JPH06256434A - Porous body, porous carrier made of porous the body, material with immobilizing function and made using the porous carrier, their production, and composition for producing porous body - Google Patents

Abstract

(57) [Summary] [Structure] An acid anhydride group-containing (meth) acrylic acid ester represented by the following formula [I] and the acid anhydride group-containing (meth) acrylic acid ester represented by the following formula [Ia] A poly (meth) acrylate derived from at least one selected from derivatives and a (meth) acrylate having an alkyl group having 1 to 4 carbon atoms, and a (meth) acrylate having an alkyl group having 1 to 4 carbon atoms. A porous body which is polymerized in the presence of the pores and has pores having a diameter of 0.1 to 20 μm formed on its surface and / or inside. [Chemical 1] [Effects] According to such a porous body, various substances having a specific function can be easily supported and immobilized under mild conditions, and thus it is suitable as a porous carrier for a specific functional substance,
In addition, it can be easily attached as a porous carrier layer or an immobilized functional substance layer on a substrate or the like.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin porous body which can be used as a suitable carrier for immobilizing a compound having a specific function, its use and a production method, and more specifically, a specific acid anhydride group. A porous body obtained by polymerizing a mixture containing a contained (meth) acrylic acid ester as a polymerizable monomer, a porous carrier using the same, an immobilized functional substance using the porous carrier, a production method thereof, and The present invention relates to a composition for producing a porous body.

[0002]

BACKGROUND OF THE INVENTION A carrier made of a resin supports and immobilizes a functional substance having a specific function such as an inorganic compound such as a catalyst and a biological product such as an enzyme or an antibody, and immobilizes these functional substances. It is often used to adapt to specific applications.

For example, in recent years, an enzyme that recognizes various substrates such as nucleic acids, sugars and proteins, and catalyzes a synthetic reaction, a decomposition reaction or a modification reaction using these substrates as a starting material, has been recently used as a synthetic resin carrier. It is used as a reactor in which the immobilized enzyme is immobilized on the substrate to bring it into contact with a substrate solution.

Further, an immobilized antibody obtained by immobilizing an antibody having a function of specifically recognizing a specific substrate such as a protein and binding to the specific substrate on a carrier made of synthetic resin is used to test various specific substrates. Applied to laws and separation methods.

The resin carrier for immobilizing such a substance having a specific function is porous for the purpose of facilitating immobilization of the functional substance or increasing the contact area between the substrate and the functional compound. It is desirable to be sex. Also,
The resin carrier must be able to easily support and immobilize it under conditions that do not inactivate or reduce the function of the functional substance that is the substance to be immobilized. Further, the resin carrier may be used by further adhering it to a specific substrate or the like, and there is an increasing demand for a resin material capable of performing such an adhering operation easily and surely.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in order to solve the problems associated with such conventional techniques, and easily supports various substances having a porous surface, a large surface area and a specific function under mild conditions. -A porous body suitable as a carrier that can be immobilized and that can be easily attached as a porous carrier layer on a substrate or the like, a porous carrier composed of this porous body, and an immobilizing function using the porous carrier. It is an object of the present invention to provide a substance, a method for producing the same, and a composition for producing a porous body.

[0007]

SUMMARY OF THE INVENTION The porous body according to the present invention comprises an acid anhydride group-containing (meth) acrylic acid ester represented by the following formula [I] and the following formula [Ia] of the acid anhydride group-containing (meth) acrylic acid ester. ] At least one selected from the derivatives represented by and a (meth) acrylate having an alkyl group having 1 to 4 carbon atoms is a poly (derived from a (meth) acrylate having an alkyl group having 1 to 4 carbon atoms. It is characterized by being polymerized in the presence of (meth) acrylate, and having pores having a diameter of 0.1 to 20 μm formed on the surface and / or inside thereof.

[0008]

[Chemical 4]

(In the above formula [I] or [Ia], n is 2
To R 6, R ¹ is hydrogen or an alkyl group having 1 to 4 carbon atoms, R ² is hydrogen, an alkyl group having 1 to 4 carbon atoms or a carboxyl group, and R ³ is each independently,
Hydrogen or an alkyl group having 1 to 4 carbon atoms, and when one is an alkyl group, the other is hydrogen. ) A porous carrier according to the present invention is characterized by comprising the above-mentioned porous body.

The immobilized functional substance according to the present invention is characterized in that a functional substance having a specific function is immobilized on the porous carrier. In the immobilized functional substance according to the present invention,
As the functional substance, a functional organic compound such as a liquid crystal compound, an enzyme, a functional protein such as an antibody, or the like can be used.

The method for producing a porous carrier according to the present invention comprises the acid anhydride group-containing (meth) acrylic acid ester represented by the formula [I] and the acid anhydride group-containing (meth) acrylic acid ester represented by the above formula. At least one selected from the derivatives represented by [Ia] and a (meth) acrylate having an alkyl group having 1 to 4 carbon atoms are derived from a (meth) acrylate having an alkyl group having 1 to 4 carbon atoms. It is characterized in that it is polymerized in the presence of poly (meth) acrylate, a polymerization initiator and water.

The method for producing an immobilized functional substance according to the present invention is a method in which the porous substance prepared by the above method is used as a carrier, and the functional substance is supported on the porous carrier. Even if the acid anhydride group-containing (meth) acrylic acid ester [I] and / or its derivative [Ia] and (meth) acrylate are allowed to coexist and be carried during the polymerization, the porous body obtained after the polymerization You may make it carry | support.

The composition for producing a porous body according to the present invention is used in the method for producing a porous body, and comprises an acid anhydride group-containing (meth) acrylic acid ester represented by the above formula [I] and the acid anhydride group. It is characterized by containing at least one selected from the derivatives of the contained (meth) acrylic acid ester represented by the above formula [Ia].

According to the porous body, the porous carrier and the immobilized functional substance according to the present invention, and the production method thereof, various compounds having a specific function can be easily carried and immobilized under mild conditions, and It is possible to easily attach it as a porous carrier layer or an immobilized functional substance layer on a substrate or the like.

The composition for producing a porous body according to the present invention can be preferably used in the production method according to the present invention,
At the time of producing the porous body, it is possible to easily produce the porous body simply by adding and mixing the composition for producing the porous body and other components necessary for polymerization.

[0016]

DETAILED DESCRIPTION OF THE INVENTION The porous material, the porous carrier, the immobilizing functional substance, the method for producing these and the composition for producing the porous material according to the present invention will be described in more detail below.

The porous material according to the present invention has the acid anhydride group-containing (meth) acrylic acid ester represented by the following formula [I] and the acid anhydride group-containing (meth) acrylic acid ester represented by the following formula [Ia]. It is produced using at least one selected from the represented derivatives.

[0018]

[Chemical 5]

However, in the above formula [I], n is an integer of 2 to 6, preferably 2 to 4, and more preferably 2. R ¹ is hydrogen or an alkyl group having 1 to 4 carbon atoms, and R ² is hydrogen, an alkyl group having 1 to 4 carbon atoms or a carboxyl group.

The acid anhydride group-containing (meth) acrylic acid ester [I] used in the present invention is specifically as follows.
4- (2-methacryloyloxyethyl) trimellitic acid anhydride and 3- (2-methacryloyloxyethyl) pyromellitic acid anhydride can be exemplified, and among these, 4- (2-methacryloyloxyethyl) trimellitic acid is particularly preferable. Anhydrous is preferred.

In the above formula [Ia], n, R ¹ and R ² are the same as in the formula [I], and R ³ is each independently
Hydrogen or an alkyl group having 1 to 4 carbon atoms, and when one is an alkyl group, the other is hydrogen.

Therefore, the derivative represented by the formula [Ia] is an acid anhydride group-containing (meth) acrylic acid ester [I].
A hydrolyzate obtained by ring-opening the cyclic acid anhydride group to a pair of carboxyl groups by reacting with water, or one of the pair of carboxyl groups of the hydrolyzate obtained by esterification It is a half-esterified product.

In the present invention, a compound selected from such an acid anhydride group-containing (meth) acrylic acid ester [I] and a derivative of the acid anhydride group-containing (meth) acrylic acid ester [Ia] is polymerized. Used as a polymerizable monomer. Further, these acid anhydride group-containing (meth) acrylic acid ester [I] and its derivative [Ia] may be used alone,
You may use it in combination.

The porous material according to the present invention has a specific (meth) acrylate polymerizable with at least one selected from the above-mentioned acid anhydride group-containing (meth) acrylic acid ester [I] and its derivative [Ia]. It is used as a monomer.

The (meth) acrylate used in the present invention is a (meth) acrylate having an alkyl group having 1 to 4 carbon atoms, and specifically, alkyl monoacrylates such as methyl acrylate, ethyl acrylate and propyl acrylate. Alkylene diacrylates such as ethylene diacrylate and propylene diacrylate; alkyl monomethacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate and butyl methacrylate; alkylene dimethacrylates such as ethylene dimethacrylate and propylene dimethacrylate. I can mention
These may be used alone or in combination.

In the present invention, such (meth) acrylate is usually used in an amount of 1 to 100 parts by weight, preferably 1 part by weight, based on 1 part by weight of the acid anhydride group-containing (meth) acrylic acid ester and / or its hydrolyzate. Is used in an amount of 10 to 50 parts by weight.

In the present invention, such an acid anhydride group-containing (meth) acrylic acid ester [I] and / or its derivative [I] and (meth) acrylate are present in the presence of a specific poly (meth) acrylate. Polymerized.

The poly (meth) acrylate has 1 to 1 carbon atoms.
It is a poly (meth) acrylate derived from a (meth) acrylate having 4 alkyl groups. Specific examples of the (meth) acrylate used for preparing such a poly (meth) acrylate include the compounds listed as specific examples of the above (meth) acrylate, and these compounds may be used alone. , May be used in combination.

Specific examples of the poly (meth) acrylate include polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polybutyl methacrylate and the like. These poly (meth) acrylates may be used alone or in combination.

The molecular weight of the poly (meth) acrylate used in the present invention is not particularly limited, but for example, 300,
000-600,000, preferably 400,000-
It is 500,000.

Further, such a poly (meth) acrylate is mixed with an acid anhydride group-containing (meth) acrylic acid ester [I] and / or its derivative [Ia], (meth) acrylate, or a mixed solution of both. If you do
Fine particles are preferable so that they can be satisfactorily dissolved or dispersed in these, and such fine particle poly (meth)
Acrylate usually has a bulk density of 0.3 to 0.5 g / cm
³ , preferably 0.35 to 0.40 g / cm ³ .

In the present invention, the poly (meth) acrylate is usually 0.1 to 100 parts by weight with respect to 1 part by weight of the acid anhydride group-containing (meth) acrylic acid ester [I] and / or its derivative [Ia]. Parts by weight, preferably 5-20
Used in parts by weight.

In the present invention, the poly (meth) acrylate is used for controlling the viscosity of the mixture at the time of polymerization, the porosity of the prepared porous material, the pore size and the like. Specifically, if the ratio of poly (meth) acrylate / acid anhydride group-containing (meth) acrylic acid ester [I] and / or derivative [Ia] (or (meth) acrylate) in the mixture is reduced, it is possible to reduce It is possible to reduce the viscosity of the prepared mixture, reduce the pore size of the resulting porous body, and increase the number of pores. Further, it is possible to reduce the thickness of the obtained porous body by lowering the viscosity of the mixture, and in this case, formation of pores communicating in the vertical direction can be expected. The porous body is usually used in the form of a film, and the thickness thereof is usually 0.1 μm to several mm, and the carrier is 1 μm to 1 mm.
The range of mm is preferred.

The porous material according to the present invention comprises one kind selected from the above-mentioned acid anhydride group-containing (meth) acrylic acid ester [I] and its derivative [Ia], and (meth).
Acrylate is polymerized in the presence of poly (meth) acrylate, and pores having a diameter of 0.1 to 20 μm are formed on the surface and / or inside, and 50% or more of the pores have a diameter of 1 to 10 μm. It is a very small hole.

Such a porous material can be preferably prepared by polymerizing the above polymerizable monomer component in the presence of water and a polymerization initiator in addition to poly (meth) acrylate. Hereinafter, the method for producing the porous body according to the present invention will be described in detail.

The polymerization initiator used in the method for producing a porous body according to the present invention is not particularly limited as long as it is a polymerization initiator generally used when producing an acrylic polymer at around room temperature, and is not specifically limited. Include a redox-based polymerization initiator, tri-n-, which is a combination of benzoyl peroxide and an amine.
Examples thereof include alkylboron such as butylboron, and partial oxides of alkylboron, and tri-n-butylboron and partial oxides thereof are particularly preferable.

Such a polymerization initiator is usually used in an amount of 0.01 to 10 with respect to 1 part by weight of the acid anhydride group-containing (meth) acrylic acid ester [I] and / or its hydrolyzate.
It is used in an amount of parts by weight, preferably 0.1 to 2.0 parts by weight.

The components described above are mixed to form a mixture at the time of manufacturing the porous body. Such a mixture may contain, in addition to the above components, a functional substance used for supporting and immobilizing.

In the preparation of such a mixture, the above-mentioned acid anhydride group-containing (meth) acrylic acid ester [I] and / or its derivative [Ia], (meth) acrylate, poly (meth) acrylate and a polymerization initiator are used. The mixing order is not particularly limited, and these components may be mixed in any order. However, from the viewpoint of obtaining a uniform mixed state of the respective components, particularly the polymerizable monomers, the acid anhydride group-containing (meth) acrylic acid ester [I] and / or its derivative [Ia] is (meth) It is preferable to dissolve in acrylate and then add the poly (meth) acrylate and the polymerization initiator to prepare a mixture. The preparation of such a mixture is usually performed at a temperature of 0 to 50 ° C, preferably 5 to 15 ° C.

The composition for producing a porous body according to the present invention comprises an acid anhydride group-containing (meth) acrylic acid ester [I] and / or
Alternatively, by adding the other component which contains the derivative [Ia] and is insufficient during the polymerization, that is, the above-mentioned (meth) acrylate, poly (meth) acrylate and the polymerization initiator, it becomes a starting material in the production of the porous body. The above mixture can be prepared. This composition for producing a porous body,
(Meth) acrylate may be contained, and in this case,
At the time of polymerization, poly (meth) acrylate and a polymerization initiator are added to the composition for producing a porous body. Such a composition, together with other ingredients for preparing the mixture,
Each can be housed in a container to form a kit.

By bringing the mixture thus prepared into contact with water, water is supplied into the polymerization reaction system, and the acid anhydride group-containing (meth) acrylic acid ester [I] and / or its hydrolyzate is supplied. And (meth) acrylate polymerizes in the presence of poly (meth) acrylate, a polymerization initiator and water to form a porous body.

As the method for supplying water into the polymerization reaction system during the polymerization reaction, the mixture is brought into contact with steam,
Examples thereof include a method of directly contacting with water or a suitable aqueous solution, a method of contacting with a water-containing material containing water or an aqueous solution, and the like.

When the above mixture is brought into contact with steam, the mixture and steam may be sealed in a suitable container to polymerize the mixture, or the mixture may be polymerized while spraying steam.

When the above mixture is brought into contact with water or a suitable aqueous solution, the mixture may be polymerized while floating on the water surface or the aqueous solution surface, or the mixture may be immersed in water or an aqueous solution for polymerization.

The aqueous solution can be selected according to the functional substance or the like to be carried. For example, when the functional substance is a functional protein such as an antibody or an enzyme, deactivation of these functional proteins is prevented. To do this, the aqueous solution is Tris,
It may be a buffer solution containing acetate, borate, metal salt and the like. Further, the aqueous solution may contain an organic solvent, and examples of such an organic solvent include acetone and carbon atoms of 1
Alcohols of 4 can be mentioned. Such an organic solvent is usually 10% by volume or less, preferably 1% by volume.
Below, more preferably, it is used in an amount of 0.1 vol% or less. When the mixture is floated on the water surface or the aqueous solution surface for polymerization, the polymerization may be performed in a closed system or an open system.

Further, when the mixture is brought into contact with a water-containing substance, examples of the water-containing substance that can be used include woven fabrics, non-woven fabrics and the like impregnated with water or the above aqueous solution, paper such as filter paper and agar. The inner filter paper and agar are preferably used because they are easy to handle and obtain. The contact between the water-containing material and the mixture may be performed in a closed system or an open system.

When agar is used as the water-containing substance and the mixture is poured onto the surface of the agar to polymerize it to produce a membrane-like porous body, agarose is used in order to give the agar an appropriate water content and mechanical strength. Agar preferably contains about 0.1 to 1.5% by weight.

Thus, the polymerization reaction in the presence of water is
It is usually carried out at a temperature of 10 to 50 ° C, preferably 10 to 30 ° C. Further, the polymerization reaction is usually completed within a short time of 1 hour, although it depends on the conditions.

Depending on the contact conditions of the mixture and water,
The pore size and the number of pores of the obtained porous body are affected, and for example, when the amount of water in the polymerization system increases, the pore size and the number of pores tend to increase. Therefore, when a sufficient pore size and the number of pores are not obtained in the open system, the same contact method may be performed in the closed system. If the pore size is too large or the number of pores is too large, the amount of water in the reaction system is reduced.

Specifically, 0.84 part by weight of poly (meth) acrylate powder and tri (tri) acrylate powder are added to 1 part by weight of the total of the acid anhydride group-containing (meth) acrylic acid ester [I] and (meth) acrylate. The membranous porous body obtained by polymerizing a mixture containing 0.05 part by weight of -n-butylboron has a pore diameter of 0.1 to 1 by adjusting the amount of water in the polymerization system.
It is possible to adjust 0 μm and the number of holes in the range of 10 to 10,000 holes / mm ² .

In the present invention, as a method preferably applicable to the production of a porous body, for example, an acid anhydride group-containing (meth) acrylic acid ester [I] and / or its derivative [Ia] (meth) can be used. ) Dissolve in acrylate, and after adding and mixing poly (meth) acrylate to the obtained mixed solution, add a polymerization initiator to the obtained mixed solution to prepare a mixed solution containing a polymerization initiator, and after adding the polymerization initiator It is possible to exemplify a method of developing on a hydrous material within 5 minutes, preferably within 1 minute, and more preferably within 10 seconds. In this method, it is possible to control the pore diameter, the number of pores, etc. of the obtained porous body by adjusting the time from the preparation of the polymerization initiator-containing mixed solution to the development on the water-containing material. In addition, it is possible to increase the number of pores in the porous body by shortening the above time.

The porous material formed after the polymerization is taken out from the reaction system and, if desired, washed with water or a predetermined aqueous solution to be isolated. The taken out porous body can be stored at room temperature and atmospheric pressure, but may be dried and stored under reduced pressure if necessary.

In the method for producing a porous body according to the present invention described above, as described above, the pore diameter and the number of pores per unit area of the produced porous body can be adjusted in a wide range, and the surface area thereof can be set to a desired size. The obtained porous body can be suitably used for various applications.

The porous material of the present invention prepared by such a method can be impregnated with a functional substance in the pores, and the polymerization temperature of the mixture to be polymerized at the time of preparation of the porous material is low, so that the polymerization conditions are mild. Therefore, the functional substance can be fixed by adding the functional substance to the above-mentioned mixture for polymerization, and it can be suitably used as a porous carrier.

When the porous body according to the present invention is used as a porous carrier, the functional substance is physically fixed by utilizing the pores formed on the surface and / or inside thereof, or obtained by polymerization. Since the obtained polymer has a carboxyl group, it is possible to chemically fix the functional substance using this group.

The porous material according to the present invention is adhered to the substrate by applying the polymerization mixture onto a substrate or the like to cause a polymerization reaction, or by once forming the porous material and then adhering it to the substrate. A porous carrier can be formed.

The porous carrier according to the present invention can be applied to various immobilized functional substances by selecting, from these immobilization methods, a condition that does not inactivate or reduce the function of the functional substance. The immobilized functional substance according to the present invention can be suitably used for various devices using the same.

Examples of the functional substance used for the immobilized functional substance according to the present invention include functional inorganic compounds of catalysts, and functional organic compounds such as liquid crystal compounds and functional proteins. it can.

Examples of the functional organic compound used in the present invention include liquid crystal compounds. The immobilized liquid crystal compound of the present invention can be produced by impregnating a porous carrier with the liquid crystal compound by a reduced pressure method or a normal pressure infiltration method.

In the depressurization method, after the porous carrier is formed, the porous carrier is placed in a depressurized chamber, and then immersed in the liquid crystal compound melted under normal pressure, and the liquid crystal is introduced into the pores of the porous carrier by the pressure difference. It is a method of permeating a compound. The normal pressure infiltration method is a method in which a porous carrier is immersed in a liquid crystal compound under normal pressure, and the liquid crystal compound is permeated into the pores by a capillary phenomenon.

Examples of the liquid crystal compound used as the immobilized liquid crystal compound include twist nematic liquid crystal, ferroelectric liquid crystal and antiferroelectric liquid crystal. Such an immobilized liquid crystal compound can be used for a dispersion type liquid crystal device. This distributed device is used for a display device such as a display, a light control device installed in a window or a door, and a light modulation device.

Specific examples of the functional protein used in the present invention include enzymes and antibodies. Enzymes obtained from microorganisms, fungi or animals and plants recognize substrates such as nucleic acids, sugars and proteins, and catalyze specific synthetic reactions, decomposition reactions or modification reactions using these substrates as starting materials. In the present invention, these enzymes themselves, or intracellular organelles containing / producing the enzymes, microbial cells, and animal / plant cells can be immobilized on the above-mentioned porous carrier to prepare immobilized enzymes.

Such an immobilized enzyme is, for example, an enzyme itself, or an intracellular organelle that contains / produces the enzyme in a buffer solution such as Tris / hydrochloric acid containing a metal ion such as magnesium or zinc as necessary. It can be prepared by dissolving or dispersing microbial cells, animal and plant cells and the like to prepare an enzyme-containing (production) solution, and then applying any of the following methods.

That is, the first method is a method of impregnating a porous carrier prepared in advance with an enzyme-containing (production) solution, and whichever of the above-mentioned reduced pressure method or atmospheric pressure permeation method is applied. Good.

In the second method, the acid anhydride group-containing (meth) acrylic acid ester [I] and / or its derivative [Ia], (meth) acrylate and poly (meth) acrylate are used.
In this method, a polymerization initiator, particularly preferably tri-n-butylboron, is added to a mixed solution containing acrylate, and then the obtained mixed solution containing a polymerization initiator is brought into contact with an enzyme-containing (production) solution. The mixed solution before the addition of the polymerization initiator has an acid anhydride group-containing (meth) acrylic acid ester [I] and / or
Alternatively, it is preferable that the derivative [Ia] and (meth) acrylate are uniformly mixed and then poly (meth) acrylate is added to the mixture.

Mixture containing polymerization initiator and enzyme (production)
For contact with the solution, the polymerization initiator-containing mixed solution is put into the enzyme-containing (production) solution and mixed, or the enzyme-containing (production) solution is added.
This can be carried out by preliminarily developing the solution on agar, and then overlaying the polymerization initiator-containing mixed solution on this agar, of which the latter is suitable for forming the immobilized enzyme on the membrane. Is.

The contact between the polymerization initiator-containing mixed solution and the enzyme-containing (production) solution should be performed within 5 minutes, preferably within 1 minute, and particularly preferably within 10 seconds after the addition of the polymerization initiator. Is preferred.

Such an immobilized enzyme can be used as a reactor for the above synthesis reaction, decomposition reaction or modification reaction by contacting it with a substrate solution. Moreover, the antibody can specifically recognize and bind to a specific substrate such as a protein. The immobilized antibody can be produced according to the method for producing an immobilized enzyme as described above, by selecting the conditions that do not inactivate the antibody. Such an immobilized antibody can be applied to a specific substrate separation method such as affinity chromatography and a specific substrate inspection method such as Elisa method.

Furthermore, the immobilized enzyme or the immobilized antibody according to the present invention is characterized by a change in electrical characteristics based on a chemical reaction of a specific substrate catalyzed by an enzyme or a binding reaction of an antibody to a specific substrate, such as a potential difference, a current or It can also be used as a biosensor that measures a change in resistance value to measure the specific substrate. This biosensor is composed of a detection electrode and the above-mentioned immobilized enzyme or immobilized antibody. According to the present invention, the mixture is directly applied on the detection electrode to form the porous carrier layer, and the enzyme or the antibody is carried on the porous carrier layer, whereby the immobilized enzyme layer or the immobilized antibody skin layer is easily deposited on the electrode. The formed sensor can be configured.

[0070]

EFFECTS OF THE INVENTION According to the porous body, the porous carrier, the immobilized functional substance, and the method for producing the same according to the present invention,
It is possible to easily support and immobilize various compounds having specific functions under mild conditions, and it is possible to easily attach it to a desired substrate such as an electrode as a porous carrier layer or an immobilized functional substance layer. .

The composition for producing a porous body according to the present invention can be preferably used in the production method according to the present invention,
At the time of producing the porous body, the composition for producing the porous body and other components necessary for the polymerization, or a functional substance and the like are simply added and mixed to easily form the porous body, the porous carrier or the immobilized functional substance. Can be manufactured.

Hereinafter, the present invention will be described more specifically by way of examples, but the present invention is not limited to these examples.

[0073]

Example 1 4- (2-methacryloyloxyethyl)
50 mg of trimellitic anhydride and 950 mg of methyl methacrylate were mixed to form a uniform solution, and the resulting solution was polymethyl methacrylate (molecular weight: 4300
00 and bulk density 0.37 g / cm ³ 530 mg were added and stirred to prepare a uniform mixture. Then, 30 mg of tri-n-butylboron was added dropwise to the obtained mixture with stirring to prepare a pre-curing mixture.

The obtained pre-curing mixture was placed on agar having a water content of 0.995 g / cm ^{3 and} stored in a container to a thickness of about 1 m.
m was developed, and then the container was kept sealed at a temperature of 18 ° C. for 1 hour to obtain a porous polymer sample 1.

Similarly, the pre-cured mixture spread on agar was maintained at a temperature of 18 ° C. for 1 hour while the container was opened to prepare a porous polymer sample 2, and dry air was introduced into the container. A porous polymer sample 3 was prepared while maintaining the flow state.

The surfaces of the obtained porous body samples 1, 2 and 3 were observed with a scanning electron microscope. Porous polymer samples 1, 2
Scanning electron micrographs of and are shown in FIGS. 1, 2 and 3, respectively.

As shown in FIGS. 1, 2 and 3, the order in which the humidity during preparation of the porous body is high, that is, sample 1 prepared in a closed container, sample 2 prepared in an open container and dry air are circulated. It can be seen that in the order of the prepared sample 3, the pore size is small and the ratio of the open area per unit area or the number of open holes is small.

[0078]

Example 2 Alkaline phosphatase (Escherichia co
li K12 sw 1033 / pk1-5) 50 units of 50 mM Tris-HCl buffer containing 1 mM magnesium chloride (p
H8.0) was dissolved in 1 ml to prepare an enzyme solution.

500 ml of the obtained enzyme solution was spread on agar containing a water content of 0.995 g / cm ³ . Next, 500 μl of the pre-curing mixture prepared in the same manner as in Example 1 was overlaid on the enzyme solution on agar, and the temperature was adjusted to 1
The mixture was allowed to cure by keeping the container sealed at 8 ° C for 1 hour. The obtained cured product was treated with 50 mM Tris-HCl buffer solution (pH 8.0) containing 1 mM magnesium chloride 2
Immobilized alkaline phosphatase was obtained by washing 3 times with ml.

When the p-nilothophenyl phosphate-decomposing activity of the obtained immobilized alkaline phosphatase was measured, it was found that there was approximately 20% of the activity of alkaline phosphatase contained in 500 μl of the enzyme solution used.

[Brief description of drawings]

FIG. 1 is a scanning electron micrograph showing the surface of a porous body sample 1 of Example 1,

FIG. 2 is a scanning electron micrograph showing the surface of the porous body sample 2 of Example 1,

FIG. 3 is a scanning electron micrograph showing the surface of the porous body sample 2 of Example 1.

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Claims (12)

[Claims] 1. An acid anhydride group-containing (meth) acrylic acid ester represented by the following formula [I] and a derivative of the acid anhydride group-containing (meth) acrylic acid ester represented by the following formula [Ia]: And (meth) acrylate having an alkyl group having 1 to 4 carbon atoms in the presence of a poly (meth) acrylate derived from a (meth) acrylate having an alkyl group having 1 to 4 carbon atoms. A porous body having pores with a diameter of 0.1 to 20 μm formed on its surface and / or inside. [Chemical 1] (In the above formula [I] or [Ia], n is an integer of 2 to 6, R ¹ is hydrogen or an alkyl group having 1 to 4 carbon atoms, R ² is hydrogen, alkyl having 1 to 4 carbon atoms. R ³ is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and when one is an alkyl group, the other is hydrogen.) 2. A porous carrier comprising the porous body according to claim 1. 3. An immobilized functional substance, wherein the porous carrier according to claim 2 is immobilized with a functional compound having a specific function. 4. The immobilized functional substance according to claim 3, wherein the functional substance is a liquid crystal compound. 5. The immobilized functional protein according to claim 3, wherein the functional substance is a functional protein. 6. A compound selected from an acid anhydride group-containing (meth) acrylic acid ester represented by the following formula [I] and a derivative of the acid anhydride group-containing (meth) acrylic acid ester represented by the following formula [Ia]. And a (meth) acrylate having an alkyl group having 1 to 4 carbon atoms, a poly (meth) acrylate derived from a (meth) acrylate having an alkyl group having 1 to 4 carbon atoms, a polymerization initiator, and A method for producing a porous body, which comprises polymerizing in the presence of water. [Chemical 2] (In the above formula [I] or [Ia], n is an integer of 2 to 6, R ¹ is hydrogen or an alkyl group having 1 to 4 carbon atoms, R ² is hydrogen, alkyl having 1 to 4 carbon atoms. R ³ is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and when one is an alkyl group, the other is hydrogen.) 7. An acid anhydride group-containing (meth) acrylic acid ester represented by the formula [I] according to claim 6 and the acid anhydride group-containing (meth) acrylic acid ester represented by the formula [Ia]. Poly (meth) acrylate derived from at least one selected from derivatives and (meth) acrylate having an alkyl group having 1 to 4 carbon atoms, and (meth) acrylate having an alkyl group having 1 to 4 carbon atoms, A method for producing an immobilized functional substance, which comprises producing a porous carrier by polymerization in the presence of a polymerization initiator and water, and then immobilizing a functional substance having a specific function on the porous carrier. 8. An acid anhydride group-containing (meth) acrylic acid ester represented by the formula [I] according to claim 6 and the acid anhydride group-containing (meth) acrylic acid ester represented by the formula [Ia]. Poly (meth) acrylate derived from at least one selected from derivatives and (meth) acrylate having an alkyl group having 1 to 4 carbon atoms, and (meth) acrylate having an alkyl group having 1 to 4 carbon atoms, Immobilized functional substance characterized by polymerizing in the presence of a polymerization initiator, water and a functional substance having a specific function to produce a porous carrier, and immobilizing the functional substance on the porous carrier. Manufacturing method. 9. The method for producing an immobilized functional substance according to claim 7, wherein the functional substance is a liquid crystal compound. 10. The method for producing an immobilized functional substance according to claim 7, wherein the functional substance is a functional protein having a specific function. 11. An acid anhydride group-containing (meth) acrylic acid ester represented by the following formula [I] and a derivative of the acid anhydride group-containing (meth) acrylic acid ester represented by the following formula [Ia]: A composition for producing a porous body, comprising at least one of the following: [Chemical 3] (In the above formula [I] or [Ia], n is an integer of 2 to 6, R ¹ is hydrogen or an alkyl group having 1 to 4 carbon atoms, R ² is hydrogen, alkyl having 1 to 4 carbon atoms. R ³ is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and when one is an alkyl group, the other is hydrogen.) 12. An acid anhydride group-containing (meth) acrylic acid ester represented by the above formula [I] and a derivative of the acid anhydride group-containing (meth) acrylic acid ester represented by the above formula [Ia]. 12. The composition for producing a porous body according to claim 11, comprising at least one of the following and a (meth) acrylate having an alkyl group having 1 to 4 carbon atoms.