JPH061142B2 - Freezing method for frozen material and freezing device for liquid material in container - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION "Industrial field of application" The present invention relates to a freeze-vacuum drying means for freezing a material to be dried and freeze-drying the material at a predetermined vacuum degree, which is housed in a container having an opening. The present invention relates to an improvement of a freezing method for preliminary freezing performed as a first step in freeze-drying a material to be frozen such as a biological material, a drug, a food, etc., which is a material to be dried, and an apparatus therefor.

"Prior art" In the prior art, roughly, the container containing the material to be frozen is made to stand on its own, and it is kept stationary or cooled while moving to cool the internal liquid material. A first means for freezing and a shell in which a container having a cylindrical body containing a liquid material is cooled while being rotated, and the liquid material inside is spread in a thin layer along the inner wall surface of the container to be frozen. There is a second method called the freeze method.

Then, in the first means, as means for cooling the container containing the material to be frozen, which is kept independent, (a) the container containing the material to be frozen is placed in the air cooled by the cooler. Place and freeze by the air flow. (b) A container containing the material liquid to be frozen is sprayed with a liquid having a sufficiently low boiling point of 0 ° C. or lower, for example, liquid nitrogen, or is immersed in the liquid and frozen. (c) Spray the antifreeze liquid cooled by the cooler on the container containing the material liquid to be frozen or immerse the container in the antifreeze liquid to freeze. (d) A container containing a material liquid to be frozen is placed on a metal surface cooled by a cooler and frozen by contact heat transfer. (e) Further, the inventor of the present invention previously invented and filed as Japanese Patent Application Laid-Open No. 1-155176, which is a hygienic acceptable liquid which does not freeze in the required temperature range and easily volatilizes into a thin layer. There are various means such as placing a container containing the material liquid to be frozen on the surface of the sprayed or applied cooling metal to freeze it.

Further, in the second means, (a), the container v containing the liquid material to be frozen is placed in an upright posture as shown in FIG. 1 in a cooling medium such as liquid nitrogen spray or antifreeze liquid, and The axis of the cylindrical body is rotated about the axis of rotation as a rotation axis, and the centrifugal force thereby causes the material liquid to be pressed against the inner peripheral wall of the body of the container v and frozen along the inner peripheral wall. (b),
The container v containing the material to be frozen is arranged in an upright posture in the same manner as described above, and it is rotated at high speed with the vertical center line as the axis of rotation, and the liquid is pressed against the inner cylinder wall surface by centrifugal force. Evacuate, take latent heat by vacuum evaporation and freeze. (c), as shown in FIG. 2, using a bath w filled with various cooling media, a container v containing the material liquid to be frozen is
Inclining until the liquid material to be frozen inside does not flow out of the mouth of the container v until reaching a horizontal level, and cooling to the extent that the cooling medium such as the antifreeze liquid in the bathtub w does not flow from that mouth. So that the outer peripheral surface of the body of the container v is immersed in the medium,
The container v is supported between a pair of adjacent rotating rollers R and R that are axially supported in the bath w, and in this state, the container v is rotated about the axis of the cylindrical body of the container v, The freeze-dried material liquid stored in is frozen along the inner wall surface of the body of the container v. (d) A container v containing a large number of material liquids to be frozen is formed in a disk body 1 formed in a disk shape as shown in FIG. By inserting the body of the container v into the recesses 1a ..., the container v is held in an upright posture with respect to the board surface, and the board body 1 is supported by the support shaft 10 along the center line thereof. Support shaft 10
As shown in FIG. 4, the frozen material liquid in a large number of containers v held is tilted almost horizontally to the extent that it does not flow out of the mouth of the container v, and in this state, the spindle 10 is used as a rotation axis for the plate body. While rotating 1, the board 1 is cooled, or the board 1 is placed in a cooling medium such as liquid nitrogen to cool the container v through the board 1 and to cover the inside of the container v. There are means such as freezing the frozen material liquid along the inner wall surface of the body of each container v.

"Problems to be solved by the invention" As is well known, many biological materials, pharmaceuticals, and functional foods have special physical properties that are fragile and are preserved by freezing or drying. A method that does not change the quality of the product or contaminate it with foreign substances must be adopted. For this reason, a method has been pursued in which the freezing process can be accurately controlled and the processing can be performed rapidly.

The Shelvuriz method, which is the second means of the above-mentioned conventional technique, is
This is a means developed for this purpose. When the container v for containing the material liquid to be frozen is a cylindrical container (medicine bottle) having a commonly used shape, the container v is upright and non-rotating, and the inside of the container is frozen. The freezing layer expands to the inner wall surface of the container v which is 5 to 10 times wider than the freezing layer thickness when the material liquid is frozen on the bottom surface inside the container v. 5 to 1
/ 10 can be thinned. As a result, the freezing time is shortened by the synergistic effect of expanding the cooling area for freezing and reducing the heat transfer resistance of the freezing layer by thinning the freezing layer, and the quality due to uneven freezing speed in the thickness direction of the freezing layer. The unevenness can be greatly eased. Especially when it is carried out as a preliminary freezing for freeze-drying, enlargement of the area of the frozen layer and thinning of the frozen layer are one of the important drawbacks of freeze-drying, which is a problem of longer drying time. Is a revolutionary solution.

However, despite the fact that the effect is clear,
The use of the shelving method is limited to a laboratory or a very small amount of productive use, and an industrial means is a means for freezing the container containing the material liquid to be frozen in an upright, non-rotating manner. .

The reason for this is that the conventional shelf-reeds method is not suitable for large-scale automatic processing or continuous processing of a container containing a material liquid to be frozen. That is, this Shelving method requires that the individual containers be firmly attached and fixed to the rotating shaft that rotates at high speed in the means of (a) and (b) described above, and the detaching operation for this purpose. Is not suitable for continuous processing, and the means of (c) may rotate each container v in the bathtub w in which antifreeze liquid is spread, although the rotation speed of the container v may be slow. It is not easy to automate the operation of mounting on the mechanism (for example, the rollers R / R) because the liquid level of the cooling medium such as antifreeze in the bath w wobbles due to the rotation operation of the rotary drive mechanism in the bath w. There is. Further, the means of (d) also has a complicated problem of automating the detaching operation of the container v with respect to the plate body, such as the insertion of each container v into the large number of recesses 1a provided on the upper surface of the plate body 1.

Further, in all of the conventional means, the use of liquid nitrogen as a cooling medium, the use of a vacuum chamber, and the use of an antifreeze bath have a problem in handling in all of them, and when the board 1 is used. Has a problem in that the efficiency of contact heat transfer from the board 1 to the container v is poor and the freezing speed is too slow.

"Means for Solving Problems" The present invention has been made to solve these problems occurring in the conventional means, and it is a simple facility and is troublesome for the container containing the material liquid to be frozen. A new means that enables continuous automation of the operation of rapidly freezing the material liquid to be frozen inside by the Shelvleys method without requiring a special desorption operation and improving the efficiency of heat conduction. The purpose is to provide.

[Means for Solving the Problem] Next, the means of the present invention for achieving this object will be described.

In the means of the present invention, as a means for giving rotation to a container having a cylindrical body containing a liquid to be frozen (a typical example is a vial <cylindrical drug bottle>), a container having a cylindrical body is used. By tilting the mouth so that the central axis is at an angle α with respect to the horizontal plane, with the mouth facing in the direction of the rising slope, and the angle α (α = α = (Including the case of 0), lay the container on the upper surface of the coolable base plate formed on the inclined surface so as to support the state, with the mouth facing upward and in the gradient direction,
In this state, a means for rolling (rolling without slip) the container on the upper surface of the base plate in a direction orthogonal to the central axis of the container is used. This eliminates the inconvenience of the attachment / detachment operation to / from the rotation operation mechanism of the container, and the rotation movement itself for the rotation operation of the container is the container from the inlet to the outlet of the shelf reels device configured by the coolable base plate. It is used for transporting the container or, in addition, for supplying a container to a coolable base plate that constitutes the shelf-less device and for discharging a frozen container from the coolable base plate, and performs continuous automation. .

As the member for rolling and transporting the container, for example, a support tool that gently restrains the outer peripheral surface of the body of the container is used to the extent that the container lying on the upper surface of the base plate is allowed to rotate. The moving speed of the supporting tool regulates the carrying speed of the container. If the coolable base plate that constitutes the shelving unit is fixed, the transport speed by rolling the container at the same time determines the rotation speed of the container, but in addition to the movement of the support, the base plate If a motion is also given to the upper surface of the container, the difference between the moving speed of the upper surface of the base plate and the moving speed of the supporting member determines the rotation speed of the container, thereby increasing the degree of freedom in selection.

If the top surface of the base plate is a conical inclined surface that forms an angle α with the horizontal surface, the rolling orbit of the container will be a circular path, and the top surface of the base plate will be a flat plate with an inclined surface that forms an angle α with the horizontal surface. If so, the rolling trajectory of the container becomes a straight line.

As the means for cooling the container containing the material liquid to be frozen, the means invented by the inventor of the present invention and already applied as JP-A-1-155176 is used. That is, the base plate that rotatably supports the container can be cooled, and a thin antifreeze liquid, such as ethanol, that is hygienically acceptable, does not freeze in the necessary temperature range, and easily exerts on the upper surface of the base plate. It is sprayed (or applied) on a layer, a vial is laid on the liquid film of the thin layer, and the rolling vial is cooled and frozen by wet contact heat conduction.

5 to 14 are explanatory views of the means of the present invention.

FIG. 5 shows the standard shape of a container (vial) v that is widely used for freeze-drying pharmaceutical products (usually, the inner height hi of a cylindrical body is 1.5 to 2 times its inner diameter Di). degree),
And without worrying about the outflow of the frozen material liquid stored inside,
The upper surface 2 of the base plate 2 on which the container v can be laid and supported
An example of the relationship between the angle α of 0 and the liquid amount is shown. The container v in the illustrated example has Di = 27 mm, hi = 47 mm, a liquid volume of 5.7 m,
1 is the liquid surface when standing upright, the liquid depth at this time is 10 mm,
2 is the liquid level when tilted at an angle α (gradient 1/6). If there is a small amount of liquid inside, of course a gentle slope is enough,
Even if the angle α with respect to the horizontal plane is α = 0, there is a case where the outflow does not occur.

FIGS. 6, 8 and 10 show typical aspects of the antifreeze film formed on the upper surface 20 of the base plate 2, and the upper surface 2 of the base plate 2.
The shape of the wetting contact surface formed between the outer peripheral surface of the container v laid on 0 and the upper surface 20 of the base plate 2 is shown. 6 and 8
10A and 10B, a solid line 20 indicates the upper surface of the base plate 2 formed on the slope, v indicates a container laid on the upper surface 20 of the base plate 2, and arrows indicate ethanol Et, which is an antifreeze solution satisfying the above-described conditions. The supply location, the broken line shows the liquid surface of ethanol when the container v is not placed, and the dotted line shows the liquid surface of ethanol Et after the container v is arranged.

FIG. 6 shows the upper surface 20 of the base plate 2 on which the container v is laid.
This is an example in which the liquid pool 3 is provided by the ridges 30 and the ethanol Et is supplied to the liquid pool 3 along the locus along which the ... Rolls. The liquid level of the ethanol Et before the container v is arranged is In the longitudinal direction of the cylindrical body of the container v, it does not reach the middle thereof, but when the container v is placed, the ethanol solution extends to substantially the entire length of the cylindrical body of the container v, and A wet contact surface Z shown in a mesh shape in the drawing is formed.

FIGS. 8 and 10 show an example in which the ethanol liquid is supplied to the upper surface 20 of the base plate 2 at a position higher than the trajectory of the container v in the rising direction of the gradient. The wetting film of a certain thickness formed by the supplied ethanol liquid,
Even if the upper surface 20 of the base plate 2 is an inclined surface, it remains with a uniform thickness,
As shown in FIG. 10, the liquid pool 3 is not provided or the liquid pool 3 is not provided.
The width of the wetting contact surface Z when the container v is placed at a position away from is approximately equal on the bottom side and the shoulder side of the container v, as shown in FIG. Further, as shown in FIG. 8, when the container v is arranged so as to roll along the liquid pool 3 as shown in FIG. 8, the width of the wet contact surface Z is as shown in FIG. It becomes a trapezoid wider than the width of.

Depending on the shape of the wetting contact surface Z, the shelf-freeze layer naturally has a different shape. In the case of pre-freezing of freeze-drying, the optimum wetting contact surface can be selected according to the heating conditions during drying.

FIGS. 12 and 13 show an xz cross section (container v, which is orthogonal to the central axis of the container v when the container v laid on the upper surface 20 of the base plate 2 is transferred by rolling with the support tool 4. 2 is an explanatory view showing two typical examples of the action of force in the advancing direction x, and in the direction z perpendicular to the base plate surface, and FIG. 14 is a view of the rolling container v in FIG. 13 as seen from the rear in the moving direction. is there.

In the case of FIG. 12, the container v laid on the upper surface 20 of the base plate 2 which is an inclined surface has the vertical line of the upper surface 20 of the base plate 2 passing through the center line of the cylindrical body of the container v and the body of the container v. When an external force Q (having a component Qz for pushing the outer surface of the straight body portion and a component Qx along the surface) is added to an intersection q with the outer surface of the part, W is a z component of gravity,
R is the z component of drag. Since the maximum frictional force at the contact point o between the container v and the upper surface 20 of the base plate 2 and the intersection point q is generally larger than the maximum rolling frictional force, the external force Qx is the sum (F + f) of the x components of the frictional force at the points o and q. Upon passing, the container v rolls on the bed plate without slipping. When the external force Q is applied by the belt 40 parallel to the upper surface 20 of the base plate 2, the moving speed of the container v is 1/2 of the rotating speed of the belt 40.

In FIG. 13, the container v laid on the upper surface 20 of the base plate 2 which is an inclined surface has the z component W of the weight of the container v at the center of gravity of the container v.
And the z component R (= W) of the drag acts on the contact point o between the container v and the upper surface 20 of the base plate 2, and the container v is moved to the upper surface 20 of the base plate 2.
Although it is supported above, when an external force P is applied to the side surface of the outer peripheral surface of the body of the container v and the contact point p of the pushing portion 41 of the support tool 4 and gently pushed in the x direction, a frictional force F equal to the external force P. Occurs in the direction opposite to the external force P to prevent the container v from slipping in the x direction and to rotate the container v around its center of gravity g, so that the contact point between the pushing portion 41 of the support 4 and the container v is The z component f of the frictional force that blocks the rotation of the container v is added to p. The resistance R of the contact point o increases to (W + f) as a result of applying an external force to the point p. Since the maximum frictional force is proportional to the external force in the normal direction applied to the contact portion, if the x component of the external force P required for rolling the container v, Px, is smaller than the drag force Pz at the contact point o with the upper surface 20 of the base plate 2, , Even if the friction coefficient at the contact point o and the contact point p are the same, when the external force p is gradually increased, slippage occurs between the pushing part 41 of the support 4 and the outer peripheral surface of the body part of the container v, and the container v becomes Rolling motion is performed on the upper surface 20 of the base plate 2 without slipping.

Due to the existence of the liquid film of ethanol Et on the upper surface 20 of the base plate 2 and the body of the container v which comes into contact with the liquid film, the friction coefficient shows that the condensation of atmospheric water vapor on ethanol (increase of water content in aqueous ethanol solution). Since the surface tension and viscosity of the coating liquid including the influence are involved, a device for sufficiently reducing the friction coefficient at the point P, for example, as shown in FIG. 13 and FIG.
It is desirable to take measures such as forming a pair of small protrusions (black dots in the figure) at 41. The support portion 42 of the support tool 4 is coupled to a container transport mechanism K, which will be described later, and restrains the container v so that it can roll on a predetermined track. The restricting portion 43 on the opposite side of the pushing portion 41 of the support tool 4 is a portion for restricting the container v from moving ahead of the support tool 4 in a case where a large number of support sections 42 are arranged in series. It is also possible to omit it and replace it with the back surface (rear surface) of the pressing portion 41 of the support tool 4 immediately in front.
The stopper 44 (not shown in FIG. 13) shown in FIG. 14 can be omitted when the track for rolling the container v has the ridges 30, but of the base plate 2 in which the container v is an inclined surface. It prevents the upper surface 20 from slipping off and deviating from the sideways.

When the upper surface 20 of the base plate 2 is fixed, one rotation of the container v advances by the circumferential length of the outer peripheral surface of the cylindrical body of the container v, and the rotation speed determines the moving speed on the orbit. It Therefore, when the upper surface 20 of the base plate 2 is simultaneously moved in the same direction (positive or negative) as the direction of the trajectory of the container v, the moving speed of the container v becomes the operating speed of the container transport mechanism K.
The rotation speed of the container v is determined by the difference between the speed of the container transport mechanism K and the speed of the upper surface 20 of the base plate 2, and each optimum value can be individually selected.

If the upper surface 20 of the base plate 2 that is an inclined surface is a flat surface, the container v
Is a straight line parallel to the intersection of the upper surface 20 of the base plate 2 and the horizontal plane. If the upper surface 20 of the base plate 2 to be an inclined surface is a part of a conical surface, the trajectory of the container v rolling. Is an orbit of a virtual circle and a concentric circle centered on the axis of the conical surface.

By attaching the support members 4 in parallel to the container transport mechanism K in a plurality of rows, the orbits along which the containers v roll can be made to be a plurality of concentric parallel orbits.

The means for supporting the containers v lying on the upper surface 20 of the base plate 2 in the means shown in FIG. 12 can cope with the containers v of various sizes only by adjusting the height of the belt 40.
If there is a vertical pulsation in the container v, the rolling of the container v becomes irregular. On the other hand, in the case of the means shown in FIG. 13, the vertical pulsation of the support tool 4 can be made to have a margin. Depending on the situation, it is necessary to replace the supporting tool 4 itself with one having an appropriate size and shape, and it is selected depending on the situation.

Next, a means for spraying or applying an antifreeze liquid according to a predetermined condition such as ethanol Et on the upper surface 20 of the base plate 2 in the present invention will be described.

As described above, even if handling of the container v is performed on the upper surface 20 of the dry and coolable metal base plate 2, shelving of the frozen material liquid contained in the container v may be successful. However, since the contact transmission between the outer peripheral surface of the cylindrical body of the container v and the upper surface 20 of the base plate 2 is small, it takes a long time to freeze. From this, when the upper surface 20 of the base plate 2 is fixed, the upper surface 20
For rolling until the liquid material to be freeze-dried freezes, the length of the orbit becomes very long, which makes it unsuitable for industrial means, and also the outer peripheral surface of the container v and the upper surface 20 of the base plate 2. Due to poor heat transfer between the two, the generated ice crystals do not take root on the inner wall surface of the body of the container v, and the rotation of the container v due to rolling causes the frozen layer to separate from the inner wall surface of the container v. There are many cases in which the formation of a pie fails.

Therefore, in the present invention, the base plate for rolling the container v can be cooled, and the upper surface 20 of the base plate 2 is a liquid that is sanitarily acceptable, does not freeze in the required temperature range, and easily volatilizes, such as ethanol. Means for spraying (or applying) Et in a thin layer, laying the container v on the liquid film of the thin layer, rolling it, and cooling and freezing the rolling container v by heat conduction by wet contact Is used.

Here, "hygiene acceptable" has a literal meaning, and the necessary temperature range is a temperature range necessary for freezing the above-mentioned pharmaceutical product, that is, at least -50 ° C.
It means that it does not freeze before and after, and that it volatilizes easily, it volatilizes within an allowable time in the atmosphere or under reduced pressure even at a low temperature where the frozen state of the internal liquid can be maintained, and the volatilized on the outer surface of the container v. It means that it does not remain. An example of a liquid that satisfies these three conditions is an aqueous ethanol solution. Another advantage of ethanol is that even if water vapor in the atmosphere condenses on the cooling surface to be applied, ethanol dissolves water well, and even if the ethanol concentration decreases to about 75% to 80%, ice crystals That is, the heat transfer due to the wet contact between the wet metal surface (the upper surface 20 of the base plate 2) and the solid surface placed thereon and the smooth rolling of the container v cannot be prevented.

The coating liquid (hereinafter, the representative example, the name of ethanol is used to represent the coating liquid in general) is air (heat conductivity 0.02 kcal / m).
The contact heat transfer between the container v and the upper surface 20 of the base plate 2 is significantly increased in order to fill the gap near the contact portion instead of hr. The liquid that fills the gap is ethanol (thermal conductivity 0.15
In the case of kcal / mhr ° C), it increases about 7.5 times. Not only is the freezing time shortened by this, but the portion of the outer peripheral surface of the container v that contacts the upper surface 20 of the base plate 2 is deeply cooled by the wet contact surface Z. The risk of the frozen layer frozen on the inner wall surface of the container v being loosened and peeling off from the inner wall surface due to the temperature rise while coming into contact with the upper surface 20 of the base plate 2 again is eliminated.

[Example] Next, an example will be described in detail with reference to the drawings.

15 and 16 show an example of the embodiment of the present invention. FIG. 15 is a front view of the main part of the apparatus as seen from the rear in the rolling and conveying direction of the container v, and FIG. 16 is a side view from the X direction shown in FIG.

This example is an example of a device having a double-track orbit, and two orbits for rolling the containers v are provided on the upper surface 20 of the common base plate 2 in series. Above each orbit, the container transport mechanism K is provided. Are provided in parallel in two lines.

In the figure, 2 is the angle α with respect to the horizontal surface of the upper surface 20.
An antifreeze heat transfer fluid whose inside is cooled by a coolable base plate with an inclined surface (including α = 0) (the dotted line on the surface is the liquid film surface of the coating liquid such as ethanol). Although it is formed in a flat casing in which the heat is circulated and the lower surface side and the side surface are surrounded by a heat insulating material, the cooling method is not limited.

Reference numeral 6 denotes a liquid supply mechanism for supplying a coating liquid such as ethanol. In this example, a perforated spray pipe (tube) installed above the upper surface 20 of the base plate 2 and in parallel with the orbit of the container v rolling on the upper surface 20. The radius shown in the cross section is the nozzle direction). Since the liquid supply mechanism 6 only needs to replenish a small amount of the coating liquid that adheres to the outer peripheral surface of the container v rolling on the upper surface 20 of the base plate 2 and disappears, the container v rolls intermittently. It may be sprayed on the upper side of the slope of the upper surface 20 of the base plate 2 (on the right side of the container v in the figure) along the trajectory. Alternatively, a method of continuously bleeding from the nozzle hole may be used. The upper surface 20 of the base plate 2 which is an inclined surface
Even if the gradient is gentle or horizontal, the liquid film spreads to the contact surface between the container v and the upper surface 20 of the base plate 2 and is supplied to the orbit around which the container v rolls.

6'is another liquid supply mechanism formed in the same manner as the liquid supply mechanism 6 and provided on the lower side of the slope of the upper surface 20 of the base plate 2.
When the liquid pool 3 is provided on the bottom side of the container v on the orbit for rolling the container v, the supply of the coating liquid may be performed to the liquid pool 3. The liquid supply mechanism 6'in this embodiment is
It is a perforated spray tube that also serves as a protrusion for the liquid pool 3. Incidentally, in FIG. 16, the liquid supply mechanism 6 and the liquid supply mechanism 6'are omitted in the drawing. These liquid supply mechanism 6
The coating liquid supplied at 6'and accumulated in the liquid pool 3 spreads to the shoulder portion of the container v due to the capillary phenomenon by contact with the outer peripheral surface of the container v, and forms a preferable wet contact surface Z.

Reference numeral 4 denotes a support tool that supports (or restrains) the container v (4 'indicates an empty support tool). In the embodiment shown in FIG. 15 and FIG. 16, the support member 4 has the rotating shafts 70, 70.
Is attached to the outer peripheral side of an endless chain 72 that is endlessly hung on a pair of sprockets 71, 71 having their axial directions inclined along the direction of the slope of the upper surface 20 of the base plate 2 to convey the container. It constitutes the mechanism K. Then, after completing the previous steps [injection of the liquid material to be frozen into the container v, half-capping of a rubber stopper for vacuum (filling with nitrogen), etc.], the container v supplied from the terminal E of the container supply conveyor is continuously supplied. And position it at the front end (the left end side in FIG. 16) of the upper surface 20 of the base plate 2,
Subsequently, this is tumbled and conveyed to mount the frozen container v on the base plate 2
From the terminal (the right end side in FIG. 16) of the upper surface 20 of the above, to the front end side S of the conveyor to the next step (arrangement of the container v and loading into the freeze dryer in the case of freeze drying). The drive speed of the chain and the temperature of the base plate can be adjusted according to the physical properties of the liquid material and the amount of liquid.

Although not shown in FIG. 15, as shown conceptually in FIG. 16, the main part of the apparatus is covered with a removable heat-proof / moisture-proof cover 9 and, if necessary, dehumidified clean air is provided. It is possible to take measures such as being sent from the nozzle 91 provided in the cover 9 into the cover 9 and gently blowing out from the inlets / outlets 9a and 9b of the container v. As shown in FIG. 16, a structure in which the container v for discharging and supplying is temporarily retained in the container inlet / outlet ports 9a and 9b of the cover 9 (for example, the regulating plate 92 provided at the inlet port 9a).
Is opened from the solid line position to the dotted line position in conjunction with the chain 72, and the opening operation thereof causes the leading container v to pass,
If the passage 9b returns to the position indicated by the solid line, the passage of the next container v is blocked, and the outlet 9b is also provided with a similar restriction plate (not shown in the drawing). It is possible to sufficiently prevent moisture from entering from 9a and 9b.

In FIG. 15, the orbits for rolling the containers v ... Are in two rows, but it goes without saying that any number of parallel orbits can be provided on the upper surface 20 of the common base plate 2 depending on the required processing capacity. .

17 and 18 show another embodiment. The main difference from the above-described embodiment shown in FIGS. 15 and 16 is that
The upper rotation part of the conveyor 80, which is an endless belt or chain, is an endless belt wound around a pair of rollers (or sprockets) 72, 72 instead of the upper surface 20 of the base plate 2 serving as a cooling surface being a fixed surface. Inclination plane part 8 of 80a
1 is the point that is configured. FIG. 17 is a front view from the direction corresponding to FIG. 15 in the above-described embodiment.
FIG. 8 corresponds to FIG. 16 of the above-described embodiment (however, the right half on the outlet 9b side of the container v is not shown).

In this embodiment, the upper surface 20 of the base plate 2 serving as a cooling surface is an endless carrier made of a belt or chain stretched so as to rotate endlessly in a bath w into which the coating liquid applied to the upper surface 20 is stuck. It is constituted by the upper surface of the upper turning portion 80a of 80. Then, the endless carrier 80
Has its lower rotating part 80b rotate in a liquid of a coating liquid such as ethanol, which is filled in the bath w, and the upper rotating part 80b.
a is stretched so as to rotate above the liquid surface of the coating liquid, whereby the lower rotating portion 80b rotates in the coating liquid that is a cooling antifreeze liquid, so that it is automatically cooled. Further, the application liquid for wet contact is automatically applied to the upper surface of the inclined flat surface portion 81 of the upper rotating portion 80a which is the upper surface 20 of the base plate 2. Therefore, in the above embodiment,
A mechanism corresponding to the liquid supply mechanism 6.6 'is unnecessary. However, if the heat capacity of the endless carrier 80 is small, the base plate 2
The temperature of the upper turning portion 80a that constitutes the upper surface 20 of the above gradually rises. To this end, a cooling support plate 83 is provided on the lower surface side of the upper turning part 80a to prevent the upper turning part 80a from bending, and the support plate 83 is cooled by the coating liquid in the bath w. Or, cool it with your own cooling source,
This can be dealt with by adopting a system in which the lower surface of the upper rotating portion 80a of the endless carrier 80 is contacted and supported by the upper surface of the support plate 83 to be cooled and moved.

When the support means 4 shown in FIG. 12 for rolling the container v by forming the support tool 4 on the belt 40 and applying it to the upper surface of the outer peripheral surface of the body of the container v, the support means of FIG. 15, FIG. 16, FIG. Figure, 18th
The channel-shaped or angle-shaped support tool 4 shown in the drawing is omitted, and the lower surface of the belt 40 is in direct contact with the upper surface of the body of the container v, as shown in FIGS. 15, 16, 17, and 18. The configuration is similar to that of the above-described embodiment shown.

Although the mechanism shown in FIGS. 17 and 18 is slightly more complicated than that of the embodiment shown in FIGS. 15 and 16 described above, the movement of the container v It is possible to independently adjust the rotation speed of the container and the transfer speed of the container v. According to the experiment, the inner and outer surfaces of the cylindrical body of the container v have a considerably wide range of rotation speed suitable for forming a freezing tank having a uniform thickness. Therefore, in many cases, by decreasing the rotation speed, Although it is sufficient to lower the transfer rate and extend the freezing time, the embodiments of FIGS. 17 and 18 can be adapted to a wider range of different conditions.

Next, FIGS. 19 and 20 show a third embodiment.
The main difference between this embodiment and the first and second embodiments described above is that the upper surface 20 of the base plate 2 is inclined at an angle α with respect to the horizontal plane.
It is a point where a conical surface having a gradient (including α = 0) or a part of the conical surface is used, and a trajectory for rolling and transporting the container v is a circular trajectory (single or a plurality of concentric circles). . The base plate 2 having the upper surface 20 as a conical surface or a part of the conical surface may be made rotatable by a fixed case or by a rotation axis along the central axis of the conical surface forming the table surface 20. .

FIG. 19 is a cross-sectional view of the orbit of the container v passing through the conical center axis O on the upper surface 20 of the base plate 2 formed in the conical surface (FIG. 10).
(0-c cross section), the support tool 4 for supporting the container v has a rotating shaft 5 passing through the central axis O of the conical surface 20 in this embodiment.
It is attached to a rotary arm 5 that rotates by 0.
As described above, the support tool 4 restrains the container v on the transportation track, but it functions as a loose support tool that allows the container v to roll on the upper surface 20 of the base plate 2. If the base plate 2 is fixed, the rotation speed of the rotary arm 5 regulates the rotation speed of the container v and the revolution speed on a circular orbit centered on the central axis O. If the container v can rotate about the revolution speed of the container v,
The rotation speed of the container v is determined by the difference between the rotation speed of the rotating arm 5 and the rotation speed of the base plate 2.

The container v supplied from the previous process is received on the upper surface 20 of the base plate 2 and the frozen container v is sent to the subsequent process.
Various methods are possible for fixing and rotating, respectively, and FIG. 20 shows an embodiment which can be adopted for both the fixed base plate 2 and the rotary base plate 2. .

FIG. 20 is a conceptual diagram showing the relationship between the circular orbit around which the container v rolls set on the upper surface 20 of the base plate 2 constituting the freezing device and the conveyor line in the front-back process. In the figure, A is tangentially placed on the outer circumference of a circular orbit around which the container v set on the upper surface 20 of the base plate 2 that constitutes the freezing device in the conveyor zone from the previous process rolls. The terminal a is connected to an arc-shaped standby zone B having an angle θ (30 ° in FIG. 20) along the outer circumference of the circular orbit of the freezing device. Part of the circular orbit C (double orbit of outer C1 and inner C2 in the figure) of the freezing device, and the portion corresponding to the standby zone B is Cb
(C1b and C2b). The support 4 arranged above the circular orbit C is supported by the rotating arm 5 (not shown) shown in FIG. 19 described above, and the rotating arm 5 has N parts forming an angle θ (in the figure, Twelve, but the right half of the circular orbit is omitted, and the boundary of each part is shown by a chain double-dashed line), and each part is n (4 in the figure / orbit x 2 orbit = 8) containers v to bound. Each part of the rotary arm 5 stops for a short time when it rotates to the part Cb, and during this period, the rotary arm 5
A feeding mechanism (not shown in FIG. 20) attached to each part or interlocked with the movement of the rotary arm 5 moves the container v in the standby zone B to the portion Cb of the circular orbit C and the portion Cb of the circular orbit C is frozen. The container v is sequentially fed to the take-out zone D (in the figure, the container v after the forward feed from the standby zone B to the part C1b, the part C1b to the part C2b, and the part C2b to the take-out zone D is shown by a solid line, and the container v The position is indicated by a broken line).
If the containers v in the zones B, C, and D are located on the line passing through the center of the circular orbit as shown in FIG. 20, the progressive feeding is easy.

FIG. 21 shows an example of the feeding mechanism. FIG. 21 is a sectional view taken along the line b-o of FIG. 20, showing a portion Cb of the circular orbit from the standby zone B.
And the endless belt 51 hung up to the take-out zone D
And a pair of rollers 52 (4 rows in the example of FIG. 20 for each row of each container v), and each time the rotating arm 5 is stopped,
The belt 51 has one pitch p in the direction shown by the arrow in FIG.
Go to t (width of each zone).

In general, the angle α suitable for shelves is sufficiently smaller than the sliding friction angle between the container v and the belt surface, so that the container v advances one pitch with the belt. Thus, the frozen container v sent from the standby zone B to the take-out zone D via the circular orbit C (two rounds of C1 and C2 in the figure) is transferred to the conveyor for the next process by the discharging mechanism (not shown).

Next, the operation will be described with reference to experimental examples carried out by the embodiments shown in FIGS. 15 and 16.

1) A straight projection with a height of 3 mm is provided on the intersection of the horizontal plane of the stainless steel plane with a slope (angle α) of 1 / 6.6 with respect to the horizontal plane, and 20 g of ethanol is placed along the projection per 1 m of track. Pour into the container v liquid reservoir along the track (width 14 mm, depth about 2
The upper surface 20 of the base plate 2 was cooled to -70 ° C.

2) Container v has a total height of 40 mm, body (outer diameter 20 mm, height 30 m
m), made of glass with a wall thickness of 1 mm on the bottom and body. A lactose aqueous solution having a concentration of 20% by weight was injected at 1.75 m. (The amount of this liquid is 7 mm in the upright state, equivalent to a thickness of 1 mm by shelf-leaving evenly on the inside of the entire body and bottom surface.) 3) At the mouth of the above-mentioned container v at room temperature (+ 25 ° C) Good on the slope, lay the bottom of it on the puddle along the above-mentioned protrusion, 1.
When rolling at various speeds from 0 m / min to 3.0 / min,
At any speed, a good shelf-reed product was obtained within 1 minute.

4) The pitch of the supports 4 mounted in series was 3 cm, and a continuous shelf chain with a capacity of 60 pieces / minute was realized by a bed plate transport chain with a track length of 1.8 m and a track width of 0.1 m.

5) When the container v frozen by the above means was freeze-dried, a good quality dried product was obtained in 5 hours, and there was still room for shortening the time. Since the conventional shelf-less method is not suitable for industry, freeze-drying is performed in an upright non-rotating freezing container v, and if the drying time following freezing time 0.5 to 1 hour is shortened to less than 24 hours, partial melting will occur. So, it saved a lot of time.

6) The product container v obtained by the experiment was cut, and the properties of the freeze-dried product were inspected. As a result, the product was of good quality and had an appropriate shape as shown in Fig. 22 (cross-sectional view of the shelf-completed container v). . The cross section of the layer of the dried product has a frozen layer formed on all bottom surfaces and the inner surface of the straight body part except for the black-painted part 11 in the figure and the blank part of the center of the bottom of about 2 mm [2b in the figure]. The thickness of the frozen layer at the corner of the section is about 2 mm [2t 'in the figure], and the other frozen layers are almost evenly about 1 mm [2t in the figure]. In the case of, the surface of the layer has a depth of 7 mm). All the dimensional units of the container v10 in the figure are mm.

Generally, the freeze-drying time is proportional to the maximum thickness of the frozen layer to the power of 1.5. If a sufficient amount of latent heat for sublimation can be supplied, the thickness ratio according to this shelf Lees example is 2 mm / 7 mm, and (2/7) =
Since it is 1 / 6.55, the freeze-drying time can be shortened to 1/6 or 1/7.

7) With this method, the amount of ethanol adhering to the straight body part of the container v is about 0.1 g, and it is sufficient to supplement 1 kg of ethanol even if 10000 pieces are treated.

[Effect] As described above, the present invention applies a liquid such as ethanol according to a predetermined condition to the upper surface 20 of the coolable base plate 2 by spraying or coating, and the cylindrical cylinder of the container v laid on the upper surface 20. The wetting contact surface Z is formed between the outer peripheral surface of the base and the upper surface 20 of the base plate 2, and the container v is rolled on the upper surface 20 of the base plate 2 by simple handling, and thus the shelves are attached. Since the necessary strong cooling and rotation of the container v and the transportation of the container v advantageous for continuous processing are simultaneously achieved, rapid freezing by shelf shelves, which has conventionally been a laboratory means, can be performed. A drastic reduction in freeze-drying time can be adopted industrially.

[Brief description of drawings]

1 to 4 are explanatory views of a conventional shelf-releasing method, FIG. 1 is an explanatory view of an example in which a container is rotated at a high speed around a vertical centerline in an upright state, and FIG. 2 is an antifreeze liquid. FIG. 3 is an explanatory view of an example in which the container is obliquely tilted and immersed and rotated, FIG. 3 is an explanatory view of a side view of the same means, and FIG. 4 is an example of an example in which a container is supported by a rotating plate body by an inclined rotating shaft. It is a figure. 5 to 14 are explanatory views of the means of the present invention, and FIG. 5 is an explanatory view of the basic form of the means of the present invention, FIG. 6, FIG.
FIG. 10 is an explanatory view of each aspect of the antifreeze film formed on the upper surface of the base plate, FIG. 7, FIG. 9, and FIG. 11 are explanatory views of the shape of each wet contact surface in each of the previous aspects, FIG. FIG. 13, first
FIG. 4 is an explanatory view of means for transferring the container. 15 to 21 show an embodiment of the present invention.
FIG. 16 is a partially cutaway front view of the first embodiment, and FIG. 16 is a partially omitted vertical side view of the same. FIG. 17 is a partially cutaway front view of an essential part of the second embodiment, and FIG. 18 is a vertical cross-sectional side view of the essential part of the same. FIG. 19 is a partially cutaway side view of an essential part of the third embodiment, FIG. 20 is a plan view of the same with a part omitted, and FIG. 21 is a sectional view taken along line vo of FIG. FIG. 22 is an explanatory view of the operation of the present invention. DESCRIPTION OF DRAWING CODE A ... Conveyor zone B ... Standby zone C ... Circular orbit D ... Take-out zone K ... Container transport mechanism R ... Rotating roller Z ... Wetting contact surface Et ... Ethanol v ... Container w ... Bathtub 1 ... Board 1a ... Concave Cavity 10 ... Spindle 2 ... Base plate 20 ... Upper surface 3 ... Liquid pool 30 ... Projection 4 ... Supporting member 40 ... Belt 41 ... Pushing part 42 ... Supporting part 43 ... Restricting part 44 ... Stopping part 5 ... Rotating arm 50 ... Rotating Shaft 51 ... endless belt 52 ... pair of rollers 6.6 '... liquid supply mechanism 70 ... rotating shaft 71 ... sprocket 72 ... chain 80 ... carrier 80a ... upper turning part 80b ... lower turning part 81 ... inclined plane Part 83 ... Support plate 9 ... Heat-proof / moisture-proof cover 9a / 9b ... Doorway 91 ... Nozzle 92 ... Restriction plate

Claims (5)

[Claims] 1. An upper surface of a coolable base plate having a slope of an angle α (including a case of α = 0) with respect to a horizontal plane,
A body that is hygienic, does not freeze in the required temperature range, and that volatilizes easily is sprayed or applied in a thin layer, and the top of the base plate has a cylindrical body filled with the material to be frozen. Lay the container so that the liquid material inside the container does not flow out of the mouth of the container so that the mouth of the container faces the rising direction of the slope of the base plate, and while cooling the base plate, the container Characterized in that the liquid material in the container is frozen along the entire circumference of the inner peripheral surface of the body of the container by rolling in a direction orthogonal to the axial direction of the cylindrical body of the container. Freezing method for frozen material. 2. An upper surface of a conical, coolable base plate having an inclination of an angle α (including a case of α = 0) with respect to a horizontal plane,
A body that is hygienic, does not freeze in the required temperature range, and that volatilizes easily is sprayed or applied in a thin layer, and the top of the base plate has a cylindrical body filled with the material to be frozen. Lay the container so that the liquid material inside the container does not flow out of the mouth of the container, and the mouth of the container is oriented in the direction of rising slope of the upper surface of the base plate, while cooling the base plate. , The container is rolled along a circular orbit centered on the center of the conical upper surface of the base plate to freeze the liquid material in the container along the entire circumference of the inner cylindrical surface of the body of the container. A method for freezing a material to be frozen, comprising: 3. The aircraft has an upper surface at an angle α (α = α) with respect to a horizontal plane.
(Including the case of 0), a slanted base plate that can be cooled, an antifreeze liquid supply mechanism that sprays or applies an antifreeze liquid on the upper surface of the base plate, and a single or a plurality of cylindrical body parts. The freezing container is rotatably supported with its mouth facing the rising direction of the slope of the upper surface of the base plate, and supports the upper surface of the base plate along a direction orthogonal to the direction of the slope of the upper surface of the base plate. And a freezing target container supporting and conveying mechanism for rolling and moving the container. 4. An endless, coolable carrier which is endlessly wound around a pair of wheels whose rotation axis forms an angle α (including α = 0) with respect to a horizontal plane is sanitarily permitted and required. In a tank filled with a liquid that does not freeze in the temperature range and is easily volatilized, the lower rotating portion rotates in the liquid in the tank and the upper rotating portion is above the liquid surface of the liquid in the tank. The upper end of the endless carrier is laid on the upper surface of the upper end of the endless carrier so that the mouth is laid on the upper surface of the endless conveyor in a posture in which the cylinder rises. An apparatus for freezing a liquid material in a container, comprising: a container transporting member that rolls and transports a circular freezing container from one end side to the other end side in the rotating direction of the upward rotating portion. 5. A coolable base plate having a conical base surface having an inclination of an angle α (including α = 0) with respect to a horizontal plane is fixed or along a central axis of the conical base surface. It is rotatably provided by a rotary shaft, and an antifreeze liquid supply mechanism for spraying or applying an antifreeze liquid is provided on the base surface of the base plate, and above the base plate, a mouth portion is formed on the base surface of the base plate with the slope rising. A container with a cylindrical body that can be laid down in the direction of the direction is rotatably supported on the base surface of the base plate and rolls along a circular orbit substantially concentric with the conical shape of the base surface of the base plate. A freezing device for a liquid material in a container, which is provided with a container supporting and transporting member for urging.