A paper pressing device for an image forming apparatus including an intermediate tray for temporarily holding a sheet of copy paper in the course of conveying the sheet of copy paper from a discharging side of the image forming apparatus to a feeding side of the image forming apparatus, a conveying path changer pivotably provided above the intermediate tray for changeably providing a first position of permitting a sheet of copy paper smaller than a predetermined size to move over the conveying path changer, and a second position of permitting a sheet of copy paper larger than the predetermined size to move under the conveying path changer, a pressing device attached to the conveying path changer and made of resilient material, the pressing means being pressable on a surface of the intermediate tray when the conveying path changer is set in the second position.

This invention relates to a paper pressing device for preventing warp of copy paper to be conveyed into an intermediate tray of an image forming apparatus, such as a copying machine.
In such a copying machine as both-side copyable copying machine and image-compositable copying machine, in which an image forming process is practiced to the same sheet of copy paper twice or more, after being passed through a fixing device, the copy paper is conveyed into an intermediate tray. The copy paper is temporarily kept in the intermediate tray and then conveyed again to an image forming position. When being passed through the fixing device, the copy paper is heated to one side thereof. Also, when being conveyed into the intermediate tray, the copy paper is bent in a large curvature, then causing a forward end poriton of the copy paper to warp upwards. Consequently, the copy paper is likely to jam in a copying mahcine. There has been needed a paper pressing device for preventing copy paper from warping.
FIG. 4 shows a conventional paper pressing device. Indicated at 81, 82, and 83 are pairs of conveying rollers for conveying copy paper to an intermediate tray 80. Between the two pairs of rollers 81 and 82 is a conveying path changer 85 pivotable about a horizontal shaft 84. When a small sheet of copy paper is conveyed, the conveying path changer 85 is set at a position illustrated by solid lines so that the copy paper is conveyed from the pair of conveying rollers 81 to the pair of conveying rollers 82 disposed in the downstream. When a large sheet of copy paper is conveyed, the conveying path changer 85 is set at another position illustrated by imaginary lines so that the copy paper is conveyed from the underside of the conveying path changer 85 directly onto the intermediate tray 80 as shown an arrow in FIG. 4.
A paper guide plate 86 is disposed in the downstream of the pair of conveying rollers 83. A pressing member 87 which is in the form of a strip and made of resilient material is disposed under the paper guide plate 86. An upper end poriton of the pressing member 87 is fixed on the underside of the paper guide plate 86 and a lower end portion of the pressing member 87 is pressed on an upper surface of the intermediate tray 80. The pressing member 87 is disposed in such a way that the lower portion of the pressing member 87 can press down an upward-warped forward end portion of a sheet of copy paper conveyed from the pairs of conveying roller 81, 83. After being passed through the pressing member 87, the copy paper is conveyed to a refeeding device 88, and conveyed to the image forming position again.
In the conventional device having the conveying path changer 85, the pressing member 87 can effectively press the upward-warped forward end portion of a small sheet of copy paper conveyed form the pair of conveying rollers 83. However, a large sheet of copy paper is conveyed directly onto the intermediate tray 80. Accordingly, there is a considerable distance between the pair of conveying rollers 81 and the pressing member 87. It could be seen that the forward end portion of the large sheet is likely to greatly warp upward before reaching the pressing member 87 as illustrated by an imaginary line P, and the pressing member 87 is likely to hinder the warped forward end portion of the large sheet to cause jamming.

Paper pressing device for an image forming apparatus


In a method of recognizing an irradiation field on a recording region of a recording medium on which one or more radiation image is recorded by limitation of the irradiation field, the recording region is divided into a plurality of small regions and the irradiation field is recognized for each of the small regions on the basis of image signals corresponding to the small region.

1. Field of the Invention
This invention relates to a method of recognizing an irradiation field in the case where a radiation image is recorded on a recording medium such as a stimulable phosphor sheet by limitation of the irradiation field of a radiation.
More particularly, this invention relates to a method of recognizing the irradiation field which can be effectively applied to both a case where only a single radiation image is recorded on one recording medium (This will be referred to as "single recording", hereinbelow.) and a case where the recording region on one recording medium is divided into a plurality of subdivisions and a plurality of radiation images are recorded on the respective subdivisions (This will be referred to as "subdivision image recording", hereinbelow.).
2. Description of the Prior Art
When certain kinds of phosphors are exposed to a radiation such as X-rays, .alpha.-rays, .beta.-rays, .gamma.-rays, cathode rays or ultraviolet rays, they store a part of the energy of the radiation. Then, when the phosphor which has been exposed to the radiation is exposed to stimulating rays such as visible light, light is emitted by the phosphor in proportion to the stored energy of the radiation. A phosphor exhibiting such properties is referred to as a stimulable phosphor.
As disclosed in U.S. Pat. No. 4,258,264 and Japanese Unexamined Patent Publication No. 56(1981)-11395, it has been proposed to use a stimulable phosphor in a radiation image recording and reproducing system. Specifically, a sheet provided with a layer of the stimulable phosphor (hereinafter referred to as a stimulable phosphor sheet) is first exposed to a radiation passing through an object such as the human body to have a radiation image of the object stored thereon, and is then exposed to stimulating rays such as a laser beam which cause the stimulable phosphor sheet to emit light in proportion to the stored radiation energy. The light emitted by the stimulable phosphor sheet upon stimulation thereof is photoelectrically detected and converted into an electric image signal, image processing is carried out on the electric image signal, and the radiation image of the object is reproduced as a visible image by use of the processed image signal on a recording medium such as a photographic film, a display device such as a cathode ray tube (CRT), or the like.
In the aforesaid radiation image recording and reproducing system, the level of the radiation energy stored on the stimulable phosphor sheet is caused to fluctuate among radiation images by changes in the object, the image recording portion thereof, radiation dose, or the like.
However, in the aforesaid radiation image recording and reproducing system, characteristics of the stored image information of each radiation image, particularly the level of the radiation energy or the like of each radiation image stored on the stimulable phosphor sheet, may be ascertained in advance, and the light emitted by the stimulable phosphor sheet may be photoelectrically detected by use of read-out conditions such as a read-out gain and a scale factor adjusted to appropriate values in accordance with the characteristics of the stored image information of each radiation image. In this case, for each radiation image, it becomes possible to obtain a visible image free from adverse effects of the fluctuation in the level of the radiation energy stored on the stimulable phosphor sheet and suitable for viewing, particularly for diagnostic purposes, for example, a visible image wherein the necessary object image information is always expressed within the correct density range suitable for viewing, particularly for diagnostic purposes.
Also, in the aforesaid radiation image recording and reproducing system, image processing of the image signal detected photoelectrically is carried out by use of image processing conditions such as gradation processing conditions adjusted for each radiation image based on the image recording portion of the object such as the head, chest or abdomen, and/or the image recording method such as plain image recording or contrasted image recording so that a visible image suitable for viewing, particularly for diagnostic purposes, can be obtained. However, for example, in the case where detection of the image signal is carried out without using the read-out conditions adjusted in accordance with the characteristics of the stored image information of each radiation image, the image processing conditions should preferably be adjusted by considering the characteristics of the stored image information of each radiation image, which have been ascertained in advance, besides the image recording portion of the object and/or the image recording method. In this manner, it becomes possible to obtain a visible image suitable for viewing, particularly for diagnostic purposes, wherein the necessary object image information is expressed within the correct density range.
Ascertaining of the characteristics of the image information stored on the stimulable phosphor sheet prior to the image read-out and image processing may be carried out by use of the method as disclosed in U.S. Pat. No. 4,527,060. In the disclosed method, a read-out operation for ascertaining the image information of a radiation image stored on the stimulable phosphor sheet (hereinafter referred to as the preliminary read-out) is carried out in advance by use of stimulating rays having stimulation energy of a level lower than the level of the stimulation energy of stimulating rays used in a read-out operation for obtaining a visible image for viewing, particularly for diagnostic purposes (hereinafter referred to as the final read-out), and thereafter the final read-out is carried out. The characteristics of the stored image information are ascertained based on the image information (preliminary read-out image signal) obtained by the preliminary read-out.
As mentioned above, the level of the stimulating rays used in the preliminary read-out is lower than the level of the stimulating rays used in the final read-out. Specifically, the effective energy of the stimulating rays which the stimulable phosphor sheet receives per unit area in the preliminary read-out should be lower than the effective energy of the stimulating rays used in the final read-out.
Another approach to the ascertaining of the characteristics of the image information stored on the stimulable phosphor sheet prior to image processing is to ascertain it based on the image information (image signal) detected by the final read-out. Though the characteristics of the stored image information ascertained in this manner cannot be used for adjusting the read-out conditions in the final read-out, they can be used for adjusting the image processing conditions. This method is effective in the radiation image recording and reproducing system wherein the preliminary read-out is not carried out.
Various methods have been proposed for ascertaining the characteristics of the stored image information based on the preliminary read-out image signal obtained by the preliminary read-out or the final read-out image signal obtained by the final read-out. As one of such methods, it has heretofore been known to utilize a histogram of the image signals (image signal levels). With this method, the characteristics of the stored image information may be ascertained based on, for example, the maximum signal value, the minimum signal value, or a signal value at which the frequency is the maximum in the histogram. Therefore, it becomes possible to reproduce a visible image having an improved image quality, particularly a high diagnostic efficiency and accuracy, by adjusting the final read-out conditions such as the read-out gain and the scale factor and/or the image processing conditions such as the gradation processing conditions and the frequency response processing conditions based on the maximum signal value, the minimum signal value, a signal value at which the frequency is the maximum, or the like in the histogram.
On the other hand, in the course of radiation image recording, it is often desired that portions of the object not related to diagnosis or the like be prevented from exposure to a radiation. Further, when the object portions not related to diagnosis or the like are exposed to a radiation, the radiation is scattered by such portions to the portion related to diagnosis or the like, and the contrast and resolution are adversely affected by the scattered radiation. Therefore, in many cases, the irradiation field is limited to an area smaller than the overall recording region on the stimulable phosphor sheet when a radiation image is recorded.
However, when the characteristics of the image information stored on the stimulable phosphor sheet are ascertained based on the histogram of the image signals, the problem as described below arises. As shown in FIG. 9, when an irradiation field 14 is limited to an area smaller than an image recording region 12 on a stimulable phosphor sheet 10 (In the case of the sheet 10 shown in FIG. 9, the image recording region 12 covers the whole area of the sheet 10.) and the preliminary read-out or the final read-out is carried out over an area markedly larger than the irradiation field 14, for example, over the overall image recording region 12 on the stimulable phosphor sheet 10, the characteristics of the image information actually stored within the irradiation field 14 are ascertained incorrectly. Specifically, in the aforesaid case, since the image signals at regions outside of the irradiation field 14 are also included in the histogram, the histogram does not accurately represent the actual image information stored within the irradiation field 14.
Therefore, in the case where radiation image recording is carried out by limiting the irradiation field, the characteristics of the stored image information are to be ascertained based on the preliminary read-out image signal or the final read-out image signal by the method as mentioned above, and the final read-out conditions and/or the image processing conditions are to be adjusted based on the ascertained characteristics, the irradiation field should be recognized and the characteristics of the stored image information should be accurately ascertained based only on the image signal within the irradiation field, thereby to eliminate adverse effects of the scattered radiation outside of the irradiation field.
Besides the case wherein the read-out conditions and/or the image processing conditions are to be adjusted for a radiation image stored on the stimulable phosphor sheet, recognition of the irradiation field is also necessary for various purposes in the case where a radiation image is recorded on a recording medium by limitation of the irradiation field.
The applicants have proposed various methods of recognizing the irradiation field 14 as disclosed in, for example, U.S. Pat. No. 4,851,678. However, though those methods can be suitably applied in the case of the single recording where only a single radiation image is recorded on one single recording medium and accordingly, only one irradiation field is on the recording medium, most of them are difficult to apply in the case of the subdivision image recording where a plurality of radiation images are recorded on a plurality of respective subdivisions of one recording medium with the irradiation field being limited for each recording and accordingly, a plurality of irradiation fields are on the recording medium.
For example, as a method of recognizing the irradiation field, there has been proposed an algorism utilizing Hough conversion. In the algorism, prospective edge points which are considered to be edge (contour) portions of the irradiation field on the recording medium are detected from image signals read out from the recording region of the recording medium, curves represented by formula EQU .SIGMA.=x.sub.o cos .theta.+y.sub.o sin .theta.
are obtained for the respective prospective points wherein x.sub.o and y.sub.o respectively represent the x coordinate (constant) and the y coordinate (constant) of a given prospective point when the positions of the prospective points are expressed with an x-y orthogonal coordinate system, straight lines defined by formula EQU .rho..sub.o =x cos .theta..sub.o +y sin .theta.o
in the orthogonal coordinate system (straight lines along the prospective points, e.g., straight lines 1.sub.1 to 1.sub.4 in FIG. 9) are obtained on the basis of the intersections of the curves thus obtained, and the regions surrounded by the straight lines or the regions surrounded by the straight lines and the outer edge of the recording region (in the case that the irradiation field 14 is positioned as shown in FIG. 10 with respect to the recording region 12 of the recording medium) are recognized as the irradiation field.
In this algorism, there can be a plurality of regions surrounded by the straight lines obtained by Hough conversion or by the straight lines and the outer edge of the recording region, and sometimes which region is the true irradiation field must be determined. For example, which region is the true irradiation field can be determined by detecting the center point of the recording region or the center of density (image signal level) gravity and recognizing the region including the center point or the center of density gravity as the irradiation center.
However, though the center point of the recording region or the center of density gravity is inherently positioned in the irradiation field in the case of the single recording, they are apt to be positioned outside the irradiation fields in the case of the subdivision image recording. Particularly, the center of density gravity can be positioned only in one of the irradiation fields in the case of the subdivision image recording.
Accordingly, though the irradiation field recognizing algorism can be suitably applied in the case of the single recording, a region outside the irradiation field can be mistaken for the irradiation field or only one of the irradiation fields can be recognized when the algorism is applied in the case of the subdivision image recording. That is, the algorism can be applied only when it is known in advance that the recording on a given recording medium is the single recording, and when the recording on a given recording medium is the subdivision image recording, or when it is not known which of the single recording and the subdivision image recording has been made on a given recording medium, the algorism is difficult to apply.


Described is a preferred rotary spray chamber device for conditioning an aerosol. The device has chamber walls defining an internal chamber and an inlet opening into the internal chamber. The inlet opening is located such that an aerosol directed into the chamber through the inlet opening tangentially contacts chamber wall areas adapted to impart a rotary motion to the aerosol within the chamber. An impact member extends inwardly into the chamber from a chamber wall location such that the member is impacted by the aerosol in its rotary motion so as to remove large droplets and thus form a conditioned aerosol. An exit opening is defined by the chamber walls through which the conditioned aerosol can exit the chamber, and a drain opening is also defined by the chamber walls through which liquid removed from the aerosol and collected in the chamber can exit the chamber.

The present invention relates generally to a device for conditioning an aerosol such as that resulting from the nebulization of a liquid sample, and more particularly to a device for removing large droplets from an aerosol stream so as to enable improved stability of analytical signals derived from the aerosol.
Since the early days of flame emission spectrometry, it has been realized that a spray chamber placed between the nebulizer and burner could function as a droplet separator and a flow buffer to remove large droplets from the sample aerosol and thereby improve the stability of analytical signals derived from the aerosol. Usually such spray chambers were made from available laboratory glassware. Yet, even these relative crude early designs were so effective that similar spray chamber units are still commonly employed today in atomic absorption and flame emission instrumentation. These spray chambers were later scaled down, somewhat modified and adapted to use in inductively coupled plasma spectrometry.
In all of these spray chambers, the removal of large droplets is inevitably accompanied by a reduction in the transport efficiency of aerosol and analyte to the subsequent atomization/excitation source. For example, measurements carried out on a typical inductively coupled plasma (ICP) nebulizer/spray chamber system reveal that more than 98% of the aerosol is lost to waste. As a result, the transport efficiency of a typical ICP system is only in the range of about 0.5%-2%. Also, fine droplets are suspended and circulate inside the spray chamber, resulting in relatively long wash-out times. For a typical system, it usually takes several minutes to change a sample. Such recognized low transport efficiencies and large memory effects have existed in atomic spectrometry for nearly a half century and they remain among the weak links in the field.
Continuing efforts have been made to improve nebulizer/spray chamber systems. Single- and double-barrel Scott-type spray chambers, cyclone configurations, baffles, and gravitational sedimentation chambers have been used in inductively coupled plasma emission spectrometry (ICP-AES). Other techniques have also been explored to circumvent conventional nebulizer-spray chamber systems. For example, jet-impact and direct-injection nebulization have been used with inductively coupled plasma emission and mass spectrometry. Fundamental investigations into aerosol characterization have offered some insight into the performance of aerosol chambers and its dependence on centrifugal force, evaporation, gravitation, impaction, and turbulence. Nevertheless, there still exists a need for improved spray chambers providing increased throughput and stability to analytical signals derived from sample aerosols. The present invention addresses this need.

Rotary spray chamber device for conditioning aerosols


The invention provides for a method of operating a magnetic resonance imaging system for imaging a subject. The method comprises acquiring (700) tagged magnetic resonance data (642) and a first portion (644) of fingerprinting magnetic resonance data by controlling the magnetic resonance imaging system with tagging pulse sequence commands (100). The tagging pulse sequence commands comprise a tagging inversion pulse portion (102) for spin labeling a tagging location within the subject. The tagging pulse sequence commands comprise a background suppression portion (104). The background suppression portion comprises MRF pulse sequence commands for acquiring fingerprinting magnetic resonance data according to a magnetic resonance fingerprinting protocol. The tagging pulse sequence commands comprise an image acquisition portion (106). The method comprises acquiring (702) control magnetic resonance data (646) and a second portion (648) of the fingerprinting magnetic resonance data by controlling the magnetic resonance imaging system with control pulse sequence commands. The control pulse sequence commands comprise a control inversion pulse portion (202). The control pulse sequence commands comprise the background suppression portion (104′). The control pulse sequence commands comprise the image acquisition portion (106). The method comprises reconstructing (704) tagged magnitude images (650) using the tagged magnetic resonance data. The method comprises reconstructing (706) a control magnitude images (652) using the control magnetic resonance data. The method comprises constructing (708) an ASL image by subtracting the control magnitude images and the tagged magnitude images from each other. The method comprises reconstructing (710) a series of magnetic resonance fingerprinting images (656) using the first portion of the fingerprinting magnetic resonance data and/or the second portion of the fingerprinting magnetic resonance data. The method comprises generating (712) at least one magnetic resonance parametric map (658) by comparing the series of magnetic resonance fingerprinting images with a magnetic resonance fingerprinting dictionary.

Magnetic Resonance fingerprinting (MRF) is a technique where a number of RF pulses often associated with appropriate gradient switching, distributed in time, are applied such that they cause signals from different materials or tissues to have a unique contribution to the measured Magnetic Resonance (MR) signal. A dictionary of precalculated signal contributions from a large set or a fixed number of substances is compared to the measured MR signals within each single voxel. Furthermore, also the composition within each voxel can further be determined. For example if it is known that a voxel only contains gray matter, white matter, CSF, or fat the contribution from these three materials need only be considered to accurately determine the composition of the voxel. If a larger dictionary with higher resolution is used, MR fingerprinting can be used to determine different tissue parameters of a voxel (such as T1, T2, . . . ) simultaneously and quantitatively.
The magnetic resonance fingerprinting technique was introduced in the journal article Ma et al., "Magnetic Resonance Fingerprinting," Nature, Vol. 495, pp. 187 to 193, doi:10.1038/nature 11971. The magnetic fingerprinting technique is also described in United States patent applications US 2013/0271132 A1 and US 2013/0265047 A1. A large static magnetic field is used by Magnetic Resonance Imaging (MRI) scanners to align the nuclear spins of atoms as part of the procedure for producing images within the body of a patient. This large static magnetic field is referred to as the B0 field.
During an MRI scan, Radio Frequency (RF) pulses generated by one or more transmitter coils cause a called B1 field. Additionally applied gradient fields and the B1 field cause perturbations to the effective local magnetic field. RF signals are then emitted by the nuclear spins and detected by one or more receiver coils. These RF signals are used to construct the MR images. These coils can also be referred to as antennas.
MRI scanners are able to construct images of either slices or volumes. A slice is a thin volume that is only one voxel thick. A voxel is a small volume element over which the MR signal is averaged, and represents the resolution of the MR image. A voxel may also be referred to as a pixel (picture element) herein if a single slice is considered.
By performing different magnetic resonance imaging protocols (which are implemented as pulse sequences or pulse sequence commands), different types of information can be measured about a subject. For example, there are various techniques, which enable the encoding of spins such that the flow or diffusion of fluid can be directly measured. Arterial spin tagging is a technique where the spins of blood passing through a group of arteries or even single arteries can be magnetically labeled and then imaged. The reference book "Handbook of MRI Pulse Sequences" (hereafter "Handbook of MRI Pulse Sequences") by Bernstein et. al., Elsevier, 2004, ISBN 978-0-12-092861-3 describes in section 17.1 (pp. 802 through 829) provides a review of several different arterial spin tagging techniques.

Combined arterial spin labeling and magnetic resonance fingerprinting


A wood adhesive formulation containing furfuryl alcohol, lignin, maleic anhydride, and iron and zinc catalysts.

The present disclosure relates to a novel and economical process for preparing bonded wooden substrates using an adhesive formulation based on a by-product obtained from a chemical pulping process. The adhesive formulation, which is novel and also forms part of the present invention, contains two parts, a reactive component and a catalyst component. When the two parts are mixed together and heated under pressure, they produce a strong, persistent bond.
The process of the present disclosure differs from processes commonly known in the arts to produce bonded wooden substrates. The wooded substrates are not pretreated with a chemical prior to bonding. It is not preferred to have a pretreatment step because it is an extra and expensive operation. Also, the chemical pretreatment is often performed with a substance having a low pH. Such acidic substances can cause degradation of the wood and weakening of the adhesive bond. The present process therefore avoids any chemical pretreatment of the wood prior to bonding.
The present process also differs from processes in the prior art in that the adhesive formulation contains a synergistic mixture that allows for spreading and assembly before curing, but cures very quickly upon heating. This allows for the preparation of a strong chemical bond, because the adhesive formulation is prevented from penetrating too deeply into the wood. A strong bond is therefore formed before the glue line is starved.
It is also an advantage of the present invention to employ a by-product from a chemical pulping process which is usually discarded as a waste product. Lignin is the inter-cellular material which binds together wood fibers to make solid wood. Lignin also stiffens the cell wall of the wood. Chemical pulping processes break down the lignin to release the wood fibers, the lignin being solubilized and removed, at least in part. The final product is a useful wood fiber pulp and a waste by-product of lignin in water or an organic solvent. There has been an ongoing search for new uses of lignin because of the large volumes of chemical pulp produced in the world. To this date, there have been limited opportunities for upgrading dissolved lignin.
Lignin is an adhesive in its natural state. Since dissolved lignin has reactive groups that should allow it to react in adhesive formulations, lignin has been employed in various wood adhesive formulations. Usually the lignin is employed simply as an extender in adhesives based on phenol-formaldehyde and the like.
U.S. Pat. No. 5,288,774, issued to Gardziella et al, relates to a refractory molding composition containing a novel binding agent. The binding agent is a lignin-furan resin mixture, the lignin being sulfur-free and having a low molecular weight. The furan resin is preferably a co-condensation resin of furfuryl alcohol and at least one member selected from the group consisting of formaldehyde and urea. The binding agents produced from these resin mixtures split off formaldehyde in the curing process to a greatly reduced extent in comparison to conventional furfuryl alcohol-formaldehyde resins and they are therefore not only more economical but also not harmful to the environment since the formaldehyde content at the workplace can be considerably lowered through the use of the raw material lignin.
U.S. Pat. No. 4,474,636, issued to Bogner, relates to novel binder compositions useful in the fabrication of composite articles such as fiber reinforced composite articles. In a most preferred embodiment, the resin binders for fabricating glass-reinforced laminates are furfuryl alcohol homopolymers, diluted with hydroxymethyl furfural. Also, the binder compositions have excellent strength characteristics and can be used advantageously in the manufacture of pressure molded medium or high density composite articles such as particle board, wafer board, oriented fiberboard, mat board, hardboard, pressboard, fiberglass board, and the like. The binder compositions can also be used in the manufacture of low density non-molded composite articles such as acoustical tile and thermal insulating mats or boards.
U.S. Pat. No. 4,357,194, issued to Stofko, relates to a method of bonding solid lignocellulosic materials with an adhesive-free bonding material comprising at least one sugar, starch or mixture thereof. The method includes the step of using live steam to heat the interior of the solid lignocellulosic material to a temperature of about 320xc2x0 F. to about 420xc2x0 F. The live steam activates phenolic material on the surfaces of the solid material, the activated phenolic material then reacting with the sugar, starch or mixture thereof. The phenolic material is preferably a lignin. In a preferred embodiment, the adhesive-free bonding material is a mixture of molasses and sulfonated lignin.
U.S. Pat. No. 4,183,997, issued to Stofko, relates to a method of bonding solid lignocellulosic materials with an adhesive-free bonding composition having a specified pH and containing sugar, starch or mixtures thereof. The adhesive-free composition also contains an alkaline buffering agent and a suitable catalyst. A suitable catalyst is zinc chloride.
U.S. Pat. No. 4,769,434, issued to Van der Klashorst et al, relates to a polymeric material which contains a reaction product from grass plant lignin derivatives. Lignin polymer fragments which have been recovered from black liquor obtained in the pulping of grass plant material are reacted with an electrophilic compound capable of reacting twice at one site or at least once at each of two different sites of the compound. The polymeric material is substantially the result of a cross-linking of the various lignin fragments by the electrophilic reactant. In a preferred embodiment, the electrophilic reactant is an aldehyde. The polymeric material can be employed as an adhesive used in the manufacture of wood products such as particle board, plywood, finger joints and the like. A filler such as nut shell flour can be included in the adhesive.
Canadian Pat. No. 409,226, issued to Marathon Paper Mills Company, relates to a resin product which is prepared by reacting furfuryl alcohol with a partially desulfonated lignin-sulfuric acid.
Canadian Pat. No. 1,128,241, issued to Holmens Bruk A B, Sweden, relates to a method of producing an adhesive for wood products. In the method, a waste product containing sugar and lignin is heated in a strongly acidic environment. This step gives a reaction mixture containing furfural derivatives. The reaction mixture is then further reacted to give a reaction product between the furfural derivatives and the lignin, the reaction product being an adhesive binder containing the condensation products of lignin and furfural derivatives.
The preferred process for producing the bonding wooden substrates employs a novel adhesive formulation which is a two-part composition which can be mixed and used as a wood adhesive. The two-part composition comprises: (a) a reactive component comprising furfuryl alcohol monomer and a by-product obtained from a chemical pulping process, and (b) a catalyst component comprising zinc chloride, iron (III) chloride hex hydrate and maleic anhydride. The by-product is a polymer mixture comprising lignin and a liquid solvent. The liquid solvent is selected from water, an organic solvent and mixtures thereof. Typical organic solvents are hydrocarbons, ethers, alcohols and the like.
The lignin can be obtained from the wood of coniferous trees a well as lignin obtained from the wood of deciduous trees. In a preferred embodiment, the lignin can be obtained from the organosolve process under comparatively mild conditions, since its chemical structure has only slightly been changed through the effect of the processing conditions.
The process of the present invention comprises the steps of; obtaining two or more wooden substrates; coating at least one of the wooden substrates with the two-part adhesive formulation disclosed above; contracting the at least one coated substrate with a second wooden substrate to obtain a bondable wooden structure; and heating the bondable wooden structure, optionally under pressure, to obtain a bonded wooden structure. In a preferred embodiment, the heating step is performed in a hot press under suitable conditions of temperature and pressure.
The wooden substrate can be selected from a variety of well-known products. Some examples of these products are: lumber, veneer, plywood, wood wafers and wood particles and wood fibres.
In a preferred embodiment, the two-part adhesive composition comprises lignin in an amount of about 10% to about 30% by weight. The furfuryl alcohol monomer is present in an amount of about 30% to about 50% by weight. The maleic anhydride component, which acts both as part of the catalyst complex and also as a coupling agent to enhance bonding to the wood, is present in an amount of about 5% to about 15% by weight.
The zinc chloride is present in an amount of about 0.5% to about 5% by weight. The iron (III) chloride hexahydrate is present in an amount of about 0.5% to about 5% by weight.
The catalyst component can also contain nut shell flour and methanol. The nut shell flour can be present in an amount of about 5% to about 20% by weight.
In another preferred embodiment, the novel adhesive formulation can be a one-part composition comprising: furfuryl alcohol monomer, a by-product obtained from a chemical pulping process, zinc chloride, iron (III) chloride hexahydrate and maleic anhydride. The by-product contains lignin. The one-part composition can also contain nut shell flour and a solvent such as methanol.
According to one embodiment of the invention, wooden surface to be bonded are covered either by a continuous or discontinuous film, eg., by a mist of droplets, of an adhesive formulation comprising furfuryl alcohol monomer, a lignin containing by-product obtained from a chemical pulping process, zinc chloride, iron (III) chloride hexahydrate, maleic anhydride and, optionally, nut shell flour and a solvent such as methanol. The so coated surfaces are brought into contact with other wooden surfaces, themselves either similarly coated or not, and the so contacting surfaces are consolidated by heat and pressure for a time sufficient to effect the bonding by chemical transformation reaction of the components.
While the invention is described in relation to the bonding of wooden (lignocellulosic) materials, it will be understood that bonding formulations, containing furfuryl alcohol and/or polymerized furfuryl alcohol resin along with a lignin material and various catalytic agents as described above, can also be used for the bonding of a wide variety of materials such as glass and other mineral fibers, foundry sands, rubber, synthetic polymers and many other substances, either by themselves or in admixture with one another or in admixture with lignocellulose. An example of a product formed from material other than wood is a flexible, stress-resistant composite mat prepared from glass fibers and the herein described adhesive formulation.
Adhesive compositions for use in the present invention and containing furfuryl alcohol and/or furfuryl alcohol resin, a lignin-containing by-product material and catalytic agents as described above, can be applied to the surfaces to be bonded in a variety of ways. For example, such compositions can be used in liquid form such as in water solution-suspension, or in powder form. Liquid formulations can be applied either hot or cold, and the surfaces to be bonded can also be either hot or cold.
As sources of lignin there can be used any kind of lignin containing material such as spent sulfite liquor or kraft spent liquor produced as wastes or by-products in pulping wood, or lignin from wood alcoholysis, phenolysis or hydrolysis.
The adhesive compositions may also contain other optional materials including other chemical reagents capable of affecting the bonding reaction, eg., accelerating agents, retarding agents, plasticizes, cross linking agents and the like.
The amount of bonding composition to be used is also subject to considerable variation, depending on the nature of the product, the surface roughness and the desired properties of the product. In production of wood laminates such as plywood, the quantity of bonding composition will range between about 2 and about 50 grams of mixed solids per 1,000 cm2 of the surface to be bonded. In the production of composite products such as particle board or fiber board, the quantity of bonding composition on dry basis will be between about 1% and 25% of solids in the composition to 100% dry weight of substrate, depending on the desired final properties.
Conditions in the hot press may also vary widely depending on a number of variables, such as the type of lignin, type of wood, presence or absence of optional materials, and requirements of the product. As is usual in the pressing of wood products, the lower the temperature the longer the press time required, and vice versa. In general, the preferred temperature range is about 140xc2x0 C. to about 250xc2x0 C. The pressing time required under these conditions is the time needed to raise the temperature in the center of the product to a level of about 150xc2x0 C. to about 220xc2x0 C.
Lignin is the most abundant natural aromatic organic polymer found in all vascular plants. Lignin is composed of coniferyl, p-coumaryl and sinapyl alcohols. This invention relates to the utilization of lignin derivatives produced as waste products in the pulping industry. Large tonnages of such materials are produced during the chemical pulping of wood and other plant material, but they have been used principally only for their combustion value in the formation of an incinerator product from which pulping chemicals can be recovered. In some cases the black liquor containing the lignin derivatives and spent pulping chemical is simply discarded into rivers and the sea, causing a pollution problem.
It has been proposed to utilize the lignin derivatives contained in black liquors obtained from the pulping of hardwoods and softwoods both by the sulphite and alkali pulping processes, but as yet no major commercial use of the waste products has transpired. The principal direction of investigation of uses for lignin derivatives has been in the polymer field, lignins being high molecular weight compounds formed by the biosynthetic polymerization of certain closely related phenyl-propenol precursors. During pulping the lignin polymers are broken down to provide the lignin derivatives which are by nature degradation products comprising lignin polymer fragments incorporating phenyl propane units which may present reactive sites through which re-polymerization reactions can occur.
Much work has been directed at the separation of alkali lignin and lignosulfonate degradation products from black liquors, and the reaction of these with aldehydes for the formation of phenol-formaldehyde type resins and adhesives. This has included the partial substitution of the phenol by the lignin derivatives, but without a satisfactory product having been achieved. It is believed that the main reason for the lack of success is the poor reactivity of the lignin polymer fragments due to the insufficient number of sites on each fragment which are reactive with formaldehyde. The poor reactivity manifests itself in unsatisfactory cross linking in a proportion of the lignin fragments which results in poor adhesive properties.
During alkaline pulping the lignin macromolecule is degraded by cleavage of base labile ether bonds. The cleavage of aryl ether bonds results in the formation of phenols which exist as phenolate salts under the alkaline conditions during pulping and render the lignin fragments soluble. A decrease of the pH to below the pH value of the phenol reverses the dissociation of the lignin phenol groups and the lignin precipitates from the solution.
Preferably, the two-part adhesive composition is prepared as follows. The reactive component of the composition is prepared by forming a solution of methanol, zinc chloride and iron (III) chloride hexahydrate. An amount of furfuryl alcohol (2-hydroxymethyl furan) is added to this solution. The solution is then heated under conditions suitable for polymerizing the furfuryl alcohol. The polymerized product should have a viscosity of about 800 centipoises. To this polymerized product is added the lignin-containing by-product and walnut shell flour. The so-obtained reactive component can then be activated by addition of the catalyst component prior to hot pressing. Ingredients of the catalyst component are: maleic anhydride, zinc chloride and iron (III) chloride hexahydrate. In an alternative embodiment, the two-part adhesive composition is prepared by obtaining a reactive component as follows. A lignin-containing by-product is mixed with furfuryl alcohol monomer. To this mixture is added a solution of maleic anhydride in methanol. The ratio of maleic anhydride to furfuryl alcohol, based on weight, is about 1:25. The entire mixture is then heated at a temperature of about 75xc2x0 C. to obtain a resin composition having a viscosity of about 200 centipoises. The so-obtained reactive component can then be activated by addition of the catalyst component prior to hot pressing, Ingredients of the catalyst component are: maleic anhydride, zinc chloride and iron (III) chloride hexahydrate.
The invention will be illustrated in greater detail by the specific examples which follow, it being understood that these preferred embodiments are illustrative of, but not limited to, procedures which may be used in the production of adhesively bonded wood products. Parts and percentages are by weight unless otherwise indicated.

Furfuryl alcohol and lignin adhesive composition


A pair of bracket assemblies for mounting on the handlebars of a bicycle to enable use of a bicycle lock as an auxiliary handlebar. The bicycle lock includes a U-shaped member with spaced parallel legs. Each of the legs is supported in a separate bracket assembly. The bracket assemblies incorporate arm rests and permit longitudinal adjustment of the legs. Various types of release and securing mechanisms are disclosed which enable adjustment and removal of the bicycle lock, including angular adjustments of the legs of the U-shaped member with respect to the handlebar.

1. Field of the Invention
This invention relates to a combination bicycle lock/handlebar assembly, and more specifically to such a device in which a lock is capable of use for locking a bicycle in a standard manner, and in which the lock also is removably attachable to existing handlebars of the bicycle to provide an auxiliary handlebar-and-arm rest assembly, which enables a rider to adopt a riding position which is both comfortable and aerodynamic.
2. Description of the Prior Art
As bicycling continues to play an increasing role in personal transportation, such as for commuting, running errands, shopping and/or for other reasons, including exercise and pleasure, the ability to immobilize the bicycle against movement to prevent theft, such as by securing parts of the bicycle together and/or to a stationary object, has become more and more important. At the same time, the ability of a rider to ride in an enjoyable and efficient manner, including the ability to assume various aerodynamic positions with ease and comfort, also has become similarly important.
Bicycle locks of the type comprising a U-shaped shackle member having a bight portion and spaced parallel legs which can be releasably locked to an elongated cross-bar member, are known in the prior art. For example, such locking devices are disclosed in U.S. Pat. Nos. 4,674,306 to Offer Halpern, 4,888,967 to Li-Tsao Kuo and 5,092,142 to Michael S. Zane et al. The use of a handlebar which comprises a generally U-shaped portion extending forward over a front wheel of a bicycle, with an upwardly inclined forward end portion to facilitate gripping of the handlebar by the rider, also is known from U.S. Pat. No. 4,951,525 to Lucio Borromeo. U.S. Pat. No. 4,878,397 to Dan C. Lennon further discloses a handlebar having a forwardly extending gripping portion and provided with arm rests for the rider, and handlebars with arm rests also are disclosed in U.S. Pat. Nos. 4,873,886 to Rolf Renner and 5,000,469 to Cedric J. Smith.
U.S. Pat. No. 5,163,339 to Edward H. Giard, Jr. et al discloses an auxiliary handlebar with arm rests, wherein the handlebar is longitudinally extendible. PCT application WO 91/16231 published Oct. 31, 1991 by applicant Badgematic, GmbH, discloses an auxiliary handlebar with arm rests which are longitudinally and transversely adjustable.
With prior known bicycle locks, however, when the bicycle is being used for riding and the lock thus is not being used for locking purposes, it then is necessary to store the lock on the bicycle in a suitable manner. This is disadvantageous from the rider's standpoint, particularly in the case of certain locks which are relatively cumbersome and difficult to store, since the storage of the lock on the bicycle interferes with the ability of the rider to ride the bicycle in an enjoyable, comfortable and unimpeded manner.
It has been suggested in U.S. Pat. No. 5,133,568 to Alisa M. Balterman and in U.S Pat. No. 5,138,901 to Ara N. Dabandjian, et al, that a U-shaped bicycle lock can be mounted on the handlebar and used as an auxiliary handlebar to steer the bicycle. These latter patents, however serve to clamp the lock cross member in one or more brackets and have no provision for longitudinal adjustment, i.e., in a front-to-back direction, for rider comfort or for accommodating different styles of bicycle handlebars. Furthermore, the mounting brackets have no provision for arm rests which must be separately provided.
Accordingly, a purpose of this invention is to provide a combination bicycle lock/handlebar assembly by which a lock can be used to lock the bicycle when the bicycle is not in use, and the lock also can be used as an auxiliary handlebar which contributes to the ease and comfort of the rider when the bicycle is being used for riding purposes. To achieve this purpose, the combination bicycle lock/handlebar assembly further includes bracket mechanisms by which the lock can be quick-releasably mounted on existing handlebars of a bicycle, with the bracket mechanisms further including arm rests which cooperate with the lock in its auxiliary handlebar position.
Another object of the inventions to provide adjustable bracket mechanisms for such an auxiliary handlebar, which include arm rests and accommodate a variety of handlebar shapes and rider preferences.

Combination bicycle lock/handlebar assembly


Technologies and techniques for supporting an autonomous vehicle wherein objects in surroundings of the vehicle are captured by a sensor system, and wherein objects are identified and recognized by object recognition from captured data relating to the surroundings. When an unknown object is present in the surroundings, the unknown object if found in at least one database, typical properties of the unknown object are determined on the basis of the search result, a recommended course of action is derived for the autonomous vehicle on the basis of the typical properties of the unknown object, and the derived recommended course of action are provided to the vehicle.

Corner cases, in particular the appearance of unknown objects in the surroundings, pose a major challenge for autonomous vehicles. The reason for this is that algorithmic processes or artificial-intelligence-based processes cannot recognize all objects, due to the large number of objects that can be encountered in any surroundings. Therefore, situations occur, again and again, when unrecognized objects are present in the surroundings of the vehicle. Such objects may be, for example, animals, persons on a roadway, accumulations of leaves or other objects which are generally not or only seldom encountered in traffic. In such a situation, the vehicle usually stops the autonomous trip and awaits a human operator's instructions.
DE 10 2015 006 255 T5 discloses an object recognition device. This object recognition device includes a capturing unit configured to capture a recognition target image serving as an object to be recognized; a retrieval unit configured to search an image database storing a plurality of image data in association with tag information and to retrieve a similar image that matches the recognition target image; and a recognition unit configured to recognize the object contained in the recognition target image on the basis of tag information associated with a similar image obtained by the retrieval unit. The recognition action may select the tag information that is most frequently encountered among the pieces of tag information that is associated with the similar image as a recognition result. The recognition unit may also calculate a tag information reliability score of the similar image in the retrieval result and recognize an object taking into account the reliability score.
US 2018/0217607 A1 discloses a system for object recognition. In this case, objects are recognized in captured sensor data on the basis of a road object database, an image feature database and/or an Internet-coupled database and taken into account for autonomous driving.
DE 10 2009 016 580 A1 discloses a data processing system and a process for providing at least one driver assistance function. By capturing an image, a stationary receiving unit for receiving image data receives the surroundings of the vehicle by means of at least one image capturing unit of a vehicle and generates image data. A stationary processing unit processes at least a part of the received image data, wherein the stationary processing unit generates driver assistance data with at least one piece of driver assistance information on the basis of the image data, wherein, with the aid of the generated driver assistance information, at least one piece of driver assistance information can be generated in the vehicle. A sending unit sends the driver assistance data to the vehicle.
DE 10 2012 107 886 A1 discloses a process for electronic recognition of traffic signs, wherein basic patterns, which are typical of a traffic sign, are recognized from the image data from a camera disposed in a vehicle, wherein it is provided for the data of the recognized basic pattern to be transferred wirelessly to an external server unit by means of a communication device of the vehicle for transmitting and receiving data, pattern recognition to be carried out by means of a pattern recognition algorithm from the external server unit, and as a result of the pattern recognition the data of the recognized traffic sign to be transferred to the communication unit of the vehicle, and a corresponding traffic sign to be shown, in particular, on a display unit.
U.S. Pat. No. 9,495,874 B1 discloses a process and apparatus for determining one or more behavior models used by an autonomous vehicle to predict the behavior of detected objects. The autonomous vehicle may collect and record the object behavior using one or more sensors. The autonomous vehicle may then communicate the recorded object behavior to a server operative to determine the behavior models. The server may determine the behavior models according to a given object classification, actions of interest performed by the object, and the object's perceived surroundings.
Methods for handling unknown objects while engaging in autonomous driving are currently unsatisfactory.
The present disclosure is based on the object of providing a process and a system for supporting an autonomous vehicle, which improves the handling of unknown objects in the surroundings of the vehicle.

Process and system for supporting an autonomous vehicle


A machine for fitting and removing a tyre from a corresponding rim of a wheel of a vehicle, comprising: a wheel-holder unit rotating about a first axis (A) and slidably coupled to a groove provided in a base; a column; an upper operating head, provided with at least one upper fitting tool, at least one further tool, angularly spaced from the upper fitting tool, by a predetermined angle, and a wall pressing tool that can be placed in a working position which is operatively in contact with the wheel simultaneously with the upper fitting tool.

This invention relates to a machine and a method for fitting and removing a tyre.
To perform the removal of a tyre from a rim and the subsequent fitting operation, the state of the art consists of tyre changer machines having a wheel-holder unit and at least one operating unit.
The wheel-holder unit is designed to support and rotate the wheel about an axis. The operating unit comprises the tools used in different operating steps which entail:                detaching the bead of the tyre from the annular end (that is, edge) of the rim (process also known as bead breaking);        removing the tyre from the rim, that is, removing the tyre from the housing defined by the space between the two annular edges of the rim;        fitting a new tyre on the rim, that is, positioning a new tyre in the housing.
It should be noted that the expression "tyre changer machine" is commonly understood to refer to a machine which is able to both remove the tyre from the rim and then perform the fitting operation. It should also be noted that the term "bead" denotes the portion of the tyre running round the annular edge of the rim.
The wheel-holder unit comprises, for example, a locking system which fixes the wheel to a rotary supporting plate. Typically, the axis of rotation is vertical, even though it is preferable to adopt a solution with a horizontal axis if the machine is designed to operate on wheels of heavy vehicles.
The operating unit usually comprises at least one bead breaker tool (or bead breaker disc). During use, the rubber of the tyre bead overheats and the bead adheres to the rim due to a rubber vulcanization phenomena; it is therefore necessary to detach the bead from the edge of the rim before starting the removal step. During the bead breaking step, the wheel is rotated by the wheel-holder unit and the bead breaker tool exerts a pressure on the side wall of the tyre close to the bead causing detachment from the edge of the rim.
It should be noted that a tyre has two beads, corresponding to the two annular edges of the rim, so the tyre changer machines usually have a pair of bead breaker disks, each of which is designed to act on a corresponding bead of the tyre.
The rotary wheel-holder unit has a free end, to which the wheel is fixed, and an opposite end, connected to a drive unit. The positioning of the wheel on the wheel-holder unit makes it possible to define a lower side and a bead of the tyre, facing towards the end of the wheel-holder unit connected to the drive unit, and an upper side and a bead of the tyre, facing in the opposite direction to the lower side.
For this reason, the tools designed to act on the upper bead are referred to as upper tools, whilst the tools designed to act on the lower bead are referred to as lower tools.
In the tyre changer machines wherein the wheel-holder unit is configured with a vertical axis, the lower side and bead of the tyre face towards the supporting surface of the machine, that is to say, downwards, whilst the upper side and bead of the tyre face in the opposite direction relative to the lower side, that is to say, upwards.
The tyre changer machines are equipped with numerous tools, for bead breaking, removal and fitting of the tyre; typically, the tyre changer machines have tools designed to operate (in the bead breaking, removal and fitting steps) on the upper bead of the tyre and other, different, tools designed to operate (in the bead breaking, removal and fitting steps) on the lower bead of the tyre.
Each operating step requires the use of a specific tool or a specific combination of tools. In light of this, it should be noted that, typically, each tool is mounted on a respective supporting arm, actuated by a respective actuator and moved on a relative guide.
The presence of many movement apparatuses limits the vision of the operator in the proximity of the zone in which the machine operates on the wheel, hindering the freedom of movement of the operator.
This also translates into a significant increase in the dimensions of the tyre changer machines, which have a rather complex structure. The complexity of the machines increases the production and maintenance costs. Moreover, the increased complexity of these machines makes them more difficult to use by the operator to detriment of the reliability, thereby increasing the risks of error.
A partial solution to these problems is provided by patent document EP1479539, which has a machine having an operating head wherein a bead breaker disc is connected to a fitting/removal tool; this tyre changing tool is moved by a mechanism which allows it to change from one working position (that is, operational) to a non-interference position (that is, rest).
Patent document EP2125394 shows a machine having a rotary operating head with two tools; more specifically, the operating head has a bead breaker disc and a removal tool. The rotation of the head allows the selection of the tool. The same arm is connected to a fitting tool which, thanks to a hinge coupling, can be lowered or raised to adopt alternatively an operating position or a non-interference position.
Patent document EP1946946 shows a machine having a rotary operating head which supports three tools (a bead breaker tool, a removal tool and a fitting tool) arranged at 120°, in such a way as to be selectively and alternatively positionable in the operating position by rotating the operating head.
However, these tyre changer machines also have certain shortcomings, because they do not allow the tyre to be mounted in a particularly simple, reliable and comfortable fashion, with a particularly reduced number of actions by the tyre repair specialist.

This patent is subject to a terminal disclaimer.

Machine and method for fitting and removing a tyre


A detection system for the approach recognition of a hand or arm movement in the direction a display or control unit. The detection takes place in two stages by way of long-range detection and close-range detection. The first stage detects using at least one optical or acoustic sensor.

1. Field of the Invention
The invention relates to a detection system for recognizing the approach of a hand or arm movement in a direction towards a display and operating unit, detection being carried out in two stages.
2. Related Art
Proximity and touch sensors are being used more and more often in the interior of vehicles to optimize interaction between a user and an information and assistance system in a user-friendly manner. In this case, gestures or approaches are detected and analyzed. This is effected by generating a physical measurement variable and converting the physical measured variable into an electrical signal. An action is then triggered using a control device.
To support interaction between a user and an information system, a few systems are known that detect when a display or an operating element is approached and/or allow the driver and passenger to be differentiated. The display and operating concept is then changed in a manner adapted to the context based on the detection result. Approach detection apparatuses are cited in a few documents.
The document WO 2007/006514 A1 discloses an approach detection apparatus having a transmitting and receiving unit. In this case, the apparatus operates optoelectronically in an area outside the vehicle. When a person approaches from a predetermined, central direction, a control signal is triggered in a close range of the vehicle using a code transmitter carried by the person.
Detection in known apparatuses is carried out in a defined detection range in the close range of a display or an operating unit. Signals are permanently injected into the user by using capacitive sensors.
The known apparatuses and methods have the disadvantage that the user must carry a transmitting unit or a code transmitter, in the form of a chip card, or a transmitting unit integrated in the car key in order to trigger a control signal. Furthermore, a large amount of energy is required as a result of signals being permanently injected into the human body. Detection devices may be perceived to be harmful to health by the user as a result of the permanent signal injection, that is to say as a result of the user being exposed to magnetic and/or electric fields.

Detection system for approach recognition


A close tolerance fluid pressure relief or check valve includes a one-piece silicone poppet within a valve body. The poppet makes line contact with a concave seat surface at the inlet end of the body when the poppet is closed. A stem of the poppet extends into an inlet passage of the body to guide poppet movement centrally between open and closed positions. The poppet is biased to its closed position by a spring within the body, the pressure setting of which is controlled by a threaded nut or fitting defining an outlet passage and closing the outlet end of the body.

Certain applications require relief or check valves that are responsive to critical low pressures within close tolerances. For example, a blood pressure cuff requires a reliable relief valve that predictably and consistently responds to a predetermined relief pressure setting to limit the maximum pressure that can be applied through the cuff.
There are several drawbacks to the prior art relief valve designs currently used: Firstly, the seal on the poppet of a typical prior art relief valve has such a large surface area that it tends to stick to the valve body, resulting in relief pressures that sometimes exceed by up to 25 percent the desired pressure relief setting. Secondly, the seal is usually retained within a groove in a separate metal poppet, which can lead to malfunctions such as leakage of pressurized air past the closed poppet through its seal groove. The seal is squeezed into the groove and conforms thereto at sufficiently high pressure. A tight seal assures close tolerance "cracking-pressure and also close tolerance resealing. Pressure below the threshold to deform the seal to fit the groove cannot provide a close tolerance seal. Thirdly, the poppet of the typical prior art relief valve is subject to excessive vibration when unseated, sometimes causing the poppet to reseat off-center, leading to leakage and to inconsistent, unpredictable and inaccurate relief pressures.
From the foregoing it will be apparent that there is a need for a low pressure sensitive valve that responds accurately and consistently to a predetermined pressure setting, within close tolerances. To this end, objectives of the invention are to provide such a valve with (1) a poppet seal that does not stick or leak, and (2) a poppet that is relatively vibration-free when unseated and consistently reseats in a fully closed position.


A laminated film is provided which is constituted essentially of a resin substrate and a coated film disposed thereon. The coated film comprises a montmorillonite containing a cation exchanger other than sodium ions and a water-soluble polymer. The laminated film offers a high oxygen-permeability barrier at high humidity and firm bonding between the coated film and the resin substrate at high humidity. A packaging material derived from the laminated film is also provided.

1. Field of the Invention
The present invention relates to a laminated film that has an excellent oxygen-permeability barrier at high humidity and firm bonding between the coated film and the resin substrate at high humidity. This invention further relates to a packaging material derived from such a laminated film.
2. Description of the Related Art
With regard to packaging materials for use with foods or medicines, the contents in such packaging materials tend to denature on exposure to oxygen gas which permeates the outside into the packaging material. Therefore, the contents cannot be stored over a long period of time. This has given impetus to the development of a film which is so resistant to gas permeation as to preclude gas entering from the outside.
As disclosed in xe2x80x9cPolymer Engineering and Sciencexe2x80x9d, Vol. 20, No. 22, pp. 1543-1546 (December, 1986), conventional gas barrier films have been formed from polyvinylidene chloride, polyacrylonitrile or polyvinyl alcohol. Recently, however, a serious problem has arisen in that polyvinylidene chloride and polyacrylonitrile are detrimental to the environment when the films formed from these polymers are disposed of. This is because polyvinylidene chloride has chlorine atoms attached to its molecular structure, and polyacrylonitrile has xe2x80x94CN groups attached to its molecular structure. On the other hand, polyvinyl alcohol has a superior gas permeation barrier at low humidity, but largely depends on humidity, resulting in a sharp decline in the gas permeation barrier at high humidity.
In Japanese Unexamined Patent Application Publications No. 10-296929 and No. 11-151786, barrier films against gas permeation have been proposed in which a lamella composed of inorganic particles is laminated on a water-soluble polymer film. Such a barrier film is sufficiently impermeable to gas since it is less dependent on humidity. However, it poses a problem in that the bonding between the coated film and the resin substrate becomes markedly poor at high humidity.
Accordingly, it is one object of the present invention to provide a laminated film which has an excellent oxygen-permeability barrier even at high humidity and firm bonding between the coated film and the resin substrate even at high humidity. Another object of this invention is to provide a packaging material using such a laminated film.
The above objects of the present invention can be achieved by the provision of a laminated film comprising a resin substrate and a coated film laminated thereon, wherein the coated film comprises a montmorillonite containing a cation exchanger other than sodium ions and a water-soluble polymer.
More specifically, according to a first aspect of the present invention, a laminated film comprising a resin substrate and a coated film laminated thereon is provided, wherein the coated film comprises a montmorillonite and a water-soluble polymer, and the content of a potassium element in the coated film is in the range of 0.1% by weight to 5% by weight.
According to a second aspect of this invention, a laminated film comprising a resin substrate and a coated film laminated thereon is provided, wherein the coated film comprises a montmorillonite and a water-soluble polymer, and the content of a sodium element in the coated film is 0.6% by weight or less.
According to a third aspect of this invention, a laminated film comprising a resin substrate and a coated film laminated thereon is provided, wherein the coated film comprises a montmorillonite and a water-soluble polymer, and said water-soluble polymer comprises at least two water-soluble resins having different polymerization degrees.
According to a fourth aspect of this invention, a packaging material is provided comprising a laminated film described in one of the first to third aspects.
According to a fifth aspect of this invention, a packaging material is provided comprising a laminated film described in one of the first to third aspects and a supporting material disposed on the laminated film.
In general, montmorillonite has a configuration in which a tetrahedral structure-constituting layer and an octahedral structure-constituting layer are bonded to each other in a 2 to 1 ratio and in a plate-like formation. In the tetrahedral layer, Si4+ is coordinated relative to O2xe2x88x92, and in the octahedral layer, Al3+, Mg2+, Fe2+, Fe3+, Li+ and the like are coordinated relative to O2xe2x88x92 and OHxe2x88x92. Montmorillonite is mineral clay which has a tendency to incorporate and absorb water between its crystalline plate-like layer units, is very thin and is formed as a single particulate plate from one such crystalline layer unit or those layer units overlaid on each other.
Moreover, montmorillonite has a water molecule-accompanying cation exchanger existing between the crystalline layers (this cation exchanger also being called an interlaminar cation exchanger). The cation exchanger usually includes Mg2+, Ca2+, Na+, K+ and H+. Naturally occurring montmorillonite is broadly grouped into sodium ion-type montmorillonite (Na-montmorillonite), which is abundant in sodium ions as the cation exchanger, and calcium ion-type montmorillonite (Ca-montmorillonite), which is abundant in calcium ions as the cation exchanger.
Montmorillonite suitable for the present invention contains a cation exchanger other than sodium ions. The cation exchanger other than sodium ions, which can be used in this invention, is chosen from alkaline metal ions excluding sodium ions, alkaline earth metal ions, benzoruthenium ions, alkyldimethylammonium ions, quaternary alkylammonium ions such as aminosilanes made quaternary, and surface active agents capable of developing complex ions. The sodium ions contained in the montmorillonite can be replaced by such a cation exchanger. This replacement prevents the montmorillonite from swelling, so that the resulting laminated film yields a high oxygen-permeation barrier at high humidity and firm bonding between the coated film and the resin substrate at high humidity. Replacing the sodium ions with potassium ions is particularly preferred because the above effects can be further enhanced.
In the laminated film of the present invention, the potassium element content in the coated film is set within the range of 0.1% by weight to 5% by weight in order to improve the oxygen-permeation barrier and film-to-substrate bonding at high humidity. A content of 0.3% by weight to 1.2% by weight is more preferable.
The term xe2x80x9cpotassium element content in the coated filmxe2x80x9d used here refers to the potassium element content based on the total weight of all the components in the coated film containing montmorillonite and a water-soluble polymer.
In addition, in the laminated film of the present invention, the sodium element content in the coated film is set at 0.6% by weight or less in order to improve the oxygen-permeation barrier and the film-to-substrate bonding at high humidity. A content of 0.4% by weight or less is more preferable, and a content of 0.2% by weight or less is still more preferable.
For analytical examination of the above contents of elements, conventional atomic spectrometry and ICP may be used.
In the montmorillonite according to the present invention, the leaching of a cation exchanger other than sodium ions is preferably 40 or more (milliequivalent per 100 g of montmorillonite), and the leaching of potassium ions is preferably 10 or more (milliequivalent/100 g). A leaching of potassium of 40 or more (milliequivalent/100 g) is particularly preferable. When the leaching of a cation exchanger other than sodium ions is within the above specified range, a good oxygen-permeation barrier and film-to-substrate bonding can be obtained.
The term xe2x80x9cleaching of a cation exchangerxe2x80x9d used here represents the amount of a cation exchanger contained between the crystalline layers in the montmorillonite.
With further regard to the leaching of sodium ions in the montmorillonite, 40 or less (milliequivalent/100 g) is preferable, and 30 or less (milliequivalent/100 g) is more preferable.
If the average particle diameter of the montmorillonite is 0.2 xcexcm or less, preferably 0.1 xcexcm or less, and more preferably 0.05 xcexcm or less, the film-to-substrate bonding can be improved. If the average particle diameter is 0.5 xcexcm or more, preferably 1 xcexcm or more, and more preferably 5 xcexcm or more, the gas-permeation barrier can be improved. In the case where two or more montmorillonites with different average particle diameters are combined, the respective properties of both clays can be attained in a balanced state.
Also preferably, two or more montmorillonites with different cation exchangers may be used in combination. For example, when a Na-montmorillonite and a K-montmorillonite are combined, the content of the K-montmorillonite in the whole montmorillonite is preferably 10% by weight to 100% by weight, more preferably 90% by weight to 100% by weight.
The average particle diameters of the montmorillonites may be measured from photographs taken at a magnification of 10,000 times to 100,000 times using any suitable conventional analytical process such as diffraction/scattering, dynamic light scattering or transmission electron microscopy.
Specific examples of the water-soluble polymer are polyvinyl alcohol or copolymers thereof, cellulose derivatives such as carboxymethylcellulose and hydroxyethylcellulose, starches such as oxide starch, esterified starch and dextrin, polyvinyl pyrrolidone, polyester copolymers containing a polar group such as sulfoisophthalic acid or the like, vinyl polymers such as polyhydroxyethyl methacrylate or copolymers thereof, acrylic resin, urethane resin and ether resin. Other varieties of polymers can also be used which are obtained by modifying the above-listed polymers with a functional group such as carboxyl, amino or methylol. Ideally, polyvinyl alcohol or its copolymers are preferable. Polyvinyl alcohol is a product derived from saponification of polyvinyl acetate. A polyvinyl alcohol with a saponification value of 80% by mol or more is particularly preferable. The polyvinyl alcohol copolymer preferred here is structured such as to have a vinyl alcohol unit in an amount of 60% by mol or more. Especially, a saponified product of an ethylene-vinyl acetate copolymer is suitably chosen which contributes markedly to enhancing the oxygen-permeation barrier under highly humid conditions.
In the water-soluble polymer according to the present invention, the average polymerization degree is preferably 100 to 5,000, more preferably 200 to 2,500, and most preferably 400 to 1,800. The term xe2x80x9caverage polymerization degreexe2x80x9d represents the number-average polymerization degree. If the average polymerization degree is observed within this specific range, the resulting coated film has increased strength and is easy to form with uniformity.
In the present invention, it is desired that two or more water-soluble resins with different average polymerization degrees be used as the water-soluble polymer to yield a coated film having good transparency in addition to an excellent oxygen-permeation barrier and film-to-substrate bonding. A water-soluble resin with a lower average polymerization degree of 200 to 800 and a water-soluble resin with a higher average polymerization degree of 1,000 to 2,000 are mixed to enhance the oxygen-permeation barrier and film-to-substrate bonding even at high humidity. More preferably, the lower average polymerization degree is set at 300 to 700 and the higher average polymerization degree at 1,300 to 1,700.
In the coated film according to the present invention, the content of the montmorillonite is preferably 1% to 60% by weight ratio, and more preferably 10% to 50%. This specific montmorillonite content permits both the oxygen-permeation barrier and film-to-substrate bonding to be improved at the same time.
In the coated film according to the present invention, the thickness is preferably 0.01 xcexcm to 10 xcexcm from the viewpoint of the oxygen-permeation barrier. When a layer composed of a metal and/or a metal oxide is disposed, the coated film thickness is preferably 0.05 xcexcm to 3 xcexcm.
To the coated film, various additives may be added in amounts of 30% or less by weight ratio if they do not adversely affect the oxygen-permeation barrier and transparency. Examples of the additives are chosen from an antioxidant, a weathering agent, a heat stabilizer, a lubricating agent, a crystal nucleator, an ultraviolet absorber, a coloring agent and the like. Inorganic or organic particles may also be added at amounts of 20% or less by weight ratio if they do not impair the transparency and oxygen-permeation barrier. These particles are chosen, for example, from calcium carbonate, titanium oxide, silicon oxide, calcium fluoride, lithium fluoride, alumina, barium sulfate, zirconia, calcium phosphate and crosslinked polystyrene particles.
The resin substrate suitable for the present invention is a film derived from a specific selected polymer. The material for the above resin substrate includes polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate, polybutylene terephthalate and polyethylene-2,6-naphthalate, polyamides such as nylon 6 and nylon 12, polyvinyl chloride, ethylene-vinyl acetate copolymer or a saponified product thereof, polystyrene, polycarbonate, polysulfone, polyphenylene oxide, polyphenylene sulfide, aromatic polyamide, polyimide, polyamide imide, cellulose, cellulose acetate, polyvinylidene chloride, polyacrylonitrile and polyvinyl alcohol, and copolymers thereof. A polyester such as polyethylene terephthalate and polyolefins such as polyethylene and polypropylene are preferred from the viewpoints of the transparency and oxygen-permeation barrier. Polyolefins such as polyethylene and polypropylene are particularly preferable since they are highly resistant to moisture vapor transmission.
More preferably, the resin substrate can be surface-treated, prior to formation of the coated film thereon, by means of corona discharge treatment, flaming treatment or plasma treatment.
The resin substrate may be of a nonstretched film, a monoaxially stretched film or a biaxially stretched film, and with dimensional stability and mechanical properties in mind, a biaxially stretched film is the most preferable. To the resin substrate, various additives may be added which are chosen, for example, from an antioxidant, a weathering agent, a heat stabilizer, a lubricating agent, a crystal nucleator, an ultraviolet absorber, a coloring agent and the like. Inorganic or organic particles may also be added if they do not impair the transparency. Examples of the particles are talc, kaolinite, calcium carbonate, titanium oxide, silicon oxide, calcium fluoride, lithium fluoride, alumina, barium sulfate, zirconia, mica, calcium phosphate and crosslinked polystyrene particles. The average particle diameter of the above particles is preferably 0.001 xcexcm to 10 xcexcm, and more preferably 0.003 xcexcm to 5 xcexcm. The term xe2x80x9caverage particle diameterxe2x80x9d used here refers to the particle diameter measured as the average number of particles from photographs taken at a magnification of 10,000 times to 100,000 times by transmission electron microscopy.
The above resin substrate is preferably transparent in nature and has a light transmission of preferably 40% or more, and more preferably 60% or more. Further, the resin substrate surface is preferably smooth and has a thickness of preferably 2 xcexcm to 1,000 xcexcm although this range is not restrictive.
In the laminated film of the present invention, haze is preferably 20% or less, more preferably 15% or less. If a laminated film with a haze of more than 20% is used as a packaging material, the color and shape of the contents are difficult to observe from an external view.
From the viewpoints of the oxygen-permeation barrier and film-to-substrate bonding, and extension barrier and printability in particular, it is desired that a layer formed from one of a metal or an oxide thereof and a non-metal or an oxide thereof be further disposed on either one or both of the surfaces of the resin substrate, followed by formation of the above-specified coated film on the resulting metallic layer. As for the metal or the oxide thereof and the non-metal or the oxide thereof, metals such as aluminum, zinc and magnesium and oxides thereof, and a non-metal such as silicon and an oxide thereof are preferred. Where transparency is required, oxides are preferably used, among which a metal oxide of aluminum and a non-metal oxide of silicon are particularly preferred from the viewpoints of the oxygen-permeation barrier, extension barrier and productivity.
Alternatively, the layer formed from a metal or an oxide thereof, or a non-metal or an oxide thereof may be disposed on the coated film formed in direct contact with the resin substrate. Also in such an instance, the resulting laminated film has an improved oxygen-permeation.
In addition and more preferably, an anchor layer may be disposed on the resin substrate using an anchoring agent such as urethane resin, epoxy resin or polyethylene imine, followed by formation of the coated film on the anchor layer. Such a construction can improve the film-to-substrate bonding. Although not restricted, the thickness of the anchor layer is preferably set from 0.1 xcexcm to 0.3 xcexcm.
In the laminated film of the present invention, the peeling strength between the coated film and the resin substrate is preferably 0.5 N/cm or more at a temperature of 40xc2x0 C. and at a humidity of 90%. This laminated film provides a packaging material for use with foods or medicines, which provides superior hermetic sealing and a shelf stability of the utmost reliability.
To produce a packaging material, the laminated film of the present invention can be used as it is, or after being disposed on another supporting material. Here, no limitation is placed on the supporting material if it is known in the art, but examples are paper, a metal such as aluminum or an oxide thereof, a non-metal such as silicon or an oxide thereof, nonwoven fabric and polymeric film. Of the listed materials, the polymeric film includes a non-stretched film, biaxially stretched film, co-extruded film, coated film, deposited film and melt-extruded resin. The base material for the above polymeric film includes polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate, polybutylene terephthalate and polyethylene-2,6-naphthalate, polyamides such as nylon 6 and nylon 12, polyvinyl chloride, ethylene-vinyl acetate copolymer or a saponified product thereof, polystyrene, polycarbonate, polysulfone, polyphenylene oxide, polyphenylene sulfide, aromatic polyamide, polyimide, polyamide imide, cellulose, cellulose acetate and polyacrylonitrile, and copolymers thereof. No limits are imposed on the manner in which the laminated film of this invention is disposed on the supporting material, and therefore, a print layer, an adhesive layer or an anchor layer may be interposed between the laminated film and the supporting material.
An explanation will now be provided with regard to a specific typical method by which the laminated film according to the present invention can be produced. However, such a method should not be construed as limiting this invention.
To form the coated film on the resin substrate, the components of the coated film are dispersed in a selected solvent to prepare a dispersion which is preferably coated using gravure coating, reverse coating, spray coating, kiss coating, comma coating, die coating, knife coating, air-knife coating or metering-bar coating. Each such coating means can form a thin film at high speed. More preferably, the resin substrate is pretreated so as to be bondable by nature, prior to formation of the coated film thereon, by the use of corona discharge treatment effected for example in air, in nitrogen gas, in a mixture of nitrogen-carbon dioxide gases, or in any other environment, or plasma treatment effected under reduced pressure, flaming treatment or ultraviolet treatment. Also preferably, anchoring treatment is performed using an anchoring agent such as urethane resin, epoxy resin or polyethylene imine.
When the resin substrate is formed from a biaxially stretched film of either a polyester such as polyethylene terephthalate or a polyolefin such as polypropylene, both off-line coating and in-line coating may be used. Off-line coating denotes that coating is carried out after the film-forming steps are completed, whereas in-line coating denotes that coating is carried out during film formation. If the in-line coating process is used, coating is effected preferably before heat setting of the film. The term xe2x80x9cheat settingxe2x80x9d used here means that a stretched film is permitted to crystallize upon heat treatment while the film is maintained at a temperature higher than the stretching temperature, but lower than the melting point. Thus, coating is preferably effected with respect to a nonstretched film, a film just stretched monoaxially in its machine or transverse direction, or a film just stretched biaxially. A film just stretched monoaxially is particularly preferred and then undergoes further stretching along one or more axes and subsequent heat setting.
The coated film may be dried by hot rolling, contacting with a heated medium (air or oil), infrared heating or microwave heating. With the oxygen-permeation barrier in mind, the drying temperature is preferably 60xc2x0 C. to 180xc2x0 C. in the case of off-line coating and preferably 80xc2x0 C. to 250xc2x0 C. in the case of in-line coating. The drying time is preferably 1 second to 60 seconds, and more preferably 3 seconds to 30 seconds.
In a coating liquid prepared to contain the components of the coated film, it is desired that the montmorillonite particles be homogeneously dispersed or swollen in a selected solvent and that the water-soluble polymer be homogeneously dissolved in the solvent. Examples of the solvent used here are chosen from water and a mixture of water and a lower alcohol. A water-lower alcohol mixture is preferable.
The solid content of the coating liquid is preferably 2.5% or more from the productivity viewpoints such as the viscosity and drying efficiency of the coating liquid. In the instance where a coating liquid with a solid content of less than 2.5% is used, a low-boiling solvent, which solvent has an affinity for water and is highly volatile, may be added to the coating liquid. Alternatively, the resulting coated film may be dried at a temperature higher than 100xc2x0 C.
To increase coatability of the coating liquid, another water-soluble organic compound may be added as a third component to the water-lower alcohol mixture if the dispersion is maintained stable. Examples of the water-soluble organic compound include alcohols such as methanol, ethanol, n-propanol, isopropanol and the like, glycols such as ethylene glycol, propylene glycol and the like, glycol derivatives such as methyl cellosolve, ethyl cellosolve, n-butyl cellosolve and the like, polyhydric alcohols such as glycerin, wax and the like, ethers such as dioxane and the like, esters such as ethyl acetate and the like, and ketones such as methyl ethyl ketone and the like. The pH of the dispersion is preferably 2 to 11 from the stability viewpoint.
The process for preparing the above coating liquid is not restricted, but a process is preferred in which the montmorillonite is homogeneously dispersed in a selected solvent, followed by mixing of the dispersion with a solution obtained by homogeneously dissolving the water-soluble polymer in the solvent. It is desired that both the water-soluble polymer and the montmorillonite be markedly homogeneously dispersed in the coating liquid. Because the montmorillonite in particular may have been secondarily agglomerated in the resulting dispersion, forced dispersion is further required after the montmorillonite is dispersed in a selected solvent. To this end, a homomixer, a jet agitator, a ball mill, a kneader, a sand mill or a three-roll mill is used in which shearing force and sliding stress are applied. For example, the montmorillonite is homogeneously dispersed in water at a solid content of several weight percentages and then treated by means of mechanical dispersion using a homomixer or the like, followed by mixing of the dispersion with an aqueous solution of the water-soluble polymer obtained by homogeneously dispersing the same in water at a solid content of several weight percentages. In succession, the resulting mixture is once again subjected to dispersion treatment, and the solid content of this dispersion is adjusted by the addition of a lower alcohol and water. Moreover, the coating liquid may be mixed, where desired, with a crosslinking agent, particles and the like.
The present invention will be further described with reference to the following examples.
Evaluation Methods of Various Characteristics
First of all, the evaluation methods of various characteristics used in this invention are explained below.
(1) Oxygen-permeability Barrier
Oxygen-permeability barrier was measured according to ASTM D-3985 with an oxygen-permeability measuring instrument (OX-TRAN 2/20 manufactured by Mocon Co.). Measuring conditions were at a temperature of 23xc2x0 C. and at a relative humidity (RH) of 80%.
(2) Bonding Between Coated Film and Resin Substrate (Moisture-Resistant Peeling Strength)
Firstly, a coated film-laden surface of the film (OPP) according to the present invention was allowed to dry-laminate with one surface of a nonstretched polypropylene film (CPP; T3501 manufactured by Toray Synthetic Film Co., Ltd.; 50 xcexcm) using a polyurethane adhesive (xe2x80x9cDICDRYxe2x80x9d, LX-401A, SP-60 manufactured by Dainippon Ink and Chemicals, Incorporated; mixing ratio: LX-401A:SP-60=1:1; diluting solvent: ethyl acetate; drying temperature: 70xc2x0 C.; drying time: 30 seconds; coating weight: 2.0 g/m2 based on dry weight of essential components in the coating liquid). Aging was effected at 40xc2x0 C. for 48 hours. Subsequently, the resulting laminated film was cut to obtain a test film of 15 mm in a transverse direction (TD) and 10 cm in a machine direction (MD) in size. The test film was humid-aged in a thermo-hygrostat controlled at 40xc2x0 C. and at 90% RH. Immediately after completion of the humid aging, the peeling resistance of both CPP and OPP was measured with a tensile machine (Autograph 1M-100 Model manufactured by Shimadzu Corporation.).
(3) Haze
Turbidity was measured while the coated film-laden surface of the test film was irradiated with light rays with a direct-reading haze computer (HGM-2DP manufactured by Suga Test Instruments Co., Ltd.).
(4) Cation Exchange Capacity of Montmorillonite
Measurement was performed according to the method described in the xe2x80x9cClay Handbookxe2x80x9d, 2nd Ed., pp. 681-684 (The Clay Science Society of Japan), xe2x80x9cChapter II: Analyses and Tests, 6. Analysis Methods of Soil Clay, 6.9 Measurements of Ion Exchange Capacitiesxe2x80x9d.
(5) Cation Exchanger Leaching in Montmorillonite
A montmorillonite at an amount of 0.4 to 0.5 g was used as a sample. Using a cation exchange measuring instrument (manufactured by Fujiwara Scientific Company Ltd.), the cation contained in the sample was leached in 100 ml of a 1N-ammonium acetate solution over 4 to 24 hours. The quantity of the cation leached in this solution was measured by ion chromatography (as described in the xe2x80x9cNendo Handbookxe2x80x9d (Clay Handbook in Japanese), 2nd Ed., pp. 371-372 (The Clay Science Society of Japan), xe2x80x9cChapter II: Analyses and Tests 1. Analysis Methods of Soil Clay, g. Ion Chromatographyxe2x80x9d) or by atomic spectrometry. The equivalent weights of sodium ions, potassium ions and other cations per 100 g of the dry montmorillonite were calculated. Alternatively, this leaching may be determined by the method of Inoue et al. (A. Inoue and H. Minato, xe2x80x9cClay Sciencexe2x80x9d, 5, 125-126 (1978)).
(6) Contents of Potassium and Sodium Elements in the Coated Film
A suitable size for measurement was cut from the laminated film to obtain a test film. After weighing, the test film was immersed in hot water heated at 100xc2x0 C., followed by release of the coated film from the resin substrate. The contents of the potassium and sodium elements in the coated film were measured by atomic spectrometry. The coated film-free resin substrate was dried to measure the weight, which was then subtracted from the initial weight of the coated film-laden resin substrate, in which releasing had not yet been effected. The weight difference thus counted was determined to be the weight of the coated film in the test film. In this way, the contents of the potassium and sodium elements in the coated film were calculated.