A pressure sensitive hot melt adhesive formulation is provided that contains, as the sole adhesive component, a solid polybutadiene which has been produced from an unhydrogenated polybutadiene having a vinyl content of at least 50 percent and subsequently has been hydrogenated to a vinyl content of less than 15 percent. The hot melt adhesive formulation also contains a sufficient amount of a tackifier, preferably a hydrogenated rosin, to produce an adhesive formulation having a viscosity at 350.degree. F. of from about 1,500 to about 1 million, preferably about 15,000 to about 350,000 cps. The formulation can also contain up to 5 percent by weight of the total combination of the polybutadiene and tackifier of heat and light stabilizing compounds.

This invention relates to hot melt adhesive compositions. According to one aspect of this invention, it relates to hot melt adhesive compositions comprising a single adhesive component admixed with a sufficient amount of tackifier to permit proper function of the composition in the apparatus currently used in hot melt adhesive application. In another of its aspects this invention relates to pressure sensitive hot melt adhesive formulations. In a further aspect this invention relates to the use of hydrogenated polybutadiene as the adhesive constituent in hot melt adhesive formulations.
One of the more significant developments in adhesive technology in recent years has occurred in the area of hot melt adhesives. Growth in the use of hot melt systems has been particularly marked by various segments of the packaging, book binding, and shoe industries. Increased interest in hot melts has in turn encouraged development of special types of plastic resins to serve as base constituents in commercial formulations.
Polybutadiene has been considered as a possible base constituent for hot melt adhesives, but development of these polymers for hot melt adhesive application has been hampered because early testing of hydrogenated polybutadienes disclosed that the materials tested were not effectively adhesive. It has now been discovered that hydrogenated polybutadiene having a low vinyl content in the hydrogenated polymer is well suited as the adhesive constituent in hot melt adhesive formulations if the hydrogenated polymer is prepared from an unhydrogenated polybutadiene having a vinyl content of at least about 50 percent.
Other aspects as well as the several advantages in this invention will be apparent to those skilled in the art upon reading the specification and the appended claims.
In accordance with the invention, hot melt adhesive formulation useful particularly as pressure sensitive adhesives are prepared by hydrogenating an unhydrogenated polybutadiene having a vinyl content of at least 50 percent to produce a hydrogenated polybutadiene having a vinyl content of less than about 15 percent and incorporating with this polymer a sufficient amount of a tackifying compound to produce a formulation having a viscosity to give an adequate performance in hot melt adhesive application equipment. In general, a suitable viscosity range for performance of a hot melt adhesive can be stated as about 1,500 to about 1 million, preferably about 15,000 to about 350,000 cps at a temperature of 350.degree. F.
Polybutadienes suitable for use in this invention are made by polymerizing 1,3-butadiene using a suitable catalyst such as an alkali metal alkyl and modifiers to produce high vinyl polybutadienes by a method such as set forth in copending application Ser. No. 488,995, filed July 16, 1974. The polymers thus produced range from liquids to rubbery products having a variable content of cis, trans and vinyl unsaturation as determined from infra-red data. In general, solid polybutadienes having a vinyl content of 50-95 percent which can be hydrogenated to a double bond content of less than 15 percent, preferably less than 10 percent, are suitable. It is preferred that the vinyl content of the parent polybutadiene is between 60 and 90 percent. While a vinyl content of 100 percent is theoretically possible and is considered operable for the purposes of this invention, it is considered that there is a practical limitation of 95 percent vinyl content of the unhydrogenated rubber with economic considerations reducing the upper limit of vinyl content to 90 percent.
The butadiene polymers most suitable for this invention can be defined as having at least one long chain branch per polymer molecule. It is realized that because of the method employed in preparing the branched high vinyl polymers, the final polymer product may contain a small amount of linear or unbranched base polymer, and linear coupled base polymer. The branched high vinyl polymer is therefore described as a polymer which has on the average at least one long chain branch per polymer molecule. The branched high vinyl polymer is formed from the coupling or joining of, on the average, more than two base polymer molecules resulting in a radial polymer having, preferably, a majority, i.e., more than 50 percent, of branched polymer chains.
Branched or radial high vinyl polybutadiene, i.e., polybutadiene having high side-chain unsaturation, for example, can be prepared by first forming a high vinyl base polymer of butadiene having one or two terminally reactive alkali metal atoms per base polymer molecule. The terminally reactive high vinyl base polymer is then reacted with a coupling or joining agent capable of joining, on the average, more than two base polymer molecules in an essentially end-to-end arrangement.
Suitable initiators for the formation of the terminally reactive high vinyl base polymer are based on alkali metal or organic compounds thereof and are of two general types. Type I initiators comprise the alkali metals, other than lithium, and their hydrocarbyl derivatives, or adducts of these metals with condensed ring aromatic hydrocarbon, or mixtures thereof. Examples of suitable Type I initiators include finely divided sodium metal, n-amylsodium, phenylpotassium, potassium naphthalene adduct, butylcesium, rubidium metal, sodium naphthalene adduct and the like. Type II initiators comprise lithium, lithium hydrocarbyl compounds, or lithium adducts with condensed ring aromatic hydrocarbons in conjunction with an effective amount of vinyl promoter.
A vinyl promoter is a compound which promotes, for example, 1,2-addition in the polymerization of butadiene. The vinyl promoters useful with the above lithium-based initiators are selected from the group consisting of nonreactive polar organic compounds such as ethers, thioethers, tertiary amines, and the alkali metals such as sodium, potassium, rubidium, cesium, or organic compounds thereof. Examples of preferred vinyl promoters include tetrahydrofuran (THF), 1,3-dioxane, triethylamine, N,N,N',N'-tetramethylethylenediamine (TMEDA), potassium tert-butoxide, and potassium tert-amyloxide.
Specific examples of polar materials which are vinyl promoters include dimethyl ether, diethyl ether, ethylmethyl ether, ethylpropyl ether, di-n-propyl ether, di-n-octyl ether, dibenzyl ether, diphenyl ether, anisole, dimethylsulfide, diethylsulfide, tri-n-butylamine, trimethylamine, triethylamine, aniline, pyridine, quinoline, and the like. Further it is to be understood that mixtures of these polar compounds can be employed in the practice of the instant invention.
The amount of vinyl promoter employed with the Type II polymerization initiator depends on the vinyl content desired in the polybutadiene base and final polymers, and on the vinyl promoting effectiveness of the particular promoter employed. The vinyl promoting effectiveness of a particular promoter is, in turn, influenced by the temperature employed in the polymerization step. In general, the more vinyl promoter employed, the higher will be the vinyl content of the polybutadiene base and final polymers prepared with a Type II initiator. Examples of suitable Type II initiators and vinyl promoter combinations include n-butyllithium/THF, lithium metal/1,3-dioxane, sec-butyllithium/TMEDA, lithium metal/n-amylsodium, n-butyllithium/potassium tert-butoxide, sec-butyllithium/potassium tertamyloxide, phenyllithium/phenylpotassium and the like.
The high vinyl base polymer prepared with the initiators described above and having at least one terminally reactive alkali metal atom is then treated with a coupling or joining agent capable of joining or coupling, on the average, more than two of the base polymer molecules by reaction with the terminal alkali metal atom. In general, such coupling is preferably achieved by employing compounds having at least three reactive sites per molecule. Polyfunctional reagents having at least three reactive sites per molecule react with the alkali metal-carbon bond in the polymer thereby coupling the reagent to the polymer at this bond. For this reason, compounds containing active hydrogen atoms such as water, alcohol, acids and the likes, are to be avoided since such compounds replace the lithium atom with hydrogen and do not affect the desired coupling. It should be understood, however, that compounds containing relatively small amounts of active hydrogen can be used provided the reactive sites capable of producing coupling are present in sufficient quantity to offset the effect of the inactivation produced by the active hydrogen. Types of treating agents which can be used include the polyepoxides, polyisocyanates, polyimines, polyaldehydes, polyketones, polyanhydrides, polyesters, polyhalides, and the like. These compounds can contain two or more types of functional groups such as the combination of epoxy and aldehyde groups or isocyanate and halide groups. In addition to these reagents, compounds such as divinylbenzene, carbon monoxide, carbon dioxide, and esters of dicarboxylic acids can also produce branched or radial high vinyl polybutadiene. The amount of coupling agent employed can vary but is generally sufficient to provide one equivalent of reactive coupling group per equivalent of terminally reactive alkali metal atom on the prepared base polymer.
The reaction conditions employed in the formation of the base polymer and in the coupling reaction are those known for conventional polymerization of, for example, butadiene with lithium-based initiators and a subsequent coupling reaction. Generally, an inert hydrocarbon diluent having from 4 to 10 carbon atoms per molecule is employed in such polymerizations. Temperatures of from -100.degree. to 200.degree. C. are conventional. Initiator amounts are generally in the range of from 0.25 to 100 milliequivalents of alkali metal in the initiator per 100 grams of butadiene.
Recovery of the coupled, radial or branched high vinyl polybutadiene can be conventionally accomplished, for example, by steam stripping, alcohol coagulation, diluent evaporation, and the like. An antioxidant can be added to the polymer in a reaction mixture containing the polymer prior to the recovery step.
Hydrogenation of the base polymer can be effected by any of the known methods of hydrogenating high vinyl-containing polymers. It has been effective for the purpose of this invention to continuously hydrogenate the polybutadiene in packed, jacketed columns at a temperature within the range of about 355.degree.-380.degree. F. using as a catalyst a solution comprising nickel octoate and triethyl aluminum and cyclohexane. Such hydrogenation methods are known in the art and are not per se part of this invention. The hydrogenated polymers having a vinyl content of no more than about 15 percent and preferably less than 10 percent can be recovered by treatment of the hydrogenation effluent with ammonium phosphate to remove the catalyst solids by filtering, steam stripping, and drying as set forth in U.S. Pat. No. 3,531,448.
To produce a hot melt adhesive operative in equipment currently in use hydrogenated polybutadiene must be mixed with a sufficient amount of a tackifying compound to produce a formulation having a viscosity in a range operable with current equipment. The tackifying compound can be chosen from among those compounds commonly used in the art as tackifiers. Especially useful with the polybutadienes in producing formulations according to the process of this invention are pentaerythritol esters of hydrogenated rosin, synthetic polyterpenes, thermoplastic olefins, and tall oil rosins, among others. The tackifier is incorporated into the formulation with the polybutadiene so that from about 30 to about 65 percent by weight of the total composition of the two components is tackifier. The preferred amount of tackifier within this range is chosen so that the viscosity of the adhesive formulation at 350.degree. F. is within the range of about 1,500 to about 1 million cps. It is preferable that the amount of tackifier in the formulation yield a viscosity at 350.degree. F. in the range of about 15,000 to about 350,000 cps, because, even though machinery is available that will handle viscosity toward the upper end of the range, performance of the adhesive is generally better toward the lower end of the broad range.
The polybutadiene and tackifier can be blended by any convenient method known in the art for melt blending tackifiers into adhesive compositions. One well-known method comprises stirring of one of the materials into a melted batch of the other material using a mixer to assure adequate agitation for complete dispersion of one material within the other.
By the process of this invention minor amounts of stabilizing compounds compatible with polybutadiene and the tackifiers can be added to the formulation in amounts of up to about 5 weight percent of the mixture of the tackifier and polybutadiene. Such heat stabilizing materials as dilaurylthiodipropionate and alkylated-arylated bis-phenolic phosphite are particularly suitable as thermoplastic stabilizing compounds.
The adhesive formulations produced by the process of this invention have the desirable attributes of good heat stability and the development of less color on prolonged heating as compared to many of the hot melt adhesive formulations currently commercially available. These desirable properties result in a long pot life for extended glueing operations such as carton sealing. These properties are commercially in demand, particularly in the area of pressure sensitive hot melt adhesives.
The hot melt adhesive formulation to this invention and the process of preparing it are illustrated by the following examples which are meant to be exemplary and not exclusive.
EXAMPLE I ______________________________________ Preparation of High Vinyl Polybutadiene A 20 gallon reactor was used for each batch. The charge comprised: ______________________________________ Cyclohexane 800 parts by weight Butadiene 100 Butyl lithium Variable Tetrahydrofuran (THF) Variable Tetramethylethylenediamine (TMED) Variable ______________________________________
The polymerizations were carried out adiabatically with the initiation temperature at 120.degree. F. The ingredients were charged in the order: cyclohexane, THF or TMED, butadiene, butyllithium. The run was terminated when all of the butadiene had been polymerized.


The invention is a multi-sensor device which generates a signal comprised of one or more electromagnetic waveforms, that are transmitted against a first target material, such as a wall, whereupon said wave or portion thereof is reflected by a first surface and a second wave or portion of said first wave will penetrate the target material and be reflected in part by a second surface for the purpose of ascertaining if the cavity between said first target surface and said second target surface contains a quantity of United States currency.

The present invention relates generally to surface penetrating object detection and, more specifically, to a multi-sensor module for detecting quantities of United States currency secreted from view within sealed containers or concealed from view by placement in cavities within floors, ceilings, or walls.
The multi-sensor device is a handheld portable device comprised of a housing having electronic circuits for selectively transmitting variable wavelength electromagnetic waves and electronic circuits for receiving electromagnetic waves.
Further said device has electronic storage means for maintaining a database of known responses for a plurality of predetermined electromagnetic wavelengths and a plurality of target materials and known responses for objects contained within or behind said plurality of target materials.
In addition said device has electronic circuits including microprocessor, memory, antenna, filters and power supply for receiving, analyzing, recording and comparing returning electromagnetic waveforms to said database. Said device further having means for generating visual and/or audible signals based on said analytical comparison.
There are other currency verification devices. Typical of these is U.S. Pat. No. 4,618,257 issued to Bayne et al. on Oct. 21, 1986.
Another patent was issued to Ishida on Aug. 20, 1985 as U.S. Pat. No. 4,536,709. Another patent was issued to Gorgone on Feb. 24, 1987 as U.S. Pat. No. 4,645,936. Yet another U.S. Pat. No. 4,973,851 was issued to Lee on Nov. 27, 1990. Another U.S. Pat. No. 5,358,088 was issued to Barnes et al. on Oct. 25, 1994 and yet another was issued on May 30, 1995 to Harbaugh as U.S. Pat. No. 5,419,424 and still yet another was issued on Jul. 18, 1995 to Crane et al. as U.S. Pat. No. 5,434,427.
Another patent was issued to Ebstein et al. on Nov. 21, 1995 as U.S. Pat. No. 5,468,971. Yet another U.S. Pat. No. 5,535,871 was issued to Harbaugh on Jul. 16, 1996. Another U.S. Pat. No. 5,761,089 was issued to McInerny on Jun. 2, 1998. Yet another U.S. Pat. No. 5,810,146 was issued to Harbaugh on Sep. 22, 1998 and another U.S. Pat. No. 5,892,239 was issued to Nagase on Apr. 6, 1999.
A color sensitive currency verifier operating with a plurality of narrowband light sourced optically coupled to a single broadband photodetector and including means for automatically balancing the color outputs of the various light sources. Color balancing is accomplished just prior to the examination of a specimen bill. The data samples are taken under the control of a microprocessor and used to authenticate the specimen bill both on the basis of pattern and color information stored in memory. Multiple data samples from a single target area are divided to compensate for soiling condition of the bill, and further compensation for condition of the bill is provided by adjusting the conversion scale factor of an A/D converter on the basis of data samples taken from a reference target area on the surface of the specimen bill before test or data samples are taken.
The metal detecting device includes first and second coils provided on both sides of a passageway for paper money. This metal detecting device is designed for use in detecting a metal strip embedded in the paper money in order to determine whether the paper money is genuine or counterfeit. The first coil is connected to a high frequency AC source to generate an AC magnetic field. The second coil is connected to a capacitor to form a resonance circuit which resonates at the same frequency as the AC current. The variation of the Q factor of the resonance circuit due to eddy-current losses produced in the metal strip of the paper money is used by a detecting circuit to determine whether the paper money passing through the space between the first and second coils is genuine.
A detection system for utilization with a paper security or currency validation apparatus wherein a correlation is made between reference patterns and cross hatch lines located in the portrait background on the paper and the preference of one of two paper currencies is determined. Fundamentally the invention consists of a single reticle which contains a lens whereon are located the cross hatch references for two different paper currency denominations. Within the reticle assembly are located two photosensitive cells, one for each reference pattern. Each photosensitive cell is connected to its own authenticating circuitry which validates the presence of a specific paper currency note. Should the tested paper pass the authenticity test of one authenticity circuitry, the other is disabled. Should the tested paper fail both authenticating tests, it is rejected.
An article of paper currency to be validated is scanned magnetically along the front to obtain a set of magnetic sample values and optically along the back to obtain a set of optical sample data values. Position-shifted versions of the magnetic data values are compared with stored sets of magnetic reference values for various denominations to obtain error figures for each denomination and degree of position shifting tested. A first indication of the denomination of the currency is generated on the basis of the least of the error figures so obtained. Position-shifted and amplitude-shifted versions of the optical data values are similarly compared with stored sets of optical reference values for various denominations to obtain error figures for each denomination and combination of position and amplitude shifting tested. A second indication of the denomination of the currency is generated on the basis of the least of the error figures obtained by this latter method and compared with the first indication. If the two indications of denomination correspond and the least error figures obtained by the two methods fall within predetermined limits, a credit signal is generated indicating a genuine bill of the indicated denomination.
A currency paper has a security thread embedded therein. The thread comprises a plastic substrate having a plurality of alphanumeric, metallic, electrically-conductive characters formed thereon. The characters have predetermined heights and widths and spacings therebetween. The verification device comprises an oscillator electrode and associated horizontal and vertical electrodes. A time-varying oscillator signal is coupled to the oscillator electrode. The spacing of the horizontal and vertical electrodes in relation to the oscillator electrode is determined by the spacing between the metallized characters on the thread. A valid security thread capacitively couples the oscillator signal into the horizontal electrode but not the vertical electrode. On the other hand, a counterfeit security thread will couple the oscillator signal into both the horizontal and vertical electrodes. Signal processing electronics is provided to sense these valid and counterfeit conditions.
A photodiode and a photo transistor are positioned on opposite sides of a document subjected to verification for authenticity under transmitted light. A logic circuit determines the presence or absence of the security feature and correspondingly provides visual or audible indication thereof. The photodiode, photo transistor and related circuitry are arranged with an enclosure that is attached to a currency receiving device such as a cash register. The visual or audible indicators are mounted on the cash register for immediate indication of the currency verification to the cashier. A simplified capacitive proximity sensor can be employed, per se, for inexpensive applications or for redundant verification in combination with an optical detector. The shape of the capacitive sensor is configured to that of the security thread to discriminate between the security thread and the currency paper. Additional optical circuits are employed to detect counterfeit markings on the currency surface.
An apparatus and method for detecting magnetic data on media is disclosed which utilizes an array or arrays of horizontal magnetoresistive sensors. The present invention detects the pitch or separation of magnetic transition data on the magnetic medium under test, and generates a signal that is independent of the velocity of the medium. In one embodiment, the magnetoresistive sensors employed in an array are spaced apart a distance which corresponds to the separation of magnetic transition data of interest, and the output of each sensor is connected to a voltage adder. The signal from the voltage adder is at a maximum when the separation of the magnetic transition data corresponds to the sensor separation. A comparator is connected to the output of the voltage adder, and compares the voltage adder output to a predetermined threshold voltage before indicating that a medium having a particular magnetic transition data pattern is detected. Alternate embodiments contemplate connecting linear circuitry, digital circuitry, fuzzy logic or other electronic circuitry to the array of magnetoresistive sensors. An apparatus according to the present invention is accurate, requires a minimum of parts, is simple and inexpensive to manufacture, and may be employed in a currency validator, magnetic card reader or the like.
A linear array of photo emitters and photo diodes are positioned on opposite sides of currency paper for denomination and verification determination under transmitted light. The photo emitters are arranged for projecting an image of the indicia printed on the security thread embedded within the currency paper. The photo diodes receive the image and connect with a processor circuit which determines the presence or absence of the security feature, reads the denomination indicia and correspondingly provides indication thereof. The processor contains stored information identifying currency denomination and a comparison is made at the time of verification to also determine the denomination of the proffered currency.
A security thread for documents such as currency and banknote paper comprises a plastic substrate coated with a plurality of discrete metallic patterns of electrically-conductive material, such as aluminum. The metallic patterns are arranged on the surface of the thread to indicate the particular denomination of the currency paper. The thread is typically embedded entirely with the currency paper. A first embodiment of a verification device determines the authenticity and denomination of the currency paper by counting the number of conductive metallic patterns on the thread and comparing the count to various count ranges. A second embodiment of the verification device scans the thread in a narrow-edge direction such that it simultaneously encounters all of the conductive thread segments. Capacitive coupling of an oscillator signal into one or more sensing pads result in an electrical signal having a distinct pattern. This signal is compared to a plurality of signals stored in memory that are indicative of valid thread denominations.
A document processing apparatus incorporates a counterfeit detection system for identifying counterfeit suspect documents on the basis of the magnetic characteristics of the documents. Each document is transported within the vicinity of a magnetic read head, which produces an electronic signal in response thereto. The signal from the read head is conditioned by a conditioning circuit to be compatible with the analog-to-digital converter. The conditioning circuit includes one or more amplifiers, a filter, a rectifier, and an integrator. The conditioned signal from the integrator is provided to the analog-to-digital converter and is optionally limited to a compatible voltage level. As each document is detected a plurality of sample values are obtained by the analog-to-digital converter. The sample values are accumulated to produce one or more cumulative values representative of the document. The cumulative values are compared with one or more predetermined reference values associated with a genuine document in order to determine whether the detected document is counterfeit suspect document.
A document verification device detects the presence of a metal security thread embedded in a document such as currency paper. The device includes a sensor pad arrangement and corresponding signal processing electronics. The arrangement includes a single central sensing pad flanked by an array of twenty-seven pairs of outer pads. Each pair of outer pads in the array is electrically connected together. Every pad is made of conductive material. The width dimension of each outer pad in the array is greater than the width of the security thread. Each outer pad in the array is preferably angled to improve the reliability of detection of the security thread. The electronics generates a square wave oscillator signal that is applied to the outer array pads in a pattern that includes two adjacent pairs of array pads having the positive voltage level portion of the square wave signal applied thereto, and the following two adjacent pairs of array pads having the negative voltage level portion of the square wave signal applied thereto. This pattern is sequenced in time over the entire array. The document to be verified is transported with respect to the sensor pad arrangement such that the wide edge of the document is the leading edge. As the thread passes over the array, the pattern is sequenced throughout the pads fast enough such that, at a point in time, the thread will bridge the central sensing pad with a pair of outer two pads first having the positive voltage level portion of the square wave signal applied thereto, and then later the thread will bridge the central sensing pad with the same pair of outer two pads now having the negative voltage level portion of the square wave signal applied thereto. Since the thread is metallic, it will capacitively couple the square wave signal into the central sensing pad. The electronics senses the signal coupled to the sensing pad and interprets a valid security thread as being present in the currency from certain characteristics of the sensed signal.
A bill or security discriminating apparatus includes at least one irradiating device for irradiating a surface of a bill or security at a predetermined angle with the surface thereof, at least one polarization separating device for receiving light reflected by the surface of the bill or security and separating the received light into P-polarized light and S-polarized light, at least one first light detector for photoelectrically detecting the P-polarized light separated by the at least one polarization separating device and generating an electrical signal in accordance with intensity of the detected light, at least one second light detector for photoelectrically detecting the S-polarized light separated by the at least one polarization separating device and generating an electrical signal in accordance with intensity of the detected light, and a discriminator for discriminating the bill or security in accordance with the intensity of the P-polarized light and S-polarized light based on the electrical signals input from the at least one first light detector and the at least one second light detector. According to the thus constituted bill or security discriminating apparatus, it is possible to discriminate bills or securities with high accuracy even if they are damaged or wrinkled.
While these currency verification and/or detection devices may be suitable for the purposes for which they were designed, they would not be as suitable for the purposes of the present invention, as hereinafter described.
The present invention provides a multi-sensor device which generates a signal comprised of one or more electromagnetic waveforms, for example, near infrared, radar and/or microwaves that are transmitted against a first target material, such as a wall, whereupon said wave or portion thereof is reflected by a first surface and a second wave or portion of said first wave will penetrate the target material and be reflected in part by a second surface.
The multi-sensor module having one or more antenna and means for storing time differential, amplitude, and frequency of the returning waves as a signature waveform for a target material of a structure. Whereupon, the remainder of the structure can be scanned using the multi-sensor device searching for deviation from the signature waveform and having means for generating audio and/or visual signals for a predetermined variance from the signature waveform. Any deviation from the signature waveform would indicate an anomaly which will be compared to a database of known responses for a plurality of materials and electromagnetic waves and may result in the recording and addition to said database for future reference and/or may result in audio and/or visual indicators signaling a potential storage site for currency.
Further said device has a number of user selectable preprogrammed presets using areas of the electromagnetic spectrum having known responses to the target material.
In addition, the multi-sensor device further has means for generating a magnetic field whereby the multi-sensor device can be brought into close proximity of an anomaly to determine if the anomaly has the predetermined characteristics for a quantity of currency.
Still further the multi-sensor device has storage means for containing an updatable database of known responses, e.g. bx cable contained within a wood lath plaster wall, bx cable contained within a wood lath plaster wall having a lead based paint, bx cable contained within a wood framed wall covered by gypsum wallboard etc,. The incorporated database can be tailored to a specific type of construction, such as a wood frame structure or cinder block construction.
A primary object of the present invention is to provide a multi-sensor device that can be used to detect currency hidden in walls, floors and ceiling cavities.
Another object of the present invention is to provide a multi-sensor device which is portable.
Yet another object of the present invention is to provide a multi-sensor device that can generate a plurality of electromagnetic waves.
Still yet another object of the present invention is to provide a multi-sensor device having one or more antenna for transmitting and receiving an electromagnetic wave.
Another object of the present invention is to provide a multi-sensor device having means for storing the frequency, amplitude, and time differential between a first and second returning electromagnetic wave.
Yet another object of the present invention is to provide a multi-sensor device having a plurality of preset electromagnetic waveforms established using predetermined responses to the target material.
Still yet another object of the present invention is to provide a multi-sensor device having means for indicating an aberration between a stored wave reception time differential and a current reception time differential.
Another object of the present invention is to provide a multi-sensor device having means for storing magnetic sample values for currency.
Yet another object of the present invention is to provide a multi-sensor device having a magnetic detector.
Still yet object of the present invention is to provide a multi-sensor device having means for generating a magnetic field.
Another object of the present invention is to provide a multi-sensor device having electrically conductive transmit and receive coils.
Yet another object of the present invention is to provide a multi-sensor device having electronic circuitry for recording and processing disturbances within the transmit coils magnetic field which generates a signal within the receiving coil.
Still yet object of the present invention is to provide a multi-sensor device having electronic circuitry for analyzing characteristic of the disturbance to determine if target characteristics are within stored currency parameters.
Additional objects of the present invention will appear as the description proceeds.
The present invention overcomes the shortcomings of the prior art devices by providing a multi-sensor device that can be used to scan target structures in a timely fashion to determine if there exists quantities of currency secreted within walls, floors, and/or ceilings.
The foregoing and other objects and advantages will appear from the description to follow. In the description reference is made to the accompanying drawing, which forms a part hereof, and in which is shown by way of illustration specific embodiments in which the invention may be practiced. These embodiments will be described in sufficient detail to enable those skilled in the art to practice the invention, and it is to be understood that other embodiments may be utilized and that structural changes may be made without departing from the scope of the invention. In the accompanying drawing, like reference characters designate the same or similar parts throughout the several views.
The following detailed description is, therefore, not to be taken in a limiting sense, and the scope of the present invention is best defined by the appended claims.
10 multi-sensor device
12 operator
14 first electromagnetic waveform transmitted
16 first electromagnetic waveform received
18 second electromagnetic waveform transmitted
20 second electromagnetic waveform received
22 first coil
24 second coil
26 magnetic signal
28 currency
30 first target surface
32 second target surface
34 meter
36 on/off switch
38 meter display
40 presets selector switch
42 operational selector switch
44 mode selector switch
46 MHZ selector switch
48 handle
50 display
52 antenna
54 power supply
56 coils
58 signal generator
60 signal processor
62 comparator
64 microprocessor
66 alarm
68 database
70 select structure to search
72 turn power on
74 initiate auto select
76 preset selection
78 test frequency selection
80 frequency valid
82 scan mode
84 scan surface
86 anomaly variation
88 conditional alarm indicator
90 magnetic detector
92 magnetic field anomaly scanned
94 magnetic field anomaly
96 magnetic field variance determination
98 conditional indicator response
100 currency detection indicator

Method and device for detecting currency


A paper-feeding system includes a paper tray for positioning a print medium, a pickup roller installed in front of the paper tray for picking up the print medium, a pickup arm connected to the pickup roller including a first retainer, a first elastic component connected to the pickup arm for providing an elastic force to the pickup arm so that the pickup roller can press the print medium, and a swing arm fixed to a shaft at one end. The swing arm includes a second retainer installed at the other end for fixing the first retainer.

1. Field of the Invention
The present invention relates to a paper-feeding system, and more particularly, to a paper-feeding system capable of switching paper-feeding statuses manually or automatically.
2. Description of the Prior Art
Please refer to FIG. 1. FIG. 1 is a diagram of a paper-feeding system 10 in the prior art. The paper-feeding system 10 includes a paper tray 12 for positioning a print medium 14, such as paper or a transparency, a burster 16 installed below the paper tray 12, a pickup arm 18, and a pickup roller 20. One end of the pickup arm 18 is connected to the pickup roller 20, and the other end of the pickup arm 18 is applied a force by an elastic component (not shown in FIG. 1) so that the pickup roller 20 is capable of applying a normal force to the print medium 14. The pickup arm 18 keeps pressing the print medium 14 so that the pickup roller 20 can press an upper surface of the print medium 14 steady.
Please refer to FIG. 2 and FIG. 3. FIG. 2 is a lateral view of the paper-feeding system 10 when print media are loaded fully in the prior art. FIG. 3 is a lateral view of the paper-feeding system 10 when no print medium is loaded in the prior art. The pickup roller 20 continues pressing the upper surface of the print medium 14 so as to apply the normal force to the print medium 14 for generating a corresponding friction force to drive the print medium 14 to move downward. The burster 16 blocks a bottom of the print medium 14 so that the print medium 14 buckles. The upper print medium 14 can be separated from other print media alone.
Because the pickup roller 20 needs to continue pressing the upper surface of the print medium so as to provide a normal force to the print medium 14, the normal force has to be overcome when positioning the print medium 14 inside the paper-feeding system 10 at a correct location. When the print medium 14 is loaded improperly, the print medium 14 might enter to a print area incorrectly. In addition, the normal force increases difficulty of repairing a paper jam of the paper-feeding system 10.

Paper-feeding system capable of switching paper-feeding statuses


In a method and device for carrying out at least one processing operation on a slaughtered bird which is hung by its legs, the bird is conveyed on a hook of a conveyor towards and into the processing area of a processing device in order for the at least one processing operation to be carried out on the bird. The bird is positioned in the processing area of the processing device by externally supporting the bird at at least two locations, which are selected from the group of locations which comprises the back, the sternum, the area of the clavicle, the wings and the sides of the bird. Then, the at least one processing operation is carried out in the processing device in the area of the breast of the bird. The bird may also be positioned in the processing area of the processing device by internally supporting the bird on the side of the sternum facing the abdominal cavity of the bird.

This invention relates to a method and device for processing a slaughtered bird which is hung by its legs from a hook of a moving conveyor. Methods and devices of this nature are generally known.
A special processing operation carried out on a slaughtered and eviscerated bird is a partial processing operation in which an automatic or semi-automatic processing device is used to obtain bird parts which are each of substantially identical weight or contain an equal amount of meat, irrespective of the body part (such as breast, wing, thigh, drumstick) which the bird part comprises. Since the amount of meat per bird part is relatively limited, the division must be carried out as accurately and reproducibly as possible, in order to keep differences in weight or amount of meat between the different bird parts within predetermined limits. A division which satisfies this requirement can only be carried out if the bird is accurately positioned in the processing device. The known methods and devices are not entirely satisfactory with regard to this point.
EP-B-0,033,177 describes a device for dividing a bird into nine parts, each of substantially the same weight. To this end, the bird has to be manually arranged on a positioning support which acts on the bird at the location of the ankle joints and the wings, and also supports the bird at the sides of the body, the top of the thighs, behind the spinal column and on the back. Then, various blades are used to automatically cut through the carcass, the breast and a first wing being cut off successively, and then a body longitudinal-halving cut being made, the other wing and the complete legs being cut off, and the drumsticks being cut free from the thighs.
A drawback of the device described in EP-B-0,033,177 is that it is not suitable for picking up and processing birds which have been supplied in a conveyor, such as an overhead suspension conveyor, without human intervention; the birds have to be arranged manually on the positioning supports. Furthermore, the bird is not optimally positioned on the positioning support.
EP-A-0,545,040 describes a device for cutting off a breast part of a bird, the wings already having been removed from the bird. The bird is hung by its legs from a hook and is internally supported by means of a mandrel which substantially fills the body cavity and causes the breast of the bird to project outwardly by exerting pressure on the ribs of the chest. On the outside of the carcass, there is a pivotable retention plate which interacts with an opposite surface of the mandrel and, on the side which is to face the mandrel, comprises a projection which clamps the clavicle of the bird against the mandrel. The retention plate also supports the shoulders of the bird. After the bird has been fixed in position in this way, firstly a stationary blade is used to make a transverse guide cut, at an angle to the carcass surface, in the abdomen of the bird, between the pelvis and the breastbone. Then, a rotating blade is used to make a transverse cut, at an angle to the carcass surface, in the breast of the bird, in order to separate the breast from the neck, shoulders and upper back of the bird. Finally, in the path of the transverse guide cut, a second cut is made with a rotating blade, in order to separate the breast from the pelvis and the lower back of the bird.
A drawback of the device according to EP-A-0,545,040 is that it is necessary for a voluminous mandrel to be introduced into the body cavity of the bird in order to make the desired cuts, but the positioning of the breast of the bird is not optimum for a cut/cuts to be made, as a result of the breast being supported by the mandrel in the area of the ribs. Also, since the positioning of the breast is not optimum, asymmetric breast parts are often cut off, which are increasingly unacceptable for purchasers of the breast pieces.
An object of the invention is to improve the positioning of the bird, in particular of its breast, in order for breast-related processing operations to be carried out. It is also an object to optimize the breast cut(s).
A further object of the invention is to optimize the way in which the wings and the legs of the bird are cut off.
Another object of the invention is to provide the option for the division of the bird to take place completely automatically.
In order for one or more of the above-mentioned objects to be achieved, the method according to the invention for carrying out at least one processing operation on a slaughtered bird which is hung by its legs comprises the steps: providing a conveyor with at least one hook for hanging and conveying the bird; providing a processing device with a processing area for carrying out the at least one processing operation on the bird; using the conveyor to convey the bird towards and into the processing area of the processing device; positioning the bird in the processing area of the processing device by externally supporting the bird at at least two locations, selected from the group of locations which comprises the back, the sternum, the area of the clavicle, the wings and the sides of the bird; and carrying out the at least one processing operation in the processing device in the area of the breast of the bird.
Alternatively, the step of positioning the bird in the method according to the invention comprises the step of internally supporting the bird on that side of the sternum which faces towards the abdominal cavity of the bird.
In the two ways mentioned above, it is possible to obtain a very accurate, stable and reproducible positioning of the bird for a wide variety of breast-related processing operations, such as: cutting off part of the breast; removing the skin from the breast; deboning the breast; dividing the carcass into a front half and a rear half; separating the wings from the carcass; and injecting a substance into the breast.
An additional processing operation for a breast-related processing operation is, for example, making a transverse incision in the abdomen below the sternum. In this case, use is preferably made of a sternum support element which acts on that side of the sternum which is directed towards the abdominal cavity of the bird, in the area of the free end of the trabecula mediana. Since this part of the sternum is accessible to the sternum support element from the outside of the bird, this is regarded as external support of the bird. The sternum support element, which may, for example, comprise a guide rail which extends in the path of the sternum, ensures that during the transverse incision the sternum is kept out of the path of the cutting means used, such as a rotating knife.
A similar external sternum support element in the form of a guide which extends in the path of the sternum can be used for cutting off part of the breast, comprising part of the trabecula mediana and each trabecula intermedia. This sternum support element also preferably acts on the sternum in the area of the free end of the trabecula mediana.
Preferably, another sternum support element is introduced into the abdominal cavity of the bird from a neck opening or drawing opening of the bird which has been made in an earlier processing stage, in order to reach the desired location in the area of the sternum, in particular the area of the rostrum sterni or the area of the ventricle.
In a preferred embodiment, the latter sternum support element comprises an arm which can move in a controllable manner, a free end of the arm being adapted to engage the side of the sternum facing the abdominal cavity. In order to make it easier to introduce the sternum support element into the body of the slaughtered animal, a first part of the arm may be pivotably connected to a second part of the arm, in which case the first part can be oriented, in a controllable manner, both substantially in line with the second part and at an angle with respect thereto, for example an angle of substantially 90xc2x0.
In an expedient embodiment, the means for positioning the sternum form a single unit with means for positioning the clavicle, so that positioning inaccuracies resulting from tolerances in the tools used are reduced to a minimum.
Preferably, a clavicle support element acts on the concave side of the clavicle, to which end the clavicle support element advantageously comprises a substantially L-shaped arm with a short limb and a long limb, the short limb being intended to engage the concave side of the clavicle. In this case, for optimum positioning of the clavicle, the arm is preferably moved such that the angle between the longitudinal axis of the short limb and a horizontal plane when the short limb is engaging the clavicle is larger than when it is at a distance from the clavicle. As a result, the sternum, which is connected to the clavicle, is pressed against a sternum support element.
Positioning of the body of the bird for the purpose of a partial processing operation comprises the step of: moving the wings with respect to the body, substantially in a direction away from the hips. For this purpose, it is possible to provide a pair of forks which can be displaced in a controllable manner in the vertical direction and each have a pair of downwardly directed limbs, the distance between the limbs of each fork substantially corresponding to a transverse dimension of a wing. Each of the forks is intended to be placed between the hips and the shoulders of the bird, and the forks can pivot, in a controllable manner, between a first angular position, in which the distance between the ends of the pairs of limbs substantially corresponds to the width of the body of a bird between the hips and the shoulders, and a second angular position, in which there is a greater distance between said ends of said pairs of limbs than in said first angular position. In the first angular position of the forks, the body of the bird is positioned between the forks. Then, the forks are moved downwards, with the humerus of each wing moving in between the limbs of a fork. At the same time, or next, the forks are pivoted into their second angular position, with the result that the body of the bird is stretched as a result of a tensile force which is thus exerted between the legs and the wings. This makes it easier to carry out the cutting processing operations on the body.
In a preferred embodiment, the forks are arranged on a common body member, which body member may also comprise a pivotable plate, at least a section of which is intended to be brought into contact with the back of the bird in order to position the back.
In another preferred embodiment, the positioning means comprise a pair of wing support elements which can be displaced in a controllable manner in the vertical direction and each have a downwardly directed hook-like end, which wing support elements are each intended to be placed between the hips and the shoulders of the bird and can pivot, in a controllable manner, between a first angular position, in which their hook-like ends are directed downwards, and a second angular position, in which said ends hook around the wings and are directed substantially towards the back of the bird.
Preferably, while a part of the breast is being cut off, the breast of the bird is pushed away substantially parallel to the plane of the cut and in the direction in which the cut is being made, in particular by means of at least one belt conveyor. In this way, an optimum cut for obtaining a symmetrical breast part of the desired dimensions is obtained both in the method and device according to the invention, but also in other devices, such as devices according to the prior art. The conveying speed of the belt conveyor is preferably selected in such a way that it is greater than or equal to the conveying speed of the conveyor. An optimum action of the conveyor on the breast part which is to be cut off is obtained if the material of the belt is resilient.
In the prior art, the connections between the legs and the body of the bird ensure that cuts for separating the legs from the bird cannot be carried out optimally, since the mobility of the legs with respect to the body is limited. If firstly a transverse incision is made in the abdomen itself, or the breast part is cut off, and the legs are only separated from the body after this, the legs can be directed much more easily and, in addition, are much more accessible to knives in the hip area. Before the legs are cut off the body of the bird, the hips of the bird can be dislocated, which can be easily achieved as a result of the easier manipulation of the legs after the breast part has been cut off the bird in accordance with the invention. Other advantages are obtained during any further processing operations, such as roasting, frying, coating with breadcrumbs and marinating, since undesirable cavities in which substances such as water, breadcrumbs and marinade could accumulate, are avoided.
According to the invention, the dislocation of the hips of the bird which is suspended by its legs from a hook of a moving conveyor comprises the steps of: placing a leg support element against each leg on the side of the leg which faces towards the breast side of the bird; placing a hip support element against each hip on the side of the hip which faces the back of the bird; and exerting oppositely directed forces on the bird by means of the leg support element and the hip support element in order to dislocate the hip joints. Such a method can be carried out completely automatically very well, both in combination with other processing operations on the bird and independently of such operations.
Preferably, the legs are spread apart by exerting oppositely directed forces in the hollows of the knees of the legs, and the leg support element engages the leg in the area of the drumstick. Dislocating the hips of a bird which is suspended from a hook of a moving conveyor can be carried out most easily if the legs of the bird are situated one behind the other, as seen in the conveying direction of the conveyor. In this case, the hip dislocating forces are exerted in a direction which is substantially transverse with respect to the direction of movement of the conveyor while the bird is being conveyed.
In a preferred embodiment, the leg support element and/or the hip support element comprise a guide which runs substantially parallel to or at a small angle to the conveying direction of the conveyor. It is thus extremely simple to obtain an effective hip dislocating device.
In another preferred embodiment, the means for supporting the hip comprise a pair of pins, of which the areas between the ends thereof are designed so as to engage the hips. In particular, the longitudinal axis of the pins is oriented substantially vertically. The use of the pins offers the advantage that the dislocation can be controlled separately for each of the two hips of a bird. As an alternative to pins, it is also possible for the hip support means used to be a pair of wheels, the circumferential sides of which are designed to engage the hips.
According to the invention, the wings of the bird, including a part of the breast or the back of the bird, can be cut off optimally, both in combination with other partial processing operations and independently from such operations, by means of a rotating knife, the corresponding shoulder joint of the bird moving past the knife near the underside thereof, and the active part of the knife moving in substantially the same direction as the shoulder joint. Advantageously, the legs of the bird are in this case situated next to one another, as seen in the conveying direction of the conveyor. The particular manner of cutting allows the wings of the bird to be guided past the knife in a substantially natural position of the wings.
The claims and advantages will be more readily appreciated as the same becomes better understood by reference to the following detailed description and considered in connection with the accompanying drawings in which like reference symbols designate like parts.

Method and device for processing poultry


The invention relates to a transparent medium comprising pearl lustre pigments having angle-selective reflection and/or transmission properties and to the use thereof, especially in transparent thermal insulation systems (TIMs).

The invention relates to the use of functional pearl lustre pigments in transparent media notable for their angle-selective transmission and/or reflection properties.
Transparent thermal insulation is a technology for solar space heating. Transparent insulation materials (TIMs) combine low thermal conductivity with a high level of transmission for solar radiation. On a transparently insulated exterior wall, a TIM element is located in front of a solid wall to which a black absorber coat has been applied. This system guides the incident solar energy from the outside of a facade through a system of glass tubes brought to the wall-forming component and converted into heat. The TIM systems employed at present, although supplying good thermal insulation and energy recovery in the winter as well, have a mode of operation which nevertheless, in summer, leads to overheating of the wall and to unpleasant interior wall temperatures where there are no mechanical shading systems provided, such as roller blinds, venetian blinds, shutters, air exhaust systems, etc. In addition, the black absorber coats required for absorbing the energy restrict the decorative design options for facades.
Building facades have to date been seen only as areas for decoration; viewing facades as a useful functional surface in the context of thermal insulation promises considerable advances in terms of the insulation and heating of buildings, which is equivalent to sparing use of resources.
The sun is an inexhaustible and environmentally friendly energy source which provides us with a potential energy for heating buildings. In total, four times more energy shines on a building than is consumed as heating energy inside it.
The solar radiation which is incident on a building facade changes its angle of incidence depending on the time of day and time of year (winter/summer). In winter, the angle of incidence on a south-facing facade when the sun is at its highest (midday) is about 12xc2x0, whereas in the summer it is about 68xc2x0 in Germany (depending on latitude).
The object of the present invention, then, is not only to utilize building facades as areas for decoration but also to deploy these facades as functional surfaces in regulating the heat balance of a building.
Pearl lustre pigments are no longer of interest solely for their colouring action but are increasingly being employed in functional areas. In the visible wavelength range, pearl lustre pigments exhibit selective reflection and/or transmission, properties which are responsible for the perceived colour. This wavelength-dependent reflection and/or transmission can be extended to the near infrared region and is used in part for agricultural films.
In addition, pearl lustre pigments exhibit different reflection and/or transmission depending on the angle of incidence of the incoming radiation.
A completely new functional area of use for pearl lustre pigments should therefore lie in the building sector, in facade design.
It has surprisingly now been found that transparent media comprising functional pearl lustre pigments based on platelet-shaped substrates, applied, for example, to the surface of a facade, result in angle-selective shading of the building.
The so-called functional pigments have the feature that their reflection in the visible spectral range is low under an almost perpendicular angle of incidence (e.g. up to about 12xc2x0 deviation from the perpendicular, corresponding to winter conditions) while at a flat angle of incidence (i.e. up to about 68xc2x0 deviation from the perpendicular, corresponding to summer conditions) it is large.
With appropriate application of these functional pigments to a facade it is possible to achieve transmission of the solar radiation, and hence heating of the facade, in winter but reflection of the solar radiation, i.e. shading of the facade, in summer.
The invention therefore provides transparent media comprising pearl lustre pigments based on platelet-shaped substrates having angle-selective reflection and/or transmission properties, characterized in that the proportion of the solar transmission level in summer (angle of incidence of solar radiation from 55 to 70xc2x0) to the solar transmission level in winter (angle of incidence of solar radiation from 5 to 20xc2x0) is in the range of 50-85%.
The angle-selective properties of the functional pigments in the transparent media are concentrated on the spectral range of solar radiation, i.e. from 0.25 to 2.5 xcexcm. Within this wavelength range it is possible to measure the directional hemispherical degrees of transmission and reflection, for example in glass supports to which the functional pigments have been applied. From these measurements it is possible, by weighting them with the solar spectrum and/or with the light sensitivity of the human eye, to calculate solar or visual, respectively, degrees of transmission and reflection in accordance with DIN 67507.
DE-A-195 01 114 discloses a process which uses simple measures to incorporate the direct and diffuse solar irradiation present in winter into the heat balance of a house in a positive manner. The prior art describes a coating material which can be formulated to be reflective in the visible region of the electromagnetic spectrum and, by virtue of a pigment mixture, absorbent in the near infrared region. Unlike the present invention, in DE-A-195 01 114 only the solar irradiation present in winter has a positive effect on the heat balance of a house. In this context, however, it is disadvantageous that the much more intense solar irradiation in spring, summer and autumn may cause overheating of the house which can be countered only by air exhaust measures. The pigmented transparent medium in accordance with the invention has as its objective not only to utilize the solar irradiation in winter but also to protect buildings against summer overheating.
In the present invention, suitable functional pigments are all those pearl lustre pigments known to the person skilled in the art which have angle-selective reflection and/or transmission properties and whose ratio of the solar transmission level in summer (angle of incidence of the solar radiation from 55 to 70xc2x0) to the solar transmission level in winter (angle of incidence of the solar radiation from 5 to 20xc2x0) is within the range from 50 to 85%, preferably less than 80% and, in particular, not more than 75%.
To assist the angle-selective transmission and/or reflection properties of the functional pearl lustre pigments it is advisable to apply the platelet-shaped pigments to a textured substrate which in turn defines the orientation of the platelets. Given appropriate alignment of the pigment platelets, the angle-selective effect is efficiently intensified. The texturing can be achieved, for example, by applying the pigmented transparent medium to an embossed film or by embossing the transparent medium itself.
The angle-selective properties of the functional pigments are only manifested in the transparent medium when the pigment is employed in amounts of from 5 to 70% by weight, preferably from 10 to 50% by weight and, in particular, from 30 to 40% by weight. The concentration in which they are used is dependent, however, on the transparent medium employed.
Preferred functional platelet-shaped pigments are those based on metal oxide platelets, examples being those of iron oxides or alumina, of layered silicates, such as natural or synthetic mica, talc, kaolin, SiO2 flakes, glass or other silicatic materials, which are coated with one or more metal oxide coats. Metal oxides used in this context include both colourless metal oxides of high refractive index, such as titanium dioxide or zirconium dioxide, and coloured metal oxides, such as chromium oxide, nickel oxide, copper oxide, cobalt oxide and, in particular, iron oxides, such as Fe2O3 or Fe3O4, for example. These platelet-shaped pigments are known, and many of them are obtainable commercially and/or can be prepared by standard techniques known to the person skilled in the art. Examples of suitable pearl lustre pigments are described in the German Patents and Patent Applications 14 67 468, 19 59 998, 20 09 566, 22 14 454, 22 15 191, 22 44 298, 23 13 331, 25 225 72, 31 37 808, 31 37 809, 31 51 343, 31 51 354, 31 51 355, 31 116 02 and 32 35 017. Functional pigments based on SiO2 flakes and produced by the belt technique are the subject, for example, of WO 93/08237. Multicoat pigments are described in particular in DE-A-42 38 378, DE-A-196 18 563, DE-A-196 18 566 and DE-A-196 569. In order to increase their temperature stability and weathering resistance, the functional pigments may also have been aftercoated. It is also possible, furthermore, to employ special-effect pigments based on liquid-crystal polymers (LCPs).
Functional pearl lustre pigments employed with particular preference are electrically conductive pigments as disclosed, for example, in DE-A-38 42 330, DE-A-42 12 950 and EP 0 139 557. These pigments preferably have a tin dioxide coat doped with antimony, indium, bismuth, copper, gallium, germanium or fluorine, especially antimony. Pigments of this type are obtainable, for example, under the trade name Minatec(copyright) (produced by Merck KGaA, FRG).
The transparent medium of the invention may also comprise a mixture of different functional pigments, since in many cases the use of at least two different pigments makes it possible to obtain special effects. In that case the pigments can be mixed in any proportion, although the overall content of all functional pigments in the transparent medium should not exceed 70% by weight.
Suitable transparent media are, in particular, glass, varnishes, aqueous lacquers and plastics, especially plastics films. The transparent medium is preferably glass or a transparent polymer.
Binders employed are customary coatings binders, such as polyurethane-acrylate resins, acrylate-melamine resins, alkyd resins, polyester resins and epoxy resins, hydrocarbon resins, nitrocellulose, nitrocellulose derivatives, cellulose acetopropionate, cellulose acetobutyrate, ketone resins, aldehyde resins, polyvinyl-butyral, xcex1-methylstyrene-acrylonitrile copolymers, polyesterimide, acrylate resin based on butyl acrylate, polyacrylic esters, especially polyacrylic butyl esters, an aqueous dispersion based on polyethylene, an aqueous dispersion based on polyethylene oxidate, an aqueous dispersion based on ethylene-acrylic acid copolymers, an aqueous dispersion based on methacrylate, one based on acrylate/styrene, a vinylpyrrolidone-vinyl acetate copolymer, or else a mixture of these dispersions and binders.
The formulation is generally prepared by introducing the functional pigment as initial charge and mixing it homogeneously with the binder and any non-opaque additives. The pigmented coating material can subsequently be applied, for example, to glass plates, aluminium panels or steel panels by means, for example, of dipping, brushing, knife-coating, printing, etc. It is also possible for the functional pigment or pigment mixture to be applied in dry form to a support, for example a thermoplastic. The support is then melted and the pigment is distributed homogeneously in the transparent medium.
Further suitable candidates as the transparent medium are all thermoplastics known to the person skilled in the art, as are described, for example, in Ullmann, Vol. 15, p. 457 ff., Verlag VCH. Examples of suitable plastics are polyethylene, polypropylene, polyamides, polyesters, polyester esters, polyether esters, polyphenylene ethers, polyacetal, polybutylene terephthalate, polymethyl methacrylate, polyvinyl acetal, polystyrene, polyurethanes, acrylonitriie-butadiene-styrene (ABS), acrylonitrile-styrene-acrylate (ASA), polycarbonate, polyether sulfones, polyether ketones, and their copolymers and/or mixtures.
The functional pigments are incorporated into the plastic by mixing the plastics granules with the pigment and then deforming the mixture under the action of heat. The plastics granules/pigment mixture is generally prepared by introducing the plastics granules as initial charge in an appropriate mixer, wetting them with any additives, and then adding the pigment and mixing the constituents. Pigmentation of the plastic is generally carried using a colour concentrate (masterbatch) or compound formulation. The resulting mixture can then be processed directly in an extruder or injection-moulding machine. The shaped articles formed on processing, such as plastic sheets, for example, exhibit very homogeneous distribution of the pigment.
The pigments can also be incorporated in glass or ceramics. In this case, the lustre pigments are mixed under gentle conditions with the glass or ceramic frits, the powder mixture is applied to a support, and firing is carried out for 5-20 minutes at temperatures from 400-1100xc2x0 C., preferably at 400-850xc2x0 C.
The medium according to the invention can be applied for shading andxe2x80x94at the same timexe2x80x94decorative purposes to any desired substrate materials, examples being metals such as iron, steel, aluminium, copper, bronze and brass, metal foils, and metal-coated surfaces of glass, ceramic, concrete, packaging materials, films or to other materials. The use of functional pearl lustre pigments has been found to be extremely effective, in particular, in the field of so-called transparent insulation materials (TIMS) on building facades.
The invention likewise provides TIM systems which comprise coloured absorber coats in combination with glass coatings having an angle-selective shading action.
The tranparent media of the invention are of considerable economic significance, especially by virtue of their use in TIMs, in terms of energy saving and hence the sparing use of resources.

Transparent medium with angular-selective transmitting or reflecting properties


A soldering flux suitable for soldering of small electronic components comprises 0.1-50 mass percent of an organic acid, 5-40 mass percent of a solvent, and 10-95 mass percent of a thermosetting resin (including a curing agent), which is preferably a bisphenol A epoxy resin and an acid anhydride or amine curing agent. This flux can be used to prepare a solder paste by mixing with solder powder. This soldering flux can secure an electronic component simultaneously by soldering and by the resin, simply by a soldering operation at a soldering temperature of at least 150xc2x0 C., and cleaning after soldering is no longer necessary.

This invention relates to a soldering flux suitable for soldering of components and particularly small electronic components, and to a soldering paste which uses it and to a soldering method for components. When small electronic components are soldered using a flux according to the present invention, simultaneous with soldering, components can be strongly secured by a resin.
Fluxes which are used for soldering generally function to clean soldered joints, to prevent oxidation of metal, and to lower the surface tension of molten solder to improve wettability. Conventional fluxes were an auxiliary material for facilitating soldering through such functions, and they had no use after soldering. For this reason, there have been many proposals for adjusting the compositions thereof so as to make flux removal after soldering easy, and of means for rendering flux residue harmless.
With recent advances in reducing the size of electronic components, the electrodes, which are the areas of electronic components which are soldered, have also decreased in size. For this reason, an adequate amount of solder can not be used, and the joining strength by soldering alone has come to be inadequate to secure components. Namely, with small electronic components, the area and the volume of the region to be soldered is small, so a component can not be adequately joined and maintained by soldering alone, and it is necessary to further provide some other component-securing means.
As a component-securing means for strengthening joining by soldering, components are secured by covering the periphery of a soldered area with a resin by underfilling or resin molding. For this purpose, it is necessary to perform cleaning and clean off flux residue. However, with small electronic components, spaces have a small size of at most 100 micrometers, and cleaning can not be effectively carried out, so it is difficult to adopt such a securing means.
Merely for the purpose of increasing joining strength, it is also conceivable to employ an adhesive. However, after soldering, solder is present at the joining interface, so it is difficult to apply an adhesive thereto.
It is also possible to carry out electrically conducting joining of components without using solder by using an electrically conducting adhesive which contains an electrically conducting filler. However, with an electrically conducting adhesive, the electrical conductivity of the joint is not sufficiently high, so for joining electronic components, soldering is best.
Accordingly, an object of the invention is to provide a new means which can increase the joining strength of electronic components when carrying out soldering of small electronic components.
Another object of this invention is to provide a soldering method, which can strongly join small electronic components by carrying out only conventional soldering operations without the addition of new steps and which does not require cleaning after soldering, and a flux for use therein.
The present inventors noted that of the joining surfaces of a component being soldered, in addition to the area occupied by electrodes, an area about the same as that of the electrodes remains, and that area can also be utilized for securing of the component. They also found that by including a thermosetting resin such as an epoxy resin in flux, when soldering small electronic components, in addition to soldering due to melting of solder on electrodes, a securing action is also exhibited at the same time by the thermal curing of the thermosetting resin in the flux around its periphery, and that it is possible to achieve the above-described objects.
According to one aspect, this invention is a soldering flux comprising 0.1-70 mass percent of an organic acid, 5-40 mass percent of a solvent, and a total of 10-95 mass percent of a thermosetting resin and a curing agent, wherein when a component is being soldered, it exhibits a function of securing the component by means of the thermosetting resin.
In a preferred embodiment, the organic acid is one or more classes selected from the group consisting of rosin, carboxylic acids, and carboxylic acid anhydrides. It is particularly preferable for the organic acid to contain a rosin as at least a portion thereof. The thermosetting resin is preferably an epoxy resin, and more preferably a bisphenol A epoxy resin obtained by reaction of bisphenol A and epichlorohydrin. In this case, the curing agent for the thermosetting resin is preferably one or more classes selected from the group consisting of carboxylic acid anhydrides and amines. The flux of this invention may further contain 0.1-10 mass percent of a thixotropic agent.
According to another aspect, the present invention provides a solder paste which is a mixture of a powder of a solder alloy with a melting point of at least 150xc2x0 C. and the above-described flux. In particular, in the case of a solder paste, the total amount of the thermosetting resin and the curing agent in the flux is preferably in the range of 50-95 mass percent so that they are the main component of the flux.
According to yet another aspect, the present invention relates to a method for soldering a first member and a second member using the above-described flux and solder, or the above-described solder paste. Preferably the first member is an electronic component and the second member is a substrate having a large number of electrodes, such as a printed circuit board, and the soldering temperature is at least 150xc2x0 C. In a soldering method according to the present invention, securing by soldering and by the thermosetting resin in the flux can be simultaneously achieved.
Incorporation of an epoxy resin as a thermosetting resin in a soldering flux is disclosed in Japanese Published Unexamined Patent Application Hei 8-90283 and Japanese Patent No. 2,503,099. However, as will be next explained, neither of these is aimed at securing an electronic component by the resin in the flux.
The flux which is disclosed in Japanese Published Unexamined Patent Application Hei 8-90283 contains 10-40 mass percent of an epoxy resin which is incorporated in the flux in place of rosin in order to prevent flux residue remaining on the surface of components after soldering from peeling off of the components. It is intended to facilitate coverage of an electronic component with resin when the soldered component is subjected to resin molding with the same resin after soldering.
The flux disclosed in Japanese Patent No. 2,503,099 is used with a solder for reflow soldering of a printed substrate. It contains an epoxy resin or a carboxyl containing resin or the like which is added so that flux residue will not crack and so as to prevent, when a rosin flux is liquefied at high temperature, the ionic components present therein from being liberated and acting as a cause of corrosion. The amount of the epoxy resin which is added is at most 20 mass percent.
In Japanese Published Unexamined Patent Application Hei 6-269980, an electrically conducting paste for soldering leads is disclosed which consists essentially of solder powder and an epoxy resin. In addition to solder, this electrically conducting paste consists essentially of the epoxy resin, and the electrically conducting paste does not function as a flux.
A soldering flux according to this invention can be prepared by adding a thermosetting resin (such as an epoxy resin) to a conventional rosin flux, for example. When the flux is heated to preferably at least 150xc2x0 C. during soldering, such as during reflow of solder paste, curing of the thermosetting resin in the flux occurs, so joining by the thermosetting resin is added to joining by soldering. Thus, the securing force is increased, and even in the case of soldering small electronic components, a sufficient joining strength can be provided by soldering operation alone.
Namely, in this invention, the flux component remaining after soldering, which is conventionally referred to as flux residue, can also be used in joining of components. The thermoset flux component remaining after soldering can contain, in addition to the thermoset resin, non-volatile components in the flux such as rosin. Even if flux components such as rosin remain, they are secured by the thermosetting resin, and it becomes difficult for them to peel off, so they have no adverse effect on the joint. Accordingly, it is not necessary to perform cleaning, which was conventionally carried out in order to remove flux residue after soldering.
When the thermosetting resin is an epoxy resin, properties such as the joining strength of a component, the hardness of flux residue (adhered resin), and solderability when soldering is carried out using a flux according to the present invention can be controlled by factors such as the epoxy equivalent and the amount of the epoxy resin, and the type and the amount of the curing agent.
Components which are suitable for soldering using the flux according to the present invention are small electronic components. They include, for example, semiconductor packages such as flip chips and CSP""s (chip size packages) and other small chip components which have conventionally required underfilling (resin securing). Examples of small electronic components of this type are flip chips with a bump pitch of at most 0.3 mm and fine pitch CSP""s; components which have small electrodes for soldering and which are weak when joined only by soldering, such as LGA""s (land grid arrays); and minute chip resistors, coils, capacitors, transistors, and the like such as 0603 components (length 0.6 mm, width 0.3 mm), and the like. In addition, components having a narrow gap (such as at most 0.1 mm) between areas to be soldered of the components and a substrate and which can not be made adequately clean even if cleaning is performed are suitable for soldering according to the present invention.
When a flux according to the present invention is used for coating an area to be soldered separately from solder, it is suitable for solder bump formation using solder balls, for electrodes which are precoated with solder, and for reflow of preformed solder.
A flux according to the present invention can be uniformly mixed with a solder powder (a powder of a solder alloy) and used as a solder paste. After this solder paste is applied to an area to be soldered by printing or with a dispenser of the like, a chip component can be mounted thereon and reflow soldering can be carried out.
When soldering is carried out by applying just the flux to an area to be soldered, a single flux can simultaneously perform a fluxing action during soldering and can perform securing by means of the thermosetting resin surrounding the solder. When carrying out soldering of chip components using a solder paste obtained by mixing a flux and a solder powder, at the time of heating, the flux in the paste penetrates between the chip component and the printed substrate, and when soldering is completed, the thermosetting resin secures the chip component to the printed substrate.
Due to the securing action of the thermosetting resin, a flux according to the present invention can make the joining strength of an electronic component which has a small soldering region and which had an inadequate strength by soldering alone the same as or greater than the joining strength of a conventional electronic component having a large soldering region and using a large amount of solder. Accordingly, it becomes unnecessary to carry out underfilling or resin molding in addition to soldering.
A flux according to the present invention can be prepared by, for example, adding a thermosetting resin and a curing agent to a conventional rosin flux. The thermosetting resin which is added is preferably one which sets at or above the liquidus temperature of the solder alloy which is used with the flux. If the thermosetting resin sets before the solder melts, deformation of the solder may be impeded.
The amount of the thermosetting resin in the flux of the present invention (when a curing agent is used, the total amount including the curing agent) is in the range of 10-95 mass percent. If the amount of the thermosetting resin is less than 10 mass percent, the above-described desired effects can not be sufficiently obtained, and if it exceeds 95 mass percent, a fluxing action is not sufficiently exhibited. The amount of the thermosetting resin is preferably at least 25 mass percent, and more preferably, it is at least 50 mass percent so as to be the main component of the flux and in particular it is preferably made a large amount of more than 50 mass percent. In particular, when the flux is used in the form of a solder paste, the thermosetting resin is preferably used in a large amount in this manner. The amount of the thermosetting resin is most preferably 60-85 mass percent.
One example of a thermosetting resin which is suitable for use in a flux according to the present invention is an epoxy GEM resin. Representative examples of epoxy resins are bisphenol A epoxy resins which are obtained by reacting bisphenol A and epichlorohydrin, and novolac epoxy resins which are obtained by reacting an orthocresol novolac resin or a phenolic novolac resin with epichlorohydrin, and they are preferably used. However, other epoxy resins such as brominated epoxy resins, glycidyl ester epoxy resins, glycidyl amine epoxy resins, and alicyclic epoxy resins can also be used.
As a curing agent for curing the epoxy resin, it is preferable to use a polyamine or a carboxylic acid anhydride. The curing temperature of the epoxy resin depends upon the particular curing agent, so the curing agent which is used is preferably selected such that curing of the epoxy resin takes place at a temperature at or above the liquidus temperature of the solder.
For example, as an amine curing agent, an aromatic amine having a high curing temperature, such as 4,4xe2x80x2-diaminodiphenyl sulfone is suitable. Examples of carboxylic acid anhydrides suitable as a curing agent include phthalic anhydride, tetrahydrophthalic anhydride, and trimellitic anhydride.
When a carboxylic acid anhydride is used as a curing agent for the epoxy resin, the anhydride functions not only as a curing agent but, as will be described below, functions as an organic acid component to exhibit a fluxing action. For this reason, it is more preferable to use an acid anhydride rather than a polyamine as a curing agent.
A cure accelerator which is commonly used in the curing of an epoxy resin may be added in order to lower the curing temperature or increase the securing strength. Amines, sulfonic acids, amine boron trifluorides, polyamide resins, and the like can be used as a cure accelerator.
In addition to the above-described thermosetting resin, a flux according to the present invention also contains an organic acid which is commonly used in soldering flux. The organic acid is necessary in order to exhibit the fluxing action, i.e., to clean the area to be joined and improve the wettability by solder of the area. A typical example of the organic acid is a rosin, but other carboxylic acids or anhydrides thereof may be used, and two or more classes thereof may be used in combination. As stated above, in a flux according to the present invention, a carboxylic acid anhydride performs the functions of both an epoxy curing agent and an organic acid.
The rosin can be selected from all the types which are used in conventional rosin fluxes. Specific examples thereof include ordinary gum rosin, tall oil rosin, wood rosin, as well as their derivatives such as polymerized rosins, hydrogenated rosins, rosin esters, rosin modified resins, and the like. Rosins exhibit a large fluxing action, so preferably a rosin is present in the flux as at least a portion of the organic acid.
As a carboxylic acid, aliphatic, alicyclic, and aromatic mono and polycarboxylic acids having 4-22 carbon atoms can be used. Some specific examples of such acids include capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachic acid, behenic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, fumaric acid, and the like.
A carboxylic acid anhydride can also be used as the organic acid. A carboxylic acid anhydride functions as an epoxy curing agent, so as stated with respect to curing agents, it is preferable to use such a class that produces an epoxy curing reaction at or above the liquidus temperature of the solder.
The amount of the organic acid in a flux according to the present invention is 0.1-70 mass percent. When an acid anhydride is used as the epoxy curing agent, the amount of the organic acid also includes the amount of the acid anhydride. If the amount of the organic acid is less than 0.1 mass percent, a fluxing effect is not exhibited, while if the amount exceeds 70 mass percent, the securing strength after soldering is no longer adequate. The amount of the organic acid is preferably at most 50 mass percent.
Even when the flux contains an acid anhydride as a curing agent, the flux preferably contains another organic acid which does not function as a curing agent, and preferably a rosin in addition to the acid anhydride. Using another organic acid in addition to the acid anhydride which is a curing agent increases the fluxing action. The amount of the other organic acid is preferably at least 0.5 mass percent, it is more preferably at least 3 mass percent, and it is particularly preferable for it to be at least 5 mass percent. The upper limit can be as high as 50 mass percent, but preferably it is 20 mass percent. Similarly, in the case when the curing agent is an amine, the flux preferably contains as an organic acid another organic acid which does not function as a curing agent in the same amount as described above.
The solvent can be one which is conventionally used in a soldering flux and particularly in a rosin flux. For example, alcoholic solvents such as ethyl alcohol, isopropyl alcohol, and butyl carbitol, ester solvents such as ethyl acetate and butyl acetate, hydrocarbon solvents such as toluene, ketone solvents such as acetone and methyl ethyl ketone, and glycol solvents such as ethylene glycol can be given as examples.
The amount of the solvent can be such as to give the flux a density and viscosity suitable for the intended use. In general, the amount of the solvent is in the range of 5-40 mass percent.
A flux according to the present invention may contain additives such as a thixotropic agent and an activator which are conventionally added to a flux.
Preferred thixotropic agents are hardened castor oil, stearamide, and the like. The amount of the thixotropic agent is preferably 0.1-10 mass percent.
An activator is added in order to improve the solderability of the flux. For example, in a rosin flux, there are cases in which an organic acid is used as an activator, but in the present invention, an organic acid is not considered as an activator. Preferred materials for use as an activator in a flux according to the present invention are hydrohalides of amines, among which polyamine hydrobromides such as triethanolamine hydrobromide and diphenylguanidine hydrobromide and the like are suitable.
By incorporating a thixotropic agent, a flux according to the present invention can be formed into a viscous liquid suitable for a flux which can be applied by printing, transfer, or the like, or for a flux for use in preparing a solder paste.
When performing soldering using a flux according to the present invention, the thermosetting resin in the flux is cured with a temperature and time profile for reflow of a eutectic solder (Sn 63%, Pb 37%), for example, and soldering of a component and securing of the component can be carried out simultaneously.
When the flux is applied by itself, the application of the flux can be carried out by screen printing, transfer, spin coating, brush application, and the like. Then, local heating for soldering can be carried out with a light beam, a soldering iron, a laser, or the like.
According to another embodiment, a flux according to the present invention and a solder alloy powder can be uniformly mixed to prepare a paste, and this can be used for soldering.
Typical examples of a solder alloy for use in a solder paste are eutectic solder (63% Snxe2x80x9437% Pb, melting point 183xc2x0 C.) and Snxe2x80x94Ag based lead-free solder alloys [for example, 97.75% Snxe2x80x943.5% Agxe2x80x940.75% Cu (melting point 220xc2x0 C.), and 96% Snxe2x80x942.5% Agxe2x80x941% Bixe2x80x940.5% Cu (melting point 220xc2x0 C.)], but solder alloys other than these can also be used. A powder of the solder alloy is preferably a spherical powder obtained by the centrifugal atomizing method or the gas atomizing method. The particle size of the solder alloy is normally in the range of 200-400 mesh, but a finer powder can also be used.
Preferably the solder paste contains 50-95 mass percent and more preferably 70-90 mass percent of the solder alloy powder and 5-50 mass percent and more preferably 10-30 mass percent of flux.
Soldering with the solder paste is carried out by applying a prescribed amount in a location to be soldered by a means such as screen printing, and then heating to a reflow temperature of at least 150xc2x0 C., such as to approximately 220xc2x0 C. in the case of the above-described eutectic solder and to at least 240xc2x0 C. in the case of the above-described Sn-Ag based lead-free solder.
When soldering an electronic component, the melting temperature of the solder alloy is at least 150xc2x0 C., preferably greater than 150xc2x0 C., and more preferably at least 180xc2x0 C., and the reflow temperature is at least 200xc2x0 C., usually in the range of 200-270xc2x0 C., and preferably 230-270xc2x0 C.
According to the present invention, as illustrated by the below-described examples, even in the case of a small electronic component in the form of a 0603 (0.6 mm longxc3x970.3 mm wide) or a 1005 (1.0 mm longxc3x970.5 mm wide), soldering can be performed with certainty, and at the same time, it can be secured to a substrate by a flux comprising a thermosetting resin, and additional securing steps such as underfilling or cleaning steps for removing flux residue after soldering become unnecessary, so the economic merits of a soldering method according to the present invention are significant.

Thermosetting soldering flux and soldering process