between CHG and chlorine.
Therefore, a composition and a process are needed that will remove the CHG from textiles completely, thereby allowing for the textile to be laundered with chlorine-based bleaching systems and, for example, in alkaline conditions. Such a composition and process would not result in a permanent stain.

Composition and method for removing stains derived from chlorhexidine gluconate


A stability and, thus, also a quality of mosaic generation is improved by exploiting the advantages of global optimization while giving up performing the optimization fully on the basis of mutual alignment of the image information alone, i.e. on the basis of the result of a search for similarities, but when, additionally, information about error statistics of the capturing device, which took over portion-by-portion capturing of the object plane, is instead also taken into account in the positioning of the subimages in that a secondary constraint (secondary constraint) is set up for the capturing position variables in the optimization problem.

Conventional light microscopy is one of the most widely used and efficient techniques of examining and diagnosing biological samples. However, said techniques are limited by several factors. Stain colors may change or fade over time. This applies particularly to immunofluorescence staining techniques, which are frequently usable during a very short period of time only [14]. Biological samples tend to age. However, slides that are used are unique and cannot be reproduced, e.g. when the slide glass breaks. Unfortunately, microscopes visualize only a small part of a slide at any one time, and the magnifications are limited to the available objectives. Simultaneous viewing of a slide is limited to a very small number of persons, and the slide has to be physically present. In addition, it is not possible to annotate regions of interest on the slide.
One goal of virtual microscopy consists in solving said problems by replacing direct work with the microscope and the slide with utilization of digitized samples. To this end, the slide is scanned once by a fully automated robotic microscope and is digitally stored. Such digitized samples exhibit none of the above-mentioned problems. In addition, it is possible to examine such digitized samples from a distance from any computer as if the sample was physically present. Any regions of interest, for example cancerous cells, can be annotated on the slide, and consequently, it is still possible to understand at a later point in time why a certain examining person made a specific diagnosis. Consequently, in the long term, virtual microscopy may possibly replace traditional microscopy.
However, there are still problems that have not been entirely solved. One of said problems consists in the need to correctly register (align) any fields of view in biological samples with larger areas of no information content, such as samples from cytometry. A slide is simply too large to be detected with one image at a reasonable magnification. One may imagine, for example, the case of a 20-fold magnification and of a typical color camera producing a 1000×1000 pixel image and comprising a cell size of 7.4 μm×7.4 μm. This would mean that each pixel covered an area of 0.37 μm×0.37 μm, and that each field of view had an area of 0.37 mm×0.37 mm. Of course, this depends on the type of sample being scanned, but to simply give an example, the valid area to be scanned may be 2 cm×3 cm, for example, which would mean that about 55×82=4510 fields of view would have to be detected. The scanning operation of the slide to be virtualized is typically performed by computer-controlled, motorized positioning tables (stages) which, additionally, may be accurately calibrated. However, irrespective of the degree of precision of their calibration, positioning tables will invariably have positioning errors which may accumulate, in turn, during the scanning operation and may consequently result in alignment errors in the virtual image of the slide. As a result, a great challenge in virtual microscopy is to develop algorithms which mutually align any detected fields of view in such a manner that the originally scanned slide is fully reconstructed.
The conventional approach to stitching fields of view in the manner of a mosaic (mosaicing) consists in scanning the slide in a first step and, in a second step, to align each field of view with its neighboring fields of view, which is sometimes followed by an optimization step. In a naïve approach, the fields of view are simply mutually aligned one after the other in the sequence in which they have been detected. It is better to take into account the mosaic by optimization while considering the interaction effects between the change in the relative locations of two fields of view on the matching of the other field-of-view pictures.
In other words, in virtual microscopy there is the problem of joining (stitching) adjoining microscopic views to form a contiguous larger image also referred to as a mosaic. A microscope slide is digitized in that a computer-controlled stage is displaced in a controlled manner, a picture being taken following each displacing operation. The stage is displaced by a defined travel in each case, so that the next field of view either directly borders on the preceding one or overlaps the preceding one in a defined manner. However, the mechanics of microscope stages is inaccurate, so that there will be mispositionings. Therefore, the captured fields of view are typically registered toward one another on the part of software in a second step. In this context, different similarity measures such as area-based SSD or cross-correlation or least squares correlation as well as feature-based measures are employed. The precise positioning offset, or the transform between two images, is determined by determining the position in which the similarity measure reaches its maximum in the overlap area.
The transforms thus determined may be used for stitching the mosaic in a sequential manner, such as in the shape of a meander. However, since registration determination on the part of software is also faulty, such an approach will see an accumulation of alignment errors, and there will be a visual offset of the fields of view in the mosaic.
The need for a comprehensively operating optimization scheme becomes obvious when considering three images which have been aligned against one another and thus result in three transforms such as translational displacements about an offset vector in order to mutually align the three images correctly. In a perfect environment, said transforms will result in an overdetermined but consistent equation system: when concatenated they will result in an identity transform. However, since the transforms are measurements on real-world images exposed to noise and other deteriorations, the transforms will be susceptible to errors. The idea of optimization consists in minimizing the average measurement errors, for example by equally distributing same over all of the transforms.
There are several approaches which try to solve the problem that misalignments may accumulate in the event of a sequential alignment of the subimages. As was described above, the transforms should not only be taken into account sequentially, but the transforms from all of the overlap areas should be taken into account, such as in [7], for example. In this context, an equation system is set up which may be solved by means of an equalization calculation or other optimization methods. The technique described in [6] also falls into the category of said approaches.
Since the transforms determined are based on observations, not all of them are exact. Any solution of an equation system thus disturbed will therefore still be erroneous. An approach which minimizes said errors would be desirable.
Some works have already comprehensively addressed the problem set forth above. Said mosaicing algorithms may typically be categorized into two separate steps. In the first step, neighboring images are aligned in a pairwise manner by applying an area-based or feature-based registration algorithm. In a second step, the transform parameters thus estimated are then bundle-adjusted to obtain a globally consistent transform space. Szeliski [3] has presented an authoritative survey of both local and global image stitching methods. However, Szeliski's focus is on aligning multiple viewpoint images and producing panoramic images under affine transform constraints. However, this poses a more general problem than arises in virtual microscopy, where the transform space of the images is strictly translational. Consequently, in virtual microscopy, more specialized mosaicing algorithms may be used in order to obtain an optimum mosaic.
Davis [4] addresses the stitching of scenes with moving objects. Davis obtained a system of linear equations from pairwise alignments and solved the system by using a least squares approach to obtain a globally optimized transform space. What is problematic about Davis' approach is that by solving the system in a least error squares sense, Davis distributes the error equally over all transforms. However, this is justified only if the error in the transforms is strictly Gaussian in shape, which is not always the case. Kang et al. [5] proposes a graph-theoretic approach for global registration of 2D mosaics under projective secondary transform constraints. Surprisingly, there are only few articles directly dealing with stitching virtual slides. Sun et al. use feature matching with the Harris Corner detector and perform global geometric correction with an objective function which minimizes the Euclidean distance between the feature points when the transform is applied [6]. Appleton et al. address the image stitching problem as a global optimization problem [7]. They use dynamic programming and a similarity function in order to place a complete row of images with previously placed rows at a point in time. However, since they place only one row at a time, this is only partly a global optimization, which, in order to be complete, would involve placing all of the images at once. In addition, the process presented there would use an overlap of 45% between the images in order to achieve good results. This, again, results in a very long scan time. In [8], Davis' [4] idea of producing a linear equation system was used for the optimization problem and was weighted by weighting each transform according to its reliability. Consequently, the equation system was solved in a weighted least error squares sense. This approach entailed objectively improved results as compared to the unweighted approach. However, under specific conditions, even the latter approach still exhibits errors. It is mostly with slides having significantly large areas of low information content and, consequently, low correlation values that some of the subimages in these areas are not correctly repositioned.
In [14], a method of automatically creating a virtual microscope slide is described. Images are positioned exclusively on the basis of the erroneous positioning properties of the stage.
In [18], a method of software-related registration of virtual microscope slides is described. However, what is registered is only ever that part of the microscope slide which is currently rendered on the screen. Mosaic registration is effected sequentially.
In [17], a system of digitizing slides is described, but no registration algorithmics.
In [15], a method of automatically creating a virtual microscope slide is described. The system creates a microscope slide in that each image is automatically registered with the preceding one. A correction value is calculated from the offset information in terms of control engineering, and the stage is displaced in a corrected manner for capturing the next image. By using this method, a relatively precise virtual microscope slide may be created even by means of relatively imprecise stages. The accuracy of the stage is therefore taken into account, specifically in order to correct the stage in terms of control engineering. Mosaic registration is effected sequentially.
It would be desirable to have a concept for generating a mosaic picture of an object plane which functions in a more stable and, thus, in a qualitatively improved manner.

Fraunhofer-Gesellschaft zur Foerderung der angewandten Forschung e.V.


An optical measurement system includes an integrating sphere having a reflecting surface on its inner wall and having a first window. The optical measurement system further includes a support member for supporting a light source at a substantially central position of the integrating sphere, and a first baffle arranged on a line connecting the first window and the light source supported by the support member. The support member is connected, in a region opposite to the first window with respect to the light source, to the inner wall of the integrating sphere.

As a typical apparatus for measuring the total luminous flux emitted from a light source, a photometer including an integrating sphere is known. The integrating sphere has on its inner wall a reflecting surface formed by application of a diffuse reflecting material (such as barium sulfate or PTFE (polytetrafluoroethylene) for example). A light source to be measured (hereinafter also referred to as "sample light source") is lit in the state of being arranged in this integrating sphere. The luminous flux emitted from the light source is repeatedly reflected from the reflecting surface of the integrating sphere's inner wall and accordingly the illuminance on the integrating sphere's inner wall is made uniform. The fact that the illuminance which has thus been made uniform is proportional to the total luminous flux emitted from the light source is utilized to measure the total luminous flux of the light source. Since the total luminous flux measured by such a photometer is commonly a relative value, the value of the total luminous flux is compared with a detected value (standard value) obtained by using a known standard light source to thereby measure a calibrated value of the total luminous flux emitted from the sample light source.
The photometer including such an integrating sphere cannot avoid absorption of light by parts such as a support member used for arranging the light source in the integrating sphere and a light shielding plate (baffle) used for preventing the light from the light source from directly irradiating a photodetector. Further, the sample light source itself absorbs light.
In order to address such light absorption, Japanese Industrial Standards JIS C 8152: 2007, "Measuring Methods of White Light Emitting Diode (LED) for General Lighting," Jul. 20, 2007 (NPL 1) discloses that a factor for correcting for self absorption of a sample light source (self absorption correction factor) is used. This self absorption correction factor is calculated in the following manner. A light source for measuring self absorption (typically incandescent or tungsten halogen lamp) is provided in an integrating sphere. Under respective conditions that the sample light source is arranged in the integrating sphere and the sample light source is not arranged in the integrating sphere, the light source for measuring self absorption is lit. The values detected under respective conditions are compared with each other to thereby calculate the self absorption correction factor.
Further, with the purpose of avoiding influences of light absorption by the support member for example, a photometer including a hemispherical integrator (hereinafter also referred to as "integrating hemisphere") like the one disclosed in Japanese Patent Laying-Open No. 06-167388 (PTL 1) has been proposed (the photometer will also be referred to as "hemisphere photometer" hereinafter). This hemisphere photometer has, instead of the integrating sphere, an integrating hemisphere made up of a hemispherical portion having a reflecting surface formed on its inner wall and a circular mirror plate arranged so that its reflecting surface covers the opening of the hemispherical portion. A light source is disposed at the center of the mirror plate so that the center of the light source coincides with the center of curvature of the hemispherical portion.
In such a configuration, the light source and a virtual image of the light source generated by the minor plate are each present in an imaginary integrating sphere (a composite space made up of the real space in the hemispherical portion and the virtual image of the hemispherical portion). Namely, the hemisphere photometer enables the sample light source to be arranged in the imaginary integrating sphere without using the support member for supporting the light source. An error due to absorption of light by the support member for example can thus be reduced.

Optical measurement system, optical measurement method, and mirror plate for optical measurement system


A semiconductor module includes a base plate made of a metal, an insulating frame provided on a peripheral edge portion of the base plate, a lead made of a metal and provided on the frame, and a semiconductor device mounted on the base plate in a space surrounded by the frame, wherein the frame is fixed to the base plate by a bonding material containing silver, the frame has concave portions formed in an inner portion which is a corner portion on a space side and an outer portion which is a corner portion on a side opposite to the inner portion in a surface thereof which faces the base plate, and the concave portions are filled with a coating material.

1. Field of the Invention
The disclosure relates to a semiconductor module and a semiconductor device container.
2. Background Arts
Conventionally, a configuration which includes a base made of a metal, an insulating frame provided on the base, and a lead terminal provided on the frame and in which a semiconductor device is mounted in an opening portion of the frame is known as a semiconductor module (for example, refer to Japanese Unexamined Patent Publication No. H10-163353).
In the semiconductor module described above, a frame is fixed to the base by, for example, a solder containing silver. In such a configuration, when an electric field is present between a lead and the base, especially in high humidity, ion migration in which an ionized metal moves on a surface of a substance in the electric field occurs. When ion migration occurs, and metal ions which have been moved by the electric field return to a metal from the ionized state for some reason, the metal is accumulated, and thus dendrites (dendritic crystals) may be generated. When the dendrites grow, a short circuit occurs between electrodes, and there is a possibility that a circuit or a semiconductor may be eventually destroyed.
Therefore, one aspect of the disclosure is to curb occurrence of ion migration.

Semiconductor module and semiconductor device container

SUMITOMO ELECTRIC DEVICE INNOVATIONS, INC.


Metal panel roofs, and load support structures for supporting loads on such roofs. Side rails provide primary support for loads on such roofs. The side rails can be fabricated from sheet metal or can be extruded. A side rail includes a standing seam cavity which is lowered, and covers, the standing seam. Side walls of the standing seam cavity. An upstanding web extends up from the cavity, and lower shoulders may extend laterally, optionally downwardly, from the walls which define the cavity, on either one side, or both sides, of the cavity. Building roof insulation can extend up through an aperture in the roof, surrounded by such load support structure, and extend up to the top of the side rail, thus providing a thermal break between the load support structure elements and the space surrounded by the load support structure.

Various systems are known for supporting loads on roofs, and for installing skylights and/or smoke vents into roofs.
Commonly used skylighting systems have translucent or transparent closure members, also known as lenses, mounted on a support structure which extends through an aperture in the roof and is mounted to building support members inside the building. Ambient daylight passes through the lens and thence through the roof aperture and into the building.
Thus, conventional skylight and smoke vent installations use a complex structure beneath the exterior roofing panels and inside the building enclosure, in order to support a curb which extends through the roof and supports the skylight lens. Conventional skylight curbs, thus, are generally in the form of a preassembled box structure surrounding an aperture which extends from the top of the box structure to the bottom of the box structure. Such box structure is mounted to building framing members inside the building enclosure, and extends through a respective aperture in the roof, similar in size to the aperture which extends through the box structure while accounting for the thickness of the elements of the box structure. The skylight assembly thus mounts inside the building enclosure, and extends through an aperture in a separately mounted roof structure. Fitting skylight assemblies into such roof aperture, in a separately-mounted roof structure, presents problems in that all known conventional structures have a tendency to leak water when subjected to rain.
In light of the leakage issues, there is a need for a more effective way to support skylights and smoke vents, thus to bring daylight into buildings.
To achieve desired levels of daylighting, conventional skylight installations use multiple roof apertures spaced regularly about the length and width of a given roof surface through which daylight is to be received. Each skylight lens is installed over a separate such aperture; and the aperture for each such skylight assembly, each representing a single lens, extends across multiple elongate metal roof panels.
The opposing sides of conventional metal roof panels, to which skylight assemblies of the invention are mounted, are elevated above elongate centralized panel flats which extend the lengths of the panels, whereby the sides of adjacent such roof panels are joined to each other to form elongate elevated joints, referred to herein as elevated ribs. The aperture for a conventional skylight cuts across multiple such elevated ribs in order to provide a large enough aperture to receive conventionally-available commercial-grade skylight assemblies. The skylight assembly, itself, includes a curb which is mounted inside the building and extends, from inside the building, through the roof aperture and about the perimeter of the aperture, thus to support the skylight lens above the flats of the roof panels, as well as above the elevated ribs. Conventional pliable tube construction sealants are applied about the perimeter of the roof aperture, between the edges of the roof panels and the sides of the skylight assembly curb, including at the cut ribs. Typically, substantially all of such sealant is applied in the panel flats, which means that such sealant is the primary barrier to water leakage about substantially the entire perimeter of the skylight curb. One of the causes of roof leaks around the perimeter of conventional roof curbs which attach primarily through the panel flat at the water line are due to foot traffic, such as heel loads or other dynamic loads imposed by workers wheeling gas cylinders or other heavy equipment on the roof panel e.g. with dollies. This type of dynamic loading can cause high levels of stress on the joints that rely solely on mastic to provide seals in the wet areas, namely in the panel flats. Such leaks are common around fastener locations as the panels flex under load and cause the sealant to deform such that, in time, passages develop through the sealant, which allows for the flow of water through such passages, thus developing the above-mentioned leaks.
Such multiple curbs, each extending through a separate roof aperture, each sealed largely in the panel flats, create multiple opportunities for water to enter the interior of the building. Applicants have discovered that such opportunities are influenced by, without limitation,                (i) the number of individual apertures in the roof,        (ii) the widths of the apertures, which require cuts through the multiple ribs,        (iii) the tendency of water to collect and stay at the upper end of an aperture,        (iv) the disparate expansion and contraction of the roof panels relative to the skylight curb; and        (v) the lengths of sealed seams in the panel flats.
The traditional curb constructions and methods of attachment in most cases thus require that a complicated support structure be installed below the metal roofing and inside the building enclosure, and supported by the building structural support system which allows disparate/discordant movement of the metal roof panels and the skylight assembly relative to each other, as associated with thermal expansion and contraction of the metal roof and the building structural support system e.g. in response to differences in temperature changes inside and outside the building.
In addition, conventional curb-mounted skylights tend to accumulate condensation, especially about fasteners which extend from the outside of the building to the inside of the climate-controlled building envelope.
Thus, it would be desirable to provide a skylight system which provides a desired level of daylight in a commercial and/or industrial building while substantially reducing the incidence/frequency of leaks occurring about such skylights, as well as reducing the incidence/frequency of condensate accumulation in the areas of such skylights.
It would also be desirable to provide a smoke vent system or other roof penetration while substantially reducing the incidence/frequency of leaks occurring about such smoke vents or other roof penetrations, as well as reducing the incidence/frequency of condensate accumulation in the areas of such roof penetrations.
It would further be desirable to provide a support system, suitable for supporting roof loads, up to the load-bearing capacity of the metal roof while substantially controlling the tendency of the roof to leak about such support systems, as well as reducing the incidence/frequency of condensate accumulation in the areas of such closure support systems.


An advanced sputter target is disclosed. The advanced sputter target comprises two components, a porous carrier, and a metal material disposed within that porous carrier. The porous carrier is designed to be a high porosity, open cell structure such that molten material may flow through the carrier. The porous carrier also provides structural support for the metal material. The cell sizes of the porous carrier are dimensioned such that the capillary action and surface tension prohibits the metal material from spilling, dripping, or otherwise exiting the porous carrier. In some embodiments, the porous carrier is an open cell foam, a weave of strands or stacked meshes.

Various types of ion sources may be used to create the ions that are used in semiconductor processing equipment. For example, an indirectly heated cathode (IHC) ion source operates by supplying a current to a filament disposed behind a cathode. The filament emits thermionic electrons, which are accelerated toward and heat the cathode, in turn causing the cathode to emit electrons into the arc chamber of the ion source. The cathode is disposed at one end of an arc chamber. A repeller is typically disposed on the end of the arc chamber opposite the cathode. The cathode and repeller may be biased so as to repel the electrons, directing them back toward the center of the arc chamber. In some embodiments, a magnetic field is used to further confine the electrons within the arc chamber.
In certain embodiments, electrodes are also disposed on one or more side walls of the arc chamber. These electrodes may be positively or negatively biased so as to control the position of ions and electrons, so as to increase the ion density near the center of the arc chamber. An extraction aperture is disposed along another side, proximate the center of the arc chamber, through which the ions may be extracted.
In certain embodiments, it may be desirable to utilize a feed material that is in solid form as a dopant species. For example, the solid feed material may serve as a sputter target. Ions strike the solid feed material, emitting neutrals of the feed material, which can then be ionized and energized in a plasma and used for deposition or implantation. However, there are issues associated with using solid feed materials. For example, in the high-temperature environment of an IHC ion source, metal sputter targets are prone to melting, dripping, and generally degrading and destroying the arc chamber as liquid metal runs and pools in the arc chamber. As a result, ceramics that contain the dopant of interest are commonly used as the solid dopant material, because they have higher melt temperatures. However, these ceramic materials typically generate less beam current of the dopant of interest. If the metal sputter target could maintain its shape without dripping or deformation upon melting, significant increases in dopant beam current could be realized.
Therefore, an advanced sputter target that may be used within an ion source without these limitations would be beneficial. Further, it would be advantageous if the ion source was not contaminated by the advanced sputter target.

Advanced sputter targets for ion generation


A thermosetting resin composition has good storage properties at room temperature and an unreacted epoxy resin etc. are less likely to exude therefrom during heat compression molding. The thermosetting resin composition contains an acrylic copolymer including an epoxy group-containing (meth)acrylate unit, an epoxy resin, and a curing agent for an epoxy resin. In this thermosetting resin composition, epoxy groups in at least the acrylic copolymer are partially cross-linked with an amine compound and a thiol compound having 2 to 4 thiol groups per molecule, and the curing agent for an epoxy resin is an organic acid dihydrazide.

An adhesive used for applications of flexible printed circuit (hereinafter referred to as an "FPC") boards contains, as a curable component, a mixture of an epoxy resin and a curing agent for an epoxy resin. The adhesive further contains, for example, acrylonitrile-butadiene rubber (or Nitril-Butaadiene Rubber, hereinafter referred to as "NBR") in order to improve the peel strength of the adhesive and to impart flexibility to the adhesive. Nitrile rubber including carboxyl groups crosslinkable with an epoxy resin is widely used as the above NBR in order to obtain favorable soldering heat resistance (see Patent Literature 1).
The adhesive composition used for the FPC applications contains a large amount of epoxy resin, and this causes a problem in that a large amount of unreacted epoxy resin etc. exudes during thermal compression molding and clogs openings provided in a cover lay, a reinforcing plate, etc.
Patent Literature 2 proposes a method for preventing exudation of an adhesive composition through openings by adding an ultraviolet (UV) curable resin to the adhesive composition and applying ultraviolet rays to the openings to cure the ultraviolet curable resin.
However, in the technique described in Patent Literature 2, the step of applying ultraviolet rays is additionally provided. Therefore, capital investment for the UV application step and special storage conditions for avoiding UV rays during storage are necessary.
Accordingly, to improve the storage conditions, the applicant used a thermosetting resin composition containing a prescribed acrylic copolymer, an epoxy resin, and a curing agent for an epoxy resin (Patent Literature 3). More specifically, the applicant used, as the curing agent, an organic acid dihydrazide having a prescribed particle diameter.

Thermosetting resin composition, thermosetting adhesive sheet, and method of producing thermosetting adhesive sheet


Methods are described for the identification of genes useful for conferring tolerance in plants to abiotic stress. Transgenic plants and seeds comprising the stress tolerant genes are also described. Methods to monitor the growth rate of the transgenic plants under stressed or non-stressed conditions are also described.

Abiotic stress is the primary cause of crop loss worldwide, causing average yield losses of more than 50% for major crops (Boyer, J. S. (1982) Science 218:443-448; Bray, E. A. et al. (2000) In Biochemistry and Molecular Biology of Plants, Edited by Buchannan, B. B. et al., Amer. Soc. Plant Biol., pp. 1158-1203). Among the various abiotic stresses, drought, salinity and extreme temperature are major adverse environmental factors that limit crop productivity worldwide. Water stress in its broadest sense encompasses both drought and salinity or osmotic stress. The abiotic stresses of drought, salinity and freezing are linked by the fact that they all decrease the availability of water to plant cells. This decreased availability of water is quantified as a decrease in water potential. Plants resist low water potential and related stresses by various mechanisms such as the following: by modifying water uptake and loss to avoid low water potential; by accumulating solutes and modifying the properties of cell walls to avoid the dehydration induced by low water potential; and by using protective proteins and mechanisms to tolerate reduced water content by preventing or repairing cell damage. Salt stress also alters plant ion homeostasis (Verslues P. E. et al., (2006) Plant Journal, 45, 523-539; Koiwa, H. et al. (2006) J Exp Botany, 57(5):1119-1128; Rodriguez, M. et al. (2005) Biotecnologia Aplicada, 22:1-10).
Drought and salt stress, together with low temperature, are major problems for agriculture because these adverse environmental factors prevent plants from realizing their full genetic potential. Abiotic stress leads to a series of morphological, physiological, biochemical and molecular changes that adversely affect plant growth and productivity. Reviews on the molecular mechanisms of abiotic stress responses and the genetic regulatory networks of drought stress tolerance have been published (Valliyodan, B., and Nguyen, H. T., (2006) Curr. Opin. Plant Biol. 9:189-195; Wang, W., et al. (2003) Planta 218:1-14; Vinocur, B., and Altman, A. (2005) Curr. Opin. Biotechnol. 16:123-132; Chaves, M. M., and Oliveira, M. M. (2004) J. Exp. Bot. 55:2365-2384; Shinozaki, K., et al. (2003) Curr. Opin. Plant Biol. 6:410-417; Yamaguchi-Shinozaki, K., and Shinozaki, K. (2005) Trends Plant Sci. 10:88-94).
The application of transgenic technology, through either over- or under-expression of the transgenes, is a powerful tool for the engineering of stress-tolerant crop plants. Enhancement of resistance against abiotic stresses may also be achieved via traditional breeding, molecular breeding, and transgenic approaches.
There is a need for methods to identify plants resistant to realistic and reproducible stress conditions and which can be applicable to analyzing large numbers of lines. Such methods are important in order to develop more efficient screening procedures for germplasm evaluation and improvement of stress tolerance. Preferably, rapid and reliable screening procedures are desirable. Moreover, under natural conditions, plants rarely experience single stress factors one by one, but are much more likely to be exposed to multiple stresses simultaneously. Few studies have attempted to investigate plant responses under multiple stresses, either in the laboratory or the field. The response of plants to multiple stress combinations cannot always be extrapolated from responses to individual stress factors (Holopainen, J. K. et al. (2010) Trends Plant Sci. 15(3):176-184).

Methods for the identification of genes involved in abiotic stress tolerance in plants


The new method uses synthetic glycopeptides such as MDP and GMDP as immunological adjuvants which according to this invention are added to the antigen in purely aqueous solution in the low doses discovered to evoke the maximum production of antibody output and whereby the adjuvant is present in dry form with L-proline added for better reproducibility of experiments by minimizing adsorptive losses at the walls of the glass vials.

If an immune response is attempted in vertebrates including man by injecting antigens for the purpose of generating antibodies, be it for the protection of health by vaccination or for commercial use, the assistance of additives, called adjuvants, is often indispensable because in many cases the immune response is quite feeble.

Method for increasing the yield of antibodies in the techniques of immunology