Patent Grant
11644236
The present invention relates to a vacuum freeze-drying apparatus and a vacuum freeze-drying method.
Conventionally, a freeze-drying apparatus has been proposed in which droplets are produced, and the frozen particles freeze-solidified with the droplets are freeze-dried (Patent Document 1).
In addition, a freeze-drying apparatus has also been proposed in which a shelf for receiving frozen materials is tilted (Patent Document 2).
Further, a vacuum freeze-drying apparatus has been proposed in which frozen particles are sublimated and dried by the kinetic energy obtained at the time of spraying (Patent Document 3).
However, in the above documents, there is a problem that vacuum freeze-drying cannot be continuously performed in a short time.
Therefore, the present invention has been made in view of the above problems and provides a vacuum freeze-drying apparatus and a vacuum freeze-drying method capable of continuously performing vacuum freeze-drying in a short time.
In order to solve the above problems, (1) the present invention provides a vacuum freeze-drying apparatus comprising a vacuum freezing device for freezing a liquid, and a drying device for sublimating and drying a frozen substance frozen as above. The vacuum freeze-drying apparatus comprises an exhaust path for performing vacuum suction, and the drying device comprises a tubular member formed of a tubular shape provided with an inlet portion and an outlet portion, a temperature adjusting means provided in a plurality of regions formed toward a direction from the inlet portion to the outlet portion of a peripheral portion of the tubular member, wherein the plurality of regions are at least three or more regions whose temperature is capable of being controlled, and the temperature adjusting means adjusts a temperature of the plurality of regions in an outer surface of the tubular member, a temperature control unit for independently controlling the temperature adjusting means, and a rotating portion for rotating the tubular member. The tubular member has a spiral transfer means continuously provided adjacent to an inner wall of the tubular member toward a direction from the inlet portion to the outlet portion, and the transfer means transfers the frozen substance entering from the inlet portion sequentially to locations corresponding to the plurality of regions in the tubular member by the transfer means to continuously sublimate and dry the frozen substance.
(2) In the configuration of the above (1), the plurality of regions of the three or more regions comprise at least a temperature region of a minus temperature, a temperature region in a range from the minus temperature to plus 40° C., and a temperature region of 20° C. or higher, provided toward a direction from the inlet portion to the outlet portion respectively.
(3) In the configuration of the above (1) or (2), a substance produced therefrom is an injectable substance or a drug in solid formulation, and a periphery of a tubular member is covered with clean air.
(4) In the configuration of the above (1) to (3), the rotating portion comprises a rotational drive transmitting portion for transmitting rotational drive provided in one or a plurality of locations in an axial direction, and a rotation support portion configured by a rotary roller and/or a bearing for supporting rotation by the rotational drive transmitting portion.
(5) In the configuration of the above (1) to (4), the rotating portion has a rotation speed of 1/30 rpm or more and 1 rpm or less.
(6) In the configuration of the above (1) to (5), the transfer means is formed by providing a spiral wall portion in an inner wall of the tubular member.
(7) In the configuration of the above (1) to (5), the transfer means is configured by a groove portion formed in an inner wall of the tubular member, and the depth of the groove portion is 3 mm or more and 50 mm or less.
(8) In the configuration of the above (1) to (7), the tubular member includes a contact type or non-contact type temperature detection unit, and the temperature control unit controls a temperature of the temperature adjusting means according to a surface temperature of the tubular member or a temperature of a substance in the tubular member detected by the temperature detection unit.
(9) In the configuration of the above (1) to (8), a moisture detection unit is provided outside the tubular member for detecting a moisture content of a substance in the tubular member through a transparent glass or resin window portion, and the temperature control unit controls a temperature of the temperature adjusting means according to the moisture content of a substance in the tubular member detected by the moisture detection unit.
(10) In the configuration of the above (1) to (9), the tubular member is made of stainless steel.
(11) The present invention provides a vacuum freeze-drying method comprising a vacuum freezing step for freezing a liquid, a drying step for sublimating and drying a frozen substance frozen as above, and a step for performing vacuum suction through an exhaust path. The drying step comprises a step for rotating a tubular member formed of a tubular shape having an inlet portion and an outlet portion, wherein the tubular member has a spiral transfer means continuously provided adjacent to an inner wall of the tubular member toward a direction from the inlet portion to the outlet portion, a step for adjusting temperatures of a plurality of regions provided toward a direction from the inlet portion to the outlet portion in a peripheral portion of the tubular member, wherein the plurality of regions are at least three or more regions whose temperature is capable of being controlled, and a step for continuously sublimating and drying the frozen substance entering from the inlet portion while the frozen substance is transferred sequentially to locations corresponding to the plurality of regions in the tubular member.
(12) In the configuration of the above (1) to (10), The connecting portion is configured that by a rotation of screw arranged in a transfer pipe having one end facing the collecting portion of the vacuum freezing device and the other end facing the inside of the tubular portion, the frozen material entering from the collecting portion is moved in the axial direction of the screw.
(13) In the configuration of the above (12), a base end portion of the screw on the vacuum freezing device side is bearing by a bearing portion, a first suction port is provided in the vicinity of the bearing portion, and it is configured that the inside of the transfer pipe is constantly maintained in a vacuum through the first suction port. A tip portion of the transfer pipe on the drying device side is configured as a bearing portion to rotationally support an end member of the tubular portion of the tubular member of the drying device, a second suction port is provided between the end member and the bearing portion on the tip end side of the transfer pipe, and it is configured that the inside of the transfer pipe and the inside of the tubular portion are maintained in a vacuum through the second suction port.
(14) In the configuration of the above (12) or (13), the screw is a spiral coil structure located around a rotation axis, and provided in a state close to the inner wall of the transfer pipe. It is configured to send the frozen material received from the collecting portion to the tubular portion by a rotation of the screw.
(15) In the configuration of the above (12) to (14), the screw is rotationally driven by a rotational driving means different from the rotating portion for rotating the tubular portion.
According to the present invention, it enables to provide a vacuum freeze-drying apparatus and a vacuum freeze-drying method capable of continuously performing vacuum freeze-drying in a short time.
Next, a vacuum freeze-drying apparatus according to an embodiment to the present invention will be described. Further, the same member or a member having the same function may be designated by the same reference numeral, and the description may be omitted as appropriate after the member is described.
As shown in
Substance handled by a vacuum freeze-drying apparatus 1 is an injectable substance or a drug in solid formulation.
A vacuum freezing device 2, for example, sprays a raw material solution containing a raw material into a vacuum container from a spray nozzle 21 to produce a frozen substance by freezing a sprayed raw material solution. Further, a vacuum freezing device may be one in which a raw material solution is dropped from a nozzle into a vacuum container, so it is enable to produce a frozen substance by freezing dropped droplets. A sprayed or dropped raw material solution self-freezes due to an evaporation of water during the fall and the deprivation of latent heat of vaporization, resulting in a frozen substance which is a fine frozen particle. A frozen substance falls toward a collecting portion 22 having a tapered shape with a smaller opening, and is collected by the collecting portion 22.
A connection portion 4 connects a vacuum freezing device 2 and a drying device 3 for transporting a frozen substance produced at a vacuum freezing device 2 to a drying device 3.
A drying device 3 is to continuously sublimate and dry a frozen substance. A collection portion 5 collects a dried material formed by sublimating and drying at a drying device 3 since it is be evolved from an outlet portion 31c of a tubular member 31.
A vacuum freeze-drying apparatus 1 has an exhaust path for performing vacuum suction, wherein the exhaust path is provided in a connection portion 4 according to an embodiment. The exhaust path may be provided in a vacuum freezing device 2, a drying device 3, or a connection portion 4. By providing an exhaust path, it enables to maintain reduced-pressure atmosphere inside, to make a circumstance where liquid is difficult to be present and solid or gas is present.
A tubular member 31 and a collection portion 5 are covered by clean air 6 in the periphery. Any surrounding outer surface portion of a decomposable connecting portion of a tubular member 3 is all covered by clean air 6 so that it is configured to allow clean air to enter against a leak.
As shown in
A tubular member 31 is formed of a tubular shape extending in a linear manner in a horizontal direction, having an opening, provided with an inlet portion 31b for letting a frozen substance enter into, and an outlet portion 31c for being an outlet for a dried material sublimated and dried (See
In a tubular member 31, provided is a spiral transfer means 31a continuously provided adjacent to an inner wall of a tubular member 31 from an inlet portion 31b toward an outlet portion 31c. A frozen substance transported from a connection portion 4 enters from an inlet portion 31b of a tubular member 31 and is transferred to an outlet portion 31c by a spiral transfer means 31a, during which a frozen substance is continuously sublimated and dried.
Temperature adjusting means 30a to 30j are provided in an outer peripheral portion of a tubular member 31 and adjust temperatures of a plurality of regions 40a to 40j in an outer surface of a tubular member 31.
A plurality of regions 40a to 40j are provided from an inlet portion 31b toward an outlet portion 31c of a tubular member 31, and temperatures thereof can be independently controlled. Temperature adjusting means 30a to 30j adjust temperatures of locations in a tubular member 31 corresponding to a plurality of regions 40a to 40j by adjusting temperatures in a plurality of regions 40a to 40j.
Here, ten temperature adjusting means 30a to 30j are provided, so a plurality of regions formed by a temperature adjusting means 30a to 30j are provided ten. It is preferred that a plurality of regions 40a to 40j have at least 3 or more regions. It is noted that a plurality of a temperature adjusting means may be described collectively as a temperature adjusting means, or each temperature adjusting means may be described as a temperature adjusting means respectively.
A rotating portion 7 is for rotating a tubular member 31 at the center of a pivot. As a tubular member 31 is rotated by a rotating portion 7, a frozen substance entering from an inlet portion 31b of a tubular member 31 is sequentially transferred through a spiral transfer means 31a toward an outlet portion 31c in a tubular member 31. During the course, a frozen substance is continuously sublimated and dried. A rotating portion 7 is configured to rotate only a tubular member 31 and not to rotate temperature adjusting means 30a to 30j outside a tubular member 31. Temperature adjusting means 30a to 30j are fixed not to rotate.
A temperature control unit 8 has functions of inputting and outputting information, and independently controls temperature adjusting means 30a to 30j for adjusting temperatures of a plurality of regions 40a to 40j formed in an outer surface of a tubular member 31.
Next, temperature adjusting means 30a to 30j will be described.
As shown in
A temperature adjusting means 30a adjusts a temperature of a space of a region 40a and adjusts a temperature of a space in a tubular member 31 corresponding to a region 40a. In addition, a temperature adjusting means 30b adjusts a temperature of a space of a region 40b and adjusts a temperature of a space in a tubular member 31 corresponding to a region 40b. A temperature adjusting means 30c adjusts a temperature of a space of a region 40c and adjusts a temperature of a space in a tubular member 31 corresponding to a region 40c. Similarly, temperature adjusting means 30d to 30j adjust temperatures of spaces of regions 40d to 40j and adjust temperatures of spaces in a tubular member 31 corresponding to regions 40d to 40j.
A frozen substance entering from an inlet portion 31b of a tubular member 31 is continuously sublimated and dried by advancing through spaces where each temperature is adjusted by temperature adjusting means 30a to 30j respectively.
Next, an example of temperature adjusting means 30a to 30j will be specifically described with reference to
An air blowing means (not shown) is connected to ducts 35a and 35b, and a temperature-controlled gas is supplied. By supplying gas from ducts 35a and 35b into regions 40a to 40j covered by a wall portion 32, a wall portion 33 and a cover 34, temperatures in a plurality of regions 40a to 40j are independently controlled. For example, air can be supplied as gas, but it is not limited to air.
Although gas is used as an example to describe temperature adjusting means 30a to 30j, but not limited to gas, an electrical heater, refrigerant, etc. can be used.
The inside of wall portions 32, 33 has a circular opening matching an outer shape of a tubular member 31. The inside openings of wall portions 32, 33 are preferably close to an outer periphery of a tubular member 31.
Next, temperatures of a plurality of regions 40a to 40j are described.
A plurality of regions 40a to 40j has at least three or more regions from an inlet portion 31b toward an outlet portion 31c of a tubular member 31, these three or more regions include the following (1) to (3) temperature regions. A temperature region is defined by measuring a temperature of a tubular member 31 which is itself a tube at the time when the process gets to a stable operation state, in a manner of a contact type and/or a non-contact type to an outer surface of a tubular member 31.
Included are at least (1) a minus temperature region, (2) a temperature region in a range from the minus temperature to plus 40° C., and (3) a temperature region of plus 20° C. or higher.
A minus temperature region of (1) refers to a minus temperature region, such as −40° C., −30° C., −20° C., etc.
A temperature region (2) in a range from the minus temperature of (1) to plus 40° C. refers to a temperature region in a range from a minus temperature of the minus temperature region (1) to plus 40° C. For example, when a temperature of the minus temperature region of (1) is −40° C., since this −40° C. plus 40° C., a temperature region of (2) becomes a temperature region in a range from −40° C. to 0° C. Also, when a temperature of a minus temperature region of (1) is −20° C., since this −20° C. plus 40° C., a temperature region of (2) becomes a temperature region in a range from −20° C. to 20° C.
A temperature region of plus 20° C. or higher of (3) refers to a temperature region of 0° C.+20° C. or higher, when an upper limit temperature of (2) is 0° C.
From an inlet portion 31b toward an outlet portion 31c of a tubular member 31, a plurality of regions 40a to 40j include at least three regions of the above (1) to (3), a frozen substance or a dry substance is transferred by a transfer means 31a sequentially to locations in a tubular member 31 corresponding to a plurality of regions 40a to 40j including those (1) to (3) temperature regions, and a frozen substance or a dry substance is continuously sublimated and dried.
Next, a tubular member 31 is described.
A tubular member 31 is preferably made of stainless steel. A length of a tubular member 31 is preferably for example a range from 100 mm to 2000 mm, more preferably a range from 150 mm to 1000 mm, and more preferably a range from 200 mm to 500 mm.
A tubular member 31 is formed of one tubular shape by connecting a plurality of tubular portions 31A to 31F with attachment portions 31G to 31K. A tubular member 31 may be formed in one tubular shape without providing an attachment portion. Tubular portions 31B, 31C, 31D, 31E are formed by tubular portions of the same shape. A tubular portion 31A is one having a slightly shorter length. A tubular portion 31F is formed so that the cross-sectional shape becomes smaller toward the tip. Attachment portions 31G to 31K connect firmly adjacent tubular portions so as not to come off.
As described above, a tubular member 31 is provided with a spiral transfer means 31a continuously provided adjacent to an inner wall of a tubular member 31 from an inlet portion 31b toward an outlet portion 31c. The transfer means 31a can form a spiral shape by providing a wall portion or a groove in an inner periphery of a tubular member 31. The formation of a spiral shape also includes a method of embedding a screw in an inner periphery of a tubular member 31.
A transfer means 31a transfers a frozen substance entering from an inlet portion 31b sequentially in a tubular member 31 located inside of a plurality of regions 40a to 40j, continuously sublimating and drying a frozen substance, and guide a dry substance sublimated and dried to an outlet portion 31c.
Next, a configuration of a rotating portion will be described.
As shown in
A motor 71 is a rotational drive source. Pulleys 72, 73, a belt 74 and rotational shafts 75, 76 function as rotational drive transmitting portions for transmitting rotational drive. Rotary rollers 77, 78 are a rotation support portion for supporting a rotation by a rotational drive transmitting portion. A rotation support portion may be configured by adding a bearing to rotary rollers 77, 78, and configured by replacing a rotary roller 77 with a bearing.
A belt 74 is hanged on the pulleys 72 and 73. Rotational force of a motor 71 is transmitted via a belt 74. A rotary roller 77 is arranged below on both sides of a tubular member 31. A tubular member 31 is placed on a rotary roller 77 arranged on both sides.
A pulley 73 is attached near one end of a rotational shaft 75. A rotating roller 78 attached to a fixed base is provided inside a pulley 73, and a rotary roller 78 similarly attached to a fixed base is also provided at the other end of the rotating shaft 75. Between rotary rollers 78 and 78, eight rotary rollers 77 are attached to a rotational shaft 75.
A rotational shaft 76 has a rotary roller 78 attached to a fixed base on the one end, and has a rotary roller 78 attached to a fixed base on the other end. Between these rotary rollers 78 and 78, eight rotary rollers 77 are attached to a rotational shaft 76. Rotary rollers 77 attached to a rotational shaft 75 are driving rollers, and rotary rollers 77 attached to a rotational shaft 76 are driven rollers.
When a motor 71 rotates, a belt 74 rotates through a pulley 72, a rotational shaft 75 rotates by a rotation of a pulley 73, and by a rotation of rotary roller 77 fixed to a rotational shaft 75, a tubular member 31 rotates, and a rotary roller 77 rotates as a driven roller attached to a rotational shaft 76.
Next, a rotation speed of a tubular member 31 will be described.
It is preferred that a tubular member 31 rotates by a rotating portion 7 at a rotation speed of 1/30 rpm or more and 1 rpm or less.
Next, a temperature detection unit and a moisture detection unit will be described.
As shown in
A detection unit 37 is provided at the lower portion of a tubular member 31 where a glass window 36 is provided in a circumferential direction. A detection unit 37 includes at least three types, and includes a temperature detection unit for detecting a temperature of a substance inside a tubular member 31, a temperature detection unit for detecting a temperature of an outer surface (wall surface) of a tubular member 31, and a moisture detection unit for detecting the amount of moisture of a substance inside a tubular member 31.
When a detection unit 37 functions as a temperature detection unit for detecting a temperature of a substance inside a tubular member 31, it can be configured as a contact type or a non-contact type. When a detection unit 37 functioning as a temperature detection unit is a contact type, it detects a surface temperature of a tubular member 31. When a detection unit 37 functioning as a temperature detection unit is a non-contact type, it detects a temperature of a substance inside a tubular member 31 through a glass window 36 of a tubular member 31.
A temperature control unit 8 is capable of independently controlling temperatures of temperature adjusting means 30a to 30j, according to a surface temperature of a tubular member 31 or a temperature of a substance inside a tubular member 31 through a glass window 36 which a detection unit 37 detects.
Further, when a detection unit 37 functions as a moisture detection unit for detecting the amount of moisture of a substance inside a tubular member 31, it is capable of detecting the amount of moisture of a substance inside a tubular member 31 through a transparent glass window 36. A temperature control unit 8 is capable of independently controlling temperature of temperature adjusting means 30a to 30j, according to the amount of moisture of a substance inside a tubular member detected by a detection unit 37.
As shown in
A detection unit 37 is capable of detecting a temperature of a substance X inside a tubular member 31 and the amount of moisture of a substance inside a tubular member 31 through each of transparent glass windows 36 provided at a certain intervals in a circumferential direction of a tubular member 31. Also, since glass windows 36 and detection units 37 are provided at a plurality of positions in a longitudinal direction of a tubular member 31, a temperature and the amount of moisture of a substance can be accurately detected at each position of the tubular member 31 respectively.
Next, a transfer means 31a will be described.
In addition, in
As shown in
A part of a spiral transfer means 31a is continuously formed in a tubular portion 31B from one end to the other end.
As shown in
A height of a wall portion 31a1 and a wall portion 31a2 is a height of a transfer means 31a, and is preferably configured in a range of, for example, 3 mm or more and 50 mm or less.
A pitch of a wall portion 31a1 and a wall portion 31a2 is a pitch of a spiral transfer means 31a, and is preferably configured in a range of, for example, 5 mm or more and 20 mm or less.
As shown in
A connection portion 4 comprises an inner pipe portion 41, an outer pipe portion 42, a screw 43 provided in the inner pipe portion 41, and an intermediate pipe portion 44 extending from an end portion 301 of a drying device 3 to an inner pipe portion 41 and an outer pipe portion 42 of a connection portion 4. Between an outer pipe portion 42 and an intermediate pipe portion 44, a bearing 45 and an air seal 46 are provided from a drying device 3 side.
An air seal 46 is for sealing a rotating shaft by supplying air from a flow path without contacting a rotating shaft.
In examples shown in
A tubular portion 31B is capable of forming one tubular portion 31B by connecting two half bodies 131BX. When two half bodies 131BX of a tubular portion 31B are connected, groove portions forming a spiral transfer means 131a are respectively formed continuously. A depth of a groove portion 131a1 and a groove portion 131a2 is a depth of a transfer means 131a, and is preferably configured in a range of, for example, 3 mm or more and 50 mm or less. A pitch of a groove portion 131a1 and a groove portion 131a2 is a pitch of a transfer means 131a, and is preferably configured in a range of, for example, 5 mm or more and 20 mm or less.
By forming a spiral groove portion in an inner periphery surface of a tubular member 31 as a transfer means 131a centered on a rotating shaft, a spiral feeding action inside of a tubular member 31 is imparted, and a frozen substance or a dry substance can be transferred continuously.
According to the present embodiment, it is possible to provide a vacuum freeze-drying apparatus and a vacuum freeze-drying method capable of continuously performing vacuum freeze-drying in a short time.
A vacuum freeze-drying method of the present embodiment includes a vacuum freezing step of freezing a liquid, a drying step of sublimating and drying a frozen substance frozen, and a step of performing vacuum suction through an exhaust path. The drying step comprises a step of rotating a tubular member 31 which is a tubular member 31 formed of a tubular shape having an inlet portion 31b and an outlet portion 31c, having a spiral transfer means 31a continuously provided adjacent to an inner wall of a tubular member 31 from an inlet portion 31b toward an outlet portion 31c, a step of adjusting temperatures of a plurality of at least three or more regions 40a to 40j provided from an inlet portion 31b toward an outlet portion 31c in a peripheral portion of a tubular member 31, whose temperatures are capable of being controlled, and a step of continuously sublimating and drying the frozen substance entering from an inlet portion 31b, while transferring the frozen substance sequentially to locations corresponding to a plurality of regions 30a to 30j in a tubular member 31 by a transfer means 31a.
Next, another structure of the connection portion 4 will be described with reference to
First, in the vacuum freeze-drying apparatus provided with a vacuum freeze device 2 for freezing the liquid and a drying device 3 for sublimating and drying the frozen product, configured to move the frozen product from the vacuum freeze device 2 to the drying device 3 through the connection portion 4B, the connection portion 4B is configured so that the frozen product is moved by a screw 58 provided in the transfer pipe 55 facing the collecting section 22 of the vacuum freezing device 2 in the axial direction. However, the transfer of the screw 43 does not necessarily in the horizontal direction, and the frozen product may be transferred to the tubular portion 31.
The base end portion (left end portion) of the screw 58 is supported by a bearing portion 56 (here, a bearing), a first suction port 53 is provided in the vicinity of the bearing portion, and it is configured that the inside of the transfer pipe 55 is maintained to constantly be in a vacuum (a high degree of vacuum is sufficient). The first suction port 53 is connected to a vacuum pump, but illustration and description thereof will be omitted.
A tip portion of the transfer pipe 55 is configured to be a bearing portion 51, configured to rotationally support an end member 52 of the tubular portion 31A of the tubular portion 31 of the drying device. And a second suction port 54 is provided facing between the end member 52 and the bearing portion 51, it is configured that the inside of the transfer pipe 55 and the inside of the tubular portion 31 are maintained to in a vacuum. The suction port 54 is connected to the vacuum pump, but illustration and description thereof will be omitted here.
The screw 58 is a spiral coil structure arranged around a rotating shaft 57, and provided in a state close to the inner wall of the transfer pipe 55, and it is configured that the frozen material received from the collecting portion 22 is fed into the tubular portion 31 by the rotation thereof. The coil structure may be spiral shape, and may be a structure in which fragments form a substantial coil, and in short, it may be a structure capable of exhibiting a continuous feed function. The above-mentioned close state provision is to provide a clearance between the coil structure and the transfer pipe 55 so that the frozen material is not to be caught and damaged.
A motor 60 for driving and a coupling 59 for transmitting the driving force of the motor 60 to the rotating shaft 57 are arranged at an end of the rotating shaft 57 opposite side to the tubular portion 31. As described above, by providing a motor 60 for rotationally driving the screw 58 separately from the motor 71 for rotationally driving the tubular portion 31, it is possible to arbitrarily change the transport of the frozen material to the drying device 3, for example upping the rotation speed of the motor 60, to increase the transport amount. Further, in the connection portion 4 (see
Although the present invention has been described using above embodiments, it goes without saying that the technical scope of the present invention is not limited to the scope of the above embodiments, and it is clear to those skilled persons in the art that various modifications or improvements added to the above embodiments are possible. Further, it is clear from the description of the scope of claims that the form to which such modifications or improvements are added may be included in the technical scope of the present invention.
| Number | Date | Country | Kind |
|---|---|---|---|
| JP2020-086652 | May 2020 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2021/018879 | 5/18/2021 | WO |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2021/235459 | 11/25/2021 | WO | A |
| Number | Name | Date | Kind |
|---|---|---|---|
| 236677 | Halsey | Jan 1881 | A |
| 430652 | Jarrett | Jun 1890 | A |
| 474568 | Weller | May 1892 | A |
| 548573 | Moller et al. | Oct 1895 | A |
| 676165 | Wacker | Jun 1901 | A |
| 986107 | Wertenbruch | Mar 1911 | A |
| 1051359 | Wille | Jan 1913 | A |
| 1172479 | Motter | Feb 1916 | A |
| 1179192 | Kleinschmidt | Apr 1916 | A |
| 1303982 | Stevens | May 1919 | A |
| 1328027 | Yai | Jan 1920 | A |
| 1735393 | Hiller | Nov 1929 | A |
| 1735396 | Hiller | Nov 1929 | A |
| 2038904 | Rand | Apr 1936 | A |
| 2067506 | Silva | Jan 1937 | A |
| 2388917 | Hormel | Nov 1945 | A |
| 2411152 | Folsom | Nov 1946 | A |
| 2515098 | Smith, Jr. | Jul 1950 | A |
| 2552360 | Zichis | May 1951 | A |
| 2616604 | Folsom | Nov 1952 | A |
| 2636284 | Napier | Apr 1953 | A |
| 2743168 | Krohn | Apr 1956 | A |
| 2751687 | Colton | Jun 1956 | A |
| 2803888 | Cerletti | Aug 1957 | A |
| 3088222 | Mace | May 1963 | A |
| 3264747 | Fuentevilla | Aug 1966 | A |
| 3266169 | Smith, Jr. | Aug 1966 | A |
| 3270432 | Barbareschi | Sep 1966 | A |
| 3310881 | Fritzberg | Mar 1967 | A |
| 3316652 | Van Gelder | May 1967 | A |
| 3324565 | Smith, Jr. | Jun 1967 | A |
| 3362835 | Thuse | Jan 1968 | A |
| 3445247 | Baerwald | May 1969 | A |
| 3469327 | Catelli | Sep 1969 | A |
| 3531872 | Watson | Oct 1970 | A |
| 3601901 | Rader | Aug 1971 | A |
| 3605273 | Andersen | Sep 1971 | A |
| 3612411 | Oetjen | Oct 1971 | A |
| 3616542 | Rader | Nov 1971 | A |
| 3952541 | Rigoli | Apr 1976 | A |
| 4037331 | Brilloit | Jul 1977 | A |
| 4746968 | Wear | May 1988 | A |
| 5964043 | Oughton | Oct 1999 | A |
| 6098410 | Horigane | Aug 2000 | A |
| 7140122 | Adams | Nov 2006 | B1 |
| 8978268 | Itou | Mar 2015 | B2 |
| 10006706 | Luy | Jun 2018 | B2 |
| 10627162 | Delaveau | Apr 2020 | B2 |
| 11112176 | Nishihashi | Sep 2021 | B2 |
| 11175093 | Morimoto et al. | Nov 2021 | B1 |
| 20070022626 | Gomi | Feb 2007 | A1 |
| 20080142166 | Carson | Jun 2008 | A1 |
| 20110192047 | Itou | Aug 2011 | A1 |
| 20140026434 | Sawada | Jan 2014 | A1 |
| 20170219283 | Gebhard | Aug 2017 | A1 |
| 20210080179 | Nishihashi | Mar 2021 | A1 |
| Number | Date | Country |
|---|---|---|
| 2834324 | Nov 2012 | CA |
| 2949789 | Dec 2016 | CA |
| 110595193 | Dec 2019 | CN |
| 2101131 | Sep 2009 | EP |
| 2578974 | Apr 2013 | EP |
| 3052544 | Dec 2017 | FR |
| S47-21743 | Oct 1972 | JP |
| S51-126557 | Nov 1976 | JP |
| S55-112980 | Sep 1980 | JP |
| H11-151080 | Jun 1999 | JP |
| 2004232883 | Aug 2004 | JP |
| 3117061 | Jan 2006 | JP |
| 2006177640 | Jul 2006 | JP |
| 2017-533397 | Nov 2017 | JP |
| 6777350 | Oct 2020 | JP |
| 2018-0086953 | Aug 2018 | KR |
| WO-9629556 | Sep 1996 | WO |
| 2010005021 | Jan 2010 | WO |
| WO-2010005021 | Jan 2010 | WO |
| WO-2013036107 | Mar 2013 | WO |
| 2013050162 | Apr 2013 | WO |
| WO-2018204484 | Nov 2018 | WO |
| 2019235036 | Dec 2019 | WO |
| WO-2019235036 | Dec 2019 | WO |
| Entry |
|---|
| International Search Report for PCT/JP2021/018879 dated Aug. 24, 2021. |
| PCT written opinion dated Aug. 24, 2021. |
| Japanese decision to grant a patent dated Dec. 6, 2022. |
| Number | Date | Country | |
|---|---|---|---|
| 20230100406 A1 | Mar 2023 | US |
