An electrochromic device including an electrochromic stack and a support, the electrochromic stack successively including: a first current collector; a first electrochromic electrode; an electrolyte; a second electrochromic electrode; a second current collector. The support and the electrochromic stack are separated by a dielectric layer and a heating system in contact with the support. Further, the heating system is sized to modify at least one of the optical characteristics of the electrochromic device.

Generally, an electrochromic device is capable of modulating the optical properties (transmittance and/or reflectance and/or absorbance) when an electric field is applied thereacross. More specifically, it comprises at least one active electrochromic electrode capable of ensuring a reversible change of optical state on application of an electric charge.
A conventional electrochromic device generally comprises a support successively supporting (FIG. 6):
a first current collector (4);
a first electrochromic electrode (11);
an electrolyte (12);
a second electrochromic electrode (13); and
a second current collector (6).
At least one of the electrochromic electrodes is optically active. It enables to modulate the optical properties of an electromagnetic radiation applied to the device. Such an optical state switching is obtained by application of an electric field across the electrochromic device.
The used electrochromic materials may be organic, inorganic, or hybrid. Their nature enables to pass from one optical state to another by insertion or deinsertion of cations. Such a cation transport is easier when the cations are small; they generally are protons (H+) or lithium ions (Li+).
As already indicated, the change of optical state is triggered by application of an electric field across the electrochromic device; this property enables to modulate the reflection and the transmission of an electromagnetic radiation having a wavelength which may vary according to the range of application. Thus, the visible UV range may correspond to applications of electrochromic window type, while the infrared range may correspond to an application of heat management type.
As already indicated, electrochromic devices comprise two electrochromic electrodes. Typically, the second electrochromic electrode enables to store cations. It may be transparent (optically passive), whatever the cation flow. It may also act as a complementary electrode and have an optical state (transparent, colored . . . ) identical to that of the first electrode but with an inverse cation flow.
Electrochromic devices having this second type of configuration (complementary electrode) are generally preferred, given that they improve the optical perception of the change of optical state (contrast). For example, the first electrode may be made of a WO3 material while the second electrode may be made of NiO. This couple of materials allows the following electrochemical reactions:WO3+xLi+ (transparent)←→LixWO3 (colored)LixNiO (transparent)←→NiO+xLi+ (colored)
Generally, electrochromic materials allow a reversible bistable change of optical state when a voltage is applied across the electrochromic device. In other words, such materials have two steady states, and require no power input to be maintained in one of the two states.
The performance of electrochromic devices is particularly assessed by means of the following indicators:                contrast: the difference between the maximum and the minimum of the optical response of the device. The higher the contrast, the more effective the device is considered.        optical density: the quantity of charges to be brought to the system to switch, that is, to pass from the minimum state to the maximum state or conversely. For an equal charge, the greater the optical transformation, the more effective the device is considered.        switching time: the time necessary for the device to ensure the passing from one optical state to another, which is fixed for a given contrast. The shorter the switching time, the more effective the device is considered.
All-solid electrochromic devices operating by insertion of cations (Li+ for example) within inorganic materials may have relatively long switching times. Indeed, Li+ cations are less mobile than protons. Further, an all-solid electrolyte has a lower ion conductivity than a liquid electrolyte. Accordingly, the cation migration kinetics is slower, which lengthens the switching time.
As an example, document U.S. Pat. No. 7,265,890 describes an all-solid inorganic electrochromic device operating by insertion of Li+ cations in the infrared range. It comprises a first electrochromic electrode, an electrolyte, and a second transparent electrochromic electrode behaving as an Li+ cation storage electrode.
Such an electrochromic device is typical of prior art configurations. The second electrochromic electrode is a transparent cation storage electrode, which is thus optically passive. Generally, it has a cation storage capacity larger than that of the first electrochromic electrode forming the active electrode.
Typically, the quantity of cations (Li+ for example) injected into the storage electrode corresponds to the maximum capacity of cations which can be reversibly inserted into the available thickness and de-inserted therefrom.
The saturation of the storage electrode enables to compensate for a possible loss of cations during the cycling (insertion irreversibility). It further enables to improve the chemical stability of the device by anticipating the possible oxidation of part of the cations, which might cause a failure of the device.
Anyhow, prior art electrochromic devices are generally not compatible with a use in extreme temperature conditions, given that the temperature of use has an effect on the contrast and the switching time.
The present invention provides solving this technical problem due to the use of electrochromic devices at negative temperatures.

Electrochromic device comprising an integrated heating system

Commissariat A L'Energie Atomique et aux Energies Alternatives


A system for injecting an additive within a fuel storage tank or the fuel tank (10) of a vehicle (12) including an additive injector (22) mounted within the tubular inlet (14) of the fuel tank (10). The additive injector (22) includes an additive pump (46) driven by impeller blades (50) on an end of a pump shaft (48). The fuel discharged from the fuel nozzle (58) strikes the blades (50) to rotate the impeller (47) of pump (46) for dispensing the additive. The additive container (51) has an additive line (56) extending to a pump (46) for the supply of additive thereto for discharge from additive nozzle (54) into the flowing fuel stream. The additive is blended with the flowing fuel stream when discharged. The additive injector (22) may be utilized as a retrofit unit on an existing fuel tank by the removal of fuel tank cap (18) and the insertion of additive dispenser (22) within the tubular inlet (14). The additive container (51A) in an alternative embodiment is positioned in the fuel tank (10A) at the bottom of the body (24A) of the additive dispenser (22A).

Heretofore, additives have normally been dispensed into a fuel tank by emptying the contents of a container within a full fuel tank. However, different amounts of fuel are normally used when a fuel tank is filled, because the tank is not normally completely empty. Also, at times, an additive may not be injected when the tank is filled. Thus, an accurate amount of an additive for each gallon of fuel added to a tank is very difficult to achieve.
It is desirable to inject a predetermined amount of additive with fuel into an underground storage tank or a vehicle fuel tank on a regular continuous basis. The term "vehicle" is used in this specification to include mainly trucks and automobiles, but it also includes any machine that has a fuel tank which supplies fuel to an engine. Thus, as used herein, the term vehicle includes boats, airplanes, motorcycles and even motor/generator sets powered by gasoline or fuel oil or irrigation pumps, and the like which do not translate from point to point on the earth. Also, it is desirable that a predetermined amount of the additive be added to the fuel while the fuel is pumped into the fuel tank so that a precise proportion of the additive relative to the fuel be added to the fuel as the fuel is pumped into the fuel tank.

System for injecting additive within a fuel tank


A horizontal transporter at a roving frame level delivers full bobbins to a vertical movable carriage which picks up the bobbins from the bottom, replaces them with core sleeves, and lodges the bobbins in a second horizontal transporter at another story for the ring spinning units. The bobbin and core sleeves are always engaged from above by the horizontal transporters and remain erect when engaged from below by the vertical transporter.

A spinning factory in which two distinct levels or stories are provided and roving bobbins are transported between these levels, is described in EP 0 306 450 B1. In that system, a belt conveyor interconnects the upper and lower levels and at the upper level the bobbins are suspended, i.e. engaged from above by hangers, whereas at the lower level, the bobbins are supported from below on a horizontal conveyor belt.
There also may be systems available in which, between the levels, the bobbins or the core sleeves must be so reoriented that they are brought from an upright position into a horizontal or prone position and vice versa.
All of these systems are relatively complex, require expensive equipment and high maintenance and installation costs. The systems may not be easily compatible with the horizontal transporters or may not be easily accommodated to the requirements of horizontal transporters used in spinning plants.

Method of and apparatus for transporting full bobbins and empty bobbin cores


An image pickup apparatus capable of creating various composite images easily, and also obtaining composite images such as would be obtained at different shutter speeds even after the frame images were picked up. Successive frame images of an object are picked up in a successive image-pickup mode at predetermined time intervals. The predetermined number of frame images obtained are then stored in time series in a buffer memory. Pointers indicating composition start and end positions slidable on a bar of a range selector specify therebetween a composition range in which some successive ones of the predetermined number of frame images fall on a composing picture. The respective frame images falling in the specified range are read from the buffer memory and processed, thereby producing a composite image. In this case, by changing the composition range with the range selector, a composite image such as would be obtained at a different shutter speed is displayed on a composite result display picture.

The present invention relates to image pickup apparatus such as, for example, digital cameras and more particularly to image pickup apparatus, methods and programs with a function to create a composite image from a plurality of frame images.
Some prior-art image pickup apparatus such as digital cameras have a composite-image creating function. For example, Published Unexamined Japanese Patent Application 11-205666 discloses picking up images of objects near and far such as a person (as a central object) and a landscape present behind the person (as a background object) by setting strobe-light emission quantities optimal to the respective objects, extracting optimal-brightness image portions from the respective images, and then combining them into a composite image.
Published Unexamined Japanese Patent Application 5-224285 discloses a multi-image pickup technique for creating such a composite image in which the position of an image of an object picked up previously is indicated specifically within a finder, thereby preventing superimposition of an image of an object to be picked up next on the image of the object picked up previously.
The above prior-art image pickup apparatus, however, simply creates a composite image by combining a predetermined number of (usually, two) images respectively picked up, and cannot create various composite images in such a manner that each composite image is obtained by combining any number of successive ones selected from a plurality of frame images successively picked up.
A prior-art image pickup apparatus of this type is capable of adjusting the shutter speed to any desired value for pickup purposes. However, once a shutter speed is determined, images such as would be obtained at various shutter speeds cannot be obtained.
It is therefore an object of the present invention to provide an image pick up apparatus, image processing method and program capable of creating various composite images easily using a plurality of images obtained in the successive image pickup, and also creating various images such as would be obtained at different shutter speeds even after the image pickup has been completed.

Image pickup apparatus, method and program with composite-image creating function


A diazonium salt represented by the following general formula (1) and a thermal recording material using the diazonium salt:

1. Field of the Invention
The present invention relates to a diazonium salt and a thermal recording material using the same. More particularly, the invention relates to a diazonium salt featuring good storage stability and light fixation properties with respect to light having a long wavelength of more than 400 nm and also being useful as a synthesis intermediate for azo dye, an analytical reagent and a material for thermal recording material, as well as to a thermal recording material comprising the diazonium salt and a coupler as color forming components.
2. Description of the Related Art
The diazonium salt is known as an important synthesis intermediate for azo dyes. A variety of synthesis methods for azo dyes have conventionally been known, which include, for example, a synthesis based on oxidation reaction, a synthesis based on reduction reaction, a synthesis based on substitution reaction, a synthesis based on addition reaction, a synthesis based on condensation reaction and the like, as described in Shin-Jikken Kagaku Koza (New Experimental Chemistry Course vol. 14-III, P. 1516–1534, published by Maruzen Co., LTD.). From the viewpoint of the availability of raw materials, costs, yield and the like, a synthesis based on an azo coupling reaction between a diazonium salt and a coupler, such as aniline, phenol or the like, is widely used as an industrial production method for azo dyes. Unfortunately, in such a method there is a danger of the diazonium exploding salt during the synthesis process. Hence, there has been a demand for the development of a stable diazonium that is little risking of exploding.
As disclosed in Japanese Patent Application Laid Open (JP-A) No. 11-228517, for example, the diazonium salt is used for the quantitative analysis of bilirubin which is a main component of cholocrome which is included in body fluids. Thus, the diazonium salt is considered to be an important compound in the medical and pharmaceutical fields, as well.
In general, the diazonium salt is a compound having very high chemical activity and reacts with a so-called coupler containing a phenol derivative or an active methylene group thereby readily forming an azo dye. Furthermore, the diazonium salt is also photosensitive so that the salt is decomposed by being irradiated with light, resulting in the loss of its activity. The diazonium salt therefore has long been used in a photosensitive recording material represented by diazo copies (see, for example, "Shashin Kogaku no Kiso (Hi-ginen Shashin)" [The Fundamentals of Photographic Engineering (Nonsilver Photograph)] P. 89–117 and 182–201, edited by Nihon Shashin Gakkai, published by Corona Publishing Co., Ltd. (1982)).
Moreover recently, the diazonium salt is property of being decomposed by light and losing its activity is being utilized. The diazonium salt is also being applied to recording materials that require image fixings. A typical example of such recording materials is a light-fixing type thermal recording material proposed in "Gazou Denshi Gakkaishi", Koji Sato et al., vol. 11, No. 4, P. 290–296 (1982). This recording material comprises a recording layer that contains a diazonium salt and a coupler and which is heated and reacted based on an image signal so as to form an image. Subsequently, the resultant image is fixed by light irradiation.
In such recording materials which is the diazonium salt as a color forming component, the diazonium salt has an extremely a high chemical activity such that the diazonium salt is gradually pyrolyzed and loses its reactivity even in dark places. As a result, such recording materials have a drawback of a short shelf life. The above recording materials also have a drawback in that a diazonium salt compound remaining on a background portion that is a non-image portion is decomposed during the light fixation, thereby forming a colored decomposed product (stain) which, in turn, stains the non-image portion. Furthermore, the above recording material with the image fixed thereto is so poor in light fastness at the non-image portion that the stain on the non-image portion is grows when the recording material is placed under sunlight or a fluorescent light for an extended period of time.
Heretofore, a variety of methods to overcome the aforementioned instability of the diazonium salt have been proposed. Among the above methods one of most effective is to encapsulate the diazonium salt in microcapsules. Such micro-encapsulation achieves a notable suppression of the decomposition of the diazonium salt because the diazonium salt in the microcapsules is isolated from water and bases promoting the decomposition thereof. Accordingly, the shelf life of the recording material, which uses the above method, is dramatically improved, as described in "Denshi Shashin Gakkaishi" (Tomomasa Usami et al., vol. 26, No. 2, P. 115–125 (1987)).
Common methods for enclosing the diazonium salt in microcapsules are described in "Microcapsules" (Tomoshi Kondo, Nikkan Kogyo Shinbunsha (1970)) and "Microcapsules" (Tamotsu Kondo, et al., Sankyo Shuppan (1977)), and are as follows. First, the diazonium salt is dissolved in a hydrophobic solvent (oil phase). The resultant solution is added to an aqueous solution containing a dissolved a water-soluble polymer (aqueous phase) and then, emulsified by means of a homogenizer or the like and a monomer or a prepolymer for forming microcapsule walls is added to either the oil phase or the aqueous phase both phases so as to cause a polymerization reaction or a polymer deposition to occur at the interface between the oil phase and the aqueous phase. Thus, polymer walls of a polymer compound are formed to produce the microcapsules.
The microcapsule walls thus formed may comprise any of the various materials including crosslinked gelatins, alginates, celluloses, urea resins, urethane resins, melamine resins, nylon resins and the like.
Particularly for microcapsules which have walls formed of a material, such as a urea resin or urethane resin, having a glass transition point slightly higher than room temperature, the walls thereof are impermeable to matter at room temperature but are permeable to matter at temperatures higher than the glass transition point. Such microcapsules are called thermally responsive microcapsules and are very useful for heat sensitive recording materials.
That is, a thermal recording material comprising a thermal recording layer formed on a support, the thermal recording layer containing as main color forming components thermally responsive microcapsules which encapsale a diazonium salt, and a coupler present outside the microcapsules can stably retain the diazonium salt over an extended period of time and also can easily form a color image by heating and fix the formed image by light irradiation.
Thus, the micro-encapsulation of the diazonium salt accomplishes a dramatically improves stability of the recording materials.
Although the above method dramatically improves the stability of the thermal recording materials, the method dose not yet completely suppress the instability inherent in the diazonium salt, and falls short of ensuring adequate long-term storability of the thermal recording materials. In addition, the above method has the following problem. Namely even after printing and image fixation, when an image print is exposed to light over an extended period of time, the photodecomposed product of diazonium salt causes a photodecomposition reaction which cause the dye stain to grow. Hence, whiteness characteristics of a non-image portion (background portion) of the light-fixed image print decreases. As a result, contrast between the non-image portion and a developed color portion in the image print decreases.
In the recording materials according to the above method, the aforementioned photodecomposition reaction never occurs uniformly. It is known that various kinds of decomposition products occur depending on the ambient environment. Among dozens of kinds of such products there is one called a photodecomposition stain which has light absorptivity particularly in the visible wavelength region. If the formation of the photodecomposition stain is significant, the whiteness characteristics at the non-image portion (background portion) of the light-fixed image print and contrast between the non-image portion and the developed color portion are reduced. As a result, product quality of the recording material is seriously impaired.
However, the photodecomposition reaction of the diazonium salt is complicated and it is difficult to identify the decomposition products. Thus it is difficult to suppress the stain associated with the photodecomposition.
Hence, in recent years active studies regarding recording materials achieving long-term stability against the photodecomposition stain have been performed. For instance, JP-A No. 8-324129 has proposed a light-fixing type thermal recording material which utilizes a combination of microcapsules enclosing a light-fixing type diazonium salt and a specific hydrophobic oil, thereby achieving not only an excellent unprocessed stock storability but also such an excellent image storability that the image print is less susceptible to the degradation of the whiteness characteristics despite a long exposure to light after image formation.
Moreover, JP-A No. 11-78232 proposes a non-fixing type thermal recording material employing a novel diazonium salt directed to improving the stability of the salt itself. Specifically, a diazonium salt having a maximum light absorption in a short wavelength region of about 350 nm or less is encapsuled in microcapsules which are used in the non-fixing type thermal recording material for improving the whiteness characteristics in the background portion of the formed image and the image storability under a light having a wavelength of more than about 350 nm, which is typically represented by a fluorescent lamp.
However, depending upon the storage environments, the thermal recording material may sometimes fail to achieve adequate levels of unprocessed stock storability and image storability in the developed color portion and background portion (non-image portion) of a recorded image. At present, the thermal recording material needs to be further improved in the stability thereof.
Moreover recently, a high demand exists for reducing of image recording time, namely increasing the speed the image forming process including printing and image fixing. Particularly, the technologies achieving not only the aforementioned improvement in the stability of but also the high-speed image recording process in is a high demand of the light-fixing type thermal recording material using the diazonium salt. In order to meet such a demand, it is essential to improve the diazonium salt in the photodecomposition speed.
For these recording materials using the diazonium salt as a color forming component, it has been a common practice to irradiate the recording material with ultraviolet rays having a wavelength of about 360 nm for efficiently light fixing the image. However, the irradiation of ultraviolet rays requires a special light source and an adverse effect on the eyes is feared. In this connection, there has been a demand for a recording material using the diazonium salt and allowing for an efficient image fixation with visible light having a wavelength of more than 400 nm.
However, the recording material using the conventional diazonium salt suffers a slow and time-consuming fixing process when the diazonium salt is deactivated by the light having a wavelength of more than 400 nm. Moreover, in a case where the recording material using the conventional diazonium salt is exposed to the light for long hours in order to ensure complete fixation, products resulting from the fixing process undergo further reactions so that a developed color image may have reduced whiteness characteristics at the background portion.
In addition, the diazonium salts heretofore known in the art have yet to achieve both good light fixation performance under the source of light having the wavelength of more than 400 nm, and high storage stability (thermal stability).

Diazonium salt and thermal recording material using the same

Abstract: General Formula (1)

Abstract: wherein R1 and R2 each independently represents an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group or a carbamoyl group, and R1 and R2 may be linked each other to form a ring; and R3 to R6 each independently represents a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group or a diazonio group, and at least one of R3, R4, R5 and R6 represents the diazonio group.


A process and composition is provided for preparing substrates with both visual and thermal camouflage. The substrate is metallized through a deposition process and polished or calendered to smooth the metal layer and lower the infrared emissivity of the layer deposited onto the substrate. The metallized substrate is then visually decorated by a tarnish and/or dying process that minimally impacts the infrared emissivity of the metallized substrate.

The present invention generally relates to the field of camouflage objects. More particularly, the invention relates to processing objects or textiles in order camouflage the objects or textiles from infrared (IR) detection.
Existing camouflage garments and textiles rely on colors and patterns designed to blend into the surrounding environment to evade detection of the wearer. Dark garments are worn to evade detection in the evening or in darker environments. Patterned garments are worn to evade detection in daytime settings and to blend into more natural environments.
While some systems rely on visual spectrum scanning to detect possible intruders, other systems rely on thermal imaging or IR cameras that receive IR radiation from the surface of a body. These IR cameras typically pick up IR radiation from the skin and project an image comparing the detected radiation compared to the ambient radiation. Night vision systems typically rely on thermal imaging to detect the presence and movement of intruders where it is too dark for detection in the traditional visual spectrum.
IR imaging has its shortcomings with respect to materials with low IR emissivity. Emissivity is a measure of the efficiency in which a surface emits thermal energy. It is defined as the fraction of energy being emitted relative to that emitted by a thermally black surface (a black body). A black body is a material that is a perfect emitter of heat energy and has an emissivity value of 1. A material with an emissivity value of 0 would be considered a perfect thermal mirror. IR imaging also has trouble detecting heat behind smooth or polished metals because they have very low emissivity values. Smooth or polished metals have emissivity values close to zero and will reflect infrared radiation and act as a mirror, while oxidized or anodized metals have emissivity values closer to 1 and will absorb the radiation.
Existing camouflage garments work evade detection in the visual spectrum, however, they are not designed to evade thermal detection because their thermal emissivity for fabrics such as polyester, cotton, and nylon is close to 1. In order to evade thermal detection, the garment must completely cover the body and either be heated or cooled to the ambient temperature of the environment, or the garment must be able to reflect IR radiation back to the thermal imaging device such that it acts as a thermal mirror.
The present invention addresses the current shortcomings of camouflage garments by providing effective camouflage in visible, near infrared, mid infrared, and far infrared simultaneously without changing the fit, form, or function of existing garments.

Manufacturing process and composition for multispectral camouflage


The invention relates to a sustained-release pharmaceutical delivery system for the administration of an antioxidant drug to a patient in need of such drug, wherein said delivery system comprises said drug in combination with a polymeric matrix, said matrix comprising a polymer which does not interact with said drug or a mixture of such polymers. The pharmaceutical delivery system of the invention is useful for the treatment of pathological conditions involving pathologically increased formation of active oxygen species.

In the last decade the role of oxygen free radicals as well as other oxygen reactive metabolites has been at least somewhat elucidated. These reactive metabolites are today considered to be responsible for oxidative toxicity in mammals and resulting the biological damage Halliwell, B. and Gutteridge, J. M. C. (1989) Free Rad. Biol. Med. (2nd ed.) Clarendon Press, Oxford; Halliwell, B. (1989) Br. J. Exp. Path. 70: 737-752!.
Free radicals are defined as an atom, group of atoms or molecule which contain at least one unpaired electron in their outer shell. The oxygen molecule itself, containing two unpaired electrons is, by definition, a free radical (.sup.3 .SIGMA..sub.g O.sub.2 --biradical), although it is not a reactive one due to the arrangement of its spins it its outer shell. Reduction of the oxygen molecule is a process which does not require changes in the spin direction of movement and therefore can be easily performed.
The complete reduction of the oxygen molecule results, at the first stage, in the production of the ion radical superoxide (O.sub.2.sup.-), followed by the production of hydrogen perxide (H.sub.2 O.sub.2) which is not a free radical, although a reactive species. Addition of another electron to the hydrogen peroxide leads to the production of the hydroxyl radical (OH*), a highly reactive species Halliwell and Gutteridge (1989) ibid.!. Such a process occurs in the mitochondria for energy generation Halliwell (1989) ibid.!. In this system which contains cytochrome oxidase, the oxygen is reduced in stages. During the reduction of the oxygen molecule, active metabolites are produced. These active oxygen species can leak to the immediate surroundings and may cause biological damage.
The production of oxygen reactive metabolites is not unique to the mitochondria organ, but occurs also in many other systems. Phagocytes, for example, are known for their ability to produce the superoxide radical and other species which participate in the defence mechanism against invaders (phgocytosis) Halliwell and Gutteridge (1989) ibid.!. This process, although necessary, can also lead to biological damage in the surrounding environment. Production of the superoxide radical has been identified in liver Kupffer cells, in monocytes, basophyls, eosinofils and mast cells. In some genetic disorders, such as chronic granulomatosus disease (CGD), the phagocytes are incapable of producing the oxygen radicals and consequently the patients suffer from recurring infections which can lead to death Johnston, Jr., R. B. et al. (1975) J. Clin. Invest. 55: 1357!. Another source for free radicals are enzymes. During their catalytic activity many enzymes such as prolyl hydroxylase, lipoxygenase and cyclooxygenase, produce oxygen free radicals Halliwell and Gutteridge (1989) ibid.!.
Amongst the diseases in which free radicals have been shown to play an important role in the initiation and pathogenesis, one can find chronic inflammation, autoimmune diseases such as Hashimoto's thyroiditis, systemic lupus erythematosus, myasthenia gravis, chronic autoimmune gastritis, dermatomyositis, etc. Gutteridge, J. M. C. (1993) Free Rad. Res. Comms. 19: 141-158!. Release of a free radicals efflux by the phagocytes can increase the severity of these diseases. This is the case, for example, in rheumatoid arthritis which is characterized by chronic inflammation of the joints. In this disease, the production of the inter-joint fluid is normal, but its viscosity is changed. The major constitutent of the inter-joint fluid, hyaluronic acid, is broken down into short fragments by the oxygen reactive species Halliwell and Gutteridge (1989) ibid.!.
It has been proposed that free radicals are involved in the damage caused to the brain in brain degenerative diseases such as epilepsy, Parkinson's disease, Wilson's disease (the excess of copper in this disorder causes the transformation of the superoxide radical into a more reactive species, the hydroxyl radical, in the metal-mediated Haber-Weiss reaction) Halliwell, B. and Gutteridge J. M. C. (1984) Biochem. J. 219: 1-14!. It has also been suggest that free radicals are involved in eye diseases such as cataract and retinopathy Taylor, A. and Davies, K. J. A. (1987) Free Rad. Biol. Med. 3: 371-377!.
It has recently been demonstrated that oxygen driven free radicals play an important role in the post-ischemic damage to various biological tissues such as heart and brain. It has further been suggested that these metabolites take part in the aging process and age-related diseases such as amyloid generation, age pigmentation, neuron damage Gutteridge (1993) ibid.!
Exposure of humans to free radicals is not limited to the endogenous oxygen free radical, but also to exogenous sources. Various agrochemicals can serve as free radical generation systems as in the case of the herbicide Paraquat Kohen, R. and Chevion, M. (1985) Biochem. Pharmacol. 34: 1841-1843!. Other substances such as alloxan, isouramil, cigarette smoke, air pollutants, carcinogenic and mutagenic agents and many drugs can generate oxygen free metabolites and cause biological damage.
Exposure of living cells to continuous efflux of oxygen free radicals and reactive species led to their adaptation to living in an aerobic atmosphere. This adaptation process led to the development of several defence lines against the damage induced by these metabolites Halliwell and Gutteridge (1989) ibid.; Ames, B. N. (1983) Science 221: 1256-1264!. The defence systems vary from one species to another and between different tissues of same species.
The broad definition of an antioxidant includes compounds which can cope with the oxidative stress by various mechanisms. Amongst the different kinds, one can find compounds which can protect fatty acids against oxidation and compounds which protect proteins, DNA and other important macromolecules. The different antioxidants can be classified as follows: compounds which donate hydrogen to the damaged target; compounds which scavenge free radicals; compounds which can bind the oxidants and remove them from the target; compounds which can convert reactive species to non-reactive metabolites; compounds which can protect through stabilization of biological membranes; reducing compounds which react with the oxidants; and compounds which are capable of binding mediators, such as transition metal ions, and prevent them from participating in the Haber-Weiss reaction Kohen, R., et al. (1988) Proc. Natl. Acad. Sci. USA 85: 3175-3179!.
In contrast to the antioxidant enzymes and some other antioxidants which are produced in humans, the antioxidant vitamins (E, C and A) are present only in the diet. New molecules which possess antioxidant activity were recently found in the muscle and brain Kohen et al. (1988) ibid.!. Vitamins E and C, although not synthesized by humans, are essential for the functioning of many systems Halliwell and Gutteridge (1989) ibid.!. Elimination of these antioxidants from the diet results in severe pathological symptoms. It has been shown in many pathological cases that administration of these antioxidants results in significant improvement Halliwell and Gutteridge (1984) ibid.!. Patients undergoing irradiation therapy are given vitamin C in order to reduce some of the side effects involved with radiation. Administration of vitamin E and 2-mercaptoethylamine to rats resulted in a 30% increase of their life span Herman, D. (1982) The Free Radical Theory of Aging. In: Free Radicals in Biology, Vol. V (ed. W. A. Pryor) p. 255, Academic Press, London; Herman, D. J. (1968) Gerontology 23: 476-450!.
The enormous problems involved in using the se compounds, the difficulties in delivering them to their targets and the lack of knowledge in developing pharmaceutical dosage forms for these antioxidants, prevent their wide use in the treatment of diseases.
In order to prevent oxidative damage and due to the high reactivity of the oxygen reactive species, antioxidant molecules have to be present at the site of their biologocal targets in high concentrations and for long periods of time. To fulfill these requirements, sustained release dosage forms of antioxidant compounds are desirable.
Since the creation of the first pharmaceutical dosage forms in the early sixties, there has been a tremendous increase in the theoretical and practical development of such forms. The progress achieved in the treatment of many cancer forms over the last decade led to the urgent need for delivery and direction of drugs to their targets. There is considerable evidence that a constant level of the drug in its biological target results in decrease in the immediate and long term side effects and improves the therapeutical effects.
In contrast to conventional dosage forms, where the drug is released immediately after its administration, the advanced dosage forms allow the drug to be released in unique manners, as follows: (1) delayed-release dosage forms that significantly delay the release of the drug after its administration; (2) sustained-release dosage forms that prolong drug level in biological fluids and tissues; and (3) controlled-release dosage forms that release the drug at a constant rate.
Examples for release of the drug at a constant rate are the diffusion method Rubinstein, A. and Robinson J. R. (1986) in: Progress in Clinical Biochemistry and Medicine, Springer-Verlay!, the osmotic pressure method Theeuwes, F. (1975) J. Pharm. Sci. 64: 1987-1990! and the ion-exchange method Schach, E. H. (1983) in: Controlled Drug Delivery, Vol. 1 (ed. Burck, S. D.) Florida CRC Press, pp. 149-161!.
Several approaches are sued in the design of sustained-release dosage forms, such as the mechanical approach and the prodrug approach. The mechanical approach is usually adopted when there is a demand for a large quantity of the drug over an extended period of time. Use of prodrug is most convenient when release of the drug at a specific target is desired. In this system, the drug in its active form is only obtained after chemical or enzymatic modification of the prodrug at the biological target site.
In order to deliver a drug to its target and to release it there at a constant rate, several methods have been developed, for example particulate methods such as microencapsulation, nanocapsules, drug embedded in matrix and microspheres Robinson, T. R. (1985) in: Recent Advances in Topical Drug Delivery: Rate Control, (ed. Nimmo, W. S.) Edinburg, Churchill Livingstone, 71; Friedman, M. (1973) in: Sustained Release Granules, Thesis, The Hebrew University of Jerusalem!. Other methods involve the use of liposomes (such as for SOD and catalase Tyrrell, D. A. et al. (1976) Biochim. Biophys. Acta 57: 359-367; Turrens, J. F. et al. (1984) J. Clin. Invest. 73: 87-95!) erythrocytes Inhaler, G. M. (1983) Pharmac. Ther. 20: 151-155!, monoclonal antibodies Yelton, D. E. and Scharff, M. D. (1981) Ann. Rev. Biochem. 50: 657-680! and magnetic fields as a targeting tool Hsieh, D. S. et al. (1981) Proc. Nat. Acad. Sci. USA 78: 91863-91868!.
Many attempts to interfere with the oxidative reactions by using novel antioxidants and by removing the reactive species have been carried out and are reviewed in the literature see, for example, Halliwell, B. et al. (1992) J. Lab. Clin. Med. 119: 598-620!. The limited success reported in many of these attempt resulted, in part, from the difficulties in introducing the antioxidants into cells and biological tissues and thus increases their level at the needed site. In order to prevent oxidative stress antioxidants have to be present in high concentrations and for long periods of time at their biological targets. The present invention is directed to such sustained release pharmaceutical dosage forms.

Sustained-release pharmaceutical system for the delivery of antioxidants

Yissum Research Development Co. of the Hebrew University of Jerusalem


A three ring binder includes a spine, front cover and back cover, each of which includes a substantially solid base plate and an outer plastic shell. The spine and front cover each includes a rectangular picture frame, the outer edges of which are aligned with and welded to the bottom and side edges of the spine and cover. A clear plastic membrane is secured to the frame's interior covering the opening in the picture frame. The frame top edges are spaced inwardly and free of the shell to form insert pockets. Display inserts are slidably mounted within the insert pockets defined by the frames. The spine insert includes an upper folded edge. An L-shaped member extends through an opening in the folded edge, and includes an outer pin head. Pulling upwardly on the pin head withdraws the insert. Mount mats of a semi-solid paper are provided in the pockets to receive thin, flexible paper for insertion into the frame pockets. The inserted mat holds the display material with the insert pocket.

Documents and other sheet-like elements are often assembled and bound in a supporting binder. Ring binders are particularly widely used for holding a plurality of interrelated documents and records. The loose leaf documents are readily and conveniently inserted and removed, if necessary, and of course, the binder is readily reused if the content becomes obsolete. In cases of sales presentations as well as various business and other reports, a highly professional presentation of the bound material is desired. The binder as such should present a appearance, as well as a pleasing and interesting presentation of the subject matter. Reports and sales presentations in particular may require assembly of certain documents in a predetermined order to be presented and discussed or reviewed. The well known conventional ring binder often in the form of a three ring binder, may be used. Binders are available with a hard or soft back and front covers interconnected to a connecting base or spine. The spine may be a solid backing member to which the ring assembly is secured. The front and back cover is formed of a relatively flexible material, or of a relatively solid material interconnected to the spine through a suitable flexible connection therebetween.
Binders with special see-through cover structures are available in the prior art. In one binder, a clear plastic outer sheet is attached to the cover and/or spine with an open top edge through which an insert may be inserted. This allows a creative presentation in an initial communication of the material to be presented from within the binder. In another prior art system, a solid cover is formed with an opening with a flexible plastic sheet secured to the back side thereof to form an insert pocket. An informational insert sheet may be inserted with a framed presentation of the insert sheet. The flexible back wall is flexible and may not provide a desired presentation of the inserted display material which is restricted by the size of the window in the prior art as to an 8 1/2.times.11" sheet as widely used.
However, there is a need for a binder including an external cover presentation which provides a reliable, rugged binder while maintaining highly professional and pleasing exterior presentation of the insert, as well as permitting easy assembly and disassembly of the insert.

Loose leaf binder including an exterior picture frame


Methods of pretreating lignocellulosic biomass in preparation for enzymatic saccharification and fermentation are provided. Also provided are methods of producing ethanol from lignocellulosic biomass via enzymatic saccharification and fermentation that utilize the pretreatment method. In the methods, pretreatment is conducted in two stages. In the first stage, the lignocellulosic biomass is treated in a mildly acidic or near pH-neutral solution to promote delignification and lignin sulfonation, while minimizing the formation of degradation products that inhibit subsequent enzymatic saccharification and/or fermentation. In the second stage, the pH of the solution is decreased in order to promote the depolymerization and dissolution of hemicelluloses in the lignocellulosic biomass.

Lignocellulosic biomass, as a structural material, has natural resistance to enzymatic deconstruction for production of fermentable sugars. Pretreatment, a step to remove this recalcitrance, increases the cellulose accessibility to cellulase for efficient saccharification of the polysaccharides in lignocelluloses. However, most promising and commonly practiced acidic pretreatments, such as dilute acid, Sulfite Pretreatment to Overcome Recalcitrance of Lignocellulose (SPORL), Organosolv and SO2-catalyzed steam explosion, can also degrade sugars to undesirable compounds such as furans. Furthermore, these pretreatments can also convert acetyl groups on the hemicellulose backbone into acetic acid. The undesirable sugar degradation products and acetic acid are inhibitive to many microbes and catalysts, such as Saccharomyces cerevisiae, during conversion of sugars to biofuel and bioproducts through fermentation and catalytic processes. Removal of the inhibitive compounds through detoxification steps is possible, but at additional cost, which negatively affects production economics.

Methods of pretreating lignocellulosic biomass with reduced formation of fermentation inhibitors

The United States of America as Represented by the Secretary of Agriculture


A dry etching method whereby high anisotropy can be achieved while providing sidewall protection effects by using an appropriate alternative substance to a carbonaceous polymer. A target material layer is etched by using etching gas containing a nitrogen based compound and a sulfur based compound capable of forming free sulfur (S) in a plasma when dissociated by electric discharges while a pattern sidewall is protected by a sulfur nitride based compound occurring from the gaseous phase. The sulfur nitride based compound is composed mainly of polythiazyl (SN).sub.x, which causes no particle pollution because it will be removed from a wafer through sublimation or decomposition when the wafer is heated to temperatures above 130.degree. C. For instance, a polysilicon layer or an Al based material layer can be etched into an anisotropic shape by using S.sub.2 Cl.sub.2 /N.sub.2 mixed gas. Particularly, a silicon based compound layer can be etched while preventing chloroflurocarbon (CFC) gas effectively. The sidewall protection film composed of (SN).sub.x has such excellent resistance to attacks by radicals or incident ions that a pattern formed into an anisotropic shape will not be deformed even when over-etched with radicals.

1. Field of the Invention
The present invention relates to a dry etching method employed in such applications as production of semiconductor devices. More particularly, it relates to a dry etching method whereby high anisotropy can be achieved while providing sidewall protection effects by using an appropriate alternative substance to carbonaceous polymers. Further, the present invention relates to a dry etching method whereby generation of etching residues or attachments, deformation of the sectional shape of patterns, and other problems can be prevented, for instance, in a multi-level metallization process involving a large-scale over-etching process for metallization layers on wafers having large steps on the surface thereof.
2. Description of the Related Art
The recent trend toward larger-scale integration and higher performance of such semiconductor devices as VLSIs and ULSIs requires dry etching methods whereby correspondingly higher anisotropy, higher etchrate, higher selectivity, lower pollution, and less damage can be achieved with no compromise in these requirements in etching silicon based material layers such as single-crystal silicon, polysilicon, refractory metal silicide, and polycide layers, or aluminum based material layers.
A typical etching process for single-crystal silicon based layers is a trench forming process wherein a trench is formed for the purposes of isolating minute elements and securing cell capacitor areas. This process requires high anisotropy in order to allow filling of the trench in subsequent processes and accurate control of capacitance.
Meanwhile, a typical etching process for polysilicon, amorphous silicon, refractory metal silicide, and polycide layers is a gate electrode forming process wherein a pattern width directly affects a channel length in self-aligned formation of a transistor's source and drain regions and a sidewall size accuracy in an LDD structure. As such, this process also requires high anisotropy together with high selectivity for thin gate oxide films.
Further, a typical etching process for aluminum based material layers is, needless to say, a interconnection forming process. A problem peculiar to this process is how to prevent after-corrosion.
The recent trend toward three-dimensional device structures and resulting expansion of steps on the surface of a target wafer requires a large-scale over-etching process. Namely, if the steps expand, it is more likely that various material layers formed thereon become irregular in thickness and that wafer surface morphology effects work to decrease the quantity of etchant incident on such narrow sections as the bottoms of the steps and lower the vapor pressure on etching reaction products. Consequently, after completion of a just-etching process, etching residues called stringers sometimes remain on the bottoms of the steps and require removal in an over-etching process.
It is generally difficult in an over-etching process, however, to make high anisotropy compatible with high selectivity because an excessive quantity of radicals relative to an etching area cause migration on the surface of a target wafer and attack the sidewalls of patterns, deforming the sectional shape of patterns. Meanwhile, any attempt to set ion assisted etching conditions for fear of lower anisotropy causes damage to underlying layers or allows sputtered underlying layers to attach to the sidewalls of patterns. It is preferable to prevent generation of such attachments, which will occlude residual chlorine and promote after-corrosion, particularly when etching aluminum based material layers formed on silicon oxide (SiO.sub.2) based inter-layer insulation films.
Conventionally, sidewall protection effects using carbonaceous polymers have played a major role in solving the above-mentioned problems.
Chloroflurocarbon (CFC), typically, CFC 113 (C.sub.2 Cl.sub.3 F.sub.3), has been widely used to etch silicon based material layers. CFC gas has fluorine (F) and chlorine (Cl) atoms in each molecule thereof and will generate, under certain conditions, such radials as F.sup.* and Cl.sup.* and such ions as C.sup.+, CF.sub.X.sup.+, CCl.sub.x.sup.+, and Cl.sup.+, both of which will assist an etching reaction. When the CFC gas is dissociated by electric discharges, the resulting fragments thereof will polymerize to form in a plasma carbonaceous polymer, which will deposit on a pattern sidewall on the surface of a target wafer, providing sidewall protection effects and thereby achieving high anisotropy.
It is possible to make high anisotropy compatible with high selectivity by improving the sidewall protection effects provided by the carbonaceous polymer. The principle of this method is to reduce the energy of incident ions with no compromise in a practical etchrate and thereby achieve high selectivity while preventing the resulting anisotropy deterioration by improving the sidewall protection effects. A typical example of this method is publicized in, for instance, the Extended Abstract of the 36th Spring Meeting of the Japan Society of Applied Physics and Related Societies, 1989, p. 571, 1p - L - 5. In this instance, a tungsten polycide film is etched via an SiO.sub.2 mask by C.sub.2 Cl.sub.3 F.sub.3 (CFC 113) / SF.sub.6 mixed gas.
For Al based material layers, a carbonaceous polymer supplied by a resist mask provides sidewall protection effects. To etch Al based material layers , chlorine based gases , typically, BCl.sub.3 /Cl.sub.2 mixed gas, have been widely used. Because Al and Cl react with each other spontaneously, a mean free path of ions must be extended during etching under low gas pressure and high bias in order to ensure high anisotropy. When the resist mask is sputtered by high-energy incident ions, the resulting decomposition products will form a carbonaceous polymer, which will deposit on a pattern sidewall, providing sidewall protection effects.
Another method for achieving high anisotropy has also been proposed wherein the temperature of a target substrate (wafer) is reduced instead of providing sidewall protection effects by using the carbonaceous polymer. Called low-temperature etching, this method is designed to keep the wafer at temperatures below 0.degree. C. and thereby keep a longitudinal etchrate at a practical level with the assistance of ions while freezing or inhibiting a radical reaction on the sidewalls of patterns and preventing such etching defects as undercut. A typical example of this method is publicized, for instance, in the Extended Abstract of the 35th Spring Meeting of the Japan Society of Applied Physics and Related Societies, 1988, p. 495, 28a - G - 2. In this instance, a silicon trench and an n.sup.+ type polysilicon layer are etched by using SF.sub.6 gas with a wafer cooled to -130.degree. C.
In this connection, it is to be noted that low-temperature etching in the broad sense thereof sometimes means a dry etching method wherein a wafer is kept at room temperature, considering that the wafer, unless cooled, will be heated to temperatures around 200.degree. C. under the influence of radiation from a plasma or heat of reaction.
However, it has been pointed out that the above-mentioned methods of providing sidewall protection effects by using a carbonaceous polymer involve problems described below.
Firstly, CFC gas, typical of etching gases for silicon based material layers, is commonly known to contribute to destruction of the earth's ozone layer and the production and use thereof are likely to be prohibited in the near future. Under these circumstances, there is pressing need to find some appropriate alternative substance, and the efficient applications thereof, to CFC gas for use in dry etching.
Secondly, when silicon based material layers are etched by using CFC gas, carbon contained therein deteriorates selectivity for SiO.sub.2 based material layers. This problem is publicized in, for instance, the Extended Abstract of the 36th Spring Meeting of the Japan Society of Applied Physics and Related Societies, 1989, p. 572, 1p - L - 7 and the Monthly Journal "Semiconductor World" (published by the Press Journal Inc.), January, 1990, p. 81-84. In these instances, carbon contained in CFC gas adsorbs on the surface of an SiO.sub.2 based material layer like a gate oxide film to form a C--O bond with a high bond energy (257 kcal / mole) and weaken an Si--O bond or to reduce SiO.sub.2 to Si and make it more likely to be extracted by a halogenous etchant. This problem becomes particularly serious in forming a gate electrode on a thin gate oxide film.
Thirdly, there is a fear that a carbonaceous polymer may cause particle pollution and after-corrosion. Namely, it is most likely that a carbonaceous polymer occurring from the gaseous phase causes more serious particle pollution as design rules for semiconductor devices become more strict in the future. Particularly, in an etching process for Al based material layers, a carbonaceous polymer deposited on the sidewalls of patterns will occlude chlorine or compounds thereof, which will act as residual chlorine to promote after-corrosion. In recent years, an increasing number of electromigration prevention measures, such as adding copper (Cu) to Al based material layers and fabricating therewith such dissimilar material layers as barrier metals and anti-reflection films have been taken. Since all these measures work against after-corrosion prevention, it is required to find some appropriate alternative sidewall protection substance to a carbonaceous polymer.
There have also been proposed some measures for using other depositional gases than CFC gas. As design rules for semiconductor devices become more strict in the future, there is a greater fear that even minute particles which would otherwise be negligible may lead to considerable yield reduction.
On the other hand, low-temperature etching is expected to be one of promising CFC-free etching methods. As mentioned above, however, this method attempts to achieve high anisotropy only by freezing or inhibiting a radical reaction on the sidewalls of patterns and involves cooling a target substrate (wafer) to such a degree that requires liquid nitrogen. Hence, hardware related problems, such as increased demand for large-scale special cooling equipment and decreased reliability of vacuum sealant. Also anticipated is the fear that additional time taken to cool the wafer below room temperature and heat it back to room temperature leads to reduction in throughput as well as economy and productivity.

Dry etching method using (SN).sub.x protective layer


Provided is a support exhibiting excellent weather resistance, which is usable in an outdoor location for a long duration and is a support capable of sufficiently shielding UV radiation; and further provided are a weather-resistant article, a weather-resistant film, and an optical member which exhibit sufficient weather resistance even though receiving influences by heat, light or moisture. Disclosed is a weather-resistant article of the present invention possessing a support and provided thereon, a polymer layer containing a light stabilizer and a UV radiation reflective layer containing plural materials each having a different refractive index, the UV radiation reflective layer provided on the polymer layer.

Usually, since UV radiation has higher energy than that of another light of sunlight, it has negative health effects on the human body and others. For this reason, UV radiation is desired to be shielded. When even UV-resistant glass is used for a long duration, discoloration is produced, and the content inside the glass is further deteriorated in discoloration caused by UV radiation. Specifically, polymeric resins exhibit large degradation caused by UV radiation.
Usually, a polymer film produces cleavage of molecular chains via photooxidation reaction upon exposure to UV radiation under the existence of oxygen, whereby degradation in strength, rise in haze, and lowering of transparency and color tone caused by yellowish change or the like (deterioration in UV radiation). UV radiation of sunlight has a wavelength of 295-400 nm, and light energy in this wavelength region is almost equal to the bonding energy of C, H or O. Therefore, when a plastic molding mainly having the bonding of C, H or O is exposed to UV radiation, such a bonding is broken, whereby degradation of resin, discoloration and lowering in mechanical strength tend to be produced. Accordingly, the plastic molding cannot be used stably in an outdoor location for a long duration. For this reason, generally well known is a technique by which a light stabilizer is blended in a polymer film to improve weather resistance of the resulting polymer film.
The light stabilizer is a stabilizer used for the purpose of inhibiting photooxidation reaction of the polymer film caused by UV radiation, and as the light stabilizer, a UV absorbent, quencher, and HALS (Hindered Amine Light Stabilizer) are well known.
The UV absorbent is a light stabilizer which absorbs UV radiation, and discharges energy absorbed in the molecule by making the energy to be lower energy in the form of heat, phosphorescence, or fluorescence, and as the UV absorbent, a benzophenone type, a benzotriazol type, a benzoate type, a cyanoacrylate type and so forth are practically available.
The quencher is a light stabilizer by which one in which a chromophoric group (mainly an unsaturated hydrocarbon and its compound) being on a ground state absorbs UV radiation so as to become an excited state is returned into the original ground state, and as the quencher, Ni compounds are employed.
The HALS is a light stabilizer which traps an alkyl radical, a peroxy radical and so forth produced via exposure to UV radiation to inhibit photooxidation reaction, and the HALS is a compound having a hindered piperidine moiety.
However, even though a light stabilizer such as a UV absorbent or the like is contained in a polymer film, influence of UV radiation can not be sufficiently removed from the surface, whereby deterioration on the surface of the polymeric resin can not be suppressed. Further, in order to obtain sufficient weather resistance, a sufficient amount of a light stabilizer is desired to be contained, but the polymeric resin is exposed to an environment of heat and water, bleed-out, sublimation and so forth are generated, whereby the light stabilizer is reduced, resulting in lowering in weather resistance, lowering in transparency and rise in haze, leading to insufficient aging stability. Further, since a light stabilizer is expensive, a large cost-up results.
As another method of enhancing weather resistance, there is a method of coating a layer containing a UV absorbing material composed of an organic substance or inorganic particles (refer to Patent Documents 1 and 2). This is an effective means, but in the case of outdoor use, the surface of the coating film is exposed to rain water, oxygen in the air, or pollution substances, and exposed to UV radiation since there is no sufficient UV absorbent on the surface. Therefore, deterioration caused by UV radiation is generated, and there appears a large problem such as obstacles such as coloring such as yellowish color, lowering in transmittance and rise in haze.
Further, in the case of at least one of a UV absorbent and a hindered amine based light stabilizer, disappearance of bleed-out produced by the UV absorbent or the like is seen, resulting in insufficient weather resistance. Further, a large amount of UV absorbent is to be provided in order to obtain sufficient UV absorbability. However, when increasing a UV absorbent amount, absorbing occurs in not only a UV wavelength range, but also even a short wavelength range of visible light, resulting in lowering in transmittance from the initial to visible light region.
In cases where inorganic particles are used as a light stabilizer (Patent Document 1), they are more stable than an organic light stabilizer with respect to UV radiation, heat and so forth. However, similarly to an organic UV absorbent, influence of UV radiation to the surface can not be sufficiently eliminated, and deterioration caused by UV radiation, on the surface of a resin layer containing inorganic particles, can not be inhibited. Therefore, lowering in rise in haze, yellowish change, and visible light transmittance results. Further, inorganic UV absorbents should have an average particle diameter of 100 nm or less in order to maintain transparency and a clear property in the visible light region. When the particle diameter is small, the particles exhibit high surface energy, and coagulation of particle-to-particle is easy to be generated, whereby an aggregate thereof produces scattering of light in the visible light region, and the resulting coated film tends to lose a clear property. Further, in order to obtain sufficient UV shielding performance for protection of a resin support, coagulation of particles is further produced, since a necessary amount of inorganic UV shielding agent is larger than that of an organic UV absorbent. Further, inorganic particles tend to absorb UV radiation to activate surrounding water, oxygen and so forth (photocatalytic function). Therefore, in the case of outdoor use, water such as rain water or the like is activated with UV radiation and inorganic particles, whereby the active species decompose organic components of the coating film and the resin support, resulting in generation of a peeled coating film, rise in haze, yellowish change and so forth.
As another method of improving weather resistance, there is a method of providing a UV radiation reflective layer by a dielectric laminate in which a low refractive index layer and a high refractive index layer are alternately laminated (for example, Patent Documents 3 and 4). In the case of this method, since the dielectric is made of an inorganic substance, a UV shielding film composed of a dielectric laminate is difficult to be deteriorated even though it is exposed to UV radiation, an atmospheric pollutant, rain water or the like, leading to largely effective shielding of UV radiation for a long duration. However, in order to shield 90% or more of UV radiation, a certain amount of film thickness should be provided, resulting in high cost. Further, since at least several percent of UV radiation is transmitted, the resin support is degraded because of this several percent of UV radiation in the case of outdoor use for a long duration (at least a few years).

Weather-resistant article, weather-resistant film and optical member


A metal detector has multiple transmit and receive coils for producing multiple detection fields. In one embodiment, a transmit coil is combined with two receive coils in a configuration that enables the detector to generate two detection fields, one being substantially narrower than the other. The transmit coil is inductively balanced with the receive coils such that the transmit coil induces minimum signals in each of the two receive coils. A metal target lying within a detection field changes the coupling between transit and receive coils and produces signals in the receive coils. The received signals are utilized to identify the target's presence within one or both of the detection fields. The use of two detection fields, substantially different in size, enables the metal detector to search over a broad area for object detection and then narrow the search to more precisely locate the detected object. A further embodiment has two transit coils and one receive coil and likewise produces a broad and a narrow detection field.

Metal detectors are typically operated using a transmit coil and a receive coil within a single coil assembly. However, the transmit and receive coils can be spatially separated into two different coil assemblies or boxes. In the metal detector industry, this arrangement is commonly referred to as a two-box coil system. An example of a two-box system is shown in Design Patent D274,704 which is assigned to Garrett Electronics. The two-box coil system is very effective in detecting large, deep targets because the coil arrangement utilized by the two-box system results in a detection field much larger than the individual fields of the two coils which constitute the two-box system. However, as a result of this large detection field it is very difficult to locate the target with precision. Therefore, it is a common practice to operate the two-box detector in conjunction with an additional detector having a standard search coil which has a much more limited detection field. In this practice, the two-box detector is used for the primary searching of an area and once the two-box detector has approximately located a target, a second detector with a standard search coil is utilized to locate the target with more precision. This practice has the disadvantage of requiring the use of multiple metal detectors.


A composition comprising a polycarbonate, wherein the polycarbonate has a weight average molecular weight of greater than 15,000, comprises more than 15 mole percent structural units derived from a 2-aryl-3,3-bis(4-hydroxyaryl)phthalimide:

The present disclosure generally relates to resins and resin blends and articles comprising thermoplastic polymers derived from 2-hydrocarbyl-3,3-bis(4-hydroxyaryl)phthalimide monomers. Homopolycarbonate and Copolycarbonate resins derived from such monomers generally have a higher Tg and greater oxygen and water permeability than resins derived from the most widely available commercial polycarbonate, bisphenol A ("BPA") polycarbonate homopolymers. As described herein, it is also possible to make such copolycarbonates with the transparency of polycarbonates and good color (i.e., low yellowness index) provided this monomer is made by a method that achieves sufficient purity. More particularly, the present disclosure relates to resin blends and articles comprising a polycarbonate comprising structural units derived from phenolphthalein derivatives, such as 2-hydrocarbyl-3,3-bis(4-hydroxyaryl)phthalimide monomer and an ABS (acrylonitrile-butadiene-styrene) resin. The present disclosure further relates to resins and resin blends and articles comprising a polycarbonate comprising structural units derived from relatively pure 2-hydrocarbyl-3,3-bis(4-hydroxyaryl)phthalimide.
It would be desirable to develop a process for preparing relatively pure phenolphthalein derivatives such as 2-hydrocarbyl-3,3-bis(4-hydroxyaryl)phthalimide, which can then in turn be used for producing polycarbonates and other polymers having significant content of structural units derived from this monomer, which polymers also have good color, (e.g., a yellowness index of less than about 10), and reasonably high weight average molecular weight (e.g., at least about 15,000). Further still, there is a need for such resins and resin blends and articles having excellent fire retardance and improved physical properties.

Methods for producing and purifying 2-hydrocarbyl-3,3-bis(4-hydroxyaryl)phthalimidine monomers and polycarbonates derived therefrom

Abstract: wherein R1 is selected from the group consisting of aryl groups having 6 to 25 carbon atoms and aralkyl groups having 7 to 25 carbon atoms, and R2 is selected from the group consisting of a hydrogen, a hydrocarbyl group, and a halogen; and further wherein the polycarbonate has a yellowness index of less than 10 as measured on a 3 millimeter thick plaque in accordance with ASTM D1925 is disclosed.


An image capturing device, including an rectangular image capturing element having long sides and short sides; an image capturing optical system forming an image of a subject on the rectangular image capturing element; a first driving device which moves the rectangular image capturing element in a first direction slanted by a predetermined angle from the long side and the short side of an outer shape of the rectangular image capturing element in a plane perpendicular to an optical axis of the image capturing optical system; and a second driving device which moves the rectangular image capturing element in a second direction slanted by a predetermined angle from the long side and the short side of the outer shape of the rectangular image capturing element in the plane perpendicular to the optical axis of the image capturing optical system, but the second direction differs from the first direction.

In recent years, in the field of digital cameras, camera-shake compensating mechanisms are disclosed as an image capturing element moving method, in which an image capturing element is mounted in the lens barrel and moveable in two directions, and further the image capturing element is moved corresponding with the shake of the image capturing device (for example, see Patent Document 1). In the above conventional camera-shake compensating mechanisms in which the image capturing element is moved, a guide shaft to move the image capturing element, which is rectangular, is aligned along a direction (hereinafter referred to as direction "H") parallel to the long side of the image capturing element, and the other guide shaft is aligned along a direction (hereinafter referred to as direction "V") parallel to the short side of the image capturing element.
Because in order to make a thick digital camera, no space is available behind the image capturing element. That is, in the structure of the conventional camera-shake compensating mechanism, both a driving device (being a driving shaft and a driving element), and the image capturing element, are provided on a common plane with respect to the optical axial direction of the image capturing optical system, whereby the driving shafts are aligned in directions H and V, which effectively uses space within the digital camera.
Further, a method to improve the ability of the camera-shake compensating mechanism is disclosed (for example, see Patent Document 2), in which the camera-shake compensating means is installed 45 degrees declined against the vertical direction in the plane perpendicular to the optical axis so that the image capturing element can be moved farther in a specific direction. The method, described in Patent Document 2, moves the image capturing element in the direction perpendicular to the optical axis of the image capturing optical system, while directly using the camera-shake compensating means. Accordingly, in order to move the image capturing element in the direction perpendicular to the optical axis of the image capturing optical system, the camera-shake compensating means and the image capturing element must be arranged in the same plane.
Further, in order to design thin digital cameras, a bent optical system is also proposed in which the lenses do not project in front, even though a zooming operation is conducted, while the thickness of the camera does not change (for example see Patent Document 3).
[Patent Document 1] Unexamined Japanese Patent Application Publication No. 2003-110,928
[Patent Document 2] Unexamined Japanese Patent Application Publication No. 2004-77,711
[Patent Document 3] Unexamined Japanese Patent Application Publication No. 2000-131,610
However, in the case that the camera-shake compensating mechanism shown in Patent Document 1 is used on a thin bodied camera incorporating the light bent optical system shown in Patent Document 3, when the optical axis is bent at 90 degrees by the bent optical system toward the bottom side in the thin bodied camera, the image capturing element is to be mounted with its image capturing surface facing upward at the bottom of the thin bodied camera, and thereby, the spaces around the image capturing element, in particular, the space in direction V is very narrow, therefore, a guide shaft can not be assembled, even if the guide shaft is assembled in spite of this reason, the length of the guide shaft becomes so short that resonant frequency is reduced, and movement is too slow, or the movement is not stable, which results in problems.
Further, in the case of the camera-shake compensating means shown in Patent Document 2, space around the image capturing element is so small that the image capturing element and the camera-shake compensating means can not be assembled on a common surface, accordingly, the camera-shake compensating means of Patent Document 2 can not be applied to the thin bodied camera incorporating the light bent optical system shown in Patent Document 3.
Still further, in the thin bodied camera incorporating the light bent optical system, to arrange a flexible circuit board, through which electrical power and control signals are supplied to the image capturing element, while output signals from the image capturing element are sent to a CPU, the flexible circuit board may be bent at a sharp angle, because the space around the image capturing element is so narrow that the image capturing element may be driven by very large force due to the flexibility of the flexible circuit board (which is flexible but damage-resistant), which causes a major problem.


The application relates to a valve device, in particular for a cooling water system of a motor vehicle, comprising a housing, which has an inflow connection and a first outflow connection and a second outflow connection, and comprising a valve, which is mounted in the housing so as to shift in the axial direction, said valve having a cylindrical main part, at each end of which a valve element is arranged in order to close one of the connections in a first sliding end position of the valve and another one of the connections in a second sliding end position of the valve, and having a first spring element, which biases the valve in the direction of the first sliding end position, and having a thermally activatable actuator element, which is designed to push the valve against the force of the spring element, in the direction of the second sliding end position, upon being activated. A provision is that the first spring element and the actuator element, which is designed as a second spring element, are each axially tensioned between one of the valve elements and a bearing web protruding radially inwards from the housing.

Valve devices of the aforementioned type are known from the prior art. Thus, patent specification EP 1 334 853 B2, for example, discloses a common valve device. The valve in this case is formed as a single part with the valve bodies arranged thereon, wherein the valve bodies have sealing surfaces, which are arranged, pointing toward each other or facing each other, on the valve, in order to interact with housing valve seats positioned between the valve bodies, when the valve is pushed into the first or the second sliding end position. In this case, a spring element, which biases the valve in the first sliding end position, is assigned to a front side of the valve, and arranged to be axially tensioned or pre-tensioned between the valve and a front side of the housing. Thus, the spring element directly impacts the valve body with a tensioning force, which body is thereby pushed against the valve seat in the housing. The actuator element, which counteracts the spring force upon being activated, is assigned to the other valve body. To this end, the actuator element is connected to a temperature sensor assembly, which has a temperature sensor medium with a temperature-dependent volume, wherein a temperature-dependent volume change in the temperature sensor medium moves the stiffly designed actuator element against the force of the spring element.
The known valve device has the disadvantage that installation and production are complicated and expensive. In particular, the valve, which is designed as a single part, can only be mounted when the housing is separated into a plane parallel to the sliding axis.


Compounds containing .alpha.-discarbonyl groups are rendered capable of fluorescent emission by conjugation with carboxylic acid-terminated ortho-diaminoaryl reagents. The carboxylic acid groups serve as ionizable moieties which facilitate the conjugation reaction, and are retained in the conjugation product to enable, or enhance the ability of, the conjugated compounds to be separated in chromatographic and electromigration separation processes, notably electrophoresis. Ortho-dinitro derivatives of the reagents are also disclosed, these derivatives offering the advantage of stability as well as the ability to be used directly in the reaction in the presence of a reducing agent.

Sialic acids, such as N-acetylneuraminic acid (NANA), are .alpha.-ketoacids which occur as non-reducing terminal residues in the carbohydrate chains of glycoproteins and glycolipids. Abnormal levels of NANA have been detected in the serum and urine of cancer patients and of persons who are afflicted with certain congenital metabolic diseases. The early detection and quantitation of NANA thus offers a means of diagnosing various disease states and of providing early signals for the initiation of therapy.
The detection and measurement of sialic acid-terminated oligosaccharides has long presented a problem in biochemical investigations and routine analyses. The lack of detectable moieties which distinguish these molecules from other oligosaccharides has hindered developments in this area of glycobiology. Techniques for detection and quantitation of these molecules at early stages of their proliferation have been hampered by numerous problems, including lack of specificity of a derivatization reagent for .alpha.-keto acids or aldehydes, low sensitivity of the particular analytical technique employed, a lack of reagents which can be employed with highly polar analytes, and the instability of the derivatization reagents.
A spectrophotometric method of sialic acid determination using thiobarbituric acid has been employed, but this method lacks both selectivity and sensitivity. See, L. Warren, J. Biol. Chem. 234:1971 (1959) and D. Aminoff, Virology 7:355 (1959). Assays of NANA have also been performed as disclosed in the following publications: R. Schauer, Methods Enzymol. 50C:64 (1978), using gas chromatography (GC); I. Mononen, et al., FEBS Lett. 59:190 (1975), using gas chromatography-mass spectrometry (GC-MS); A. K. Shukla, et al., J. Chromatogr. 244:81 (1982) and H. K. B. Silver, et al., J. Chromatogr. 224:381 (1981), using high-performance liquid chromatography (HPLC) with UV detection; and S. Hara, et al., J. Chromatogr. 377:111-119 (1986), using HPLC with fluorescence detection. Both GC and HPLC with UV detection lack the sensitivity to detect NANA at picomole levels or below. Sensitivity is enhanced using GC-MS, but the cumbersome procedure for sample preparation limits the usefulness of this technique in rapid, diagnostic assays. The more recent method using HPLC with fluorescence detection involves the formation of a fluorescent quinoxaline from 1,2-diamino-4,5-dimethoxybenzene and NANA. This technique does not however permit the determination of highly polar analytes or provide for optimal reaction product behavior in electrophoresis and high-sensitivity fluorimetry. An additional problem is that the shelf life of the reagent employed is very limited.

Fluorogenic reagents for detection of glycoconjugates, .alpha.-ketoacids and diketones


Compositions and methods for forming condensates and resin compositions are provided. In one embodiment, a condensate is formed from a reaction mixture including a triazine monomer, an arylhydroxy monomer, an aldehyde monomer and an acid catalyst having a pKa value of greater than 3.8. The condensates contain up to 28 wt. % of nitrogen and have a melt viscosity of 3,000 cps or less at 175° C. The condensates may have a solubility of at least 80 wt. % solids dissolved in an organic solvent for 120 hours or greater. Also disclosed are methods for the manufacture of the condensate as well as the condensate's use in fire-retardant epoxy resin compositions suitable for the manufacture of laminates for electronic applications. There is also disclosed a glycidylated triazine-arylhydroxy-aldehyde condensate of this invention.

Epoxy resins have excellent moisture, solvent, chemical and heat resistance properties, good adhesion, and superior mechanical and electrical properties, which make epoxy resins suitable for use in constructing and packaging electronic products. In many cases, flame retardant materials are included in the epoxy resin compositions for use in electronic applications and/or electronic components that require high flame retardancy.
In one approach, the flammability of the epoxy resin can be reduced by physically blending a flame-retardant additive with the epoxy resin. Some examples of such additive-type flame retardants include antimony trioxide, aluminum trihydroxide, elemental phosphorous, and inorganic phosphorous compounds. Unfortunately, such additive-type flame retardants may be toxic. Additionally, such additive-type flame retardants may be difficult to integrate with the epoxy compositions, thereby, necessitating a high initial loading of the additive-type flame retardants that adversely influences the electrical or mechanical properties of the epoxy resin.
One commonly used flame-retardant in epoxy compositions for printed wiring boards (PWB) in electronic equipment is a halogenated aromatic flame-retardant, such as a brominated aromatic flame-retardant. The brominated aromatic flame-retardant, for example, tetrabromobisphenol A (TBBPA) based compounds, chemically bond with the polymer chain. Unfortunately, such halogenated aromatic flame-retardant may emit corrosive halides and toxic compounds during a fire. Additionally, there has been an increased global interest in environmental protection leading to a higher demand for halogen-free flame-retardants (HFFR) in the epoxy formulations for PWB.
Alternatively, phosphorous or nitrogen containing epoxies and/or epoxy curatives as flame retardants have been considered for improving flame retardancy. Unfortunately, relatively large quantities of phosphorous-based compounds are needed to provide for sufficient flame-retardancy, which quantities have been observed to greatly reduce heat and moisture resistance of the epoxy resins.
Nitrogen-based flame retardants are considered advantageous as they are observed to have a low toxicity, are physically stable, and in case of fire, have an absence of toxic and corrosive emissions with a low evolution of smoke. More recently, triazine-phenol-aldehyde (TPA) condensates have been described as flame retardant additives for epoxy resins. TPA condensates with high nitrogen content are also effective curing agents for epoxy resins leading to high efficiency in flame retardancy without compromising the mechanical and physical properties of the polymer.
However, one difficulty with TPA condensates is that the current condensate compositions exhibit higher viscosity and lower nitrogen content than desired. For example, existing processes typically produce an atomic nitrogen content of only about 1 to 10 wt. %. TPA condensates have also been observed to exhibit instability at higher temperatures that limit the large scale manufacturing of such condensates.
Conventional processes for forming TPA condensates have been found to be disadvantageous as the resulting condensates exhibited an undesirable increase in viscosity and also exhibited a decreased solubility in commons solvents, such as methyl ethyl ketone (MEK) and acetone, typically used in epoxy formulations. The solubility of the TPA condensates in such solvents is important since residues or insolubles in the epoxy resins may result in less than desirable coating of substrates and degrade the quality of the laminates made from the epoxy resins.
Other conventional TPA condensate formation processes prepare compounds with large amounts of methanol as a reactant, which present special challenges on commercial scale productions including handling, waste, and expense.
Therefore, there is a need for forming flame-retardant condensates, with improved viscosity and improved solubility that are effective curing agents, provide fire-retardant properties to epoxy compositions and which may be manufactured on a commercial scale.

Compositions and methods to produce triazine-arylhydroxy-aldehyde condensates with improved solubility


Simultaneous pump dispenser of the trigger-sprayer type has a single container with separate liquid compartments. Side-by-side main cylinders in the dispenser body have vent cylinders there-adjacent. Pistons in all cylinders are worked together by a piston/nozzle assembly separately to pump the liquids and vent the containers. A manifold in the top of the container connects supply tubes and vents in the compartments to the risers and vent passageways for the respective main and vent cylinders. The discharge may be separate spray orifices, a single spray orifice combining the liquids or a single foaming orifice.

This invention relates to a pump dispenser for simultaneous dispensing of two separate liquids. More specifically, this invention is concerned with a hand-held pump dispenser of the trigger-sprayer type for dispensing of two separate liquids particularly where it is desired or necessary to keep the liquids separate until they reach the surface onto which they are applied.
There has been, and still is, a need for dispensing two liquids which are to be kept separate in storage and in the dispensing operation. This may be where the two liquids will react. An example, recognized in the art, might be a cleaning system in which an alkaline material and an acid material are brought together on a surface to produce an efflorescing action to clean the surface and dissolve the soil on it. These reactants cannot be packaged together: they would promptly react in the bottle and their great advantage of interaction and reaction on the surface would be lost.
An example of a dispensing bottle for simultaneous pump dispensing of such liquids is disclosed in the U.S. Pat. No. 3,760,986 which issued Sep. 25, 1973 to Castner et al. In this device there is a partitioned container with two separate pumps mounted thereon having dip tubes extending into the respective compartments. The liquids are pumped separately and are emitted as sprays separately from the dispensing head on the device.
Another need for simultaneous pump dispensing is in the biological fluid field wherein, for example, blood fluids such as fibrinogen and thrombin may be stored and dispensed to combine only when sprayed onto the tissue whereon they produce a polymer having great potential benefit, both as a hemostatic agent and a tissue adhesive. An example of such a dual pump dispenser is disclosed in U.S. Pat. No. 4,902,281 which issued Feb. 20, 1990 to D. F. Avoy.
Dual pump dispensers also find use in pharmaceutical and cosmetic media wherein two reactants can be brought together and mixed just prior or during use in order to maintain a reaction time, providing particularly fresh and, therefore, effective product. As with Avoy, above, the supply container may be in the form of two separate bottles which may be selectively replaced and renewed, a device including pump means for each container and a "handle" joining the pumps and from which the two separate liquids may be separately sprayed. Such an arrangement is disclosed in Skorka et al U.S. Pat. No. 4,826,048, issued May 2, 1989.
Of course, compartmented containers and separate valves and sprayers have been employed in the aerosol trade for years, an example being disclosed in the U.S. Pat. No. 2,941,696 to R. E. Homm, issued Jun. 21, 1960.
Molded compartmented containers for dual dispensers have been disclosed in the art, aside from the Castner et al disclosure above. An example is in the twin compartment squeeze bottle disclosed in the Green U.S. Pat. No. 4,984,715, issued Jan. 15, 1991. In this arrangement the two containers have adjacent confronting vertical walls, joined by a central vertical web. The walls are non-diverging to "cooperate with each other . . . to support the bottle in a stable manner".
The old U.S. Pat. No. 3,347,420 to R. J. Donoghue, issued Oct. 17, 1967 includes separate molded compartments having confronting vertical walls joined by a central web. Also, the walls do diverge. The outlets at the top of the two compartments are formed in segments of cylinders producing in toto a single threaded cylinder finish adapted to receive a screw cap.
In the past, pump dispensers have been concerned with the venting of the head space as the liquid is used. Such venting avoids the build-up of a negative pressure which could stop the dispenser from functioning properly In order to avoid leakage, the vent passage has frequently been provided with a valve operating in tandem with the pump. An example is disclosed in the Dennis U.S. Pat. No. 4,958,754, issued Sep. 25, 1990, wherein the vent valve comprises a separate valving cylinder receiving a valving piston reciprocating in tandem with the main pump piston. The valving piston, when pulled inwardly, provides clearance between the cylinder wall to permit venting. Such an arrangement was also disclosed in the Japanese patent 52-11686 of Mar. 15, 1977.
It has also been common in the past to "dress up" the otherwise functional appearance of pump dispensers, and this has frequently been done in the form of a snap-on shroud. Examples of such arrangements are found in the U.S. patents:
U.S. Pat. No. 3,820,721 Hellenkamp Jun. 28, 1974 PA1 U.S. Pat. No. 4,191,313 Blake et al Mar. 4, 1980 PA1 U.S. Pat. No. 4,257,539 Cary et al Mar. 24, 1981 PA1 British Publication application 2,244,522 Dec. 4, 1991