JPH06228216A - Production of ph-responsive porous polymer - Google Patents

Abstract

PURPOSE:To produce an arbitrary-shape porous material excellent in filtration rate, adsorption rate and desorption rate by applying energy rays to a mixture' of an ionic monomer polymerizable by application of energy rays, a crosslinkable monomer and an inert compound. CONSTITUTION:A uniform polymerizable liquid is prepared from (A) an ionic monomer polymerizable by application of energy rays, (B) a monomer and/or an oligomer crosslinkable by application of energy rays and (C) a compound compatible with the components (A) and (B), incompatible with the polymer synthesized by application of energy rays and inert to energy rays and energy rays are applied thereto. The component (C) is removed as necessary, thus producing the objective pH-responsive porous polymer. A carboxylic group- containing (meth)acrylate is used as the component (A) and a water-soluble substance is used as the component (C). The polymerizable liquid may contain a polymerizable nonionic monomer or oligomer in addition to the component (B). Application of energy rays may be carried out in a state where the polymerizable liquid is in contact with a reinforcing material. Ultraviolet rays or electronic beams are used as the energy rays. This polymer is produced in the form of capsule.

Description

Detailed Description of the Invention

[0001]

The present invention relates to the separation of proteins, colloids, bacteria, viruses, salts, etc. in various processes such as food industry, pharmaceutical industry, electronic industry, wastewater treatment, artificial organs, desalination of seawater, etc. PH response of ultrafiltration membranes, reverse osmosis membranes, microfiltration membranes, adsorbents, packing materials for chromatography, etc. used for the purpose, such as drug delivery systems used for the purpose of sustained drug release. The present invention relates to a method for producing a porous polymer.

[0002]

2. Description of the Related Art In recent years, due to the sophistication of processes in the above industrial fields and the like, it is becoming difficult to simply meet the needs by simple filtration separation, adsorption and the like. Against this background, the development of intelligent systems using stimuli-responsive materials that change their functions in response to external signals and stimuli has attracted attention.

As one of the stimuli-responsive materials, a hydrous gel polymer which swells and contracts when the pH of the environment in which it is placed swells and has been discovered, and its application to drug delivery systems, filtration membranes and the like has been actively studied. . For example, POLYMER
PREPRINTS, JAPAN, 41, (199
2) 665, POLYMER, 31, (1990) 21
57, POLYMER PREPRINTS, JAPAN
N, 39, (1990) 1328 describes application as a filtration membrane.

In addition, JOURNAL OF CONTR
OLED RELEASE, 8, (1988) 179
-182, POLYMER COMMUNICATIO
N, 29, (1988) 204-208, JOURNA.
L OF CONTROLLED RELEASE, 1
5, (1991) 141-152 for application to drag delivery systems. In these examples, since the hydrogel polymer is molded by thermal polymerization of a mixture of an ionic monomer and a crosslinkable monomer and / or oligomer, the structure does not have pores of gel network or higher.

[0005]

The hydrogel polymer obtained by the above thermal polymerization cannot be said to have sufficient performance for practical use. That is, when it is used for a filtration membrane, an adsorbent, a drug delivery system, etc., it is very slow because the filtration rate, adsorption rate, release rate, etc. are governed by the diffusion of water, electrolyte, and drug in the polymer. Have a point. Further, there is also a problem that the time for which the filtration rate, the adsorption rate, the release rate, etc. change due to the pH change is too long, that is, the response is slow.

The object of the present invention is to have a sufficient rate for filtration, adsorption, release, etc. when used in a filtration membrane, an adsorbent, a drug delivery system, etc.
An object of the present invention is to provide a method for producing a pH-responsive porous polymer whose adsorption rate, release rate, etc. can be changed in a short time.

[0007]

The present inventors have completed the present invention as a result of intensive studies to solve the above problems.

[0008]

[Structure] That is, the present invention comprises an ionic monomer (A) polymerizable by irradiation with energy rays, a monomer and / or oligomer (B) crosslinkable by irradiation with energy rays, and a mixture thereof (A + B). Energy rays to a uniform polymerizable liquid containing a compound (C) which is dissolved and is incompatible with the polymer produced by irradiating the mixture (A + B) with energy rays and which is inactive to the energy rays. And a compound (C) is removed if necessary after the irradiation with a compound, which is a method for producing a pH-responsive porous polymer and a method for producing a pH-responsive porous polymer capsule.

The ionic monomer referred to herein is a monomer having a functional group capable of ion dissociation in a suitable pH range, and as the ionic monomer (A) which can be polymerized by irradiation with energy rays used in the present invention. , For example, there is a polymerizable monomer having a carboxyl group, a sulfone group or an amino group, and more specifically, acrylic acid, methacrylic acid, allylsulfonic acid, methallylsulfonic acid,
Vinylsulfonic acid, styrenesulfonic acid, 2-acrylamido-2-phenylpropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid,

N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropylmethacrylamide, N, N-dimethylaminopropylacrylamide and the like can be mentioned. . Among these, a carboxyl group-containing (meth) acrylate or a tertiary amino group-containing (meth) acrylate is particularly preferable because of its high polymerization rate and suitable pH responsiveness.

As the monomer (B) that can be crosslinked by the energy ray used in the present invention, any of the commonly used monomers that can be crosslinked by the energy ray can be used, but it is compatible with the ionic monomer (A). A possible monomer is preferable, and typically, a monomer having two or more double bonds in one molecule, for example, methylenebisacrylamide, ethylenebisacrylamide, diethyleneglycoldi (meth) acrylate, neopentylglycoldi (meth). Acrylate, 1,6-hexanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate,

2,2'-bis (4- (meth) acryloyloxypolyethyleneoxyphenyl) propane, 2,
A bifunctional monomer such as 2′-bis (4- (meth) acryloyloxypolypropyleneoxyphenyl) propane,
Trifunctional monomers such as trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, isocyanurate tri (meth) acrylate, tetrafunctional monomers such as pentaerythritol tetra (meth) acrylate, dipentaerythritol A hexafunctional monomer such as hexaacrylate may be used. It is of course possible to use a mixture of these monomers.

The oligomer which can be cross-linked by irradiation with energy rays used in the present invention is, for example, polymerizable by irradiation with energy rays and has a weight average molecular weight of 500 to 500.
Any of the oligomers 00 having two or more double bonds in one molecule and capable of being crosslinked by an energy ray which is usually used can be used, but it is possible to use an ionic monomer (A) and an energy ray for crosslinking. Oligomer compatible with possible monomer (B) is preferred,
More specifically, it is an oligomer of epoxy resin, polyether resin, polybutadiene resin or polyurethane resin,

For example, acrylic acid ester or methacrylic acid ester of epoxy resin, acrylic acid ester or methacrylic acid ester of polyether resin, acrylic acid ester or methacrylic acid ester of polybutadiene resin, polyurethane resin having an acrylic group or a methacrylic group at a molecular end. Etc. can be mentioned. Of course, these oligomers may be mixed and used, or may be mixed and used with a monomer.

In the present invention, for the purpose of adjusting the strength, elongation, hardness, swelling degree, response speed, etc. of the pH-responsive porous polymer, energy ray-polymerizable in addition to the monomer and / or oligomer (B). , Nonionic monomers and / or oligomers (D) can be added.
As the monomer and / or oligomer (D), any of commonly used monomers and oligomers can be used, but an oligomer compatible with the ionic monomer (A) and the monomer (B) crosslinkable by an energy ray is used. Preferably, specifically, it is a monofunctional monomer or oligomer, for example, acrylamide, methacrylamide,

Polyethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, ethyl (meth) acrylate, hydroxyethyl (meth) acrylate, n-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth ) Acrylate, phenyl (meth) acrylate, phenyl cellosolve (meth) acrylate, n-
Vinylpyrrolidone, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate and the like can be mentioned.

The compound (C) used in the present invention is compatible with the mixture (A + B), is not compatible with the polymer produced by irradiating the mixture (A + B) with energy rays, and has energy There is no particular limitation as long as it is inert to rays, water, monohydric or polyhydric alcohols, alkyl esters such as methyl caprate, dialkyl ketones such as diisobutyl ketone, liquid polyethylene glycol, Polyethylene glycol monoester, polyethylene glycol monoether, polyethylene glycol sorbitan monoester, polyethylene glycol sorbitan diester, polyethylene glycol sorbitan triester,

Polyester polyols, oligomers such as polyethylene glycol amine, cellulose acetate, ethyl cellulose, nitrocellulose, hydroxymethyl cellulose, chitosan, polystyrene, polyvinyl chloride, polycarbonate, polysulfone, polyethersulfone, polyurethane, polyacrylonitrile. Polymers such as polyacrylic acid ester, polyacrylic acid, polymethylmethacrylate, polyacrylamide, polyethylene glycol, polyvinylpyrrolidone, polyvinylmethyl ether, polyvinyl alcohol and copolymers thereof can be mentioned. Among them, oligomers having a weight average molecular weight of 200 to 10,000 are preferably used.

Of course, the compound (C) may be the above-mentioned monomers or oligomers, or a mixture containing them. When it is necessary to remove the compound (C) from the pH-responsive porous polymer of the present invention, the compound (C)
It is preferable that it is water-soluble from the viewpoint of productivity because it is easy to remove.

The viscosity of the polymerizable liquid may vary depending on the intended shape of the porous body and the film forming method, but is preferably 1 to 1,000,000 cps at 25 ° C.
More preferably, it is 0 to 10,000 cps. Outside this range, the manufacturing conditions are more restricted.

Examples of energy rays used in the present invention include electron rays, γ rays, X rays, ultraviolet rays and visible rays. Of these, ultraviolet rays are most preferable because of the ease of use and handling. The intensity of the ultraviolet rays to irradiate is 10
-5000 mw / cm ² is preferable, and the irradiation time is 0.
01 to 100 seconds is preferable. It is also preferable to accelerate the polymerization rate by performing irradiation of ultraviolet rays in an inert gas atmosphere. When ultraviolet rays are used as the energy rays, it is also preferable to add an ultraviolet polymerization initiator to the polymerizable solution for the purpose of increasing the polymerization rate.

The UV polymerization initiator to be used in the present invention is not particularly limited, but a substance soluble in a polymerizable solution is preferable, for example, p-tert-butyltrichloroacetophenone, 2,2'-di Acetophenones such as ethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one; benzophenone, 4,4′-bisdimethylaminobenzophenone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-ethyl Ketones such as thioxanthone and 2-isopropylthioxanthone; benzoin, benzoin methyl ether,

Examples thereof include benzoin ethers such as benzoin isopropyl ether and benzoin isobutyl ether; benzyl ketals such as benzyl dimethyl ketal and hydroxycyclohexyl phenyl ketone. In the present invention, when the polymerizable liquid is an aqueous solution, the pH of the polymerizable liquid may be a pH at which the polymer produced from the mixture of monomers and / or oligomers (A + B) and the compound (C) are phase-separated. preferable. A polymer obtained by polymerization in a pH range where phase separation does not occur has an incomplete formation of a porous structure, resulting in insufficient pH responsiveness.

The fact that the molded polymer has a porous structure can be determined by whether or not polymer molecules or colloidal substances permeate the polymer, and the size of the pores can be determined from the molecular weight of the permeable substance. .

There is no restriction on the shape of the porous polymer produced by the production method of the present invention, and examples thereof include lumps, plates, films, threads, nets, granules, hollow fibers,
It may be tubular, capsule-shaped or any other shape. A pH-responsive porous polymer having a desired shape can be obtained by irradiating with energy rays in a state of being molded into a desired shape, or by curing after being irradiated with energy rays and then shaping.

For example, in the case of producing a film-like porous body, the polymerizable liquid is cast on a support such as a metal plate, irradiated with energy rays, and then peeled off from the support, if necessary. Can be obtained. In addition, it is possible to obtain a hollow fiber-shaped, tubular, or capsule-shaped porous body by extruding a polymerizable liquid into a gas by using a double circular ring nozzle and curing it by irradiating with an energy ray during spontaneous fall. . The capsule manufactured using the pH-responsive porous polymer obtained by the manufacturing method of the present invention contracts or swells, or opens depending on the pH change, and releases the contents in the capsule. Capsules made of these pH-responsive porous polymers are useful not only for pharmaceuticals and agricultural chemicals, but also for industrial applications such as chemical reactions.

The porous body of the present invention can be reinforced with a reinforcing material. Examples of reinforcing materials include threads, cloths, nonwovens, papers, nets, and other porous materials. After the porous body is molded, it can be integrated with the reinforcing material, or can be integrally molded by irradiating an energy ray in a state where the polymerizable liquid and the reinforcing material are in contact with each other.

When the pH-responsive porous polymer of the present invention is reinforced with a reinforcing material, the permeation rate and permeation / interruption flow rate ratio are increased, and the response is generally improved. .

[0029]

The present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited thereto.

Example 1 (Production of Membrane) 27 parts of Aronix M-5400 (manufactured by Toa Gosei Chemical Industry Co., Ltd., a monofunctional acrylic acid ester having a carboxyl group) as an ionic monomer (A),
To control the degree of crosslinking, 63 parts of Aronix M-101 (monofunctional monomer manufactured by Toagosei Kagaku Kogyo Co., Ltd.) as a nonionic monomer and / or oligomer (D), a crosslinkable monomer and / or oligomer ( B) as New Frontier BPE-4 (manufactured by Daiichi Kogyo Co., Ltd.,
10 parts of EO-modified bisphenol A diacrylate),
Isopropyl alcohol (IPA) as compound (C)
120 copies and

With a metal halide lamp, a uniform polymerizable liquid containing 50 parts of water and Irgacure 184 (manufactured by Ciba-Geigy) as an ultraviolet polymerization initiator was sandwiched between glass plates through a silicone rubber spacer. UV intensity of 100 mw / cm ² at 365 nm is 60
After irradiating for 2 seconds, wash with water, thickness 1mm, diameter 25mm
A disk-shaped porous polymer of was obtained. The obtained porous polymer was white immediately after being irradiated with ultraviolet rays and after being washed with water.

(Measurement) The obtained porous polymer was immersed in a buffer solution having a pH of 9.18 at room temperature and gently stirred. It was lifted up 5 hours after the immersion, and the attached water was wiped off, and the weight was measured. As a result, it swelled up to 1.8 times the original weight, and it remained unchanged even after that. Subsequently, the swollen porous polymer was immersed in a buffer solution having a pH of 4.01 at room temperature and gently stirred, and then contracted to the original weight in 1 hour and 90% of the original weight after 3 hours. Contracted until it became almost constant.

Furthermore, this porous polymer was added to a pH range of 2-11.
In the buffer solution, the pH of which increases by about 1 in the range of
It was soaked for a period of time and its weight change was measured.
There is almost no change in the range of ~ 5 and pH 2 at pH 7
1.5 times the weight at pH, 1.9 times at pH 8, 2.
It swelled 1 times and 2.4 times at pH12.

Example 2 (Production of Membrane) A non-woven fabric (MF-180 manufactured by Nippon Vilene) was dipped in the same polymerizable liquid as used in Example 1 and an ultrasonic cleaning machine was used together with the container for the polymerizable liquid. After degassing for 5 minutes, the non-woven fabric is pulled up and placed on a glass plate, and a bar coater is used.
The excess liquid was dropped at (# 7). Then, with a metal halide lamp, the ultraviolet intensity at 365 nm was 10
Irradiate 0 mw / cm2 of UV light for 60 seconds, wash with water,
A membrane reinforced with a non-woven fabric was obtained.

(Measurement) The obtained membrane was mounted on a filtration type filtration tester, and one side of the membrane was treated with 3.0 kgf / of a 0.01% by weight aqueous solution of polyethylene glycol having a molecular weight of 150,000.
It is introduced at a pressure of cm2G, and the other side is released to atmospheric pressure,
When a filtration test was conducted, polyethylene glycol
The solution concentration was 0.01% by weight, the same as the stock solution. From this, it is understood that this membrane is a porous membrane having pores through which polyethylene glycol having a molecular weight of 150,000 can permeate.

Example 3 (Preparation of Membrane) 40 parts of Aronix M-5400 as the ionic monomer (A) and Aronix M-101 as the nonionic monomer and / or oligomer (D) for controlling the degree of crosslinking. As 60 parts of New Frontier B as a crosslinkable monomer and / or oligomer (B)
PE-4 10 parts, molecular weight 1000 as compound (C)
100 parts of polyvinylpyrrolidone (PVP) of 0 and 150 parts of N, N-dimethylacetamide (DMAC)
Department,

Irgacure 18 as an ultraviolet polymerization initiator
A uniform polymerizable liquid in which 7 parts of 4 was mixed was sandwiched between glass plates through a silicone rubber spacer, and the ultraviolet intensity at 365 nm was 100 m with a metal halide lamp.
It was irradiated with w / cm ² ultraviolet rays for 60 seconds and washed with water to obtain a disk-shaped porous polymer having a thickness of 1 mm and a diameter of 25 mm.
The obtained porous polymer was transparent immediately after irradiation with ultraviolet rays, but became semitransparent white when washed with water.

(Measurement) The obtained porous polymer was immersed in a phosphate buffer having a pH of 9.18 at room temperature and gently stirred. As a result, it swelled up to 3 times its original weight 5 hours after the immersion. ,
It swelled up to 3.6 times in 10 hours after the immersion, and did not change even after the swelling. Subsequently, the swollen porous polymer was immersed in a phosphate buffer solution having a pH of 4.01 at room temperature and gently stirred, and then contracted to 2 times the original weight in 2 hours and the original weight in 5 hours. Contracted to 1.3.

Example 4 (Preparation of Membrane) A non-woven fabric (MF-180 manufactured by Nippon Vilene) was dipped in the same polymerizable liquid as used in Example 3, and an ultrasonic cleaner was used together with the container for the polymerizable liquid. After degassing for 5 minutes, the non-woven fabric is pulled up and placed on a glass plate, and a bar coater is used.
The excess liquid was dropped at (# 7). Then, with a metal halide lamp, the ultraviolet intensity at 365 nm was 10
Irradiate with 0 mw / cm ² ultraviolet rays for 60 seconds, wash with water,
A membrane reinforced with a non-woven fabric was obtained.

(Measurement) A pressure of 0.5 kgf / cm ² G was applied to one side of the obtained membrane using a cross-flow type ultrafiltration tester, and the other side was opened to atmospheric pressure, and the permeation flux The test was conducted. As a stock solution, pH = 4.01 buffer and 9.1
When a cycle test was performed in which the buffer solution of 8 was replaced every 30 minutes, the results shown in FIG. 1 were obtained. In both directions of blocking → permeation and permeation → blocking, a fast response speed of the order of minutes is shown, and it can be seen that there is repeatability.

As a stock solution, 0.01% by weight of polyethylene glycol having a molecular weight of 150,000 was dissolved to obtain a pH.
When a buffer solution of 4.01 was used, the polyethylene glycol concentration of the filtrate was 0.01% by weight, which was the same as the stock solution. From this, it is understood that this membrane is a porous membrane having a communication hole through which a polymer having a molecular weight of 150,000 permeates.

Example 5 (Production of Membrane) A porous polymer was produced in the same manner as in Example 3 except that Aronix M-101 was not used.

(Measurement) The obtained porous polymer was immersed in a buffer solution having a pH of 9.18 at room temperature and continued to be gently stirred. After 5 hours of immersion, the original weight was 1.4 times the original weight. It swelled to 1.7 times its original weight in 10 hours and remained unchanged even if it was left for more time. Subsequently, when the swollen porous polymer was immersed in a buffer solution having a pH of 4.01 at room temperature and gently stirred, it contracted to 1.2 times the original weight in 2 hours,
It shrank to 1.1 times its original weight in 4 hours. It can be seen that the change amount is small when the crosslink density is high.

[Example 6] (Production of membrane) The same polymerizable liquid used in Example 2 was extruded into the nitrogen atmosphere from the annular slit of the double annular nozzle having a diameter of 5 mm, and the center of the double annular nozzle was extruded. From the hole, a 0.01% aqueous solution of polyethylene glycol having a molecular weight of 50,000 was extruded as a core agent and allowed to fall spontaneously, and the ultraviolet intensity at 365 nm was 600 in the vicinity of the droplet.
By irradiating ultraviolet rays of mw / cm ² , the diameter is about 3
mm spherical capsules containing aqueous polyethylene glycol solution were obtained.

(Measurement) This capsule was immersed in a buffer solution having a pH of 9.18, but polyethylene glycol was not detected in the buffer solution even after 30 minutes. Subsequently, when this capsule was put into a buffer solution having a pH of 4.01, it rapidly contracted to a diameter of about 2.8 mm, and after 1 minute, polyethylene glycol was detected in the buffer solution.

Comparative Example 1 (Preparation of Membrane) Example 3 was repeated except that the compound (C), which had a molecular weight of 10000, of polyvinylylpyrrolidone (PVP) and N, N-dimethylacetamide (DMAC) were not added. A polymer film was prepared in the same manner. The obtained film had the same dimensions, but was transparent both after irradiation with ultraviolet rays and after washing with water.

(Measurement) The same measurement as in Example 2 was performed on the obtained non-porous polymer. The weight change after immersion in the pH 9.18 buffer solution was 1.2% of the original weight after 17 hours.
The swelling rate was extremely slow, being 1.3 times after 25 hours, and 1.3 times after 25 hours.

[Comparative Example 2] Molecular weight 1 of compound (C)
000 Polyvinylpyrrolidone (PVP) and N,
A membrane reinforced with a nonwoven fabric was prepared in the same manner as in Example 4 except that N-dimethylacetamide (DMAC) was not added.

Using this membrane, the same filtration test as in Example 4 was carried out, except that pH = 9.18 buffer solution, pH = 4.0.
The permeation flux of both buffer solutions of 1 is the measurement limit (0.1 l / m ² ·
h) or less. From this, it can be seen that this film is a non-porous film.

Comparative Example 3 The procedure of Example 4 was repeated except that the ionic monomer (A) Aronix M-5400 was not used and 100 parts of the nonionic monomer Aronix M-101 was used. A membrane reinforced with a non-woven fabric was obtained.

The same test as in Example 4 was conducted using the obtained membrane, but the permeation flow rate of the buffer solution was about 4 even if the pH was changed.
It does not change at 100 l / m ² · h, indicating that this membrane has no pH responsiveness.

As a stock solution, 0.01% by weight of polyethylene glycol having a molecular weight of 150,000 was dissolved in pH.
When a buffer solution of 9.18 was used, the polyethylene glycol concentration of the filtrate was 0.01% by weight, which was the same as the stock solution. From this, it is understood that this membrane is a porous membrane having a communication hole through which a polymer having a molecular weight of 150,000 permeates.

[0053]

INDUSTRIAL APPLICABILITY The present invention has high filtration rate, adsorption rate, release rate, high response rate to pH change, and
It is possible to provide a method for producing a pH-responsive porous polymer in which the filtration rate, the adsorption rate, the release rate, etc. change in a short time according to the change and a porous polymer having an arbitrary shape can be easily formed.

[0054]

[Brief description of drawings]

[Figure 1]

FIG. 1 is a diagram showing the measurement conditions and the measurement results of the fourth embodiment. The lower part of the figure shows the time change (minute) of the pH of the stock solution for filtration, and the upper part of the figure shows the permeation flux (1 / m ² · h) of the membrane depending on the time change of the pH.

Claims (7)

[Claims] 1. An ionic monomer (A) which is polymerizable by irradiation with energy rays, and a monomer and / or oligomer (B) which is crosslinkable by irradiation with energy rays,
It is compatible with these mixtures (A + B),
It is necessary after irradiating the uniform polymerizable liquid containing the compound (C) which is incompatible with the polymer produced by irradiating B) with the energy beam and inactive to the energy beam, with the energy beam. A method for producing a pH-responsive porous polymer, characterized in that the compound (C) is removed according to the method. 2. The ionic monomer (A) capable of being polymerized by irradiation with energy rays contains a carboxyl group (meta).
The production method according to claim 1, which is an acrylate. 3. The production method according to claim 1, wherein the compound (C) is a water-soluble substance. 4. The polymerizable liquid contains, in addition to the monomer and / or oligomer (B), a nonionic monomer and / or oligomer (D) which can be polymerized by irradiation with energy rays. 1, 2 or 3
The manufacturing method described. 5. The pH-responsive porous polymer reinforced by the reinforcing material is produced by irradiating an energy ray with the polymerizable liquid in contact with the reinforcing material. The manufacturing method according to any one of 1 to 4. 6. The manufacturing method according to claim 1, wherein the energy rays are ultraviolet rays or electron rays. 7. A method for producing a pH-responsive porous polymer capsule by the production method according to claim 1.