JPH08157301A - Production of embedded or encapsulated material and apparatus therefor - Google Patents

Abstract

PURPOSE: To provide an embedded or encapsulating process capable of embedding even an easily damageable and deformable material in a cured resin keeping the original shape and color or encapsulating even a volatile material in a cured resin as it is and provide an apparatus for the production process. CONSTITUTION: The objective material (A) to be embedded or encapsulated is embedded or mixed in a photosetting liquid resin (B) containing a photo- reactive compound having hydrophilic acryloyl group as at least a part of the resin liquid. The produced irradiating object (AB) is filled in a container 2, kept in a refrigerator main body 1 and irradiated with ultraviolet rays with an ultraviolet lamp 3 under cooling with a refrigerant (C) of -10 to +10 deg.C. This production apparatus is provided with the refrigerator main body 1, the container 2 for holding the irradiation object AB, the ultraviolet lamp 3, a storage tank 4 for the refrigerant, a cooling apparatus 5 for supplying the refrigerant C to the refrigerant tank 4 and a refrigerant circulation machine 6.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and apparatus for producing an embedded clathrate in which an object such as a fragile substance or a volatile substance which is easily damaged or deformed is embedded or clathrated in a cured resin. It is a thing.

[0002]

2. Description of the Related Art The preparation of biological specimens is important not only for the medical field but also for purposes such as criminal investigation, academic research, and education. Therefore, it is required that the specimen can be prepared on site, and the morphology and color tone of the prepared specimen are the same as those at the beginning and are not changed for a long period of time.

Biological specimens such as organs and animals are usually stored in a glass bottle while being immersed in an antiseptic liquid such as formalin and alcohol.

In hospitals and the like, when storing tissue pieces taken out by surgery, formalin treatment is followed by ethyl alcohol treatment to obtain specimens, which are vacuum-packed with a resin film for storage. There is.

Regarding the mushroom body sample, in JP-A-5-78201, in the body tissue of mushroom, a hydrophilic UV-curable resin liquid having an acryloyl group is permeated and then cured by ultraviolet light. The method of making it proposed is proposed.

[0006]

The method of storing a biological specimen in a glass bottle while being immersed in formalin, alcohol, or the like may cause discoloration, deterioration, partial swelling or dissolution, and is therefore a long-term storage method. Is not always satisfactory. Further, storing in a glass bottle that is easily damaged and has a large occupied space poses problems in storage, transportation, and handling.

[0007] The method in which a tissue piece is treated with formalin and then treated with ethyl alcohol to prepare a sample, which is vacuum-packed with a resin film and stored, is not suitable for long-term storage, and deformation of the tissue piece is observed. However, there is a disadvantage that it is difficult to observe the tissue pieces.

The method of infiltrating the hydrophilic ultraviolet-curable resin liquid having an acryloyl group into the mushroom tissue and then curing it with ultraviolet light is interesting because it is different from the above two methods. However, in this method, when a substance that is easily damaged or deformed, such as an organ, is embedded in a cured resin product, or a volatile substance is included in a cured resin product, bubbles are generated during curing by ultraviolet irradiation. Occur,
There is a limit in that deformation and discoloration and volatile substances cannot be sufficiently prevented, and there is room for further improvement.

Under such a background, the present invention can embed an object in a resin cured product in its original form and color tone, even if the object is easily damaged or deformed.
It is another object of the present invention to provide a method for producing an embedded clathrate that can be clathrated in a cured resin as it is even if the object is a volatile substance, and an apparatus therefor.

[0010]

A method for producing an embedded clathrate according to the present invention comprises a photocurable resin liquid in which at least a part of the object (A) is a hydrophilic acryloyl group-containing photoreactive compound.
(B) Embedding in or mixing it into the irradiation target (AB), and the cooling target main body with the irradiation target (AB) filled in the container (2)
It is characterized in that the object (AB) is irradiated with ultraviolet rays from the ultraviolet lamp (3) while being placed in (1) and cooled by a refrigerant (C) at -10 ° C to 10 ° C.

The apparatus for producing an embedded inclusion of the present invention is a photocurable resin liquid in which at least a part of the cooler body (1) and the object (A) is a photoreactive compound containing a hydrophilic acryloyl group.
(B) A container (2) for filling the irradiated object (AB) embedded or mixed in it, an ultraviolet lamp (3) for irradiating the irradiated object (AB) with ultraviolet rays, and an irradiated object (AB) Refrigerant (C) in container (2)
It is provided with a refrigerant storage tank (4) cooled by, a cooling / heating machine (5) for sending the refrigerant (C) to the refrigerant storage tank (4), and a refrigerant circulation machine (6).

The present invention will be described in detail below.

The target (A) is a substance (a1) that is easily damaged or deformed in organs, animal living bodies, fragrances, fragrances,
Examples include volatile substances (a2) used for purposes such as deodorants, repellents, antibacterial agents, anti-mite agents, and rust-preventive agents.

As the photocurable resin liquid (B), at least a part thereof (usually 20% by weight or more, preferably 30% by weight or more, especially 35% by weight or more) is a hydrophilic acryloyl group-containing photoreactive compound. The photo-curable resin liquid is used.

Particularly preferred among such hydrophilic acryloyl group-containing photoreactive compounds are hydroxyalkyl acrylates such as hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate and hydroxybutyl methacrylate. (Meth) acrylate.

As the hydrophilic acryloyl group-containing photoreactive compound, a monomer, oligomer or prepolymer having another hydrophilic group may be used together with the above-mentioned hydroxyalkyl (meth) acrylate or in some cases. Also, such ingredients include
Methoxy polyethylene glycol (meth) acrylate, polyethylene glycol mono (meth) acrylate, polyethylene glycol di (meth) acrylate,
2-hydroxy-3-phenoxypropyl (meth) acrylate, (meth) acryloylmorpholine, N-methyl (meth) acrylamide, N, N-dimethyl (meth)
Acrylamide, dimethylaminopropyl (meth) acrylamide, diacetone (meth) acrylamide, N
-Methylol (meth) acrylamide, N, N'-methylenebis (meth) acrylamide, diethylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, diaminoethyl (meth) acrylate, N, N-dimethylamino Examples include monomers such as neopentyl (meth) acrylate, and oligomers and prepolymers having a hydrophilic group represented by a polyethylene glycol unit can also be used.

A photo-curing resin liquid for balancing physical properties
(B) can contain other monofunctional or polyfunctional curable monomers in addition to the hydrophilic acryloyl group-containing photoreactive compound. Examples of such other monofunctional or polyfunctional curable monomers include various alkyl (meth) acrylates, phenoxyalkyl (meth) acrylates, polyhydric alcohol mono, di, tri, tetra or hexa (meth). Examples thereof include acrylate, di (meth) acrylate of di-, tri- or tetra-alkylene glycol, alkoxy-di, mono- (meth) acrylate of tri- or tetra-alkylene glycol.

Further, the modifying polymer may include an oligomer, a prepolymer or a polymer which is compatible with the photocurable resin liquid (B). An example of the modifying resin is N-
Methoxy-6-nylon, urethane acrylate, epoxy acrylate, cellulose acrylic derivative, hydroxyethyl cellulose, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, polyvinyl alcohol, polyacrylate, polyacrylamide, alginate, starch, gelatin, casein, albumin,
Soybean protein, polyethylene oxide, polypropylene oxide, polyethylene oxide-polypropylene oxide block copolymer, polyvinylpyrrolidone, polyvinyl ether and the like.

When the photocurable resin liquid (B) contains a plastic component such as alcohols and polyhydric alcohols, it is effective in adjusting hardness and preventing whitening. In addition, when an appropriate amount of water is contained, heat generation during UV irradiation is suppressed, and the oil and fat content in the object (A) or water or the blended plastic component is prevented from flowing out, and deformation of the object (A) is prevented. It is further suppressed.

To the photocurable resin liquid (B), a small amount of a photopolymerization initiator such as a benzoin ether type, an acetophenone type, a ketal type or a benzophenone type is added (for example, about 0.1 to 5% by weight based on the above composition). However, in some cases, the photocuring reaction may proceed without adding such a photopolymerization initiator.

The above object (A) is a photocurable resin liquid (B)
It is embedded or mixed to form an irradiation object (AB).

Then, the object to be irradiated (AB) is placed in the cooler body (1) with the container (2) being filled, and then the object to be irradiated is
A container (2) filled with (AB) is irradiated with ultraviolet rays from an ultraviolet lamp (3) while being cooled by a refrigerant (C). Cold water or antifreeze is preferably used as the refrigerant (C).

In this case, the temperature of the refrigerant (C) is from -10 ° C to
The temperature is set to 10 ° C, preferably -8 ° C to 8 ° C. Refrigerant (C)
If the temperature is too low, the curing speed may become extremely slow, or the irradiated object (AB) may freeze,
On the other hand, when the temperature of the refrigerant (C) exceeds 10 ° C, bubbles may be generated in the irradiated object (AB) due to the polymerization heat at the time of ultraviolet irradiation,
The object (A) in the irradiated object (AB) may be deformed or discolored,
Volatile components in the irradiated object (AB) volatilize in a non-negligible amount.

Examples of the container (2) include a glass container, a plastic container and a plastic bag. Since UV irradiation is often performed from both the top and bottom of the container (2),
It is desirable that the container (2) be transparent to ultraviolet rays. In the case of a glass container or a plastic container, it is also possible to use a tray-shaped container having an open top. When a tray-shaped container is used, in order to maintain the smoothness of the surface of the cured product, it is possible to cover the surface of the filled irradiation target (AB) with a transparent film and perform ultraviolet irradiation.

When the object (A) is a substance (a1) that is easily damaged or deformed, such as an organ or an animal living body, it is previously stored in the container (2).
An object that consists of a substance (a1) that is liable to be damaged or deformed by the incompletely cured product that has been partially cured by irradiating it with ultraviolet light while filling a part of the photocurable resin liquid (B) Place A) and then fill the photocurable resin liquid (B) from above and irradiate with ultraviolet light once or multiple times, or while continuously filling the photocurable resin liquid (B). It can be irradiated with ultraviolet rays. If such a method is adopted, even for a thick object (A), the heat of polymerization during ultraviolet curing is not stored, and the object (A) is prevented from being deformed or deteriorated.

The hardness of the embedded inclusion after curing can be freely adjusted from agar-like soft one to glass-like hard one by selecting the composition of the photocurable resin liquid (B). be able to. When a highly flexible embedded clathrate is produced, the embedded clathrate is used to remove the
(A) can be taken out or cut out.

As an apparatus for producing the above-mentioned embedded clathrate, at least a part of the cooler body (1) and the object (A) is a photoreactive compound containing a hydrophilic acryloyl group. Container (2) for filling the irradiated object (AB) embedded or mixed in the photocurable resin liquid (B), an ultraviolet lamp (3) for irradiating the irradiated object (AB) with ultraviolet rays, and the irradiated object ( A refrigerant storage tank (4) that cools the container (2) filled with AB) with the refrigerant (C), and a cooler (5) and a refrigerant circulator (6) that send the refrigerant (C) to the refrigerant storage tank (4). A device provided with is preferably used, and is preferably equipped with a blower (9) and a ventilation port (10).

Among them, the ultraviolet lamp (3) is a refrigerant storage tank.
It is preferable to install both above and below (4), but it is also possible to install only above. Refrigerant Circulator (6)
The inlet pipe (7) and the outlet pipe (8) are connected between the refrigerant storage tank (4) and the refrigerant storage tank (4) so that the refrigerant (C) at a constant temperature is circulated and supplied to the refrigerant storage tank (4). desirable.

[0029]

In the present invention, the specific photocurable resin liquid (B)
A container filled with the irradiation target (AB) by embedding or mixing the target (A) into the irradiation target (AB).
While cooling (2) with the refrigerant (C) at 10 ° C to -10 ° C, the ultraviolet lamp (3) irradiates ultraviolet rays.

Therefore, even if the object (A) is a substance that is easily damaged or deformed or a volatile substance, the object (A) can be embedded or included in the cured resin as it is. it can.

[0031]

EXAMPLES The present invention will be further described with reference to examples. Hereinafter, "parts" refers to parts by weight.

Example 1 <Apparatus> FIG. 1 is a schematic view schematically showing an example of an apparatus for producing an embedded enclosure according to the present invention, and the door plate is not shown. FIG. 2 is a front view of FIG.

(1) is a box-shaped cooler main body, and the inside thereof is divided into three stages. A refrigerant storage tank (4) capable of introducing and discharging the refrigerant (C) is disposed at the bottom of the upper of the three stages. The container (2) filled with the irradiation object (AB) is immersed in the refrigerant storage tank (4).

At the top of the upper row are several UV lamps (3)
There are several UV lamps on the bottom of the middle stage.
(3) is arranged. That is, the irradiation object (AB) in the container (2) immersed in the refrigerant storage tank (4) is irradiated with ultraviolet light from above and below by the ultraviolet lamps (3) and (3) arranged above and below. It is supposed to be done.

A cooler / heater (5) and a refrigerant circulator (6) are installed in the lower stage. The lower refrigerant circulator (6) and the upper refrigerant storage tank (4) are connected by an inlet pipe (7) and an outlet pipe (8).
Refrigerant (C) at a constant temperature is circulated and supplied to (4).

Further, a blower (9) is provided on the upper stage of the cooler body (1).
The blower (9) is also attached to the middle stage. Furthermore, two ventilation openings (10) are provided on the upper stage.

<Method> Using the above-mentioned device, the living body of an animal was embedded according to the following procedure. An animal living body is used as the object (A), and 68 parts of 2-hydroxyethyl methacrylate and 5 parts of ethanol are used as the photocurable resin liquid (B).
Part, propylene glycol 20 parts, water 7 parts, and 2-hydroxy-2-methyl-1-phenolpropan-1-one (photopolymerization initiator) 1 part were used. This resin solution was degassed in advance and cooled to about 10 ° C. An antifreeze liquid was used as the refrigerant (C), and a polyethylene tray having a height of 70 mm was used as the container (2).

Procedure 1. The ambient temperature of the upper part of the cooler body (1) is set to 10 ° C, and the temperature of the refrigerant (C) in the refrigerant storage tank (4) is set to 3 ° C. 2. The container (2) is filled with the photocurable resin liquid (B) to a depth of 10 mm, and then the container (2) is immersed in the refrigerant storage tank (4) (the refrigerant (C) does not enter the container (2). Absent). 3. Among the UV lamps (3), only the lamp installed at the bottom of the middle stage is turned on and UV rays are irradiated from the lower side. 4. After about 10 minutes, the curing state is confirmed, and the irradiation time is adjusted until the surface becomes a soft state where it is not completely cured. 5. The object (A) that has been pretreated in advance is placed on the above semi-cured material, and the photocurable resin liquid (B) is placed on top of it for 10-15
Pour to a depth of mm. 6. The lower UV lamp (3) is turned on and UV irradiation is performed. After about 20 minutes, the curing status is confirmed, and the irradiation time is adjusted until the surface does not completely cure and becomes a soft state. 7. Add the photocurable resin liquid (B) to a depth of 10 to 15 mm, and repeat the UV irradiation of 6 and confirm the curing status. This operation is repeated several times so that the object (A) is completely embedded. 8. When the photo-curable resin liquid (B) was added at the end, put a polyester film on the surface to improve the surface finish, and turn on the UV lamps (3) and (3) on both the top and bottom to continue UV irradiation. To do. At this time, heat generation in the central portion of the irradiated object (AB) becomes remarkable, so the blower (9) is operated.

By performing the embedding operation in the above procedure,
It was possible to obtain an embedding body which was free from damage or deformation and whose color tone did not change. In the above, the photocurable resin liquid
The method of sequentially adding (B) was adopted, but a photocurable resin liquid was used.
Ultraviolet irradiation can also be carried out while continuously adding (B).

Example 2 Using the apparatus of Example 1, inclusion of a volatile substance was performed according to the following procedure. A terpene repellent (a2) is used as the object (A), and 40 parts of 2-hydroxyethyl methacrylate and 40 parts of sweet potato starch are used as the photocurable resin liquid (B).
A resin liquid containing 10 parts of polyethylene glycol, 9 parts of water, and 1 part of a benzophenone photopolymerization initiator was used. Refrigerant
An antifreeze solution was used for (C), and a polyethylene bag was used for the container (2).

Procedure 1. 15 parts of the terpene-based repellent which is the object (A) is added to 100 parts of the photocurable resin liquid (B) and uniformly mixed to form a photocurable resin liquid (B). Then this photocurable resin liquid (B)
Is filled in a container (2) consisting of a polyethylene bag, and the opening is heat-sealed. 2. The ambient temperature of the upper part of the cooler body (1) is set to 10 ° C, and the temperature of the refrigerant (C) in the refrigerant storage tank (4) is set to 3 ° C. 3. The container (2) is immersed in the refrigerant (C) in the refrigerant storage tank (4). 4. Turn on both the upper and lower UV lamps (3), (3), and
UV irradiation for 5 minutes.

By performing the embedding operation in the above procedure,
It is possible to obtain a clathrate in which the repellent which is a volatile component is not lost. Since polyethylene has an appropriate gas permeability, the clathrate can be manufactured as a product in a bag.

[0043]

According to the present invention, a specific photocurable resin liquid is used.
Using (B), the object (A) is embedded or mixed therein to form an irradiation object (AB), and the container (2) filled with the irradiation object (AB) is -10 ° C to 10 ° C. Even if the target (A) is a substance that is easily damaged or deformed or a volatile substance, the target (A) is cooled by the refrigerant (C) at ℃ while being irradiated with ultraviolet rays by the UV lamp (3). The (A) can be embedded or included in the cured resin as it is.

[Brief description of drawings]

FIG. 1 is a schematic view schematically showing an example of an apparatus for manufacturing an embedded inclusion of the present invention, in which a door plate is not shown.

FIG. 2 is a front view of FIG.

[Explanation of symbols]

 (AB) ... Irradiation object, (A) ... Target object, (B) ... Photocurable resin liquid, (C) ... Refrigerant, (1) ... Cooler body, (2) ... Container, (3) ... Ultraviolet light Lamp, (4) ... Refrigerant storage tank, (5) ... Refrigerator, (6) ... Refrigerant circulator, (7) ... Inlet pipe, (8) ... Outlet pipe, (9) ... Blower, (10) ... Ventilation port

Claims (5)

[Claims] 1. A photocurable resin liquid in which at least a part of the object (A) is a photoreactive compound containing a hydrophilic acryloyl group.
(B) Embedding in or mixing it into the irradiation target (AB), and the cooling target main body with the irradiation target (AB) filled in the container (2)
(1) The embedded inclusion, which is placed in the inside of the container and is cooled by a refrigerant (C) at -10 ° C to 10 ° C while being irradiated with ultraviolet rays on an irradiation target (AB) by an ultraviolet lamp (3). Manufacturing method. 2. The method for producing an embedded inclusion according to claim 1, wherein the object (A) is a substance (a1) or a volatile substance (a2) which is easily damaged or deformed. 3. The container (2) is filled with a part of the photo-curable resin liquid (B) in advance to be incompletely cured by irradiation with ultraviolet rays, and the incompletely cured product is damaged or deformed. Place an object (A) consisting of an easy substance (a1), and then fill the photocurable resin liquid (B) on top of it and irradiate with ultraviolet light one or more times, or use the photocurable resin liquid. The method for producing an embedded inclusion according to claim 1, wherein the ultraviolet irradiation is performed while continuously filling (B). 4. Irradiation in which a cooler body (1) and an object (A) are embedded or mixed in a photocurable resin liquid (B) at least a part of which is a photoreactive compound containing a hydrophilic acryloyl group. Stuff
Cool the container (2) filled with (AB), the ultraviolet lamp (3) for irradiating the irradiated object (AB) with ultraviolet light, and the container (2) filled with the irradiated object (AB) with the refrigerant (C). Refrigerant storage tank (4) and chiller / cooler (5) and refrigerant circulator that send refrigerant (C) to the refrigerant storage tank (4)
(6) An embedded inclusion manufacturing apparatus comprising: 5. The apparatus for manufacturing an embedded inclusion body according to claim 4, further comprising a blower (9) and a ventilation port (10).